Luminescence and OSL study of the inorganic compounds Tl-doped (NH4)2BeF4 and (NH4)2SiF6

The search of materials with efficient optically stimulated luminescence (OSL) properties and a high hydrogen content for fast neutron dosimetry has led to the development of Tl⁺-doped ammonium salts (NH₄)₂SiF₆ and (NH₄)₂BeF₄. Preliminary OSL studies have shown that the OSL in (NH₄)₂SiF₆:Tl⁺ and (NH₄)₂BeF₄:Tl⁺is efficient. In order to optimise the OSL emission and its detection, the identification of the luminescent centres in the OSL process is necessary. This study focuses on the identification of the luminescent centres associated with Tl⁺ based on optical studies in the vacuum UV (VUV) at different temperatures.     

UHV-MOCVD growth of TiO2 on SiOx/Si(1 1 1): Interfacial properties reflected in the Si 2p photoemission spectra

Metal–organic chemical vapour deposition growth of titanium oxide on moderately pre-oxidised Si(1 1 1) using the titanium(IV) isopropoxide precursor has been studied for two different growth modes, reaction-limited growth at 300 °C and flux-limited growth at 500 °C. The interfacial properties have been characterized by monitoring synchrotron radiation excited Si 2p photoemission spectra. The cross-linking from oxidised Si to bulk Si after TTIP exposure has been found to be very similar to that of SiO_x/Si(1 1 1). However, the results show that the additional oxidation of Si most probably causes a corrugation of the SiO_x/Si interface. Those conclusions are valid for both growth modes. A model is introduced in which the amorphous interface region is described as (TiO₂)_x(SiO₂)_y where x and y changes linearly and continuously over the interface. The model quantifies how (TiO₂)_x(SiO₂)_y mixing changes the relative intensities of the signals from silicon oxide and silicon. The method can be generalised and used for the analyses of other metal-oxides on silicon.     

ScF3，NaScF4，(NH4)2NaScF6的可控合成与上转换发光性能的研究

钪基氟化物化学性质稳定、声子能量低、无辐射弛豫概率较低,是一种新型高效的基质材料,并且Sc3+半径较小,能与多种氨羧络合剂形成稳定的螯合物,因而具有更加奇特的物理和化学性质,近年来,成为许多科学家研究的热点。以聚乙烯二胺(PEI)作为表面活性剂,采用水热法在反应温度为200 ℃时成功制备了ScF₃∶Yb3+/Er3+,NaScF₄∶Yb3+/Er3+,(NH₄)₂NaScF₆∶Yb3+/Er3+纳米上转换发光材料。通过X射线衍射仪(XRD)、透射电镜(TEM)、扫描电镜(SEM)和荧光光谱仪对所制备样品的晶相、形貌和发光特性进行了研究,结果显示：通过改变反应物NH₄F和Ln3+的比例(NH₄F/Ln3+=1∶1,2∶1,2.5∶1,3∶1,4∶1,6∶1,10∶1,20∶1,30∶1,40∶1,50∶1)实现了对样品产物、晶相、形貌的控制。当NH₄F/Ln3+为2.5∶1时,生成了纯立方相的ScF₃;在NH₄F/Ln3+为4∶1时,生成了六角相的NaScF₄;在NH₄F/Ln3+为40∶1时,生成了一种纯立方相的新型基质材料(NH₄)₂NaScF₆,样品结晶度高,形貌均一,有正方形片状和足球状多面体;在980 nm红外激光的激发下,不同NH₄F/Ln3+比例生成的样品发光呈现桔黄→桔红→绿→黄绿等多种颜色的变化。实验表明仅改变NH₄F一种原料的用量,就可以生成ScF₃∶Yb3+/Er3+,NaScF₄∶Yb3+/Er3+和(NH₄)₂NaScF₆∶Yb3+/Er3+ 三种不同的产物,说明NH₄F的用量对产物的生成有决定性的作用,对晶相的转换、颜色的调控亦有重要影响。     

Variation of passivation behavior induced by sputtered energetic particles and thermal annealing for ITO/SiO_x/Si system

The damage on the atomic bonding and electronic state in a SiO_x(1.4-2.3 nm)/c-Si(150 μm) interface has been investigated.This occurred in the process of depositing indium tin oxide(ITO) film onto the silicon substrate by magnetron sputtering.We observe that this damage is caused by energetic particles produced in the plasma(atoms,ions,and UV light).The passivation quality and the variation on interface states of the SiO_x/c-Si system were mainly studied by using effective minority carrier lifetime(τ_(eff)) measurement as a potential evaluation.The results showed that the samples' τ_(eff)was reduced by more than 90%after ITO formation,declined from 107 μs to 5 μs.Following vacuum annealing at 200 ℃,the τ_(eff) can be restored to 30 μs.The components of Si to O bonding states at the SiO_x/c-Si interface were analyzed by x-ray photoelectron spectroscopy(XPS) coupled with depth profiling.The amorphous phase of the SiO_x layer and the "atomistic interleaving structure" at the SiO_x/c-Si interface was observed by a transmission electron microscope(TEM).The chemical configuration of the Si-O fraction within the intermediate region is the main reason for inducing the variation of Si dangling bonds(or interface states) and effective minority carrier lifetime.After an appropriate annealing,the reduction of the Si dangling bonds between SiO_x and near the c-Si surface is helpful to improve the passivation effect.     

(NH4)2SO4，NH4NO3和(NH4)2SO4/NH4NO3混合气溶胶吸湿质量增长因子的快速测量方法

气溶胶颗粒的吸湿性决定了其尺寸、浓度、化学组成以及相态,从而显著影响着全球气候、大气异相化学以及人类健康。运用在线、原位、连续扫描衰减全反射傅里叶变换红外光谱（ATR-FTIR）技术, 结合线性湿度（RH）控制系统,实现了RH连续变化条件下气溶胶FTIR-ATR光谱的快速测量。根据水弯曲振动谱带（~1 640 cm-1）峰面积随RH的变化,得到了(NH₄)₂SO₄,NH₄NO₃和(NH₄)₂SO₄/NH₄NO₃混合气溶胶的质量增长因子（MGFs）、潮解点（DRH）和风化点（ERH）。与气溶胶的E-AIM模型预测值相比较,实验结果表现出良好的一致性,证实该方法是一种测量大气气溶胶MGFs,ERH和DRH的快速测量方法。     

Eu3+/Dy3+共掺Sr3Y2(BO3)4荧光粉的发光性质研究

稀土掺杂发光材料一直是科研领域研究的热点,被广泛应用于白光LED、温度传感、显示显像、新能源和激光等领域。基质的结构对于稀土离子光致发光特性有非常重要的影响,在众多发光基质材料中,硼酸盐具有透光范围宽、光学损伤阈值高、较好的热稳定性和化学稳定性等优点。碱土-稀土金属硼酸盐Sr₃Y₂(BO₃)₄具有出色的光学性能,对其发光性能的研究具有重要意义。稀土离子Eu3+具4f6电子层,是一种典型的下转换发光中心离子,常被选作红色发光材料的激活剂。Dy3+具4f9电子层,也是一种典型的下转换发光中心离子,在紫外光激发下,在蓝色光区和橙色光区有较强的荧光发射。采用高温固相法合成了Sr₃Y₂(BO₃)₄∶Eu3+/Dy3+荧光粉,通过XRD和SEM对样品的结构和形貌进行了表征,XRD结果表明,1 000 ℃烧结5 h,H₃BO₃过量20%为最佳制备条件,且少量的Eu3+和Dy3+掺杂并未改变Sr₃Y₂(BO₃)₄的晶格结构。SEM图像表明Sr₃Y₂(BO₃)₄基质的平均晶粒尺寸为2～4 μm,10%Eu3+单掺和5%Eu3+/5%Dy3+双掺样品与基质Sr₃Y₂(BO₃)₄的SEM图像相比,形貌和尺寸并没有发生明显的改变。Sr₃Y₂(BO₃)₄∶Eu3+荧光粉的发光结果表明,分别在395和466 nm激发下,浓度为5%,10%和15%的Eu3+单掺Sr₃Y₂(BO₃)₄荧光粉的主要发光位于593和613 nm的红光发射,峰强度随着Eu3+浓度的增加呈现先增加后降低的变化形式,掺杂浓度为10%时发光强度最大,说明存在浓度猝灭现象。色坐标结果显示,激发波长由395 nm变化到466 nm,Sr₃Y₂(BO₃)₄∶Eu3+荧光粉的发光颜色从橙红色向红色转变。引入Dy3+后,Sr₃Y₂(BO₃)₄∶Eu3+/Dy3+样品的发射光谱出现Dy3+的486 nm的蓝光发射（4F_9/2→6H_15/2）和576 nm的橙光发射（4F_9/2→6H_13/2）,并且随着Dy3+浓度的增加,对Eu3+的5D₀→7F_{1, 2, 3, 4}跃迁有抑制作用。色坐标结果显示通过调整掺杂离子Eu3+和Dy3+的比例可实现Sr₃Y₂(BO₃)₄∶Eu3+/Dy3+荧光粉的颜色从红色区域向橙色区域转变,说明其在显示方面具有良好的应用前景。     

钙钛矿锰氧化物(La1-xGdx)4/3Sr5/3Mn2O7 (x=0, 0.025) 磁性和输运性质研究

采用传统的高温固相烧结法制备了双层钙钛矿锰氧化物(La_1-xGd_x)_4/3Sr_5/3Mn₂ O₇ (x=0, 0.025)多晶样品. 通过X射线衍射仪研究发现样品为Sr₃Ti₂O₇型四方结构, 空间群为I4/mmm; 磁性测量表明, Gd³⁺掺杂后的样品(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂O₇的三维磁有序转变温度(T_C1^3D)、磁化强度(M)均降低, 这是由于Gd³⁺的掺杂引起晶格的畸变, 从而使得晶格常数发生改变, 减弱了铁磁耦合而导致的; 通过电子自旋共振谱测量发现, 在T_C^3D<T<300 K温度范围内, 两样品在顺磁的基体上均有短程的铁磁团簇存在, 出现了相分离现象. 电性测量表明: 两样品分别在T_C1^3D (La_4/3Sr_5/3Mn₂O₇ 样品的三维磁有序转变温度, T_C0^3D)<T<300 K温度范围内均以三维变程跳跃的方式导电, 分析得出Gd³⁺的掺杂使得载流子局域长度的减小. 这表明载流子需要吸收更多的能量才能克服晶格的束缚进行跳跃, 因此(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂ O₇ 样品的电阻较高.     

Visible and infrared photoluminescence from Er-doped SiOx

The annealing behaviors of photoluminescence of SiO_x and Er-doped SiO_x grown by molecular beam epitaxy in the wavelength range of visible and infrared light are studied. For SiO_x, four PL bands located at 510, 600, 716 and 810 nm, respectively, are observed. For Er-doped SiO_x, the 716 nm band, which is believed to be originated from the electron–hole recombination at the interface between crystalline Si and amorphous SiO₂, disappears in the annealing temperature range of 500–900°C. It is suggested the enhancement of Er luminescence is partially due to the energy transfer from the recombination at the interface between crystalline Si and SiO₂ to Er ions.     

Y型沸石脱铝机制和铝状态的NMR研究

对Y型沸石原粉及几种不同脱铝样品进行了几种不同NMR方法的测量,确定了不同处理过程的脱铝机制和骨架内外铝状态的变化,²⁹Si MAS NMR谱给出了骨架Si、Al分布的信息,反映了不同方法处理样品其脱铝机制的差异,据此可以控制Y沸石脱铝过程获得更高的硅铝比,²⁷Al MAS NMR谱、二维章动NMR及¹H-²⁷Al CP/MAS NMR测量表明:水热处理的Y沸石中存在4种不同的铝状态。综合²⁹Si和²⁷Al MAS NMR观测,可相当程度地推断Y型沸石分子筛脱铝改性所发生的内部过程。     

Spectral intensities in the ν1 band of NH3

Intensities have been measured for individual transitions in the Q and R branches of the ν₁ band of NH₃ using a difference-frequency laser spectrometer. The data yield an integrated band strength of S⁰_v=219.36±1.03 cm^-2/MPa at 297 K, corresponding to a transition moment of μ_v = 8.535(20) × 10^-32 C·m, and a Herman-Wallis correction factor, (1 + _jm)², where _j = 0.0209(20). The intensities of a few lines for K 7 were noticeably perturbed by a perpendicular Coriolis interaction with 2ν₄ (E, L = 2), so were excluded from the fit. A small sample of ν₃ band lines occurring in the ν₁ band scans also yields a rough estimate of the ν₃ band intensity with evident irregular perturbations.     

Structure determination, magnetic and optical properties of a new chromium(II) thioantimonate, [Cr((NH2CH2CH2)3N)]Sb4S7

The chromium(II) antimony(III) sulphide, [Cr((NH₂CH₂CH₂)₃N)]Sb₄S₇, was synthesised under solvothermal conditions from the reaction of Sb₂S₃, Cr and S dissolved in tris(2-aminoethyl)amine (tren) at 438 K. The products were characterised by single-crystal X-ray diffraction, elemental analysis, SQUID magnetometry and diffuse reflectance spectroscopy. The compound crystallises in the monoclinic space group P2₁/n with a=7.9756(7), b=10.5191(9), c=25.880(2) Å and β=90.864(5)°. Alternating SbS₃³⁻ trigonal pyramids and Sb₃S₆³⁻ semi-cubes generate Sb₄S₇²⁻ chains which are directly bonded to Cr(tren)²⁺ pendant units. The effective magnetic moment of 4.94(6)μ_B shows a negligible orbital contribution, in agreement with expectations for Cr(II):d⁴ in a ⁵A ground state. The measured band gap of 2.14(3) eV is consistent with a correlation between optical band gap and framework density that is established from analysis of a wide range of antimony sulphides.     

氨分子在000和201带的选择光离解

本文利用脉冲紫外激光(UV)选择激发氨分子到?¹A″₂电子激发态的两个最低振动能级ν′₂=0和ν′₂=1(ν₂振动),然后检测新生态H原子的飞行谱(TOF),研究了氨分子的光碎片动力学。光谱证实了最近所测的离解能D₀⁰(H-NH₂)=4.645eV;绝大多数生成的NH₂(X²B₁)基处于非振动激发,但是具有围绕a惯性轴的高度转动激发。通过NH₃(?)的ν′₂=1光离解产生的NH₂(X)基具有较高的内部激发,并且显示了在N=K_a转动能级上的反转布居。 关键词：     

Synthesis and superconductivity of (Pb0.5Cd0.5)(Sr0.9R0.1)2(R′0.7Ce0.3)2Cu2Oy

New Pb based layered superconducting cuprates (Pb_0.5Cd_0.5)(Sr_0.9R_0.1)₂(R′_0.7Ce_0.3)₂Cu₂O_y with (R,R′) = (Eu,Gd), (Eu,Dy) and (Nd,Gd), have been successfully synthesized. The structure of (Pb,Cd)(Sr,Eu)₂(Gd,Ce)₂Cu₂O_y is determined using XRD data. The X-ray powder diffraction pattern can be indexed by the tetragonal structure with lattice parameters a = 3.8250 Å, C = 29.2235 Å and a space group of I4/mmm. The effects of synthesis conditions on (Pb,Cd)(Sr,Eu)₂(Gd,Ce)₂Cu₂O_y are studied and a T_c(onset) of 26 K is obtained by resistance measurements. It is isostructural to the superconductor (Pb,Cu)(Sr,Eu)₂(Eu,Ce)₂Cu₂O_y.     

NH4H2PO4和ND4D2PO4晶体微结构的拉曼光谱研究

本文利用偏振拉曼光谱和第一性原理, 对磷酸二氢铵(NH₄H₂PO₄, ADP)和不同氘含量磷酸二氢铵DADP晶体的晶格振动模式进行了研究. 实验测得了不同几何配置、200–4000 cm^-1范围的偏振拉曼光谱, 分析在不同氘含量条件下921 cm^-1和3000 cm^-1附近拉曼峰的变化. 在ADP晶体中, 基于基本结构单元NH₄⁺ 和H₂PO₄^-基团的振动模, 用第一性原理进行了数值模拟, 进一步明确拉曼峰与晶体中原子振动的对应关系; 通过洛伦兹拟合不同氘含量DADP晶体的拉曼光谱中2000–2600 cm^-1处各峰的变化讨论了DADP 晶体的氘化过程, 结果表明氘化顺序是先NH₄⁺ 基团后H₂PO₄^-基团, 研究结果为今后此类材料的生长和性能优化奠定了基础.     

Scanning tunneling and atomic force microscopy study of the misfit layer compounds (LaS)1.14(NbS2)n (n=1, 2) and [(Pb,Sb)S)]1.14NbS2

The misfit layer compounds (LaS)_1.14(NbS₂)_n (n=1, 2) and [(Pb,Sb)S]_1.14NbS₂ were examined by scanning tunneling microscopy (STM) and atomic force microscopy (AFM). In these compounds the NaCl-type double MS (M=La, Pb, Sb) layers (Q layers) alternate with the NbS₂ layers (H layers) made up of NbS₆ trigonal prisms. It was possible to record AFM and STM images for only the H layers for (LaS)_1.14(NbS₂)_n, but for both the H- and Q-layers for [(Pb,Sb)S]_1.14NbS₂. Partial and total electron density plots of the H and Q layers were calculated to interpret the observed STM and AFM images. The bright spots in the STM and AFM images of the H layer correspond to S atoms, and those of the Q layer to Pb and Sb atoms. The STM images for the Q layers of [(Pb,Sb)S]_1.14NbS₂ suggest that a short-range ordering of the Pb and Sb atoms occurs in the (Pb,Sb)S sheets of the Q layer.     

Effects of cation- or oxide ion-defect on conductivities of apatite-type La–Ge–O system ceramics

A series of apatite-type La–Ge–O ceramics were prepared and their cation-defect at the 4f+6h sites and oxide ion-defect at 2a site were investigated. In La_xGe₆O_12+1.5x ceramics of x=6–12, the higher conductivities were obtained in the region of apatite composition, La_x(GeO₄)₆O_1.5x−12 (x=8–9.33), and the highest conductivity was achieved for La₉(GeO₄)₆O_1.5 (x=9), where the number of cation (La³⁺) occupying the 4f+6h sites is 9 and the number of oxide ion occupying the 2a site is 1.5. The ceramics with cation- and oxide ion-defects were La_9−0.66xSr_x(GeO₄)₆O_1.5 (x=0–1), La_9−1.33xZr_x(GeO₄)₆O_1.5 (x=0–1), La_9−xSr_x(GeO₄)₆O_1.5−0.5x (x=0–3), La_9−xZr_x(GeO₄)₆O_1.5+0.5x (x=0–1), La_x(GeO₄)_3x−21(AsO₄)_27−3xO_1.5 (x=0–3), La_x(GeO₄)_33−3x(AlO₄)_3x−27O_1.5 (x=0–3), La₉(GeO₄)_6−x (AlO₄)_xO_1.5−0.5x (x=0–3), La₉(GeO₄)_6−x(AsO₄)_xO_1.5+0.5x (x=0–1), La_9.33−xSr_x(GeO₄)₆O_2−0.5x (x=0–1.2) and La_x(GeO₄)_4.5(AlO₄)_1.5O_1.5x−12.75 (x=8.8–9.83), which were prepared by the partial substitution of La³⁺and GeO₄⁴⁻of the basic apatite La₉(GeO₄)₆O_1.5 with Sr²⁺ or Zr⁴⁺ and AlO₄⁵⁻ or AsO₄³⁻. Such substitutions lowered the conductivity of La₉(GeO₄)₆O_1.5. These results were discussed by the electrostatic interaction between Sr²⁺, Zr⁴⁺, AlO₄⁵⁻ or AsO₄³⁻ and oxide ion as a conductive species.     

The anomalous behaviour of Gd atoms (Fe1−xMnx)2 compounds

The educed Gd atoms in the X-structure (Th₆Mn₂₃-type) of Gd(Fe_1−xMn_x)₂ were magnetically investigated by comparing with Gd₆(Fe_1−yMn_y)₂₃ whose structure is Th₆Mn₂₃-type. The magnetic properties of Gd(Fe_1−xMn_x)₂ (0.4≤x≤0.7) were observed to be quite similar to those of Gd₆(Fe_1−yMn_y)₂₃ (0.4≤y≤0.7).     

NH+4，F-对萤石浮选的影响机理及红外光谱分析

萤石浮选过程中矿浆中的NH+₄,F-对萤石的可浮性有重要影响,而目前关于难免离子对浮选影响的研究主要集中在稳定的阳离子对浮选的活化或抑制作用机理,而关于不稳定阳离子（NH+₄）、阴离子（F-）影响油酸钠吸附萤石作用机制的研究较少。因此借助于红外光谱分析,结合纯矿物浮选、Zeta电位和溶液化学计算等手段,研究难免离子（NH+₄,F-）对油酸钠浮选萤石的作用机理。实验结果表明,在酸性条件下,NH+₄对萤石有较强的活化作用,提高了萤石的回收率, 在pH值为6时,不同NH+₄浓度下,萤石的回收率均提高到94%左右,而在碱性条件下,NH+₄对萤石的浮选的有一定的抑制作用,且随着pH值增加,抑制作用增强,回收率逐渐下降;但F-对萤石浮选有一定的抑制作用,且在pH值为6时,不同F-浓度的抑制作用均明显增强,导致萤石回收率降低;而在碱性条件下,F-对萤石的可浮性影响不大。其作用机理为阳离子（NH+₄）与萤石表面解离到溶液中的F-生成NH₄F,在酸性条件下提高了萤石表面的正电性,增强萤石表面与油酸的一聚物、二聚物和分子-离子缔合物的吸附作用,而在碱性条件下NH+₄的水解生成NH₃·H₂O,正电性降低,导致油酸钠在萤石表面的吸附作用减弱;F-抑制萤石表面F-的解离,从而抑制了油酸根在萤石表面的化学吸附。红外分析结果表明,油酸钠在萤石表面发生了化学吸附;NH+₄的加入,在酸性条件下对萤石有很强的活化作用,-CH₃,-CH₂-和-COO-的特征峰峰位红移,峰强度加强,显现出较强的化学吸附作用;而在碱性条件下,仅出现了-CH₂-的特征峰的峰位红移,且特征峰强度减弱,说明NH+₄在弱碱条件在萤石表面的化学吸附较弱,起抑制作用;当加入F-后只出现了-CH₃的反对称伸缩振动峰,峰位并未发生偏移,故F-加入后油酸钠在萤石表面并未发生任何基团的化学吸附,从而抑制了萤石的可浮性。     

铁电单晶(KxNa1-x)0.4(SryBa1-y)0.8Nb2O6的光学性质和线性电光效应

本文介绍铁电单晶(K_xNa_1-x)_0.4(Sr_yBa_1-y)_0.8Nb₂O₆的光学性质和线性电光效应的测量。实验结果表明,这种晶体具有较大的光学双折射,透光范围由4000?到5.6μm。晶体具有低的线性电光调制的半波电压,其电光调制价值指数n₀³·γ_c高达730×10 关键词：     

Ce3+, Mn2+共掺的Ca4Y6 (SiO4)6F2的发光性质和能量传递

采用高温固相法制备了Ca_4-xY_5.95 (SiO₄)₆F₂:0.05Ce³⁺, _xMn^{2 +}系列荧光粉,并对其发光性质以及Ce³⁺, Mn^{2 +}在Ca₄Y₆ (SiO₄)₆F₂ (CYSF)基质中的能量传递过程进行了研究.相结构研究表明: CYSF属于一种基于磷灰石结构的类质同象化合物.CYSF: 0.05Ce³⁺, _xMn²⁺荧光粉在200–373 nm为宽带激发光谱,Ce³⁺和Mn²⁺在408 nm和602 nm的发射峰分别由Ce³⁺的5d→4f的跃迁和Mn²⁺的⁴T₁ (⁴G)→ ⁶A₁ (⁶S)的跃迁产生.光谱重叠现象以及荧光寿命测试结果证明了Ce³⁺对Mn²⁺具有敏化作用,能级结构分析进一步证实该体系中存在Ce³⁺→Mn²⁺的能量传递过程,可有效地将Ce³⁺的蓝光转换为红橙光. 关键词： 磷灰石 发光性质 能量传递