Vacancy-oxygen Complexes Research Articles

Revealing the role of oxygen on the defect evolution of electron-irradiated tungsten: A combined experimental and simulation study

The evolution of Frenkel pairs has been studied experimentally and theoretically in tungsten, a Body-Centered Cubic metal. We used positron annihilation spectroscopy to characterize vacancy defects induced by electron irradiation in two sets of polycrystalline tungsten samples at room temperature. Doppler Broadening spectrometry showed that some positrons were trapped at pure single vacancies with a lower concentration than expected. At the same time, positron annihilation lifetime spectroscopy revealed that positrons are annihilated in unexpected states with a lifetime 1.44–1.64 times shorter than that of single vacancy (200 ps), namely unidentified (X) defects. Secondary ions mass spectrometry detected a significant concentration of oxygen in these samples, of the same order of magnitude as electron-induced single vacancy. In addition, Cluster dynamics simulated defect behaviors under experimental conditions, and Two-component density functional theory was used to calculate defect annihilation characteristics that are difficult to obtain in experiments. Finally, by combining the theoretical data, we simulated the positron signals and compared them with the experimental data. This enabled us to elucidate the interactions between oxygen and Frenkel Pairs. The X defects were identified as oxygen-vacancy complexes formed during irradiation, as oxygen is mobile in tungsten at room temperature, and can be trapped in a vacancy, while its binding to self-ion atoms leads to their immobilization thus reducing defect recombination. Therefore, we anticipate oxygen to play an important role in the evolution of tungsten microstructure under irradiation.

Oxygen solutes-regulated low temperature embrittlement and high temperature toughness in vanadium

The plasticity of body-centered cubic (BCC) metals is sensitive to interstitial trace impurities. Owing to high oxygen affinity, vanadium (V) shows a tendency of embrittlement with increasing oxygen concentration. However, how oxygen solutes affect the ductile-to-brittle transition (DBT) behavior of V remains unclear. In this study, we investigate the DBT behavior of V with different oxygen solute concentrations using small-punch test. As oxygen content increases, the DBT temperature (DBTT) rises incrementally accompanied by a widening of the semi-brittle transition zone. The reduction of the lower fracture energy plateaus indicates a classical low-temperature embrittlement, while the rising of the upper fracture energy plateaus manifests a remarkable high-temperature toughening. Below DBTT, owing to the strong pinning effect of oxygen-vacancy complexes on dislocations, only a limited number of slip systems were activated with very low dislocation density, and all screw dislocations are immobile. Above DBTT, owing to the intensive interactions between dislocation and oxygen-vacancy complexes, frequent dislocation cross-slips trigger multiple slip systems and accelerate dislocation multiplication and storage, all of which contribute to the high-temperature toughness. These findings clarify the effect of oxygen solute on the DBT of V and guide the design of high-performance refractory metals.

Oxygen-related defects in 4H-SiC from first principles

We investigated the abundance, structures, energy levels, and spin states of oxygen-related defects in 4H-SiC on the basis of first-principles calculations. We applied a hybrid functional in the overall calculations, which gives reliable defect properties, and also considered relevant defect charge states. We identified the oxygen interstitial (O i,1), substitutional oxygen (OC), and oxygen-vacancy (OC V Si) complex as prominent defects in n-type conditions. Among them, OC V Si was predicted as a spin-1 defect with NIR emission in a previous study. On the basis of the obtained results, we discuss the possible spin decoherence sources when employing OC V Si as a spin-to-photon interface.

Oxygen-vacancy defect in 4H-SiC as a near-infrared emitter: An ab initio study

Optically active spin defects in semiconductors can serve as spin-to-photon interfaces, key components in quantum technologies. Silicon carbide (SiC) is a promising host of spin defects thanks to its wide bandgap and well-established crystal growth and device technologies. In this study, we investigated the oxygen-vacancy complexes as potential spin defects in SiC by means of ab initio calculations. We found that the OCVSi defect has a substantially low formation energy compared with its counterpart, OSiVC, regardless of the Fermi level position. The OCVSi defect is stable in its neutral charge state with a high-spin ground state (S = 1) within a wide energy range near the midgap energy. The zero-phonon line (ZPL) of the OCVSi0 defect lies in the near-infrared regime, 1.11–1.24 eV (1004–1117 nm). The radiative lifetime for the ZPL transition of the defect in kk configuration is fairly short (12.5 ns). Furthermore, the estimated Debye–Waller factor for the optical transition is 13.4%, indicating a large weight of ZPL in the photoluminescence spectrum. All together, we conclude that the OCVSi0 defect possesses desirable spin and optical properties and thus is potentially attractive as a quantum bit.

Investigation of oxygen-vacancy complexes in diamond by means of ab initio calculations

Point defects in diamond may act as quantum bits. Recently, oxygen-vacancy related defects have been proposed to the origin of the so-called ST1 color center in diamond that can realize a long-living solid-state quantum memory. Motivated by this proposal we systematically investigate oxygen-vacancy complexes in diamond by means of first principles density functional theory calculations. We find that all the considered oxygen-vacancy defects have a high-spin ground state in their neutral charge state, which disregards them as an origin for the ST1 color center. We identify a high-spin metastable oxygen-vacancy complex and characterize their magneto-optical properties for identification in future experiments.

On the effect of oxygen on the creation of colour centres in swift heavy ion-irradiated AlN

We readdress the nature and creation mechanism of the defects absorbing at 4.7 eV in Swift Heavy Ion (SHI)-irradiated AlN semiconductor. Irradiations are performed in different controlled atmospheres (vacuum, oxygen, helium or argon partial pressure) to investigate the coupled effects of (i) the synergy between electronic excitations (Se) and nuclear collisions (Sn) for point defect creation and (ii) SHI-induced impurity introduction/diffusion into the AlN layer. We found that the synergy, previously reported, between Se and Sn for defect formation must also be related to the presence of oxygen during irradiation. At the same Se, the synergy parameter is indeed increased by up to two orders of magnitude during irradiation under O2 compared to irradiation under vacuum. By SHI irradiation and by a fine-tuning of the irradiation atmosphere, we then control the activation or inhibition of these light-emitted point defects (oxygen-vacancy complexes) which can be used as qubits for applications in quantum computing.

Visible and infrared photoluminescence of Er-doped AlN films: Excitation of Er ions via efficient nonradiative energy transfer from the host level

Aluminum nitride (AlN) is a multifunctional semiconductor. AlN doped with rare earth ions has broad application prospects in monochromatic lighting, color display, laser medium, medical treatment, etc. In this paper, an Er3+-doped AlN film has been prepared by radio frequency magnetron sputtering and characterized by surface morphology, chemical composition and photoluminescence (PL), focusing on the emission mechanism of Er3+ in the AlN host. The films show PL in a wide range of the visible (540, 560 and 668 nm) and near-infrared (816, 869, 985 and 1534 nm) ranges. It has been found a certain energy transfer bridge between Er3+ and AlN defect-related optical transitions. At 532 nm excitation, VAl-ON vacancy-oxygen complex in the AlN host efficiently absorbs photons, then, nonradiative energy transfer (NRET) occurs from the defect levels to the levels of Er3+ since they are in resonance. Since there is a resonance of a donor emission level and an acceptor absorption level, Förster resonance energy transfer (FRET) occurs with the transfer efficiency about 51%. This results in a very strong enhancement of excitation of the 4f related PL. On the contrary, optical excitation at other energies results in a low intensity of the Er3+ PL. As a matter of facts, a strong absorption of the AlN host and the FRET-enabling resonance of donor-acceptor levels allow for a great enhancement of the PL efficiency of Er3+ ions. The results show that the impurity defect state of AlN has an important influence on the Er3+ luminescence efficiency.

Polaronic defects in monolayer CeO2: Quantum confinement effect and strain engineering.

We uncover the structure, stability, and electronic properties of polaronic defects in monolayer (ML) CeO2 by means of first-principles calculations, with special attention paid to the quantum confinement effect induced by dimensionality reduction. Results show that the polaron can be more stabilized in ML CeO2 than in the bulk, while formation of oxygen vacancy (Vo2+) and polaron-vacancy complexes [(Vo2+-1polaron)1+, (Vo2+-2polaron)0] tends to be more difficult. The polaronic defect states sit deeper in energy within the bandgap of ML CeO2 compared to the bulk case. We further demonstrate that the epitaxial strain in ceria film, as normally exists when grown on metal substrate, plays a crucial role in regulating the defect energetics and electronic structures. In particular, the formation energies of polarons, Vo2+, (Vo2+-1polaron)1+, and (Vo2+-2polaron)0, generally decrease with tensile strain, leading to controllable defect concentration with strain and temperature. This study not only provides physical insights into the polaronic defects in ultrathin oxide films, but also sheds light on their potential technological applications in nanoelectronics, fuel cells, and catalysts.

Identification of an Oxygen Defect in Hexagonal Boron Nitride.

Paramagnetic fluorescent defects in two-dimensional hexagonal boron nitride (hBN) are promising building blocks for quantum information processing. Although numerous defect-related single-photon sources and a few quantum bits have been found, except for the boron vacancy, their identification is still elusive. Here, we demonstrate that the comparison of experimental and first-principles simulated electron paramagnetic resonance (EPR) spectra is a powerful tool for defect identification in hBN, and first-principles modeling is inevitable in this process as a result of the dense nuclear spin environment of hBN. In particular, a recently observed EPR center is associated with the negatively charged oxygen vacancy complex by means of the many-body perturbation theory method on top of hybrid density functional calculations. To our surprise, the negatively charged oxygen vacancy complex produces a coherent emission around 2 eV with a well-reproducing previously recorded photoluminescence spectrum of some quantum emitters, according to our calculations.

Ferromagnetic Behavior and Magneto-Optical Properties of Semiconducting Co-Doped ZnO.

ZnO is a well-known semiconducting material showing a wide bandgap and an n-type intrinsic behavior of high interest in applications such as transparent electronics, piezoelectricity, optoelectronics, and photovoltaics. This semiconductor becomes even more attractive when doped with a few atomic percent of a transition metal. Indeed, e.g., the introduction of substitutional Co atoms in ZnO (ZCO) induces the appearance of room temperature ferromagnetism (RT-FM) and magneto-optical effects, making this material one of the most important representatives of so-called dilute magnetic semiconductors (DMSs). In the present review, we discuss the magnetic and magneto-optical properties of Co-doped ZnO thin films by considering also the significant improvements in the properties induced by post-growth irradiation with atomic hydrogen. We also show how all of these properties can be accounted for by a theoretical model based on the formation of Co-VO (oxygen vacancy) complexes and the concurrent presence of shallow donor defects, thus giving a sound support to this model to explain the RT-FM in ZCO DMSs.

First-principles study of radiation defects in silicon

The study of the properties of defects in silicon forming under irradiation condition has been carried out for many years, however, many open questions remain. Particularly, there are not comprehensive results for variety of radiation centers calculated at the same level of theory. For example the previously calculated transition levels and formation energies show a large scatter. In this work, we focus on the important radiation-induced defect complexes in Si: double vacancy, vacancy-oxygen, vacancy-phosphorus. Additionally, the phosphorus–vacancy-oxygen complex was studied. Formation energy, charge transition levels and binding energy were calculated from first-principles using the hybrid exchange–correlation functional HSE06. Spin-polarized calculations and large supercells allows us to obtain charge transition levels which agree well with experimental measurements.

Manipulating magnetic and magnetoresistive properties by oxygen vacancy complexes in GCMO thin films

The effect of in situ annealing is investigated in Gd0.1Ca0.9MnO3 (GCMO) thin films in oxygen and vacuum atmospheres. We show that the reduction of oxygen content in GCMO lattice by vacuum annealing induced more oxygen complex vacancies in both subsurface and interface regions and larger grain domains when compared with the pristine one. Consequently, the double exchange interaction is suppressed and the metallic-ferromagnetic state below Curie temperature turned into spin-glass insulating state. In contrast, the magnetic and resistivity measurements show that the oxygen treatment increases ferromagnetic phase volume, resulting in greater magnetization (M S) and improved magnetoresistivity properties below Curie temperature by improving the double exchange interaction. The threshold field to observe the training effect is decreased in oxygen treated film. In addition, the positron annihilation spectroscopy analysis exhibits fewer open volume defects in the subsurface region for oxygen treated film when compared with the pristine sample. These results unambiguously demonstrate that the oxygen treated film with significant spin memory and greater magnetoresistance can be a potential candidate for the future memristor applications.

Calibrations coefficients for determination of concentrations of vacancy-oxygen-related complexes and oxygen dimer in silicon by means of infrared absorption spectroscopy

Vacancy-oxygen complexes VnOm (n, m ≥ 1) in crystalline silicon are nucleation centers for oxygen precipitates, which are widely used as internal getters in modern technologies of production of silicon-based electronic devices and integrated circuits. For the controllable formation of oxygen precipitates in Si crystals in the technology processes the methods of determination of concentrations of the VnOm complexes are required. The aim of the present work was to find values of the calibration coefficients for determination of concentrations of the VnOm defects in Si from intensities of infrared (IR) absorption bands associated with the local vibrational modes (LVM) of these complexes. A combined electrical (Hall effect) and optical (IR absorption) study of vacancy-oxygen defects in identical silicon crystals irradiated with 6 MeV electrons was carried out. Based on the analysis of the data obtained, the values of the calibration coefficient for the determination of concentration of the vacancy-oxygen (VO) complex in silicon by the infrared absorption method were established: for measurements at room temperature (RT) – NVO = 8.5 · 1016 · αVO-RT cm–3, in the case of low-temperature (LT, Т ≡ 10 K) measurements – NVO = 3.5 · 1016 · αVO-LT cm–3, where αVO-RT(LT) are absorption coefficients in maxima of the LVM bands due to the VO complex in the spectra measured at corresponding temperatures. Calibration coefficients for the determination of concentrations of other VnOm (VO2, VO3, VO4, V2O and V3O) complexes and the oxygen dimer (O2) from an analysis of infrared absorption spectra measured at room temperature have been also determined.

Vacancy-type defects in bulk GaN grown by oxide vapor phase epitaxy probed using positron annihilation

Defects in bulk GaN grown by the oxide vapor phase epitaxy (OVPE) method were probed by using positron annihilation spectroscopy. Measurements of the Doppler broadening spectra of the annihilation radiation and lifetime spectra of positrons revealed that the major defect species in OVPE-GaN was Ga vacancy-type defects coupled with oxygen atoms such as VGa(ON)n and VGaVN(ON)n. The formation of vacancy-oxygen complexes was attributed to the high concentration of oxygen incorporated in the samples during their growth process. A correlation between such defect complexes and sample transparencies was observed. An 8-μm-thick epitaxial film grown on OVPE-GaN by using metalorganic vapor phase epitaxy was also characterized. The vacancy concentration in the GaN film was found to be under or close to the detection limit of positron annihilation (1015 cm−3), suggesting that an epitaxial layer can be grown on without being influenced by vacancies in the substrates.

Tuned AFM–FM coupling by the formation of vacancy complex in Gd0.6Ca0.4MnO3 thin film lattice

The effect of in situ oxygen and vacuum annealings on the low bandwidth manganite Gd1−x Ca x MnO3 (GCMO) thin film with x = 0.4 was investigated. Based on the magnetic measurements, the AFM–FM coupling is suppressed by the vacuum annealing treatment via destroying the double exchange interaction and increasing the unit cell volume by converting the Mn4+ to the Mn3+. Consequently, resistance increases significantly compared to pristine film. The results are explained by a model obtained from the positron annihilation studies, where the vacuum annealing increased the annihilation lifetime in A and B sites due to the formation of vacancy complexes V A,B–V O, which was not the case in the pristine sample. The positron annihilation analysis indicated that most of the open volume defects have been detected in the interface region rather than on the subsurface layer and this result is confirmed by detailed x-ray reflection analysis. On the other hand, the effect of oxygen annealing on the unit cell volume and magnetization was insignificant. This is in agreement with positron annihilation results which demonstrated that the introduction of oxygen does not change the number of cation vacancies significantly. This work demonstrates that the modification of oxygen vacancies and vacancy complexes can tune magnetic and electronic structure of the epitaxial thin films to provide new functionalities in future applications.

In situ defect quantification and phase identification during flash sintering using Raman spectroscopy

AbstractFlash sintering has been established as a method to rapidly densify or induce phase transformation in materials by applying an electric field. Understanding rapid transformations is challenging in a laboratory setting, where phase and defect populations may change with sub‐second time scales. In this work, we apply in situ Raman spectroscopy to investigate defect complexes and phase transformations during flash sintering. We demonstrate that the oxygen vacancy complexes in Ce0.85Gd0.15O1.925 and the evolving phases in a SrCO3 + V2O5 reaction can be probed with acquisition times sufficient to monitor stage II of flash sintering. We establish how thermal effects can be separated from effects of the electric field and determine the resolution of the defect concentration. The fast characterization we demonstrate here can be combined with well‐developed models of thermal and phase evolution to elucidate the mechanism of densification during flash sintering.

Role of the intensity of high-temperature electron irradiation in accumulation of vacancy-oxygen defects in Cz n-Si

Kinetics of accumulation of oxygen–vacancy complexes, which is the dominant radiation-induced structural defect in the monocrystalline n-type Czochralski (Cz) silicon was studied experimentally and theoretically for silicon samples irradiated with electron beam pulses of various intensities and energies at 360 °C. The irradiation intensity was shown to have no effect on oxygen–vacancy complexes formation at temperatures when the complexes were unstable, but the complexes annealing efficiency revealed significant dependence on the electron beam intensity. In contrast, the electron beam energy affected the formation rate of vacancies themselves and their complexes with oxygen, but it did not influence annealing properties of oxygen–vacancy complexes. It occurred that the complexes generated in silicon at room temperature could be annealed at 360 °C much faster if irradiated with the electron beam during annealing. The results suggested an important role of radiation-induced ionization of a silicon crystal in transformation of oxygen–vacancy complexes into even more loaded complexes.

Influence of isotopic composition of silicon on local vibrational modes of vacancy-oxygen complex

Isotopic composition of natural silicon (28Si (92.23 %), 29Si (4.68 %) and 30Si (3.09 %)) affects noticeably the shape of infrared absorption bands related to the oxygen impurity atoms. The positions of local vibrational modes (LVMs), related to quasimolecules 28Si – 16OS – 29Si and 28Si – 16OS – 30Si (OS – substitutional oxygen atom) have been determined for the absorption spectra measured at Т ≅ 20 K and at room temperature (Т ≅ 300 K). An estimation of the isotopic shifts of corresponding modes in a semi empirical way has been done by the fitting the shape of the experimentally measured absorption band related to the vacancy-oxygen center in irradiated Si crystals. The LVM isotope shifts at Т ≅ 300 K are found to be (2.22 ± 0.25) сm–1 for 28Si – 16OS – 29Si and (4.19 ± 0.80) сm–1 for 28Si – 16OS – 30Si in relation to the most intense band with its maximum at (830.29 ± 0.09) cm–1 due to the vibrations of 28Si – 16OS – 28Si, and the full width at half maximum of the A-center absorption bands is (5.30 ± 0.26) cm–1. At Т ≅ 20 K the corresponding values have been determined as (1.51 ± 0.13); (2.92 ± 0.20); (835.78 ± 0.01) and (2.34 ± 0.03) сm–1. A model for the calculation of isotopic shifts in the considered case has been discussed. From an analysis of the observed isotopic shifts some information about the structure of the vacancy-oxygen complex in silicon at Т ≅ 20 K and at room temperature has been obtained.

Annealing behaviors of vacancy-type defects in AlN deposited by radio-frequency sputtering and metalorganic vapor phase epitaxy studied using monoenergetic positron beams

Vacancy-type defects in AlN films were probed by using monoenergetic positron beams. The AlN films were deposited on sapphire substrates by using a radio-frequency sputtering technique. Epitaxial films grown by metalorganic vapor phase epitaxy on the sputtered AlN films were also characterized. For the sputtered AlN, the major defect species was identified to be complexes between Al-vacancy and oxygen atoms located at nitrogen sites. Vacancy clusters were introduced after annealing at 1300 °C in the N2 atmosphere but their concentration decreased with a higher annealing temperature. The vacancy–oxygen complexes, however, still existed in the AlN film after annealing at 1700 °C. For the AlN epitaxial films, the concentration of vacancy clusters increased as the growth temperature increased up to 1300 °C but it decreased with the post-growth annealing at 1700 °C.

Oxygen solutes induced anomalous hardening, toughening and embrittlement in body-centered cubic vanadium

Vanadium (V) is sensitive to minute quantity of oxygen interstitials, which induce pronounced hardening and embrittlement. Here, we utilize oxygen to synthesize V solid solutions in order to reveal the mechanism of oxygen solutes induced hardening. With increasing of oxygen solute concentrations, the fracture modes of V samples transform from dimple, to a mixture of dimple and cleavage, and to a fully transgranular cleavage. High density of dislocations and dislocation debris are produced in strained samples. The mobility of screw dislocations is reduced and the dislocation cross-slip events are promoted by oxygen solutes. In addition to oxygen solution hardening, the generation of high density of oxygen-vacancy complexes plays a dominant role in the strengthening. High quantity of loop-shaped dislocation debris are direct evidence for the formation of oxygen-vacancy complexes. Profuse oxygen-vacancy complexes trap dislocations, promote cross-slips and assist dislocation storage, thus give rise to a superior combination of strengthening, strain hardening, and ductility in V with 1.0 at% of oxygen. Once beyond a critical oxygen concentration (>1.6 at%), V shows catastrophic brittle failure due to the exceptional high density of oxygen-vacancy complexes. These findings provide insight to design high performance refractory metals utilizing oxygen solutes.