关于Al_nC和Al_nC~+(n=1—8)团簇结构和稳定性的研究

通过采用7种密度泛函理论DFT方法对AlnC进行计算,所得结果与实验数据比较,选择了B3lyp方法和6-311G(d)基组对AlnC及AlnC+(n=1—8)团簇进行结构优化和频率分析,得到了AlnC及AlnC+基态以及亚稳态结构.当n从小到大变化时,这些团簇的结构从平面向立体过渡,平面构型以三角形为主,立体构型主要是三棱柱笼状结构;在这些团簇中的高对称性结构中,中性团簇和阳离子只能有其一是稳定构型;在所研究的团簇中,Al2C和Al5C团簇较为稳定.     

有机金属化学气相沉积法制备的Ni/Al2O3纳米复合材料的氢吸附

研究了通过有机金属化学气相沉积技术及单源分子前躯体方法制备的Ni/Al₂O₃纳米复合材料的氢吸附(存储). 在冷壁的有机金属化学气相沉积反应器中,通过降解Ni(acac)₂粉末基底上的[H₂Al(OtBu)]₂制备的Ni/Al₂O₃纳米复合材料. 通过X射线粉末衍射、扫描电镜、透射电镜以及能量色散型X射线荧光光谱等技术表征该复合材料. 采用自制Sievert's设备研究该复合材料的氢吸附(存储),可以储存约2.9%(重量比)的氢.     

Fe_nO_m~+(n+m=4)团簇的构型、电子结构特征和磁性

采用二项式方案构建了FenOm+(n+m=4)团簇的大量可能初始结构.运用广义梯度近似(GGA)密度泛函理论中的PW91交换关联泛函对这些初始结构进行优化和频率分析,得到12个稳定的异构体.在此基础上计算和分析了它们的结合能、对称性、键长、磁矩,最高占据轨道与最低未占据轨道的能隙.发现Fe—O键在FenOm+(n+m=4)团簇的稳定中具有重要作用,团簇的总磁矩主要取决于铁原子的磁矩和各个原子磁矩排布情况.     

Combined experimental and theoretical study of small aluminum oxygen clusters

We report a combined experimental and computational investigation of small Al_nO_m species (n ≤20, m ≤ 12), produced in a laser vaporization cluster source. The oxygen content in the clusters was tuned by varying the oxygen concentration in the carrier gas. Ionization energies are bracketed using different ionizing photon energies in the energy range between 5.37 and 7.89 eV. Among the singly doped Al_nO species, Al₃O and Al₁₅O are found to have relatively low ionization energies, which can be related to the magic character of the corresponding cations. Peculiarly low ionization energies also are observed for specific oxygen rich species (m > 1), suggesting the formation of ionically bound subunits. The structures and ionization energies of singly doped Al_nO^0,+ (n = 1 - 7) clusters were determined using density functional theory (B3LYP/6-311+G(d)). Electronic supplementary material Supplementary Online Material     

Cluster generation under pulsed laser ablation of zinc oxide

Neutral and cationic Zn _n O _m clusters of various stoichiometry have been produced by nanosecond laser ablation of ZnO in vacuum and investigated by time-of-flight mass spectrometry. Particular attention was paid to the effect of laser wavelength (in the range from near-IR to UV) on cluster composition. Under 193-nm laser ablation, the charged clusters are essentially substoichiometric with Zn_nO_n-1⁺\mathrm{Zn}_{n}\mathrm{O}_{n-1}^{+} and Zn_nO_n-3⁺\mathrm{Zn}_{n}\mathrm{O}_{n-3}^{+} being the most abundant series. Both sub- and stoichiometric cationic clusters are generated in abundance at 532- and 1064-nm ablation whose composition depends on the cluster size. The reactivity of small stoichiometric Zn_nO_n⁺\mathrm{Zn}_{n}\mathrm{O}_{n}^{+} clusters (n<11) toward hydrogen is found to be high, while oxygen-deficient species are less reactive. The neutral plume particles are mainly stoichiometric with Zn₄O₄ tetramer being a magic cluster. It is suggested that the Zn₄O₄ loss is the dominant fragmentation channel of large zinc oxide clusters upon electron impact. Plume expansion conditions under ZnO ablation with visible and IR laser pulses are shown to be favorable for stoichiometric cluster formation.     

In situ 1H NMR Study of Nanoreactor Interaction NH3–H2O in Zeolite Nanopores

The interaction between ammonium NH₃ and H₂O molecules in zeolitic nanopores is studied by in situ ¹H nuclear magnetic resonance (NMR) method. The powder and single crystal samples of natural zeolites, heulandites Ca₄[Al₈Si₂₈O₇₂]·24H₂O and clinoptilolite (Na, K,Ca_1/2)₆[Al₆Si₃₀O₇₂], were used as the model system. It is shown that penetration of NH₃ into the zeolitic nanopores is accompanied by disordering of the hydrogen sublattice of zeolitic water and by the fast proton exchange NH₃ + H₂O ? [NH₄]⁺ + [OH]^? characterized by correlation frequency v _c = ~40 kHz. Another nanoreactor interactions are represented by interaction of [NH₄]⁺ ions with exchangeable Na⁺ and Ca²⁺ ions of the zeolitic structure. The slow ionic exchange [NH₄]⁺ → [Na,Ca_1/2]⁺ and binding of [NH₄]⁺ in cationic sites of the framework were visualized by NMR spectroscopy along with stepwise release of (Na,Ca_1/2)OH from zeolitic pores to the external surface of zeolite grains.     

A systematic investigation of the geometries,electronic and magnetic properties of AlnAsq (q = −1, 0, +1; n = 1–16) clusters: a DFT calculation

The geometries, electronic and magnetic properties of Al_nAs^q (q = ?1, 0, +1; n = 1–16) clusters have been investigated systematically by using an unbiased CALYPSO structure searching method and density functional theory. The lowest energy structures show that the As atom prefers to occupy the peripheral position of Al_n+1 clusters instead of the endohedral position. For cationic and neutral clusters, the structural transition from bilayer-like structure to cage-like structure is observed at cluster size n = 12, while it occurs at n = 13 for anionic clusters. The calculated detachment energies (DEs), ionisation potentials (IPs) and electronic affinities (EAs) are consistent with the available experimental and theoretical results for small clusters, indicating that the calculated lowest energy structures are reliable. Furthermore, the DE, EA and IP values for cluster size n ≥ 6 are successfully predicted. A stability analysis shows that Al₅As and Al₁₂As⁺ clusters have relatively large HOMO–LUMO energy gaps, corresponding to the magic numbers of 20 and 40 valence electrons, respectively.     

Synthesis and characterization of Sr3Al2O6：Eu2＋, Dy3＋ phosphors prepared by sol-gel-combustion processing

A type of red luminescent Sr3Al2O6:Eu2+, Dy3+ phosphor powder is synthesised by sol-gel-combustion processing, with metal nitrates used as the source of metal ions and citric acid as a chelating agent of metal ions. By tracing the formation process of the sol-gel, it is found that it is necessary to reduce the amount of NO3- by dropping ethanol into the solution for forming a stable and homogeneous sol-gel. Thermogravimetric and Differential Scanning Calorimeter Analysis, x-ray diffractionmeter, scanning electron microscopy and photoluminescence spectroscopy are used to investigate the luminescent properties of the as-synthesised Sr3Al2O6:Eu2+, Dy3+. The results reveal that the Sr3Al2O6 crystallises completely when the combustion ash is sintered at 1250 C. The excitation and the emission spectra indicate that the excitation broadband lies mainly in a visible range and the phosphors emit a strong light at 618 nm under the excitation of 472 nm. The afterglow of (Sr0.94Eu0.03Dy0.03)3Al2O6 phosphors sintered at 1250 ℃ lasts for over 1000 s when the excited source is cut off.     

Geometric and electronic structures of AlnCum (n = 5–9, m = 1–3) clusters: genetic algorithm combined with ab initio models

The geometries, stabilities and electronic structures of Al _n Cu _m (n?=?5–9, m?=?1–3) clusters were explored by using the genetic algorithm combined with ab initio methods. The geometric structures are almost spherical when the valence electrons are around the magic number 20, otherwise the structures are oblate or prolate. The stabilities of the clusters are related to both the Cu/Al ratios and the electronic configurations. The clusters with lower Cu/Al ratios have high stabilities. The molecular orbitals are in accord with the shell structures predicted by the jellium model. The 3d orbitals of the Cu atoms are localised, although their orbital energies are between the 1P and 1D jellium orbitals. The Al₆Cu₂ with 20 valence electrons forms closed 1S²1P⁶1D¹⁰2S² shells, and shows large binding energy and removal energy, large ionisation potential and small electron affinity. For the no-magic clusters, the structure deformation leads to crystal-field-like splitting of the degenerate shells and stabilises the clusters.     

The enhancement of luminescence in Co-doped cubic Eu2O3 using Li and Al ions

The co-doping of Li⁺ and Al³⁺ ions drastically enhances the luminescence of cubic Eu₂O₃. The integrated emission intensity of ⁵D₀→⁷F_J bands (J=1-4) at 580-710 nm increases by a factor of about 6.7 in the co-doped Eu₂O₃ compared to the un-doped Eu₂O₃. In order to confirm that the co-doped ions were actually incorporated into the host lattice, the structural characteristics were studied using Raman spectroscopy, XPS, XRD, photoluminescence lifetime, and an SEM. These analyses consistently indicate a certain structural evolution in their results with an increase in the co-doping concentration. Variations in the crystal structure, the crystal morphology, and the intensity variation of the Raman modes at 465 and 483 cm⁻¹ are presented as the evidences showing the incorporation of the co-doped ions into the host. The luminescence enhancement is discussed in terms of concentration quenching, reduction of defect sites, and the modification of the local symmetry of the Eu³⁺ ions, especially in the inversion symmetry sites.     

Luminescence in collisions of low-energy ions with graphite and Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Excitation of H⁺, H₂ ⁺, H₃ ⁺, He⁺, and Ar⁺ ions by impact on graphite and Al₂O₃ was investigated by means of emission spectroscopy in the 50–1000 eV energy range of the projectiles. Emission of Balmer series from excited neutral hydrogen is observed for both targets. In addition, for the Al₂O₃ target a continuum emission is observed. The continuum probably originates from excited M_nO_m molecules produced in the collision cascade, when surface atoms bound by ionic bonds are released after the bond breaking caused by neutralization. The spectra obtained under Ar⁺ -bombardment show Ar II lines emitted by backscattered ions.     

Hydration-induced conformational changes in protonated 2,4-pentanedione in the gas phase

Starting with H⁺[CH₃C(O)CH₂C(O)CH₃] (denoted H⁺PD), the protonated diketone-water clusters H⁺PD(H₂O) _n (n = 1–3) have been characterized by density functional theory calculations in combination with vibrational predissociation spectroscopy to explore the conformational changes of a protonated bifunctional ion solvated by water in the gas phase. Theoretical calculations for H⁺PD revealed that the ion contains an intramolecular hydrogen bond (IHB), with two oxygen atoms bridged by the extra proton in an O—H⁺ … O form. Attachment of one water molecule to it readily ruptures this IHB, replacing the H⁺ by the H₃O⁺ moiety. Further replacement of the IHB by two water molecules occurs at n = 2 and the ?C(O)CH₂C(O)- chain is fully opened (or unfolded) after transfer of the extra proton to the water trimer at n = 3. To verify the computational findings, infrared spectroscopic measurements were performed using a vibrational predissociation ion trap spectrometer to identify cluster isomers from the signatures of hydrogen bonded and non-hydrogen bonded OH stretching spectra of H⁺PD(H₂O)_2,3 produced in a corona discharge supersonic expansion. Besides open form isomers, evidence for the formation of water-bridged structures has been found for H⁺PD(H₂O)₃ at an estimated temperature of 200 K. A detailed illustration of the unfolding steps as well as the energy profiles for the evolution of a two-water bridge isomer from the protonated H⁺PD monomer are analysed pictorially (including both stable intermediates and transition states) in the present investigation.     

Coordination and solvation of noble metal ions: Infrared spectroscopy of Ag+(H2O)n

Vibrational spectra of mass-selected Ag⁺(H₂O)_n ions are measured by infrared photodissociation spectroscopy and analyzed with the aid of density functional theory calculations. Hydrogen bonding between H₂O molecules is found to be absent for cold Ag⁺(H₂O)₃, but detected for Ag⁺(H₂O)₄ through characteristic changes in the position and intensity of OH-stretching transitions. The third H₂O coordinates directly to Ag⁺, but the fourth H₂O prefers solvation through hydrogen bonding. The preference of the tri-coordinated form is attributed to the inefficient 5s–4d hybridization in Ag⁺, in contrast to the efficient 4s–3d hybridization in Cu⁺. For Ag⁺(H₂O)₄, however, di-coordinated isomers are identified in addition to the tri-coordinated one.     

Investigation of 4H—SiC metal—insulation—semiconductor structure with Al2O3/SiO2 stacked dielectric

Atomic layer deposited (ALD) Al₂O₃/dry-oxidized ultrathin SiO₂ films as high-k gate dielectric grown on the 8° off-axis 4H-SiC (0001) epitaxial wafers are investigated in this paper. The metal-insulation-semiconductor (MIS) capacitors, respectively with different gate dielectric stacks (Al₂O₃/SiO₂, Al₂O₃, and SiO₂) are fabricated and compared with each other. The I-V measurements show that the Al₂O₃/SiO₂ stack has a high breakdown field ( ≥ 12 MV/cm) comparable to SiO₂, and a relatively low gate leakage current of 1× 10^-7 A/cm² at electric field of 4 MV/cm comparable to Al₂O₃. The 1-MHz high frequency C-V measurements exhibit that the Al₂O₃/SiO₂ stack has a smaller positive flat-band voltage shift and hysteresis voltage, indicating less effective charge and slow-trap density near the interface.     

Role of Ti in the luminescence process of Al2O3:Si,Ti

Al₂O₃:Si,Ti, prepared under oxidizing condition at high temperature, gives PL emission around 430 nm when excited with 240 nm. The Al₂O₃:C, TL/OSL phosphor, also shows emission around 430 nm, which corresponds to characteristic emission of F-center. Thus, to identify the exact nature of luminescent center in Al₂O₃:Si,Ti, fluorescence lifetime measurement studies were carried out along with the PL,TL and OSL studies. The PL and TL in Al₂O₃:Si,Ti show emission around 430 nm and the time-resolved fluorescence studies show lifetime of about 43 μs for the 430 nm emission, which is much smaller than the reported lifetime of ∼35 ms for the 430 nm emission (F-center emission) in Al₂O₃:C phosphor. Therefore, the emission observed in Al₂O₃:Si,Ti phosphor was assigned to Ti⁴⁺ charge transfer transition. Fluorescence studies of Al₂O₃:Si,Ti do not show any traces of F and F⁺ centers. Also, Ti⁴⁺ does not show any change in the charge state after gamma-irradiation. On the basis of the above studies, a mechanism for TSL/OSL process in Al₂O₃:Si,Ti is proposed.     

Electrical and structural properties of a stacked metal layer contact to n-InP

In this study, we found that the double metal contact structure in Pt/Al/n-InP diodes provides better rectification characteristics than conventional single-metal/n-InP Schottky diodes. The effective barrier height was measured to be 0.67 eV for a 400 °C-annealed Pt/Al/n-InP diode sample. The increase in the barrier height is attributed to the formation of Al₂O₃ at the metal/n-InP contact interface during thermal annealing. The formation of the phase Al₂O₃ phase was monitored by X-ray diffraction (XRD) analysis. The corresponding element profiles of Al and O were also confirmed at the metal/n-InP contact interface using secondary ion mass spectrum (SIMS) analysis. The lowering of the Schottky barrier height due to the inhomogeneity at the metal/n-InP junction is also discussed on the basis of the TE theory. The distribution of local effective Schottky barrier heights was explained by a model incorporating the existence of double Gaussian barrier heights, which represent the high barrier and low barrier of the full distribution in the temperature ranges of 83-198 and 198-300 K.     

退火对He注入及随后208Pb27+辐照的Al2O3单晶PL谱的影响

利用高能离子研究了110 keV 的He⁺注入Al₂O₃单晶及随后230 MeV的²⁰⁸Pb²⁷⁺辐照并在不同温度条件下退火样品的光致发光的特性. 从测试结果可以清楚地看到在375 nm，390 nm，413 nm 和450 nm 出现了强烈的发光峰. 经过600 K退火2 h后测试结果显示，390 nm发光峰增强剧烈，而别的发光峰显示不明显. 在900 K退火条件下，390 nm的发光峰开始减弱相反在510 nm出现了较强的发光峰，到1100 K退火完毕后390 nm的发光峰完全消失，而510 nm的发光峰相对增强. 从辐照样品的FTIR谱中看到，波数在460—510 cm^-1间的吸收是振动模式，经过离子辐照后，吸收带展宽，随着辐照量的增大，Al₂O₃振动吸收峰消失，说明Al₂O₃振动模式被完全破坏. 1000—1300 cm^-1之间为Al-O-Al桥氧的伸缩振动模式，辐照后吸收带向高波数方向移动. 退火后的FTIR谱变化不大.     

X-ray emission study of the electronic structure of nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Valence states of metal ions and the phase composition of nanocrystalline Al₂O₃ (of the original oxide and the oxide irradiated by high-energy Fe⁺ ions) are studied by using x-ray emission Al L_{2, 3} and O Kα spectra. It is established that the shape of the Al L_{2, 3} spectra strongly changes as one goes from the original (bulk) Al₂O₃ to nanocrystalline oxide, while the O Kα spectra remain practically unchanged. Moreover, irradiation by high-energy Fe⁺ ions results in slight additional changes in the x-ray spectral characteristics of the aluminum oxides under study. The obtained experimental data are compared with the results of theoretical calculations of the electronic structure of α and γ phases of Al₂O₃ performed using the LDA formalism. Using the results of x-ray spectral studies, electronic structure calculations, and x-ray diffraction analysis, it is shown that the revealed spectral differences between the nanocrystalline state of aluminum oxide and the bulk material can be interpreted as a phase transition from the α phase to the γ phase of Al₂O₃ with an addition of bayerite.     

α-Fe2O3单离子磁晶各向异性的计算及Morin转变的解释

本文根据晶场理论计算了α-Fe₂O₃的单离子磁晶各向异性。采用点电荷模型,计及近邻及次近邻对晶场的贡献,并考虑到近邻O^2-离子对次近邻Fe³⁺离子的电屏蔽效应,在六级微扰近似下,得到单离子各向异性场H_si=102.3×10²Oe。这一结果结合Artman等人对磁偶极各向异性的计算,导出了α-Fe₂O₃的Morin转变温度T _关键词：     

C/N/O centred metal clusters: super valence bonding and magic structure with 26 valence electrons

By using genetic algorithm combined with B3LYP and QCISD methods, this paper investigates the stabilities and electronic structures of Al₆OM_m (M?=?Na, K; m?=?2,4,6) and a few other Al_nXNa_m (X?=?C, N, O) clusters. The results show that the nonmetal doped metal clusters with 26 valence electrons have enhanced stabilities and large energy gaps. This paper extends the Jellium model for the application to the nonmetal doped metal clusters and explains the electronic origin of this strong magic structure. The nonmetal X atom is situated in the centre of the magic clusters. The 2s/2p orbitals of the central atom interact strongly with the superatomic 1S/1P orbitals and form bonding and antibonding orbitals. The bonding orbitals make the C/N/O atoms form s²p⁶ shell closure, and the antibonding orbitals make the metal moieties form closed 2S²2P⁶ shells. The 26 valence electrons form closed s²p⁶S²P⁶D¹⁰ shells, and this electronic configuration can be taken as the combination of the octet rule and 18-electron rule. The octahedral Al₆O^2? core is a superatomic anion with great stability, and it can be used as building blocks to assemble Zintl phase materials by interaction with alkali metals.