含氧空位SrTiO3晶体电子结构研究

运用CRYSTAL-09软件计算得到了完整和含氧空位的SrTiO3晶体的电子态密度分布、能带结构和电荷密度分布。本文先通过分析完整SrTiO3晶体的电子结构,确定晶体化学键的组成。通过分析含氧空位的SrTiO3晶体的电子结构,发现禁带中出现一条新的缺陷带,缺陷带属于Σ轨道。通过缺陷能级的分析,结果表明SrTiO3晶体中2.4 eV的发光带可能是由Σ*-Σ之间的跃迁产生。     

Doubly positively charged oxygen vacancies in silica glass

The geometric and electronic structures of doubly positively charged oxygen vacancies in a-SiO₂ are calculated. We have found four types of relaxed configurations in the amorphous matrix, corresponding to puckered and unpuckerd configurations of Si atoms of the vacancy. The predicted optical absorption strongly depends on the atomic configuration of particular center and transition energies are distributed in the range from 4.5 to 6.5 eV.     

多晶Si薄膜表面金催化Si纳米线生长

以Au膜作为催化剂和大晶粒多晶Si薄膜为衬底,利用固-液-固生长机制,制备出直径在30～ 100 nm和长度为几百微米的高密度Si纳米线.实验研究了退火温度、生长时间和N2流量对Si纳米线生长的影响.结果表明,随着退火温度的升高,生长时间的延长和N2流量的增加,Si纳米线的长度和密度都显著增加.对不同生长时间下获得的Si纳米线样品进行了X射线衍射测量,结果显示随着生长时间的延长,多晶Si薄膜和表面的Au膜成分都在减少.光致发光谱则显示出弱的蓝光发射和强的红光发射特性,前者应是由非晶SiOx壳层中的氧空位发光中心引起,后者则应归因于Si纳米线芯部与非晶SiOx壳层之间界面区域附近中的Si =O双键态或非桥键氧缺陷中心.     

TFSI钝化晶体硅表面性质的第一性原理研究

晶体硅表面钝化是高效率晶体硅太阳能电池的核心技术,直接影响晶体硅器件的性能。本文采用第一性原理方法研究了一种超强酸-双三氟甲基磺酰亚胺(TFSI)钝化晶体硅(001)表面。研究发现,TFSI的四氧原子结构能够与Si(001)表面Si原子有效成键,吸附能达到-5.124 eV。电子局域函数研究表明,TFSI的O原子与晶体硅表面的Si的成键类型为金属键。由态密度和电荷差分密度分析可知,Si表面原子的电子向TFSI转移,从而有效降低了Si表面的电子复合中心,有利于提高晶体硅的少子寿命。Bader电荷显示,伴随着TFSI钝化晶体硅表面的Si原子,表面Si原子电荷电量减少,而TFSI中的O原子和S原子电荷电量相应增加,进一步证明了TFSI钝化Si表面后的电子转移。该工作为第一性原理方法预测有机强酸钝化晶体硅表面的钝化效果提供了数据支撑。     

Stereochemistry of silicon in oxygen-containing compounds

Specific stereochemical features of silicon in oxygen-containing compounds, including hybrid silicates with all oxygen atoms of SiO_n groups (_n = 4, 5, or 6) entering into the composition of organic anions or molecules, are described by characteristics of Voronoi—Dirichlet polyhedra. It is found that in rutile-like stishovite and post-stishovite phases with the structures similar to those of СаСl₂, α-PbO₂, or pyrite FeS₂, the volume of Voronoi—Dirichlet polyhedra of silicon and oxygen atoms decreases linearly with pressure increasing to 268 GPa. Based on these results, the possibility of formation of new post-stishovite phases is shown, namely, the fluorite-like structure (transition predicted at ~400 GPa) and a body-centered cubic lattice with statistical arrangement of silicon and oxygen atoms (~900 GPa).     

Growth and structural, optical, and electrical properties of zincite crystals

An X-ray diffraction study of ZnO crystals grown by the hydrothermal method has revealed reflections that give grounds to assign them to the sp. gr. P3 rather than to P6₃ mc. The distribution of Zn1, Zn2, O1, and O2 over structural positions, along with vacancies and incorporated zinc atoms, explains the dissymmetrization observed in terms of the kinetic (growth) phase transition of the order-disorder type, which is caused by ordering Zn and O atoms over structural positions. The color of crystals of refined compositions (Zn_0.975□_0.025)Zn _i(0.015)(O_0.990□_0.010) (green) and (Zn_0.965□_0.035)Zn _i(0.035)O (bright green) is related to different oxygen contents, which is confirmed by the results of electron probe X-ray microanalysis and absorption spectroscopy. The degree of the structural quality of crystals, their resistivity, and activation energy are also related to oxygen vacancies.     

Laser-induced defects in fused silica by UV laser irradiation

The structure of fused silica with irradiation of the third harmonic of the Nd:YAG laser was investigated by Fourier transform infrared, Raman and Photoluminescence spectroscopy. Some variation in the Si/O stoichiometry of silica in the ablated spot was induced. The primary defect species are oxygen deficient centers and oxygen interstitials. The frequency shift of the Si–O–Si vibration proves that the central force constant between oxygen and silicon atoms, and the band angle of Si–O–Si increases in the UV-laser ablation spot. Small silicon clusters within SiO_x appear to be a possible explanation for the 564 nm Fluorescence peak, and the 181 cm⁻¹ Raman peak.     

钨酸钡晶体本征点缺陷的模拟计算

本文利用晶格动力学软件GULP模拟计算了钨酸钡晶体的本征点缺陷,首先利用驰豫拟合的方法得到离子之间的相互作用势,利用这些相互作用势计算得到的结果与实验结果吻合得很好,在此基础上计算晶体本征缺陷的生成能,通过对本征点缺陷生成能的分析得到以下结论:钨酸钡晶体内V2+O的数量要大于V2-Ba的数量;钨酸钡晶体内缺陷态主要以V2-Ba-V2+O空位对和F色心形式存在.     

Effects of oxygen partial pressure during sputtering growth on physical properties of Zn0.93Mn0.07O thin films

We have studied structural, optical, electrical, and magnetic properties of Zn_0.93Mn_0.07O thin films grown by RF magnetron sputtering under ambient gas mixtures of O₂ and Ar. As the oxygen partial pressure increases, the electron concentration systematically decreases and photoluminescence peaks related to oxygen vacancies gradually diminish. These results suggest that oxygen vacancies are majority donors. Smooth surface morphology and electron concentration as low as ∼10¹⁵ cm⁻³ are obtained simultaneously for the film grown in an optimal oxygen partial pressure. This film exhibits ferromagnetism with the Curie temperature of 78 K, while other films grown in higher or lower oxygen partial pressure show paramagnetic behavior down to low temperature. The disappearance of the ferromagnetism can be explained in terms of crystalline quality and surface smoothness rather than electron concentration.     

Local structure around phosphorus and silicon in the CaO–SiO2–PO2.5 system

The local structure of phosphorus and silicon in the molten CaO–SiO₂–PO_2.5 slag system was investigated by magic angle spinning nuclear magnetic resonance (MAS-NMR). The ³¹P MAS-NMR spectra revealed that phosphorus was present primarily as the monophosphate complex ion PO₄^3?, with a small amount of diphosphate ion also present. Their relative ratio to total phosphorus was independent of the phosphate concentration of the sample. In the case of the ²⁹Si MAS-NMR, the mean number of the non-bridging oxygen atoms associated with tetrahedrally coordinated silicon decreased as the phosphate concentration increased at a fixed CaO/SiO₂ ratio. This indicates that the nonbridging oxygen atoms around the silicon were replaced by bridging oxygen atoms around the phosphorus as the phosphate concentration in the samples increased.To elucidate the basicity dependence of the structure of slag, the relationship between the structure and optical basicity was also investigated. The relative ratio of Qⁿ (Qⁿ means the silicon atoms tetrahedrally bonded with “n” number of bridging oxygen atoms) strongly depends on the optical basicity. These optical basicity dependencies of the structures of phosphorus and silicon can be explained clearly by the basicity equalization concept (Duffy and Ingram, 1976) [12].     

Defects and microvoids in a-Si and a-Si:H

We report the first measurements of positron-annihilation spectra of samples of both pure and hydrogenated amorphous silicon. Comparison of these spectra with that of crystalline silicon indicates that the lowest-lifetime component can be identified as the contribution mainly from valence-band electrons. Both the pure (a-Si) and the hydrogenated (a-Si:H) samples exhibit a component with intermediate lifetime, which we attribute to small vacancies consisting of about 4 missing atoms. Finally, only a-Si:H shows a significant long-lived line (τ > 5 ns), which arises from large microvoids, with ～ 100 missing atoms. The existence of these microvoids in a-Si:H is consistent with recent reports of the presence of occluded H₂ gas under high pressure in such films.     

乙二胺用量对CeO2纳米棒合成的影响

采用水热法,以氯化铈为铈源、乙二胺为络合剂、水合肼为沉淀剂,通过改变乙二胺的用量制备了四种CeO2粉体样品,通过X射线衍射仪(XRD)、紫外可见分光光度计(UV-Vis)、荧光分光光度计(PL)和扫描电镜(SEM)对合成的CeO2样品的结构、形貌和光学性质进行表征。实验结果表明乙二胺剂量对样品的晶格常数、氧空位度、能带间隙、荧光强度等有显著影响。晶格常数随乙二胺剂量的增加先减小后增大,剂量为5 mL时晶格常数最小,氧空位度随乙二胺剂量的增加先增加后减少,剂量为5 mL时氧空位浓度最大、样品能带间隙最小、对紫外线的吸收最强、荧光强度最大。     

Role of oxygen vacancies in the origin of ferromagnetism in Mn‐doped ZnO

The relationship between the oxygen vacancy and ferromagnetism in Mn‐doped ZnO has been studied based on the first‐principles calculations. Three possible charge states of oxygen vacancies, i.e., neutral (V_O⁰), 1+ (V_O¹⁺) and 2+ (V_O²⁺) are considered. Results show that the lattice relaxations around oxygen vacancies are large difference under different charge states. It is found that V_O¹⁺ and V_O²⁺ oxygen vacancies induce ferromagnetism. However, Mn‐doped ZnO system shows ferromagnetism with V_O⁰ oxygen vacancies in hydrogenated environment, the ferromagnetism is attributed to the interstitial H, which forms a bridge bond and mediates d ‐d coupling and stabilizes the ferromagnetic state. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Studies on the effect of ammonia flow rate induced defects in gallium nitride grown by MOCVD

Gallium nitride (GaN) epitaxial layers were grown with different V/III ratios by varying the ammonia (NH₃) flow rate, keeping the flow rate of the other precursor, trimethylgallium (TMG), constant, in an MOCVD system. X-ray rocking curve widths of a (1 0 2) reflection increase with an increase in V/III ratio while the (0 0 2) rocking curve widths decrease. The dislocation density was found to increase with an increase in ammonia flow rate, as determined by hot-wet chemical etching and atomic force microscopy. 77 K photoluminescence studies show near band emission at 3.49 eV and yellow luminescence peaking at 2.2 eV. The yellow luminescence (YL) intensity decreases with an increase in V/III ratio. Positron annihilation spectroscopy studies show that the concentration of Ga-like vacancies increases with an increase in ammonia flow rate. This study confirms that the yellow luminescence in the GaN arises due to deep levels formed by gallium vacancies decorated with oxygen atoms.     

Correlations between electronic structure of transition metal atoms and performance of high-k gate dielectrics in advanced Si devices

This paper develops a classification scheme for non-crystalline dielectrics that separates them into three groups with different amorphous morphologies, and identifies a linear scaling relationship between average bond ionicity and oxygen atom coordination. The classification scheme is applied to transition metal silicate and aluminate alloys and provides a structural model for molecular orbital, MO, calculations that are based on the coordination and symmetry of transition metal atoms and the orbital energies of their oxygen neighbors. The MO calculations show that conduction band offset energies with respect to Si scale inversely with the energy difference between transition metal atomic n+1 s- and n d-states providing an important insight into the choice of alternative gate dielectrics for advanced Si devices.     

Electron Energy-Loss Spectroscopy Study of the Change in the Free-Electron Density in Thin Superconducting NbN Films under Ion-Beam Irradiation

The change in the free-electron density in ultrathin (5 nm) superconducting NbN films in the initial state and after irradiation by O⁺ ions to doses of (0.1–0.9) × 10¹⁷ cm^–2 has been studied by electron energy-loss spectroscopy (EELS). The analysis has been performed on cross section samples prepared by the focused ion beam method, using plasmon oscillations with energies up to 50 eV. The radiation-induced replacement of nitrogen atoms with oxygen atoms in niobium nitride is found to change the electrical properties of the material, which leads to a decrease in the free-electron density with an increase in the irradiation dose.     

Trapped-electron centers in pure and doped glassy silica: A review and synthesis

This paper reviews half a century of research on radiation-induced point defects in pure and doped glassy silica and its crystalline polymorph α quartz, placing emphasis on trapped-electron centers because the vast majority of all presently known point defects in various forms of SiO₂ are of the trapped-hole variety. The experimental technique most discussed here is electron spin resonance (ESR) because it provides the best means of identifying the point defects responsible for the otherwise difficult-to-attribute optical bands. It is emphasized that defects in α quartz have been unambiguously identified by exacting analyses of the angular dependencies of their ESR spectra in terms of the g matrix of the unpaired electron spin and the matrices of this spin's hyperfine interactions with non-zero-nuclear-spin ²⁹Si and ¹⁷O nuclides in pure α quartz and/or with substitutional ²⁷Al, ³¹P, or ⁷³Ge in quartz crystals respectively doped with Al, P, or Ge. Many defects in pure and doped glassy silica can be unambiguously identified by noting the virtual identities of their spin Hamiltonian parameters with those of their far better characterized doppelgangers in α quartz. In fact, the Ge(1) trapped-electron center in irradiated Ge-doped silica glass is shown here to have a crystal-like nature(!), being virtually indistinguishable from the Ge(II) center in Ge-doped α quartz [R.J. McEachern, J.A. Weil, Phys. Rev. B 49 (1994) 6698]. Still, there are other defects occurring in glassy silica that are not found in quartz, and vice versa. Nevertheless, those defects in glasses without quartz analogues can be identified by analogies with chemically similar defects found in one or both polymorphs and/or by comparison with the vast literature of ESR of paramagnetic atoms and small molecules. Oxygen “pseudo vacancies” comprising trigonally coordinated borons paired with trigonally coordinated silicons were proposed to exist in unirradiated B₂O₃–3SiO₂ glasses in order to account for observations of γ-ray-induced trapped-electron-type B- and Si-E′ centers [D.L. Griscom et al., J. Appl. Phys. 47 (1976) 960]. Analogous Al-E′ trapped-electron centers have been elucidated in silica glasses with Al impurities [K.L. Brower, Phys. Rev. B 20 (1979) 1799]). And it has been proposed [D.L. Griscom et al., J. Appl. Phys. 47 (1976) 960] that trapping of a second electron on such oxygen pseudo vacancies accounts for the predominant ESR-silent trapped-electron centers in irradiated silica glasses containing B or Al. The present paper additionally attempts to divine the identities of some of the ESR-silent radiation-induced trapped-electron centers in silica glasses free of foreign network-forming cations. This quest led to the doorstep of the most famous ESR-silent defect of all, the twofold-coordinated silicon, which is found only in silica glasses (not in quartz) and is responsible for the UV/visible optical properties of the oxygen-deficiency center known as ODC(II). The oxygen-deficiency center called ODC(I) is associated with an absorption band at 7.6 eV and, though commonly believed to be a simple oxygen mono-vacancy, is clearly more complicated than that [e.g., A.N. Trukhin, J. Non-Cryst. Solids 352 (2006) 3002]. Certain well documented but persistently enigmatic ODC(I)?ODC(II) “interconversions” [reviewed by L. Skuja, J. Non-Cryst. Solids 239 (1998) 16] have never been explained to universal satisfaction. An innovative combined ESR/thermo-stimulated-luminescence (TSL) study of a series of pure low-OH silica glasses with oxygen deficiencies of 0.000, ~ 0.015, and ~ 0.030 vol.% [A.N. Trukhin et al., J. Non-Cryst. Solids, 353 (2007) 1560] places new constraints on all future models for ODC(II). Taking this history into account, specific redefinitions of both ODC(I) and ODC(II) are proposed here. The present review also revisits a study of X-ray-induced point defects in an ultra-low-OH, high-chlorine but otherwise ultra-high-purity silica glass [D.L. Griscom, E.J. Friebele, Phys. Rev. B34 (1986) 7524], arguing that (1) most of the reported E′_γ and E′_δ centers were created via the mechanism of dissociative electron capture at chlorine-decorated oxygen vacancies, (2) the concomitantly created interstitial chloride ions serve as ESR-silent trapped-electron traps, (3) the ESR-detected “Cl⁰” centers arise from hole trapping on O₃≡ Si–Cl units without detachment of the resulting Cl atom, and (4) those chlorine atoms that are detached by homolytic bond fission are ESR-silent. Finally, in chlorine-free, low-OH, high-purity silica glasses, up to 100% of the trapped-electron centers appear to be ESR silent and are tentatively ascribed to electron trapping in pairs below the mobility edge of the conduction band. In such cases, the sum of all trapped-hole centers has been found to decay exponentially with increasing isochronal annealing temperature in the range 100 to ~ 300 K [D.L. Griscom, Nucl. Inst. & Methods B46 (1990) 12]. Overall, this review consolidates a large amount of long-existing but often underappreciated knowledge bearing on the natures of trapped-electron centers in pure and doped glassy silica, proposes new models for some of these, and raises a number of questions that cannot be fully answered without future performance of new experiments and/or ab initio calculations.     

Investigation of the electronic band structure of some linear polysilicates

The one-dimensional LCAO tight-binding method was applied to the study of the electronic structure of a model for a regular polymeric orthosilicic acid and its mono-sodium, di-sodium and calcium salts. The silicon d-orbitals are included and the orbital exponent and one-centre repulsion integral for these orbitals, together with the Mulliken-Wolfsberg A parameter, were optimised so as to produce the ‘best’ results for the acid. Replacement of H by metal atoms in the polymer is shown to perturb the system in such a way as to reduce the band gap by a factor of 3 to 4. Further, the non-bridging O atoms, along with the metal atoms themselves, become concentrated in the states bordering the band gap. Density-of-states curves are sharply peaked around the energy gap for all four systems and the peak height increases as the metal atomic number becomes larger.     

An EXAFS study of the local structure of Ce---Si---O amorphous thin films

An EXAFS study has been made on the structure of three composition ranges of Ce---Si---O amorphous thin films prepared by RF sputtering. The measurements, carried out on the K edge of silicon and the L₃ edge of cerium, reveal that in the stoichiometric oxygen films of the general formula (Ce, Si) O₂, both cerium and silicon are four-coordinated by oxygen regardless of the O : Si ratio. In the oxygen-deficient films cerium remains four-coordinated by oxygen, but, around silicon, the oxygen atoms are progressively replaced by silicon as the oxygen content of the films is reduced. In silicon-rich films which are very deficient in oxygen, the oxygen atoms prefer to ramain coordinated with cerium, rather than silicon.

A definite decrease in the Si---O distance with increase in Si---O coordination has been found. The effect is attributed to an increase in the charge of silicon with oxygen coordination, and supports a randomly bonded model for the structure.

The total oxygen coordination, derived from a consideration of bond conservation, indicates that the film structures are probably SiO₂-type continuous random networks.     

Effect of composition on ionic transport in SiO2–B2O3–Na2O glasses

Ionic diffusion was investigated in the SiO₂–B₂O₃–Na₂O glass system over a wide composition range by impedance spectroscopy measurements. The Na⁺ cation transport mechanism was described by an interstitial pair migration model based on Frenkel defects in ionic crystals. The activation energy of the static electrical conductivity is shown to be correlated with the boron coordination number in these glasses. Published ¹¹B NMR results were used to calculate the activation energies of sodium cations acting as charge compensators for the [BO_4/2]⁻ tetrahedron and of sodium cations bonded to non-bridging oxygen atoms. These values are in agreement with the activation energies of the Na₂O–B₂O₃ and Na₂O–SiO₂ binary systems, respectively.