Visible and NIR luminescence of nanocrystalline β-Ga2O3:Er prepared by solution combustion synthesis

In this paper we report on facile solution combustion synthesis of erbium doped β-Ga₂O₃ with urea as fuel. The product was characterized using powder X-ray diffraction and transmission electron microscopy (TEM). X-ray diffraction and TEM showed that the material is nanostructured. Luminescence properties of β-Ga₂O₃:Er are studied with excitation in near infrared (Nd:YAG laser at 1064 nm) and visible (argon laser at 514.5 nm). A strong NIR emission of Er³⁺ in the window of minimal optical loss in silica based optical fibers, due to the ⁴I_13/2→⁴I_15/2 transition at 1.55 μm has been observed. Codoping with Yb³⁺ significantly increases the intensity of that important emission.     

多晶AlN光学性质研究

运用X射线衍射仪和拉曼光谱仪,测量了物理气相输运(PVT)方法生长的AlN多晶材料的X射线衍射和常温拉曼光谱。常温拉曼光谱研究了晶界、晶面方向与拉曼频率的关系,观察到了E和E峰位基本不随测量位置变化,与晶界无关,但是E1(TO),A1(LO)和Quasi-LO声子峰位却明显与晶界有关,为研究晶粒间、晶粒内应力提供了有效手段。     

Direct angle resolved photoemission spectroscopy and superconductivity of strained high-T c films

Since 1997 we systematically perform direct angle resolved photoemission spectroscopy (ARPES) on in-situ grown thin (<30 nm) cuprate films. Specifically, we probe low-energy electronic structure and properties of high-T _c superconductors (HTSC) under different degrees of epitaxial (compressive vs. tensile) strain. In overdoped and underdoped in-plane compressed (the strain is induced by the choice of substrate) ≈15 nm thin La_{2 − x} Sr _x CuO₄ (LSCO) films we almost double T _c to 40 K, from 20 K and 24 K, respectively. Yet the Fermi surface (FS) remains essentially two-dimensional. In contrast, ARPES data under tensile strain exhibit the dispersion that is three-dimensional, yet T _c drastically decreases. It seems that the in-plane compressive strain tends to push the apical oxygen far away from the CuO₂ plane, enhances the two-dimensional character of the dispersion and increases T _c, while the tensile strain acts in the opposite direction and the resulting dispersion is three-dimensional. We have established the shape of the FS for both cases, and all our data are consistent with other ongoing studies, like EXAFS. As the actual lattice of cuprates is like a ‘Napoleon-cake’, i.e. rigid CuO₂ planes alternating with softer ‘reservoir’, that distort differently under strain, our data rule out all oversimplified two-dimensional (rigid lattice) mean field models. The work is still in progress on optimized La-doped Bi-2201 films with enhanced T _c.      

Structural and magnetic ordering in the VxNb1+yS2 system

The influence of composition on the structural ordering and magnetism in the V_xNb_1+yS₂ system has been investigated by X-ray diffraction and magnetic measurements. Stoichiometric V_1/3NbS₂ did not exhibit the structural ordering of vanadium between the NbS₂ layers. In the ordered structure, the vanadium composition deviated from the ideal value of to both higher and lower values, while the niobium composition was in the range of 0.05?y?0.18. Excess niobium, y>0, is thought to play an essential role in the structural ordering in this system. For samples with excess niobium and ordered structures, a magnetic transition was observed at 20-50 K, depending on the composition. The spontaneous magnetization of 3-5×10⁻³ μ_B/V atom is thought to be intrinsic to this system. The magnetization curves consisted of a constant and a proportional parts of the magnetic field, which correspond to the spontaneous magnetization and high-field susceptibility, respectively. The magnetization curves and the temperature dependencies of the high-field susceptibility were quite similar to those of the canted antiferromagnetic NiS₂. A correlation between the structural and magnetic ordering is suggested.     

The effect of controlled ion bombardment on the electronic structure of the Si(0 0 1) surface

We have studied the effects of controlled ion bombardment on the electronic structure of the Si(0 0 1) surface. The surface was exposed to various doses of Ar⁺ ions accelerated towards the surface at 500 eV. X-ray photoelectron spectroscopy (XPS) spectra of the irradiated H-terminated Si(0 0 1) surface reveal the appearance of peaks that are associated with the presence of cleaved Si bonds. Ultraviolet photoelectron spectroscopy (UPS) spectra of the irradiated Si(0 0 1)2 × 1 surface show that the dimer dangling-bond surface state decays monotonically with increasing dose. These results, coupled with previous scanning tunneling microscopy (STM) studies, indicate that the breaking of dimers, and possibly the creation of adatom-like defects, during ion irradiation are responsible for the changes in the electronic structure of the valence band for this surface.     

Synthesis and Electronic Properties of Novel 5,7-Diazapentacene Derivatives

A route to the synthesis of novel 5,7-diazapentacenes and some preliminary studies on their properties is reported. A single crystal X-ray diffraction study of the dihexyl derivative showed it had formed a dimer during the analysis. The materials possess lower lying frontier orbitals than pentacene and may have potential applications in organic electronic devices. This synthetic method may be applicable to the synthesis of other azaacenes.     

XANES/EPR Evidence of the Oxidation of Nickel(II) Quinolinylpropioamide and Its Application in Csp3−H Functionalization

An in situ generated oxidation species of nickel quinolinylpropioamide intermediate was produced. Characterization by X-ray absorption near edge structure (XANES) and EPR provides complementary insights into this oxidized nickel species. With aliphatic amides and isocyanides as substrates, a nickel-catalyzed facile synthesis of structurally diverse five-membered lactams could be achieved.     

Heteroleptic [Cu(NN)P2]+-type cuprous complexes and their structural modulation on phosphorescent color: Synthesis,structural characterization,properties, and theoretical calculations

Four new heteroleptic [Cu(NN)P₂]⁺-type cuprous complexes— 1 -TPP, 2 -POP, 3 -Xantphos, and 4 -DPPF—were designed and synthesized using a diimine ligand 2-(2′-pyridyl)benzoxazole (2-PBO) and different phosphine ligands (TPP, triphenylphosphine; POP, bis[2-(diphenylphosphino)phenyl]ether; Xantphos, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; DPPF, 1,1′-bis(diphenylphosphino)-ferrocene). All complexes were characterized using single-crystal X-ray diffraction, spectroscopic analysis (infrared, UV–Vis.), elemental analysis, and photoluminescence (PL). Single-crystal X-ray diffraction revealed complexes 1 – 4 as isolated cation complex structures with a tetrahedral CuN₂P₂ coordination geometry and diverse P–Cu–P angles. Their UV–Vis. absorption spectra exhibited a blue-shift sequence in wavelength with an enlarged P–Cu–P angle from 4 to 2 then to 3 and then to 1 . The PL emission peaks of 1 – 3 also exhibited a similar blue-shift sequence ( 2 → 3 → 1 ). Their PL lifetime in microseconds (~7.5, 5.1, and 4.7 μs for 1 , 2 , and 3 , respectively) indicated that their PL behavior represents phosphorescence. Time-dependent density functional theory (TD-DFT) calculation and wavefunction analysis revealed that S₁ and T₁ states of 1 – 3 should be assigned as metal–ligand and ligand–ligand charge-transfer (ML + L'L)CT states. Their UV–Vis. absorption and phosphorescence should be attributed to the charge transfer from the P–Cu–P segment to the 2-PBO ligand. Therefore, as the P–Cu–P angle increased (lower HOMO), the energy of S₁ and T₁ states also increased, following the change of PL color.     

Kβ X-Ray Emission Spectroscopic Study of a Second-Row Transition Metal (Mo) and Its Application to Nitrogenase-Related Model Complexes

In recent years, X-ray emission spectroscopy (XES) in the Kβ (3p-1s) and valence-to-core (valence-1s) regions has been increasingly used to study metal active sites in (bio)inorganic chemistry and catalysis, providing information about the metal spin state, oxidation state and the identity of coordinated ligands. However, to date this technique has been limited almost exclusively to first-row transition metals. In this work, we present an extension of Kβ XES (in both the 4p-1s and valence-to-1s [or VtC] regions) to the second transition row by performing a detailed experimental and theoretical analysis of the molybdenum emission lines. It is demonstrated in this work that Kβ₂ lines are dominated by spin state effects, while VtC XES of a 4d transition metal provides access to metal oxidation state and ligand identity. An extension of Mo Kβ XES to nitrogenase-relevant model complexes shows that the method is sufficiently sensitive to act as a spectator probe for redox events that are localized at the Fe atoms. Mo VtC XES thus has promise for future applications to nitrogenase, as well as a range of other Mo-containing biological cofactors. Further, the clear assignment of the origins of Mo VtC XES features opens up the possibility of applying this method to a wide range of second-row transition metals, thus providing chemists with a site-specific tool for the elucidation of 4d transition metal electronic structure.