By first-principles LSDA+U calculations, we revealed that the current physical picture of defective uranium dioxide suggested solely by neutron diffraction analysis is unsatisfactory. An understanding based on quantum theory has been established as a thermodynamical competition among point defects and cuboctahedral cluster, which naturally interprets the puzzled origin of the asymmetric O' and O'' interstitials. It also gives a clear and consistent agreement with most available experimental data. Unfortunately, the observed high occupation of O'' site cannot be accounted for in this picture and is still a challenge for theoretical simulations.
Oxygen-stripes in La0.5Ca0.5MnO3 from ab initio calculations
采用Hartree-Fock近似下的从头计算方法研究了钙钛矿型La0.5Ca0.5MnO3的电子、磁性和轨道性质.利用Radaelli等人[Phys. Rev B 55，3015（1997）]报道的实验晶体结构，我们发现了电荷有序条纹状基态。条纹的周期性和绝缘CE型磁结构与中子X射线和电子衍射实验一致。然而，详细的结构是更复杂的比简单的模型设想的Mn d-水平上的电荷和轨道顺序，并更好地描述为一个电荷密度波的氧空穴，耦合到Mn自旋/轨道顺序。
Hydrogen/nitrogen/oxygen defect complexes in silicon from computational searches
Point defect complexes in crystalline silicon composed of hydrogen, nitrogen, and oxygen atoms are studied within density-functional theory (DFT). Ab initio Random Structure Searching (AIRSS) is used to find low-energy defect structures. We find new lowest-energy structures for several defects: the triple-oxygen defect, {3O}, triple oxygen with a nitrogen atom, {N, 3O}, triple nitrogen with an oxygen atom, {3N,O}, double hydrogen and an oxygen atom, {2H,O}, double hydrogen and oxygen atoms, {2H,2O} and four hydrogen/nitrogen/oxygen complexes, {H,N,O}, {2H,N,O}, {H,2N,O} and {H,N,2O}. We find t…
Point defects in diamond are of high interest as candidates for realizing solid state quantum bits, bioimaging agents, or ultrasensitive electric or magnetic field sensors. Various artificial diamond synthesis methods should introduce oxygen contamination in diamond, however, the incorporation of oxygen into diamond crystal and the nature of oxygen-related point defects are largely unknown. Oxygen may be potentially interesting as a source of quantum bits or it may interact with other point defects which are well established solid state qubits. Here we employ plane-wave supercell calculations …
Machine learning is changing how we design and interpret experiments in materials science. In this work, we show how unsupervised learning, combined with ab initio modeling, improves our understanding of structural metastability in multicomponent alloys. We use the example case of Al-O-N alloys where the formation of aluminum vacancies in wurtzite AlN upon the incorporation of substitutional oxygen can be seen as a general mechanism of solids where crystal symmetry is reduced to stabilize defects. The ideal AlN wurtzite crystal structure occupation cannot be matched due to the presence of an a…
Although defects on graphene can degrade electron transport and its ability for use as a protection layer, they can also be helpful to tailor the local properties or activate new sites for particular adsorbates. Here, carbon vacancy defects are formed in graphene films on Ru(0001) using low energy Ar$^+$ bombardment and the materials are then reacted at room temperature with oxygen (O$_2$). Helium low energy ion scattering shows that no oxygen attaches to the intact graphene layer. When isolated single carbon vacancy defects are present, oxygen adsorbs molecularly at the defect sites and inter…
Oxygen vacancies (VO), a common type of point defects in metal oxides materials, play important roles on the physical and chemical properties. To obtain stoichiometric oxide crystal, the pre-existing VO is always removed via careful post-annealing treatment at high temperature in air or oxygen atmosphere. However, the annealing conditions is difficult to control and the removal of VO in bulk phase is restrained due to high energy barrier of VO migration. Here, we selected VO2 crystal film as the model system and developed an alternative annealing treatment aided by controllable hydrogen doping…
The dielectric breakdown at metal-oxide interfaces is a critical electronic device failure mechanism. Electronic tunneling through dielectric layers is a well-accepted explanation for this phenomenon. Theoretical band alignment studies, providing information about tunneling, have already been conducted in the literature for metal-oxide interfaces. However, most of the time materials were assumed defect free. Oxygen vacancies being very common in oxides, their effect on band lineup is of prime importance in understanding electron tunneling in realistic materials and devices. This work explores …
$\text{N}_{2}\text{V}$ defect in diamond is characterized by means of \emph{ab initio} methods relying on density functional theory calculated parameters of a Hubbard model Hamiltonian. It is shown that this approach appropriately describes the energy levels of correlated excited states induced by this defect. By determining its critical magneto-optical parameters, we propose to realize a long-living quantum memory by $\text{N}_{2}\text{V}$ defect in diamond.
Electron-defect ($e$-d) interactions govern charge carrier dynamics at low temperature, where they limit the carrier mobility and give rise to phenomena of broad relevance in condensed matter physics. Ab initio calculations of $e$-d interactions are still in their infancy, mainly because they require large supercells and computationally expensive workflows. Here we develop an efficient ab initio approach for computing elastic $e$-d interactions, their associated $e$-d relaxation times (RTs), and the low-temperature defect-limited carrier mobility. The method is applied to silicon with simple n…
The double perovskite La2NiMnO6 (LNMO) exhibits complex magnetism due to the competition of magnetic interactions that are strongly affected by structural and magnetic inhomogeneities. In this work, we study the effect of oxygen annealing on the structure and magnetism of epitaxial thin films grown by pulsed laser deposition. The key observations are that a longer annealing time leads to a reduction of saturation magnetization and an enhancement in the ferromagnetic transition temperature. We explain these results based upon epitaxial strain and oxygen defect engineering. The oxygen enrichment…
Oxygen is widely used to tune the performance of chalcogenide phase-change materials in the usage of phase-Change random access memory (PCRAM) which is considered as the most promising next-generation non-volatile memory. However, the microscopic role of oxygen in the write-erase process, i.e., the reversible phase transition between crystalline and amorphous state of phase-change materials is not clear yet. Using oxygen doped GeTe as an example, this work unravels the role of oxygen at the atomic scale by means of ab initio total energy calculations and ab initio molecular dynamics simulation…
Oxygen defects govern the behavior of a range of materials spanning catalysis, quantum computing, and nuclear energy. Understanding and controlling these defects is particularly important for the safe use, storage, and disposal of actinide oxides in the nuclear fuel cycle, since their oxidation state influences fuel lifetimes, stability, and the contamination of groundwater. However, poorly understood nanoscale fluctuations in these systems can lead to significant deviations from bulk oxidation behavior. Here we describe the first use of aberration-corrected scanning transmission electron micr…
The optoelectronic properties induced by oxygen vacancy defects in MgO(111) monolayers have been studied using hybrid level of DFT method. HSE calculations shows significant reduction in electronic band gap of MgO monolayer as a result of introduction of oxygen vacancies. The pristine monolayer has a wide band gap (4.84 eV, indirect) semiconducting behaviour, which changes gap to 2.97 eV (indirect) and 2.28 eV (direct) with increment in oxygen vacancy defect concentration of 6.25% and 12.5%,respectively. Consequently, presence of oxygen vacancies leads to energy red shift of the observed optic…
Understanding defect effect on carrier dynamics is essential for both fundamental physics and potential applications of transition metal dichalcogenides. Here, the phenomenon of oxygen impurities trapping photo-excited carriers has been studied with ultrafast pump-probe spectroscopy. Oxygen impurities are intentionally created in exfoliated multilayer MoSe2 with Ar+ plasma irradiation and air exposure. After plasma treatment, the signal of transient absorption first increases and then decreases, which is a signature of defect capturing carriers. With larger density of oxygen defects, the trapp…
Oxygen is the most common unintentional impurity found in GaN. We study the interaction between substitutional oxygen (ON) and the gallium vacancy (VGa) to form a point defect complex in GaN. The formation energy of the gallium vacancy is largely reduced in n-type GaN by complexing with oxygen, while thermodynamic and optical transition levels remain within the band gap. We study the spectroscopy of this complex using a hybrid quantum-mechanical molecular-mechanical (QM/MM) embedded-crystal approach. We reveal how a single defect center can be responsible for multiband luminescence, including …
For the purpose of elucidating the gas sensing mechanism of SnO$_2$ for NO and NO$_2$ gases, we calculate the phase diagram of SnO$_2$(110) surface in contact with an O$_2$ and NO gas environment by means of {\it ab initio} thermodynamic method. Firstly we build a range of surface slab models of oxygen pre-adsorbed SnO$_2$(110) surfaces using (1$\times$1) and (2$\times$1) surface unit cells and calculate their Gibbs free energies considering only oxygen chemical potential. The fully reduced surface containing the bridging and in-plane oxygen vacancies in the oxygen-poor condition, while the fu…
Defects in semiconductors can exhibit multiple charge states, which can be used for charge storage applications. Here we consider such charge storage in a series of oxygen deficient phases of TiO$_2$, known as Magnéli phases. These Ti$_n$O$_{2n-1}$ Magnéli phases present well-defined crystalline structures, i. e., their deviation from stoichiometry is accommodated by changes in space group as opposed to point defects. We show that these phases exhibit intermediate bands with the same electronic quadruple donor transitions akin to interstitial Ti defect levels in TiO$_2$-rutile. Thus, the Magné…
Graphene is one of the most promising 2D materials for various applications due to its unique electronic properties and high thermal stability. In previous studies, it was shown that when graphene is deposited onto some transition metal substrates, small molecules, such as O$_2$, intercalate between the graphene and the substrate and react to partially etch the graphene film when heated to desorb the intercalates. Here, carbon vacancy defects are intentionally formed on Gr/Ru(0001) and their effect on the intercalation of oxygen and etching of the graphene layer are investigated. 50 eV Ar$^+$ …
Oxygen octahedra tilting is a common structural phenomenon in perovskites and has been subject of intensive studies, particularly in rhombohedral Pb(Zr,Ti)O3 (PZT). Early reports suggest that the tilted octahedra may strongly affect the domain switching behavior, dielectric and piezoelectric properties of PZT ceramics. In a way similar to that proposed for tilts, however, charged defects, associated with oxygen vacancies, may also inhibit the motion of the domain walls, resulting macroscopically in pinched hysteresis loops and reduced piezoelectric response. Here, we revisit the early studies …
In order to perform automated calculations of defect and dopant properties in semiconductors and insulators, we developed a software package, Defect and Dopant ab-initio Simulation Package (DASP), which is composed of four modules for calculating: (i) elemental chemical potentials, (ii) defect (dopant) formation energies and transition energy levels, (iii) defect and carrier densities and (iv) carrier dynamics properties of high-density defects. DASP uses the materials genome database for quick determination of competing secondary phases and calculation of the energy above convex hull when cal…
In this work we have studied the defect structure and corresponding defect concentration investigations through the theoretical, experimental and computational works on B2-type Fe-Al alloys. We have used ab initio framework in order to investigate the defect structure. To have a proper explanation for high defect concentration in B2-FeAl, we did not confine with point defect, but extend the work on defect complexes. The possible defect formation energies were calculated with the dependence of chemical potential and carefully investigated against supercell size and the effect of magnetism. The …
Computing electron-defect (e-d) interactions from first principles has remained impractical due to computational cost. Here we develop an interpolation scheme based on maximally localized Wannier functions (WFs) to efficiently compute e-d interaction matrix elements. The interpolated matrix elements can accurately reproduce those computed directly without interpolation, and the approach can significantly speed up calculations of e-d relaxation times and defect-limited charge transport. We show example calculations of vacancy defects in silicon and copper, for which we compute the e-d relaxatio…
Defects creation and annihilation is a fundamental concept in device fabrication. This report studies the optical bandgap modification in MgO by MeV Ni ion irradiation-induced defect states between valance and conduction band. Ion implantation on MgO single crystal produces substitutional defect states along with F (anionic vacancy center), $F_2$, other oxygen vacancy center and V (cationic vacancy center) centers confirmed from absorption and photoluminescence spectra that can be applied as filament in valance charge memory based resistive random access memories. The variation of optical band…
The superconducting properties of high-\tc\ materials are functions of carriers concentration, which is controlled by the concentration of defects including heterovalent cations, interstitial oxygen ions, and oxygen vacancies. Here we combine low-temperature thermal treatment of La$_{2-x}$Sr$_{x}$CuO$_{4}$ epitaxial thin films and confocal Raman spectroscopy to control and investigate oxygen vacancies. We demonstrate that the apical site is the most favorable position to accommodate oxygen vacancies under low-temperature annealing conditions. Additionally we show that in high-quality films of …
Cubic hafnia (HfO$_2$) is of great interest for a number of applications in electronics because of its high dielectric constant. However, common defects in such applications degrade the properties of hafina. We have investigated the electronic properties of oxygen vacancies and nitrogen substitution in cubic HfO$_2$ using first principles calculations based on density functional theory (DFT) and many-body diffusion Monte Carlo (DMC) methods. We investigate five different charge defect states of oxygen vacancies, as well as substitutional N defects which can lead to local magnetic moments. Both…
