我们在此扩展了对一种新开发的、简单有效的从头算方法的描述，该方法用于计算绝缘基质中稀土原子的晶体场系数（CFCs），重点研究宽带隙氧化物基质 MgO、ZnO、TiO$_2$、CaWO$_4$ 和 PbWO$_4$ 中的 Er，这些基质体现了不同的局域格位对称性。这些杂化泛函计算纳入了来自 Hartree-Fock 理论的一部分精确交换，重现了这些氧化物经实验确定的绝缘带隙。结合能和形成能的负值证实了这些氧化物的结构和化学稳定性，而缺陷形成能表明，与 Er 掺杂 MgO 和 TiO$_2$ 相比，Er 掺杂 ZnO、CaWO$_4$ 和 PbWO$_4$ 更容易形成。掺杂在这些氧化物基质中的 Er 表现出约 3 $μ_B$ 的自旋磁矩，证实了其 3+ 价态。这些基质中 Er 的 CFCs 由非自旋极化计算得到的电荷密度和势确定，其中涉及 4\ extit{f} 芯近似。随后，这些 CFCs 被用于求解有效哈密顿量，并生成 Er 4f 的晶体场劈裂。这些计算得到的 Er 4f 能级与现有实验结果吻合良好。
英文摘要：
We expand here our description of a newly developed simple and effective ab initio method of calculating crystal field coefficients (CFCs) of rare-earth atoms in insulating hosts, focusing on Er in wide band gap oxide hosts MgO, ZnO, TiO$_2$, CaWO$_4$, and PbWO$_4$, which exemplify different local site symmetries. These hybrid functional calculations, which incorporate a portion of exact exchange from Hartree-Fock theory, reproduce the experimentally identified insulating band gaps of these oxides. The negative values of cohesive and formation energies confirm the structural and chemical stability of these oxides, whereas the defect formation energies indicate that Er doped ZnO, CaWO$_4$, and PbWO$_4$ are easier to form compared to Er doped MgO and TiO$_2$. Er doped in these oxide hosts exhibits a spin magnetic moment of $\sim$ 3 $μ_B$ confirming the $3+$ valence state. The CFCs of these hosted Er are determined from charge densities and potentials obtained from non-spin-polarized calculations, involving a 4\textit{f} core approximation. These CFCs are subsequently used to solve an effective Hamiltonian and generate the crystal field splitting of Er 4f. These calculated Er 4f energy levels are in good agreement with available experiments.
We synthesized bismuth - cobalt oxide doped by erbium with general formula Bi3-xErxCoO3-y. Compound has structure of delta-form bismuth oxide. Magnetic properties of the compound were measured by Faraday's method using quartz scales in the temperature range of 80-500 K. The magnetic susceptibility and effective magnetic moment were calculated.
Rare-earth-doped optical materials are important for light sources in optoelectronics, as well as for efficient optical amplification elements and other elements of photonics. On the basis of the previously developed method of anhydrous, low-temperature synthesis of Er/Yb oxides from their chlorides we fabricated proper nanoparticles with defined parameters and used them for the development of optically transparent, luminescent polymer nanocomposite with low optical scattering, suitable for direct, light-induced formation of photonic elements. Introduction of preformed gold nanoparticles in su…
This work reports optical functionality contained in, as well as and produced by, thin film coatings. A sol-gel process, formulated with precursor active ingredients of erbium oxide and tetraethylorthosilicate (TEOS), was used for spin-coating thin (~130 nm) erbium-doped (~6 at. %) silica films on single-crystal silicon. Annealed films produce infrared emission in the 1.5-micron band from erbium ions in the film, as well as greatly enhancing (~100X) band-gap emission from the underlying silicon. The distinctly different mechanisms for the two modes of optical activities are interpreted in term…
The replacement of SiO2 by so-called high-k oxides is one of the major challenges for the semiconductor industry to date. Based on electronic structure calculations and ab-initio molecular dynamics simulations, we are able to provide a consistent picture of the growth process of a class of epitaxial oxides around SrO and SrTiO3. The detailed understanding of the interfacial binding principles has also allowed us to propose a way to engineer the band-offsets between the oxide and the silicon substrate.
We present an efficient and general method to identify promising candidate configurations for thin-film oxides and to determine structural characteristics of (metastable) thin-film structures using ab initio calculations. At the heart of this method is the complexity of the oxide bulk structure, from which a large number of thin films with structural building blocks, that is motifs, from metastable bulk oxide systems can be extracted. These span a coarse but well-defined network of initial configurations for which density functional theory (DFT) calculations predict and implement dramatic atom…
For erbium-doped amorphous oxides, such as those that are used in compact lightwave devices interfaced with silicon, values of the refractive indices are commonly obtained empirically. This work, combining experimental and theoretical studies, examines silica as the exemplary host and the influence of erbium doping on the refractive index. Analysis of data is presented for the spectral refractive index in the ultraviolet to near infrared wavelength range of heavily erbium-doped silica thin films prepared by spin coating a sol-gel precursor on silicon and subsequent vacuum annealing. Effective …
We demonstrate generation of linearly polarized pulses from a passively Q-switched Erbium-doped fiber laser. The cavity was designed using only polarization maintaining (PM) fibers and components, resulting in linearly polarized output beam with degree of polarization (DOP) at the level of 97.6%. Reduced graphene oxide (rGO) was used as a saturable absorber for Q-switched operation. The laser was capable of delivering 1.85us pulses with 125nJ pulse energy at 115kHz repetition rate.
Using first principles calculations, we have studied the structural and elastic properties of SrTMO3 (TM = Rh, Ti, Mo, Zr) under pressure by the plane wave pseudopotential method based on the density functional theory (DFT) within the generalized gradient approximation (GGA). The optical properties have been investigated under zero pressure. It is observed that the calculated lattice parameters are in good agreement with the available experimental result and previous theoretical results.
An ab initio structure optimization technique is newly developed to determine the valley line on a total-energy surface for zone-center distortions of ferroelectric perovskite oxides and is applied to barium titanate BaTiO3 and lead titanate PbTiO3. The proposed technique is an improvement over King-Smith and Vanderbilt's scheme [Phys. Rev. B 49, p.5828 (1994)] of evaluating total energy as a function of the amplitude of atomic displacements. The results of numerical calculations show that total energy can be expressed as a fourth-order function of the amplitude of atomic displacements in BaTi…
We performed an {\it ab initio} investigation on the properties of rutile tin oxide (SnO$_{x}$) nanowires. We computed the wire properties determining the equilibrium geometries, binding energies and electronic band structures for several wire dimensions and surface facet configurations. The results allowed to establish scaling laws for the structural properties, in terms of the nanowire perimeters. The results also showed that the surface states control most of the electronic properties of the nanowires. Oxygen incorporation in the nanowire surfaces passivated the surface-related electronic s…
The local magnetic moment of Ti:ZnO is calculated from first principles by using the corrected-band-gap scheme (CBGS). The results shows that the system is magnetic with the magnetization of 0.699 $μ_B$ per dopant. The origin of the local magnetic moment is considered to be the impurity band partially occupied by the donor electrons in the conduction band. Further, the impacts of applying Hubbard U to Ti-d orbital on the magnetic moment have been investigated.
Based on first-principles calculation, it has been predicted that the magnetic anisotropy energy (MAE) in Co-doped ZnO (Co:ZnO) depends on electron-filling. Results show that the charge neutral Co:ZnO presents a "easy plane" magnetic state. While modifying the total number of electrons, the easy axis rotates from in-plane to out-of-plane. The alternation of the MAE is considered to be the change of the ground state of Co ion, resulting from the relocating of electrons on Co d-orbitals with electron-filling.
We present a fully variational generalization of the pseudo self-interaction correction (VPSIC) approach previously presented in two implementations based on plane-waves and atomic orbital basis set, known as PSIC and ASIC, respectively. The new method is essentially equivalent to the previous version for what concern the electronic properties, but it can be exploited to calculate total-energy derived properties as well, such as forces and structural optimization. We apply the method to a variety of test cases including both non-magnetic and magnetic correlated oxides and molecules, showing a …
Density functional theory (DFT) calculations are carried out to study the structure and electronic structure of amorphous zinc oxide (a-ZnO). The models were prepared by the "melt-quench" method. The models are chemically ordered with some coordination defects. The effect of trivalent dopants in the structure and electronic properties of a-ZnO is investigated. Models of a-X_0.375 Z_0.625 O (X=Al, Ga and In) were also prepared by the "melt- quench" method. The trivalent dopants reduce the four-fold Zn and O, thereby introducing some coordination defects in the network. The dopants prefer to bon…
Transient X-ray spectroscopies have become ubiquitous in studying photoexcited dynamics in solar energy materials due to their sensitivity to carrier occupations and local chemical or structural dynamics. The interpretation of solid-state photoexcited dynamics, however, is complicated by the core-hole perturbation and the resulting many-body dynamics. Here, an ab initio, Bethe-Salpeter equation (BSE) approach is developed that can incorporate photoexcited state effects for solid-state materials. The extreme ultraviolet (XUV) absorption spectra for the ground, photoexcited, and thermally expand…
We have performed quantum chemical computational studies to determine carbon dioxide affinity to carbon compounds and minerals, which could be present in shales. These studies shed light on the microscopic mechanisms of the possible carbon oxide sequestration processes. Our studies reveal that the carbon oxide can be adsorbed to various forms of carbon structures and also minerals such as periclase or illite. We find out that the strongest affinity of carbon oxide towards carbon structures occurs when the carbon structures exhibit $sp^3$ bonds.
We describe an ab initio theory of finite temperature magnetism in strongly-correlated electron systems. The formalism is based on spin density functional theory, with a self-interaction corrected local spin density approximation (SIC-LSDA). The self-interaction correction is implemented locally, within the KKR multiple-scattering method. Thermally induced magnetic fluctuations are treated using a mean-field `disordered local moment' (DLM) approach and at no stage is there a fitting to an effective Heisenberg model. We apply the theory to the 3d transition metal oxides, where our calculations …
In the present paper, the electronic, structural, thermodynamic, and elastic properties of cubic $PbGeO_{3}$ perovskite oxide are presented and computed using the WIEN2K code. The structural properties have been evaluated and they are in good agreement with the theoretical and experimental data. A phonon dispersion is made and it reveals that the cubic $PbGeO_{3}$ perovskite is dynamically stable. In addition, the electronic properties of $PbGeO_{3}$ shows an opening gap energy, meaning a semiconductor behavior with an indirect band gap equal to $1.67 eV$. Moreover, the obtained elastic consta…
Graphene oxide (GO) holds significant promise for electronic devices and nanocomposite materials. A number of models were proposed for GO structure, combining carboxyl, hydroxyl, carbonyl and epoxide groups at different locations. The complexity and variety of GO isomers, whose thermodynamic stability and formation kinetics depend on applied conditions, make determination of GO structure with atomistic precision challenging. We report high level theoretical investigation of multiple molecular configurations, which are anticipated in GO. We conclude that all oxygen containing groups at the GO s…
Transparent conducting oxides (TCOs) are essential to many technologies. These materials are doped (\emph{n}- or \emph{p}-type) oxides with a large enough band gap (ideally $>$3~eV) to ensure transparency. However, the high carrier concentration present in TCOs lead additionally to the possibility for optical transitions from the occupied conduction bands to higher states for \emph{n}-type materials and from lower states to the unoccupied valence bands for \emph{p}-type TCOs. The "second gap" formed by these transitions might limit transparency and a large second gap has been sometimes propose…
The microscopic structure of ultra-thin oxide barriers often plays a major role in modern nano-electronic devices. In the case of superconducting electronic circuits, their operation depends on the electrical non-linearity provided by one or more such oxide layers in the form of ultra-thin tunnel barriers (also known as Josephson junctions). Currently available fabrication techniques manufacture an amorphous oxide barrier, which is attributed as a major noise source within the device. The nature of this noise is currently an open question and requires both experimental and theoretical investig…
Ab initio wavefunction based methods are applied to the study of electron correlation effects on the band structure of oxide systems. We choose MgO as a prototype closed-shell ionic oxide. Our analysis is based on a local Hamiltonian approach and performed on finite fragments cut from the infinite solid. Localized Wannier functions and embedding potentials are obtained from prior periodic Hartree-Fock (HF) calculations. We investigate the role of various electron correlation effects in reducing the HF band gap and modifying the band widths. On-site and nearest-neighbor charge relaxation as wel…
Ab initio simulations carried out in different atomic cluster configurations in bcc Fe matrix containing Zr and Al suggest energetic favorability of Y-Zr-O phase nucleation, preferably with trigonal Y4Zr3O12 structure. Subsequently, the HRTEM investigation of the as-prepared Fe - 14 Cr-0.3 Y2O3 - 0.6 Zr - 4Al oxide dispersion strengthened (ODS) alloy shows 78% of precipitates with Y4Zr3O12 structure, thereby confirming the predictive power of ab initio simulations on the secondary formation in multi-component alloys.
Conventional Oxide dispersion strengthened steels are characterized by thermally stable, high density of Y-Ti-O nanoclusters, which are responsible for their high creep strength. Ti plays a major role in obtaining a high density of ultrafine particles of optimum size range of 2-10 nm. In Al-containing ODS steels developed for corrosion resistance, Y-Al-O clusters formed are of size range 20 -100 nm, and Ti fails in making dispersions finer in the presence of Al. Usage of similar alloying elements like Zr in place of Ti is widely considered. In this study, binding energies of different stages o…
Rare-earth ions (REI) have emerged as an attractive candidate for solid-state qubits, particularly as a quantum memory. Their 4f-4f transitions are shielded by filled 5s and 5p orbitals, offering a degree of protection from external electric fields. Embedded within a thin film oxide host, REIs could enable a qubit platform with significant memory capabilities. Furthermore, a silicon-compatible thin film form factor would enable the use of standard semiconductor fabrication processes to achieve chip-based integrability and scalability for functional quantum networks. Towards this goal, we have …
Using a combination of experimental techniques and density functional theory (DFT) calculations, the influence of lithium insertion on the electronic and electrochemical properties of fluourine-doped SnO$_2$ (FTO) is assessed. For this purpose, we investigate the electrochromic behavior of commercial FTO electrode embedded in a solution of lithium perclorate (LiClO$_4$). The electrochromic properties are evaluated by UV-VIS spectroscopy, cyclic voltammetry, and chronoamperometry. These tests show that FTO exhibits electrochromism with a respectable coloration efficiency ($η=47.9$ cm$^2$/C @ 63…
Nanomaterials made of the cerium oxides CeO$_2$ and Ce$_2$O$_3$ have a broad range of applications, from catalysts in automotive, industrial or energy operations to promising materials to enhance hadrontherapy effectiveness in oncological treatments. To elucidate the physico-chemical mechanisms involved in these processes, it is of paramount importance to know the electronic excitation spectra of these oxides, which are obtained here through high-accuracy linear-response time-dependent density functional theory calculations. In particular, the macroscopic dielectric response functions $\barε$ …
Active-Learning Inspired $\textit{Ab Initio}$ Theory-Experiment Loop Approach for Management of Material Defects: Application to Superconducting Qubits
Cornell University（康奈尔大学）；Syracuse University（雪城大学）；Massachusetts Institute of Technology（麻省理工学院）
Based on the van der Waals density functional theory (vdW-DFT)+U scheme, we carry out the ab initio molecular dynamics (AIMD) study of the interaction dynamics for H$_{2}$ impingement against the stoichiometric PuO$_{2}$(111), the reduced PuO$_{2}$(111), and the stoichiometric $α$-Pu$_{2}$O$_{3}$(111) surfaces. The hydrogen molecular physisorption states, which can not be captured by pure DFT+\textit{U} method, are obtained by employing the vdW-DFT+\textit{U} scheme. We show that except for the weak physisorption, PuO$_{2}$(111) surfaces are so difficult of access that almost all of the H$_{2}…
The amorphous phases of antimony oxide at three different oxidation levels have been investigated by {\it ab initio} molecular-dynamics calculations using a simulated `melt-quench' approach. The atomic and electronic structure of the amorphous phases are analyzed and compared to their crystalline counterparts. The amorphous structure of the trioxide ({\it a\,}--Sb$_2$O$_3$) resembles the $β$-phase of the crystalline form (valentinite), in agreement with previous observations. In the relaxed athermal structure, however, more senarmontite-like structural features are apparent. The phase diagram …
The correct calculation of formation enthalpy is one of the enablers of ab-initio computational materials design. For several classes of systems (e.g. oxides) standard density functional theory produces incorrect values. Here we propose the "Coordination Corrected Enthalpies" method (CCE), based on the number of nearest neighbor cation-anion bonds, and also capable of correcting relative stability of polymorphs. CCE uses calculations employing the Perdew, Burke and Ernzerhof (PBE), Local Density Approximation (LDA) and Strongly Constrained and Appropriately Normed (SCAN) exchange correlation f…
In view of the continuous theoretical efforts aimed at an accurate microscopic description of the strongly correlated transition metal oxides and related materials, we show that with continuum quantum Monte Carlo (QMC) calculations it is possible to obtain the value of the spin superexchange coupling constant of a copper oxide in a quantitatively excellent agreement with experiment. The variational nature of the QMC total energy allows us to identify the best trial wave function out of the available pool of wave functions, which makes the approach essentially free from adjustable parameters an…
We predict high thermoelectric efficiency in the layered perovskite La$_2$Ti$_2$O$_7$, based on calculations (mostly ab-initio) of the electronic structure, transport coefficients, and thermal conductivity in a wide temperature range. The figure of merit $ZT$ computed with a temperature-dependent relaxation time increases monotonically from just above 1 at room temperature to over 2.5 at 1200 K, at an optimal carrier density of around 10$^{20}$ cm$^{-3}$. The Seebeck thermopower coefficient is between 200 and 300 $μ$V/K at optimal doping, but can reach nearly 1 mV/K at low doping. Much of the …
We present detailed ab-initio lattice dynamical analysis of the Fe-O infinite-layer compounds CaFeO2 and SrFeO2 in various magnetic configurations. These indicate strong spin-phonon coupling in SrFeO2 in contrast to that in case of CaFeO2. Powder neutron inelastic scattering experiments on SrFeO2 have also been performed at temperatures from 5 K to 353 K in the antiferromagnetic phase and analyzed using the ab-initio calculations. These suggest distortion of the ideal infinite planer structure above 300 K. From our ab-initio calculations in SrFeO2 as a function of volume, we suggest that the d…
Titanium dioxide is one of the most widely investigated oxides. This is due to its broad range of applications, from catalysis to photocatalysis to photovoltaics. Despite this large interest, many of its bulk properties have been sparsely investigated using either experimental techniques or ab initio theory. Further, some of TiO2's most important properties, such as its electronic band gap, the localized character of excitons, and the localized nature of states induced by oxygen vacancies, are still under debate. We present a unified description of the properties of rutile and anatase phases, …
We present the first ab initio molecular dynamics study of collisions between metal-oxide clusters and surfaces. The resulting trajectories reveal that the internal degrees of freedom of the cluster play a defining role in collision outcome. The phase space of incoming internal temperature and translational energy exhibits regions where the collision process itself ensures that each cluster which does not rebound from the surface assimilates seamlessly onto it upon impact. This filtering may explain recent observations of a "fast smoothing mechanism" during pulsed laser deposition.
Motivated by recent electron microscopy studies on the Si3N4/rare-earth oxide interfaces, the atomic and electronic structures of bare beta-Si3N4 surfaces are investigated from first principles. The equilibrium shape of a Si3N4 crystal is found to have a hexagonal cross section and a faceted dome-like base in agreement with experimental observations. The large atomic relaxations on the prismatic planes are driven by the tendency of Si to saturate its dangling bonds, which gives rise to resonant-bond configurations or planar sp^2-type bonding. We predict three bare surfaces with lower energies …
We use \textit{ab initio} calculations to estimate formation energies of cation (transition metal) antisite defects at oxide interfaces and to understand the basic physical effects that drive or suppress the formation of these defects. Antisite defects are found to be favored in systems with substantial charge transfer across the interface, while Jahn-Teller distortions and itinerant ferromagnetism can prevent antisite defects and help stabilize atomically sharp interfaces. Our results enable identification of classes of systems that may be more and less susceptible to the formation of antisit…
We calculate ab-initio the electronic states and the Born dynamical charge Z* of the alkaline-earth oxides in the local-density approximation. We investigate the trend of increasing Z* values through the series, using band-by-band decompositions and computational experiments performed on fake materials with artificially-modified covalence. The deviations of Z* from the nominal value 2 are due to the increasing interaction between O 2p orbitals and unoccupied cation d states. We also explain the variations, along the series, of the individual contributions to Z* arising from the occupied band m…
Silicon together with its native oxide SiO$_2$ was recognized as an outstanding material system for the semiconductor industry in the 1950s. In state-of-the-art device technology, SiO$_2$ is widely used as an insulator in combination with high-$k$ dielectrics such as HfO$_2$, demanding fabrication of ultra-thin interfacial layers. The classical standard model derived by Deal and Grove accurately describes the oxidation of Si in a progressed stage, however, strongly underestimates growth rates for thin oxide layers. Recent studies report a variety of oxidation mechanisms during the growth of ox…
Ab initio techniques are used to calculate the effective work function (Weff) of a TiN/HfO2/SiO2/Si stack representing a metal-oxide-semiconductor (MOS) transistor gate taking into account first order many body effects. The required band offsets were calculated at each interface varying its composition. Finally the transitivity of LDA calculated bulk band lineups were used and completed by MBPT bulk corrections for the terminating materials (Si and TiN) of the MOS stack. With these corrections the ab initio calculations predict a Weff of a TiN metal gate on HfO2 to be close to 5.0 eV.
The discovery of ferroelectric properties of binary oxides revitalized the interest in ferroelectrics and bridged the scaling gap between the state-of-the-art semiconductor technology and ferroelectric memories. However, before hitting the markets, the origin of ferroelectricity and in-depth studies of device characteristics are needed. Establishing a correlation between the performance of the device and underlying physical mechanisms is the first step toward understanding the device and engineering guidelines for a novel, superior device. Therefore, in this paper a holistic modeling approache…
We report extensive lattice dynamical calculations of the newly discovered infinite-layer iron oxides SrFeO2 and CaFeO2. For SrFeO2, the parameters of the interatomic potential have been determined to reproduce the zone-centre phonon frequencies reported using ab-initio calculations. Further we have extended the potential model for calculations of CaFeO2. The potential parameters are found to be transferable between the two compounds, and are used to calculate the phonon spectra in the whole Brillouin zone and several thermodynamic properties for these compounds. The calculations show fair agr…
