Point Defect States Research Articles

Particle-Particle Random Phase Approximation for Predicting Correlated Excited States of Point Defects.

The particle-particle random phase approximation (ppRPA) within the hole-hole channel was recently proposed as an efficient tool for computing excitation energies of point defects in solids [J. Phys. Chem. Lett. 2024, 15, 2757-2764]. In this work, we investigate the application of ppRPA within the particle-particle channel for predicting correlated excited states of point defects, including the carbon-vacancy (VC) in diamond, the oxygen-vacancy (VO) in magnesium oxide (MgO), and the carbon dimer defect (CBCN) in two-dimensional hexagonal boron nitride (h-BN). Starting from a density functional theory calculation of the (N - 2)-electron ground state, vertical excitation energies of the N-electron system are obtained as the differences between the two-electron addition energies. We show that active-space ppRPA with the B3LYP functional yields accurate excitation energies, with errors mostly smaller than 0.1 eV for tested systems compared to available experimental values. We further develop a natural transition orbital scheme within ppRPA, which provides insights into the multireference character of defect states. This study, together with our previous work, establishes ppRPA as a low-cost and accurate method for investigating excited-state properties of point defect systems.

Defect formation energy for various charge states of point defects in CdGa2S4

Defect formation energy for various charge states of point defects in CdGa2S4

Precise Hue Control in a Single-Component White-Light Emitting Perovskite Cs2 SnCl6 through Defect Engineering Based on La3+ Doping.

Single-component white light emitters based on the all-inorganic perovskites will act as outstanding candidates for applications in solid-state lighting thanks to their abundant energy states for self-trapped excitons (STE) with ultra-high photoluminescence (PL) efficiency. Here, a complementary white light is realized by dual STEs emissions with blue and yellow colors in a single-component perovskite Cs2 SnCl6 :La3+ microcrystal (MC). The dual emission bands centered at 450 and 560nm are attributed to the intrinsic STE1 emission in host lattice Cs2 SnCl6 and the STE2 emission induced by the heterovalent La3+ doping, respectively. The hue of the white light can be tunable through energy transfer between the two STEs, the variation of excitation wavelength, and the Sn4+ /Cs+ ratios in starting materials. The effects of the doping heterovalent La3+ ions on the electronic structure and photophysical properties of the Cs2 SnCl6 crystals and the created impurity point defect states are investigated by the chemical potentials calculated using density functional theory (DFT) and confirmed by the experimental results. These results provide a facile approach to gaining novel single-component white light emitter and offer fundamental insights into the defect chemistry in the heterovalent ions doped perovskite luminescent crystals.

Experimental evidence for spin–triplet states in Titanium implanted AlN film: An electron spin resonance study

Spin carrying defects in wide-bandgap semiconductors are promising candidates for the development of quantum information and quantum sensing technology. Here we report experimental evidence for the formation of paramagnetic defects in AlN films, subjected to high-energy hydrogen and titanium ion implantation. X-ray diffraction and Raman spectroscopy show that ion species and implantation process could alter the amount of local strain in AlN films. Electron spin resonance spectroscopy reveals resonance peaks with g-value higher than the one of a free electron (2.0023) for both H-implanted and Ti-implanted AlN films. The origin of these peaks is identified and attributed to different types of point defects. For the Ti-implanted film, in addition to the central peak, a half-field resonance peak has been detected and assigned to spin–triplet (S=1). These results provide new insight into the electronic spin state of point defects in AlN, which opens up interesting perspectives for applications to quantum devices.

Quantum embedding methods for correlated excited states of point defects: Case studies and challenges

A quantitative description of the excited electronic states of point defects and impurities is crucial for understanding materials properties, and possible applications of defects in quantum technologies. This is a considerable challenge for computational methods, since Kohn-Sham density functional theory (DFT) is inherently a ground-state theory, while higher-level methods are often too computationally expensive for defect systems. Recently, embedding approaches have been applied that treat defect states with many-body methods, while using DFT to describe the bulk host material. We implement such an embedding method, based on Wannierization of defect orbitals and the constrained random-phase approximation approach, and perform systematic characterization of the method for three distinct systems with current technological relevance: a carbon dimer replacing a B and N pair in bulk hexagonal BN (${\mathrm{C}}_{\text{B}}{\mathrm{C}}_{\text{N}}$), the negatively charged nitrogen-vacancy center in diamond (${\mathrm{NV}}^{\ensuremath{-}}$), and an Fe impurity on the Al site in wurtzite AlN (${\text{Fe}}_{\text{Al}}$). In the context of these test-case defects, we demonstrate that crucial considerations of the methodology include convergence of the bulk screening of the active-space Coulomb interaction, the choice of exchange-correlation functional for the initial DFT calculation, and the treatment of the ``double-counting'' correction. For ${\mathrm{C}}_{\text{B}}{\mathrm{C}}_{\text{N}}$ we show that the embedding approach gives many-body states in agreement with analytical results on the Hubbard dimer model, which allows us to elucidate the effects of the DFT functional and double-counting correction. For the ${\mathrm{NV}}^{\ensuremath{-}}$ center, our method demonstrates good quantitative agreement with experiments for the zero-phonon line of the triplet-triplet transition. Finally, we illustrate challenges associated with this method for determining the energies and orderings of the complex spin multiplets in ${\text{Fe}}_{\text{Al}}$.

Modeling Excited States of Point Defects in Materials from Many-Body Perturbation Theory

Modeling Excited States of Point Defects in Materials from Many-Body Perturbation Theory

Interplay of Anionic Quasi-Atoms and Interstitial Point Defects in Electrides: Abnormal Interstice Occupation and Colossal Charge State of Point Defects in Dense fcc-Lithium.

Electrides are an emerging class of materials with highly localized electrons in the interstices of a crystal that behave as anions. The presence of these unusual interstitial quasi-atom (ISQ) electrons leads to interesting physical and chemical properties and wide potential applications for this new class of materials. Crystal defects often have a crucial influence on the properties of materials. Introducing impurities has been proved to be an effective approach to improve the properties of a material and to expand its applications. However, the interactions between the anionic ISQs and the crystal defects in electrides are yet unknown. Here, dense fcc-Li was employed as an archetype to explore the interplay between anionic ISQs and interstitial impurity atoms in this electride. This work reveals strong coupling among the interstitial impurity atoms, the ISQs, and the matrix Li atoms near to the defects. This complex interplay and interaction mainly manifest as the unexpected tetrahedral interstitial occupation of impurity atoms and the enhancement of electron localization in the interstices. Moreover, the Be impurity occupying the octahedral interstice shows the highest negative charge state (Be8-) discovered thus far. These results demonstrate the rich chemistry and physics of this emerging material and provide a new basis for enriching their variants for a wide range of applications.

Long-range perturbation of helical edge states by nonmagnetic defects in two-dimensional topological insulators

We study the electronic states that are formed due to the tunnel coupling between helical edge states (HESs) and bound states of nonmagnetic point defects in two-dimensional topological insulators in the general case of broken axial spin symmetry. It is found that the coupling of HESs and a single defect leads to the formation of composite HESs composed of the bound states and a set of the conventional HESs. Their spectral density near the defect has a resonance shifted relative to the energy level of the bound state. But of most importance is a long-range perturbation of the HESs around the defect, which is a cloud consisting of both Kramers partners of conventional edge states. Therefore each of the composite HESs contains both the right- and left-moving conventional HESs. The amplitude of this perturbation decreases inversely with the distance from the defect. In a system of many defects, this perturbation leads to a long-range coupling between bound states of different defects mediated by the HESs and causes amazing effects. We study these effects for a two-defect system where the proposed mechanism of indirect coupling leads to a splitting of the resonances of isolated defects even if the distance between them is very large. As a result an asymmetric structure of two-peak resonance arises that very unusually changes with the distance between the defects.

Control of charge state of dopants in insulating crystals: Case study of Ti-doped sapphire

We study mechanisms of control of charge state and concentration of different point defects in doped insulating crystals. The approach is based on the density functional theory calculations. We apply it to the problem of obtaining of Ti-doped sapphire crystals with high figure-of-merit (FOM). The FOM of a given sample is defined as the ratio of the coefficient of absorption at the pump frequency to the coefficient of absorption at the working frequency of Ti:sapphire laser. It is believed that FOM is proportional to the ratio of the concentration of isolated Ti$^{3+}$ ions to the concentration of Ti$^{3+}$-Ti$^{4+}$ pairs. We find that generally this ratio is in inverse proportion to the concentration of Ti$^{4+}$ isolated substitutional defects with the coefficient of proportionality that depends on the temperature at which the thermodynamically equilibrium concentration of defects is reached. We argue that in certain cases the inverse proportion between concentrations of Ti$^{3+}$-Ti$^{4+}$ and Ti$^{4+}$ may be violated. We show that codopants that form positively (negatively) charged defects may decrease (increase) the concentration of positively charged defects formed by the main dopants. To evaluate the effect of codoping it is important to take into account not only isolated defects but defect complexes formed by codopants, as well. In particular, we show that codoping of Ti:sapphire with nitrogen results in an essential increase of the concentration of Ti$^{4+}$ and in a decrease of the FOM, and, consequently, growth or annealing in the presence of nitrogen or its compounds is unfavorable for producing Ti:sapphire laser crystals. The approach developed can be used for determining appropriate growth and annealing conditions for obtaining doped crystals with the required characteristics.

Delineation of point defect state in Czochralski Si by modified background haze

A novel haze technique for analyzing point-defect distribution in Czochralski Si (CZ-Si) wafers without intentional contamination by transition metals was proposed. Based on the background haze in high-temperature oxidation, a three-step oxidation process including two-step low-temperature precipitation and a single-step high-temperature wet oxidation process was designed. After the newly designed heat processing and preferential etching, surface haze was formed selectively on the interstitial-dominant region of the wafer. Through electron microscopy analysis, surface defects decorated with Ni were observed, which suggested that the surface accumulation of non-gettered Ni adsorbed from the furnace causes surface haze on the interstitial-dominated region. The widths of the hazes could be optimized by adjusting the processing times of the first two steps, which affected the Ni gettering ability in the vacancy-dominated regions of the wafers. Additionally, the second stage at 1000 °C was associated with precipitate growth, as well as with haze formation.

Emergence of point defect states in a plasmonic crystal

Plasmonic crystals are well known to have band structure including a band gap, enabling the control of surface plasmon propagation and confinement. The band dispersion relation of bulk crystals has been generally measured by momentum-resolved spectroscopy using far field optical techniques while the defects introduced in the crystals have separately been investigated by near field imaging techniques so far. Particularly, defect related energy levels introduced in the plasmonic band gap have not been observed experimentally. In order to investigate such a localized mode, we performed electron energy-loss spectroscopy (EELS) on a point defect introduced in a plasmonic crystal made up of flat cylinders protruding out of a metal film and arranged on a triangular lattice. The energy level of the defect mode was observed to lie within the full band-gap energy range. This was confirmed by a momentum-resolved EELS measurement of the band gap performed on the same plasmonic crystal. Furthermore, we experimentally and theoretically investigated the emergence of the defect states by starting with a corral of flat cylinders protrusions and adding sequentially additional shells of those in order to eventually form a plasmonic band-gap crystal encompassing a single point defect. It is demonstrated that a defectlike state already forms with a crystal made up of only two shells.

Space charge control of point defect spin states in AlN

One barrier to developing quantum information systems based on impurity point defects is that the desirable spin states of the defects are often unstable for Fermi levels obtained at increased impurity concentrations. The space charge induced band bending near the interface of Si/Mg aluminum nitride (AlN) homojunction is investigated computationally as a method to control the concentration, spin state, and position of such point defects. This is done by solving Poisson's equation with the charge density described by a grand canonical defect chemistry model informed by hybrid-functional density functional theory (DFT) calculations. Previous experimental works have found unintentional carbon and oxygen impurities pervade AlN homojunctions. First principles calculations have predicted the neutral complex between an aluminum vacancy and oxygen impurity on a neighboring nitrogen site (vAl-1ON)0 has a spin triplet configuration, which is stable in a region when the Fermi level is below midgap. From defect equilibrium simulations considering 602 possible defects, vAl-1ON was found to be unstable on the Mg-doped side of the homojunction and isolated oxygen impurities are preferred. On the Si-doped side, vAl-1ON forms but as (vAl-1ON)–2, not (vAl-1ON)0. This makes vAl-1ON a prototypical test case for the proposed strategy. Simulations of the Si/Mg:AlN homojunction showed (vAl-1ON)0 is stabilized within 6 nm of the interface in the Si-doped portion. This result indicates space charge induced band bending enables control over the concentration, spin state, and position of point defects, which is critical to realizing point defect based quantum information systems.

Optical transitions and photoluminescence of fluorine-doped zinc tin oxide thin films prepared by ultrasonic spray pyrolysis

Abstract Thin films of fluorine-doped zinc tin oxide (FZTO) were deposited on borosilicate glass by ultrasonic spray pyrolysis. Structural and elemental investigations revealed that all films have a single-phase polycrystalline tetragonal rutile structure and proved the successful incorporation of zinc ions into tin sites and the fluorine ions into the sites of oxygen vacancies. A comprehensive analysis of the optical transitions in FZTO films was presented. All films show high optical transparency (≥85%) in the visible range. Four direct optical transitions were observed in the range 3.8 - 5.1 eV by spectrophotometric measurements, in addition to three transitions identified by photoluminescence. From these transitions observed for the first time in FZTO, three states of point defects were determined in the bandgap and attributed to the neutral, singly- and doubly-ionized oxygen vacancies. The ascription of these states to oxygen vacancies was supported by the x-ray photoelectron spectroscopy measurements. The band diagram of FZTO was sketched, demonstrating the observed transitions. The obtained results are expected to have their imprint on understanding the optical processes in FZTO and evaluating the future utility of it in various optoelectronic applications.

Engineering Point-Defect States in Monolayer WSe2.

Defect engineering is a key approach for tailoring the properties of the emerging two-dimensional semiconductors. Here, we report an atomic engineering of the W vacancy in monolayer WSe2 by single potassium atom decoration. The K decoration alters the energy states and reshapes the wave function such that previously hidden midgap states become visible with well-resolved multiplets in scanning tunneling spectroscopy. Their energy levels are in good agreement with first-principle calculations. More interestingly, the calculations show that an unpaired electron donated by the K atom can lead to a local magnetic moment, exhibiting an on-off switching by the odd-even number of electron filling. Experimentally the Fermi level is pinned above all defect states due to the graphite substrate, corresponding to an off state. The close agreement between theory and experiment in the off state, on the other hand, suggests the possibility of gate-programmable magnetic moments at the defects.

Photonic crystal filter based on defect mode and waveguide mode symmetry matching

In this paper, a new type of filter based on symmetry matching between the defect and waveguide modes in a square lattice photonic crystal for 1.31 μm wavelength is designed and evaluated. The filter consists of one elliptical defect and three wire defect waveguides with two single-mode waveguides and one dual-mode waveguide. Because the point defect state has four different resonant frequencies and four corresponding types of mode field symmetries, the proposed filter uses the match or mismatch between the defect and waveguide modes to realize two resonant frequency filtering outputs through a dual channel. To evaluate the device, the transmission characteristics of the electromagnetic waves in the device are simulated using the finite element method. The quality factor and transmission coefficient of the filter is 2,017 and 0.84 at the frequency of 0.4034 c/α (corresponding to 1.31 μm wavelength). This device can be applied to wave division multiplexing, filtering, and has the potential for applications in optical integrated chip and optical communications.

Wave bandgap formation and its evolution in two-dimensional phononic crystals composed of rubber matrix with periodic steel quarter-cylinders

The band structure of a two-dimensional phononic crystal, which is composed of four homogenous steel quarter-cylinders immersed in rubber matrix, is investigated and compared with the traditional steel/rubber crystal by the finite element method (FEM). It is revealed that the frequency can then be tuned by changing the distance between adjacent quarter-cylinders. When the distance is relatively small, the integrality of scatterers makes the inner region inside them almost motionless, so that they can be viewed as a whole at high-frequencies. In the case of relatively larger distance, the interaction between each quarter-cylinder and rubber will introduce some new bandgaps at relatively low-frequencies. Lastly, the point defect states induced by the four quarter-cylinders are revealed. These results will be helpful in fabricating devices, such as vibration insulators and acoustic/elastic filters, whose band frequencies can be manipulated artificially.

Green’s function-based defect identification in InAs-InAs1-xSbx strained layer superlattices

We have extended the recently developed approach that employs first-principles Hamiltonian, tight-binding Hamiltonian, and Green’s function methods to study native point defect states in InAs/InAs0.7Sb0.3 strained layer superlattices (SLS) latticed matched to GaSb. Our calculations predict a defect level at 250 meV below the GaSb valance band edge, in agreement with values deduced recently from lifetime measurements and analysis [Aytac et al. Phys. Rev. Appl., 5, 054016 (2016)]. In addition, we identify the defect level to be arising from an In-vacancy in the InAsSb region of the superlattice. The formation energy calculations further indicate that In-vacancies are easier to form in both regions of the superlattice than in bulk InAs or in InAsSb alloy. Our results suggest that In-vacancy is the most damaging native defect that limits lifetimes InAs/InAs0.7Sb0.3.

Partial chiral symmetry-breaking as a route to spectrally isolated topological defect states in two-dimensional artificial materials

Bipartite quantum systems from the chiral universality classes admit topologically protected zero modes at point defects. However, in two-dimensional systems these states can be difficult to separate from compacton-like localized states that arise from flat bands, formed if the two sublattices support a different number of sites within a unit cell. Here we identify a natural reduction of chiral symmetry, obtained by coupling sites on the majority sublattice, which gives rise to spectrally isolated point-defect states, topologically characterized as zero modes supported by the complementary minority sublattice. We observe these states in a microwave realization of a dimerized Lieb lattice with next-nearest neighbour coupling, and also demonstrate topological mode selection via sublattice-staggered absorption.

A designing principle for low dark-current strained layer superlattices

A systematic study of native point defect states is carried out to understand the origin of gap states in strained layer superlattices. Using a combination of first principles Hamiltonian, tight-binding Hamiltonian, and Green's function approach, we calculate the native point defect states in bulk InAs, bulk GaSb, and ten InAs-GaSb strained layer superlattices. We observe that the defects in strained layer superlattices located away from the interface create fewer mid gap states if the constituent bulk materials do not have defect states in that energy interval. This can be used as a design principle to shift the superlattice band gap and reduce or eliminate the mid-gap states.

Low-frequency band gap and defect state characteristics in a multi-stub phononic crystal plate with slit structure

In this paper, we investigated the low-frequency characteristics of band gaps and defect state in a two-dimensional phononic crystal structure consisting of multiple square stubs deposited on both sides of a thin slotted plate. Using the finite element method, we calculated the dispersion relationships and power transmission spectra of this structure, which agree well with each other. In contrast to a system of homogeneous plate, system of slotted plate show wide band gaps and an increased quantity of band gaps at lower frequencies. In addition, based on the finding that acoustic band gaps are very sensitive to the distance between the two adjacent square stubs in our earlier works, we investigated the point defect state in the multi-stub phononic crystal plate with slit structure. Through changing the distribution of stubs in specific scatterers, the defect phononic crystals are formed. We designed and fabricated the defect phononic crystal experimental platform to verify the existence of defect bands in the phononic crystal structure. Results show that defect bands can be induced by creating defects inside the original complete band gaps. These results will help in fabricating devices, such as acoustic filters whose band frequency can be modulated.