Li含量对Li3xLa((2/3)–x?(1/3)–2x)TiO3固态电解质表面稳定性、电子结构及Li离子输运性质的影响

Li_3xLa₍(2/3)–x^?(1/3)–2x)TiO₃(LLTO)是一类颇具前景的锂离子电池固态电解质.本文采用第一性原理结合分子动力学方法对贫锂相和富锂相两种类型的LLTO表面进行研究,分析表面Li含量对其稳定性、电子结构及Li离子输运性质的影响.结果表明,具有La/O/Li-原子终端的(001)面为最稳定晶面.对于LLTO(001)面,当贫锂相/富锂相终端Li含量为0.17/0.33,0.29/0.40,0.38/0.45时,其表面结构更为稳定.电子结构分析表明,随着Li含量的增大,不论是贫锂相还是富锂相,其(001)表面均发现金属至半导体的转变.Li离子输运性质的研究结果表明,贫锂相和富锂相LLTO(001)表面均具有沿ab平面的二维扩散通道,且当终端Li含量分别达到0.38和0.40时具有最大的Li离子扩散系数及最低的Li离子扩散能垒,最低扩散能垒分别为0.42 eV和0.30 eV.因而,改变终端Li含量有利于提高LLTO(001)表面稳定性、打开表面带隙、改善Li离子迁移性能,这有助于...     

富镧混合稀土-镍贮氢材料CO,O2和H2O中毒的表面特征

本文用UPS,XPS研究了贮氢材料MlNi₅(Ml=La,Ce,Pr,Nd)的CO,O₂和H₂O的中毒,在UPS谱中,我们观察到在E_F以下峰α(0.3eV)和峰b(1.2eV)强度随中毒气体暴露量增加有显著变化,并向低动能端位移,逐渐形成肩峰,与此同时,峰c(6eV)和峰d(9.5eV)的强度随暴露量增加而增加,并有能量位移,配合XPS分析,分别确定相应的化学态。氧中毒后的MlNi₅,经300℃加氢还原,从UPS谱可以看到峰α,b强度增加;H₂O和CO中毒后,在超高真空条件下,分别经300℃加热处理,和Ar⁺剥离方法,均获得类似的效果,XPS分析进一步证实了这些结果。实验给出了贮氢材料MlNi₅中过渡金属镍的d电子与气体自由分子轨道间电荷转移的信息,为在实际应用中认识此类贮氢合金的表面催化中毒和再生提供了依据。 关键词：     

Li掺杂对MgH2(001)表面H2分子扩散释放影响的第一性原理研究

本文利用基于密度泛函理论的第一性原理分别研究了MgH₂(001)表面H原子扩散形成H₂分子释放出去的可能路径及金属Li原子掺杂对其影响. 研究结果表明: 干净MgH₂(001)表面第一层释放H原子形成H₂分子有两种可能路径, 其释放能垒分别为2.29和2.50 eV; 当将Li原子替代Mg原子时, 两种H原子扩散释放路径的能垒分别降到了0.31和0.22 eV, 由此表明Li原子掺杂使MgH₂(001)表面H原子扩散形成H₂释放更加容易.     

SiO2-羟基表面上金属原子的第一性原理研究

采用第一性原理方法研究了SiO₂-羟基表面上几种金属原子的吸附性质，发现In和Ga在SiO₂-羟基表面上的结合很弱，而Fe，Co， Ni在该表面上与Si，O形成强的化学键.等势能面和扩散势垒计算表明In (Ga)的扩散激活能只有0.1—0.3 eV，表明这两种原子容易在表面上扩散.这些结果可以定性地解释纳米合成中的一些实验现象. 关键词： 第一性原理 表面扩散 结合能 金属原子     

掺杂离子对白色长余辉发光材料Y2O2S:Tb3+, Eu3+,M2+ (M=Mg,Ca, Sr,Ba),Zr4+性能的影响

采用高温固相法制备了白色长余辉发光材料Y₂O₂S:Tb³⁺, Eu³⁺,M²⁺(M=Mg, Ca, Sr, Ba), Zr⁴⁺, 利用X晶体衍射、发光光谱、余辉曲线和热释光曲线等对制备的材料进行表征。结果表明:掺杂离子没有改变样品晶体结构和发射峰的位置,但对其发光强度、余辉时间及陷阱深度有较大的影响。在263 nm紫外光的激发下,469 nm和626 nm的发射分别对应于Eu³⁺的⁵D₂→⁷F₀、⁵D₀→⁷F₂跃迁,544 nm的发射对应于Tb³⁺的⁵D₄→⁷F₅跃迁,主要通过它们的混合产生白光。掺杂不同二价离子样品的余辉性能按Mg²⁺、Sr²⁺、Ca²⁺、Ba²⁺的顺序递减,其中掺杂Mg²⁺的样品,色度坐标为(0.29,0.32),陷阱深度为1.17 eV,余辉时间长达320 s(≥1 mcd/m²),表现出最佳的发光性能。     

TixY1-xBa2Cu3O7-δ超导体的红外、远红外光谱

本文报道了Ti_xY_1-xBa₂Cu₃O_7-δ(x=0.2和0.4)在4.2—300K的红外、远红外光谱。在50—360cm^-1波段内发现七个反射峰。它们分别与Ba,Cu,O离子团,Y,O离子团。Ti,O离子团,以及Cu—O键的振动有关,对于x=0.2的样品,存在两个反转结构。对于x=0.4的样品,则仅发现一个反转结构。在红外光谱中观察到六个反对峰和三个吸收峰,它们的强度大多随Ti含量的增加而增强。与Y₁Ba₂Cu₃O_7-δ的光谱结果比校,讨论了声子峰及反转结构的物理起因。 关键词：     

Alq3/ITO结构的表面和界面电子状态的XPS研究

用传统的真空蒸镀法制备了Alq3/ITO样品,并用X光电子能谱（XPS）研究了Alq3/ITO紧密接触的表面和界面电子化学状态。对Alq3/ITO样品的表面分析表明,在Alq3分子中,Al原子的束缚能（Eb)为70．7eV和75．1eV,分别对应于Al(0)和Al(Ⅲ）态;C原子的束缚能为285．8eV、286．3eV和286．8eV,分别对应于C－C、C－O和C－N键;N原子的主峰位于401．0eV,对应于C－N＝C键;而O原子主要与H原子成键,其束缚能为532．8eV。为了研究Alq3/ITO的界面电子状态,我们用氩离子束对样品表面进行了溅射剥蚀,当溅射时间分别为30,35,45分种时进行XPS采谱分析。结果表明,随着氩离子束溅射时间增长,Al2p、Cls、Nls、Ols、In3d5/2和Sn3d5/2峰都向低束缚能方向有微小移动,且Al2p、Cls和Nls峰变弱,这是受ITO中扩散进入Alq3层的O、In和Sn原子的影响所致。     

金红石相VO2电子结构与光电性质的第一性原理研究

采用完全势线性缀加平面波方法(FP-LAPW)结合密度泛函+U(DFT+U)模型计算了金红石相VO₂的电子结构和光学性质. 电子态密度计算结果表明所采用的方法可以较好的描述体系的导带电子结构. 计算得到体系为导体,V-O键主要由O原子的2 p轨道与V原子的3 d轨道杂化形成,外加光场垂直和平行于c轴时体系的等离子振荡频率为3.44 eV和2.74 eV,光电导率在0-1 eV之间有一个与带内跃迁有关的德鲁德峰,而大于1 eV的光电导率主要由电子带间跃迁产生,得到并分析了带内跃迁过程和带间跃迁过程各自对反射谱和电子能量损失谱的贡献. 关键词： 光电性质 电子结构 缀加平面波方法 2')" href="#">VO₂     

Cd+离子5s2S1/2→5p2P3/2电子碰撞激发截面和退激辐射光子极化度的理论研究

本文采用全相对论扭曲波方法计算了Cd⁺离子5s²S_1/2 → 5p²P_3/2电子碰撞激发总截面、磁能级的激发截面以及退激辐射光子极化度. 详细讨论了电子关联效应对激发截面以及退激辐射光子极化度的影响. 我们发现, 在低能碰撞部分(<10 eV), Core-价关联对电子碰撞激发截面的贡献非常重要, 与不考虑Core-价关联的结果相比, Core-价关联的计算结果使得激发截面降低了1/2到2/3; 在高能碰撞部分(>80 eV), Core-价关联的贡献不是非常明显, 但与不考虑Core-价关联的结果相比, 其激发截面也降低了15%. 然而, 对于退激辐射光子极化度, Core-价关联的贡献非常小, 其影响是可以忽略的.     

缺陷黄铜矿结构Xga2S4 (X=Zn,Cd, Hg)晶体电子结构和光学性质的第一性原理研究

采用基于密度泛函理论(DFT)的第一性原理超软赝势方法对缺陷黄铜矿结构XGa₂S₄ (X=Zn, Cd, Hg)晶体的晶格结构、电学以及光学性质进行了对比研究. 分析比较了它们的晶格常数、键长、能带结构、态密度、介电函数、折射率和反射系数等性质, 并总结其变化趋势. 结果表明: 这三种材料的光学性质在中间能量区域(4 eV–10 eV)表现出较强的各向异性, 而在低能区域(<4 eV)和高能区域(>10 eV)各向异性较弱. ZnGa₂S₄和HgGa₂S₄两种材料的折射率曲线在等离子体频率ω_p处有一明显的拐点, 反射系数在ω_p处达到最大值后急剧下降. 三种晶体的强反射峰均处于紫外区域, 因此可以用作紫外光屏蔽或紫外探测材料. 关键词： 缺陷黄铜矿结构 电子结构 光学性质 第一性原理计算     

Stoichiometric and oxygen deficient MoO3(010) surfaces

The (010) surface of single crystal MoO₃ has been prepared and examined using LEED, XPS, UPS, and ELS. Three methods yield the stoichiometric surface: scraping in UHV and annealing, ion etching followed by reoxidation (770 K, 10² Pa O₂), or oxygen treatment to remove carbon contamination. LEED shows the surface periodicity is the same as that of the bulk (010). The MoO₃ valence band is 7 eV wide with density of states maxima at 1.5, 3.6, and 5.6 eV below the top of the valence band. Heating MoO₃ in vacuum reduces the surface region. XPS indicates the O/Mo atomic ratio decreases to 2.85 ± 0.12 on heating to 600 K. Ar ion bombardment disorders the surface and reduces the surface O/Mo atomic ratio to 1.6. Annealing of reduced surfaces at > 770 K incompletely reoxidizes them by diffusion of oxygen from the bulk. UPS of reduced and annealed MoO₃ exhibits two new emission features in the bandgap at 0.9 and 2.0 eV above the top of the valence band. These features originate from Mo derived states of a defect involving two or more Mo atoms, such as crystallographic shear planes. Because of the insulating nature of MoO₃, surface charging and electron beam induced damage were substantial hindrances to electron spectroscopic examination.     

Interaction of H2O with a clean and oxygen precovered Ni(110) surface studied by XPS

The adsorption and reaction of H₂O on clean and oxygen precovered Ni(110) surfaces was studied by XPS from 100 to 520 K. At low temperature (T<150 K), a multilayer adsorption of H₂O on the clean surface with nearly constant sticking coefficient was observed. The O 1s binding energy shifted with coverage from 533.5 to 534.4 eV. H₂O adsorption on an oxygen precovered Ni(110) surface in the temperature range from 150 to 300 K leads to an O 1s double peak with maxima at 531.0 and 532.6 eV for T=150 K (530.8 and 532.8 eV at 300 K), proposed to be due to hydrogen bonded O_ads… HOH species on the surface. For T>350 K, only one sharp peak at 530.0 eV binding energy was detected, due to a dissociation of H₂O into O_ads and H₂. The s-shaped O 1s intensity-exposure curves are discussed on the basis of an autocatalytic process with a temperature dependent precursor state.     

Oxidation of Al single crystal surfaces by exposure to O2 and H2O

The initial stages of oxidation of Al single crystals are studied by soft X-ray photoemission spectroscopy at photon energies hv = 30 eV and 111.13 eV using synchroton radiation. Both the valence band region and the substrate Al 2p core levels are measured with high resolution to clarify the differences between (a) the geometrical effects at different surfaces, (100) and (110), and (b) between the oxidation by pure O₂ and H₂O. There is a well established but not very dramatic differences in the O 2p induced band between the two crystal surfaces when oxidizing with O₂. The Al 2p spectra reveal an initial state of oxidation with less O atoms per Al atom than in Al₂O₃ate disappears at higher exposures with O₂ while it is absent when oxidizing with H₂O. Only about 1/4 of the exposure with H₂O is needed to obtain the same coverage as with O₂.     

X-ray photoelectron spectroscopy of Sm-doped CaO-MgO-Al2O3-SiO2 glasses and glass ceramics

Sm³⁺ doped CaO-MgO-Al₂O₃-SiO₂ glass and glass ceramics have been prepared. The diopside crystal (CaMgSi₂O₆) was identified in the glass ceramics by X-ray diffraction analysis. X-ray photoelectron spectra of the glass and glass ceramics were measured by a monochromatised Al-Kα XPS instrument. Sm 3d core level spectra for the Sm doped samples showed that Sm ions are predominantly in the Sm (III) state in glass and glass ceramics. The O 1s core spectra could be fitted by summing the contributions from bridging oxygen (BO) and non bridging oxygen (NBO) for samarium undoped glass, BO, NBO and Si-O-Sm for the doped glass. The O 1s XPS spectrum of undoped glass ceramics was curve fitted with BO and NBO in glass phase, as well as SiOSi, SiOMg and SiOCa in diopside. In addition to the five components above mentioned, SiOSm in diopside also appeared in O 1s XPS spectra of samarium doped glass ceramics. According to the fitting results, we demonstrate that the Sm₂O₃ exist in glass network as a glass modifier. After heat treatment, nearly all the Sm³⁺ existed in diopside phase as the substitution for Ca²⁺.     

First-principles study on electronic structure of Sr2Bi2O5 crystal

The electronic structure of Sr₂Bi₂O₅ is calculated by the GGA approach. Both of the valence band maximum and the conduction band minimum are located at Γ-point. This means that Sr₂Bi₂O₅ is a direct band-gap material. The wide energy-band dispersions near the valence band maximum and the conduction band minimum predict that holes and electrons generated by band gap excitation have a high mobility. The conduction band is composed of Bi 6p, Sr 4d and O 2p energy states. On the other hand, the valence band can be divided into two energy regions ranging from −9.5 to −7.9 eV (lower valence band) and from −4.13 to 0 eV (upper valence band). The former mainly consists of Bi 6s states hybridizing with O 2s and O 2p states, and the latter is mainly constructed from O 2p states strongly interacting with Bi 6s and Bi 6p states.     

Electron energy loss spectra and X-ray photoelectron spectra of Ca2V2O7

We have measured the electron energy loss spectra of Ca₂V₂O₇ in the reflexion mode, at incident energies between 200 and 2400 eV, and the X-ray photoelectron spectra excited by Al K α radiation. The abundant loss structures observed can be correlated with the possible interband transitions, collective oscillations, and excitation of O2s and V3p electrons within the V₂O₇^4- ion. The gap width and molecular orbital (MO) spread (or splitting) is about l eV larger in the V₂O₇^4- ion than in its component VO₄^3- ion. Excitation of O2s states, which may occur together with some MO over-gap transitions, displaces the collective oscillations about 7 eV towards lower energies. Deeper V3p electrons are excited with a maximum energy loss some 7 eV above their binding energy. Cross transitions from Ca3p levels into some empty states of the V₂O₇^4- ion, or direct transitions to available states of the Ca²⁺ ion could not be unambiguously identified. The energy dependence of the excitation cross section and of the electron penetration depth results in a significant variation of the relative intensity of various losses over the investigated energy range.     

X-ray photoelectron spectroscopy studies of Co-doped ZnO-Ga2O3-SiO2 nano-glass-ceramic composites

Co-doped ZnO-Ga₂O₃-SiO₂ nano-glass-ceramic composites were prepared by sol-gel method. X-ray diffraction patterns showed that the crystallization temperature was 800 °C. X-ray photoelectron spectroscopy (XPS) was used to study the effect of heat-treatment temperature on the electronic structure of Co-doped ZnO-Ga₂O₃-SiO₂ nano-glass-ceramic composites. The Zn (2p_3/2), Ga (2p_3/2) and O (1s) XPS spectra for the glass-ceramics heat-treated at 800-1000 °C could be deconvoluted into two peaks corresponding to these elements in glass network and in nanocrystals, respectively. The results indicate that the material is composed of an amorphous silicate network and ZnGa₂O₄ nanocrystalline particles. The amount of nanocrystals increases with the annealing temperature. The photoelectron peak of Si (2p) shifts to higher binding energy at higher annealing temperature, revealing the charge transfer from Si to O increased. The relationship between the microstructure of Co-doped ZnO-Ga₂O₃-SiO₂ sample and its absorption properties was discussed, and the suitable heat-treatment temperature was proposed.     

Structure, band offsets and photochemistry at epitaxial α-Cr2O3/α-Fe2O3 heterojunctions

We test the hypothesis that electron-hole pair separation following light absorption enhances photochemistry at oxide/oxide heterojunctions which exhibit a type II or staggered band alignment. We have used hole-mediated photodecomposition of trimethyl acetic acid chemisorbed on surfaces of heterojunctions made from epitaxial α-Cr₂O₃ on α-Fe₂O₃(0001) to monitor the effect of UV light of wavelength 385 nm (3.2 eV) in promoting photodissociation. Absorption of photons of energies between the bandgaps of α-Cr₂O₃ (E_g = 4.8 eV) and α-Fe₂O₃ (E_g = 2.1 eV) is expected to be strong only in the α-Fe₂O₃ layer. The staggered band alignment should then promote the segregation of holes (electrons) to the α-Cr₂O₃ (α-Fe₂O₃) layer. Surprisingly, we find that the α-Cr₂O₃ surface alone promotes photodissociation of the molecule at hν = 3.2 eV, and that any effect of the staggered band alignment, if present, is masked. We propose that the inherent photoactivity of the α-Cr₂O₃(0001) surface results from the creation of bound excitons in the surface which destabilize the chemisorption bond in the molecule, resulting in photodecomposition.     

Structure electronique des oxydes de cobalt CoO et Co3O4

The total density of occupied states in the valence band of CoO and Co₃O₄ is determined by XPS and UPS. From variations of excitation probability of the bands, the 4 e V wide O2_p band is shown to be located around 5 eV for both oxides, while structures obtained from photoionisation of the localized 3d band spread over 10 eV range below the Fermi level overlapping with O2_p band. The 3d peaks located at binding energy <3 eV correspond to the calculated energy of the d_n ?1 manifold final state in the octahedral and tetrahedral crystal field of CoO and Co₃O₄. The 3d levels at higher binding energy are shown to occur from configuration interaction in both final and initial states. These last peaks are higher in intensity for CoO relative to Co₃O₄. A superior limit for the width of the 3d initial band in a one electron energy diagram is given to be <3 eV. This value associated to the Coulomb correlation energy measured equal to ~3 eV. This value associated to the Coulomb correlation energy measured equal to ~3 eV from shake-up and Auger energy confirms the Mott insulator nature of CoO.