拉曼光谱对含Cr镁铝尖晶石热处理及其有序-无序相变研究

尖晶石的有序-无序相变作为尖晶石的一种重要性质，在国内缺少相关研究成果。运用拉曼光谱仪通过785 nm激光在液氮环境下激发含Cr的宝石级天然粉红色尖晶石，避免了532 nm激光激发下产生的469 nm的荧光峰和在常温测试下由于热振动对光谱的影响，得到清晰尖锐的拉曼光谱，为拉曼光谱参数的分析奠定基础。同时通过对一颗Cr元素致色的天然粉色镁铝尖晶石进行热处理使尖晶石逐步发生有序-无序相变，并反映在拉曼光谱的谱峰参数之中。各项参数分析结果显示，尖晶石的拉曼光谱主要由E_g，T_2g(1)，T_2g(2)，N₃和A_g，五种振动模式产生，其谱峰位置分别为407.8，312.4，667.5，720.0和769.0 cm-1；尖晶石拉曼光谱谱峰参数在800 ℃时发生突变： 各谱峰半高宽和各峰相对主峰E_g峰的相对强度明显增大，常温下几乎不可见的N₃峰在高温处理后出现，并且T_2g(1)峰向低波数偏移，T_2g(2)向高波数偏移，同时峰的对称性逐渐消失。研究结果表明尖晶石的有序-无序相变可以通过拉曼光谱检测并且可以通过谱峰参数： 半高宽、谱峰相对高度等进行半定量表征。由于拉曼光谱具有的无损检测特点，使其成为宝石级热处理尖晶石鉴定应用的重要参考依据之一。     

Ultra-broad near-infrared emission of Bi-doped SiO2 Al2O3 GeO2 optical fibers

Bi-doped SiO 2 –Al 2 O 3 –GeO 2 fiber preforms are prepared by modified chemical vapor deposition (MCVD) and solution doping process. The characteristic spectra of the preforms and fibers are experimentally investigated, and a distinct difference in emission between the two is observed. Under 808-nm excitation, an ultra-broad near-infrared (NIR) emission with full-width at half-maximum (FWHM) of 495 nm is observed in the Bi-doped fiber. This observation, to our knowledge, is the first in this field. The NIR emission consists of two bands, which may be ascribed to the Bi 0 and Bi + species, respectively. This Bi-doped fiber is promising for broadband optical amplification and widely tunable laser.     

第一性原理计算：锰酸锂掺杂Fe和Co的性质研究

文章基于密度泛函理论的第一性原理计算,研究了LiMn2O4电池材料在掺杂Fe和Co离子时的电子结构和电化学性能。发现Fe\Co取代Mn3+在热力学上是会更加稳定,提升电化学性能。掺杂Fe后,LiMn2O4电池材料晶格参数减小(约0.3%);掺杂Co后,LiMn2O4电池材料晶格参数减小(约0.5%)。这两种掺杂方式让与之相邻的Mn3+被氧化成Mn4+,从而降低了Jahn-Teller畸变情况产生可能性。对于掺Fe尖晶石型锰酸锂(Li8Mn15FeO32),Mn环境中的Li离子会更容易被提取,第一次放电电压从原来的3.7V增加至4.623V;对于掺Co尖晶石型锰酸锂(Li8Mn15CoO32),第一次放电电压从原来的3.7V增加至4.101V。研究为锂电池电容量研究提供理论数据的参考。     

Na-W-Mn/SiO_2催化剂的拉曼光谱研究

对含有不同 Na、W、Mn组分的 Na- W- Mn/ Si O2 系列催化剂进行了付里叶变换激光拉曼光谱测定和研究 ,并参考先前的与之相关催化剂的拉曼光谱 ,对它们的特征拉曼吸收谱带进行了归属。结果表明 :960 ,92 8,81 0 ,789cm-1等吸收峰是 Na- W- Mn/ Si O2 催化剂中 Na-O- W物种的特征吸收谱带 ;62 7,577,51 7,478cm-1等吸收峰是 Na- O- Mn物种的特征吸收谱带 ;Na- O- W分布在距催化剂表面较深的体相中 ;Na- O- Mn主要分布在催化剂的表面     

Mn2+∶BeAl2O4晶体的光谱特性

应用提拉法技术,采用BeO∶Al2O3∶MnO摩尔比为100∶99.85∶0.30的化学组分配比和二次化料过程,选用约60℃的固液界面温度梯度与1 mm/h生长速度等工艺参量,成功地生长出了Mn2 离子掺杂、无气泡、无云层和核心、尺寸约45 mm×80mm的粉红色Mn2 ∶BeAl2O4晶体。测定了不同部位晶体的激发光谱与荧光光谱。沿着晶体生长方向,晶体颜色逐步变深。在Mn2 ∶BeAl2O4荧光谱中观测到发光中心为543nm的荧光带,这归属于Mn2 的4T1(4G)→6A1(6S)能级跃迁所产生。在其激发光谱中观测到218nm的激发峰,这归属于电子从Mn2 基态到导带的电荷转移跃迁所致。从Mn2 离子的绿色发射情况可以推断Mn2 处于晶体中四面体场中,它取代晶体中Be2 离子的格位。从不同部位晶体的激发峰强度与颜色变化可以得到Mn2 在BeAl2O4晶体中的有效分凝系数小于1。     

Enhancement of upconversion luminescence due to the formation of nanocrystals in Er3+-doped tellurite glasses

Optically transparent Er3+-doped tellurite-based nanocrystallized glasses with the composition of 70TeO2·15Lie2O·0·15Nb2O5·0.5Er2O3(mol)have been perpared by a conventional melting quenching and the subsequent heat treatment porcesses.The sizes of grown nanocrystals in glass matrix appear to be35-50 nm from the X-ray diffraction (XRD) measurement. The microhardness measurement shows that the Vickers hardness values of the nanocrystallized tellurite glasses are larger (33%-62%) than those inthe base glass. The Raman spectra imply that the maximum phonon energy of the based glass decreases and shifts from 668 to 638 cm-1 after heat-treatment. Visible upconversion luminescence and infrared luminescence of the base glass and heat-treated glasses under 980-nm laser diode (LD) excitation are investigated. The 524-, 546- and 656-nm upconversion intensities by 980-nm pumping increase significantly.     

微波-模板法合成锂离子电池正极材料LiMn2O4机理的光谱学研究

采用微波-PAM模板法合成了具有尖晶石结构的锰酸锂材料,利用动态红外光谱（FTIR）对该方法的反应机理进行了研究。在前驱体的制备和在LiMn2O4晶核形成过程中,由于聚丙烯酰胺与反应母体之间的弱键合作用,使其在晶粒生长过程中对LiMn2O4的团聚规律与缺陷结构起到重要调控作用。     

用受激拉曼泵浦方法高效制备v=2振动激发态氘分子

We report the preparation of D₂ molecules in v=2 level in molecular beam condition. A single longitudinal mode laser system was used for excitation of D₂ from (v=0, j=0) to (v=2, j=0) with the scheme of stimulated Raman pumping. An excitation efficiency of 25.2% has been achieved, which was determined by the scheme of resonance-enhanced multiphoton ionization. Dependence of relative excitation efficiency on laser energy has been measured. We found that the increasing rate of excitation efficiency became slower as pulse energy of Stokes laser increase, while the excitation efficiency still increases approximately linearly with pump pulse energies up to 60 mJ. The spectral line shapes of Raman transition was also measured at different laser energies and considerable dynamical Stark effect was observed. A single peak was found on the three dimension surface of relative excitation efficiency, indicating the process occurred in the present study is a process of stimulated Raman pumping instead of stimulated adiabatic Raman passage.     

High luminance of new green emitting phosphor, Mg2SnO4:Mn

Mg₂SnO₄, which has an inverse spinel structure, was adopted as the host material of a new green emitting phosphor. Luminescence properties of the manganese-doped magnesium tin oxide prepared by the solid state reaction were investigated under vacuum ultraviolet (VUV) ray and low-voltage electron excitation. The Mg₂SnO₄:Mn phosphor exhibited green luminescence with the emission spectrum centered at 500 nm due to spin flip transition of the d-orbital electron associated with the Mn²⁺ ion. Optimum Mn concentration of Mg₂SnO₄:Mn under VUV excitation with 147 nm wavelength and electron beam excitation with 800 V excitation voltage are 0.25 and 0.6 mol%, respectively. The emission intensities of Mg₂SnO₄:Mn phosphors under the two excitation sources are higher than those of Zn₂SiO₄:Mn and ZnGa₂O₄:Mn phosphors. At 0.25 mol% of Mn concentration, on the other hand, the decay time is shorter than 10 ms.     

γ-Al_2O_3表面担载钒物种的紫外拉曼光谱

本文采用常规的等体积浸渍法制备了不同担载量的V2 O5 γ -Al2 O3担载氧化物催化剂 ,在水气存在的条件下分别使用不同的激发波长得到了相应的可见拉曼光谱和紫外拉曼光谱。结果表明在表面钒物种微弱水合的情况下 ,3 2 5nm波长紫外激光激发的紫外拉曼光谱由于部分的共振拉曼效应 ,仍然可以灵敏的检测到表面钒物种配位结构随担载量增加而发生的变化。低担载时表面钒物种主要以孤立状态存在 ,随担载量增加逐渐向聚合态结构过渡 ,当担载量超过钒在载体表面的单层分散容量时形成体相V2 O5晶体覆盖表面钒物种造成拉曼信号的减弱 ,由此可以从另一个角度判断表面单层分散容量。     

钨酸锌晶体的受激拉曼散射和光致发光研究

采用皮秒532nm 激光激发，研究了ZnWO₄晶体的受激拉曼散射和本征荧光发射.在SRS光谱中观察到一级(558.7nm)和二级(588.6nm)斯托克斯光，线宽分别为130和77cm^－1, 一级斯托克斯光的抽运阈值为6.8mJ.在532nm激光抽运下ZnWO₄晶体的荧光光谱呈现出由能量为2.30，2.45和2.83eV的3个高斯分量组成的独特结构.光致发光表明晶体具有从400nm到650nm的宽带本征发光，其峰值波长为472.0nm，相应于钨氧之间的辐射跃迁. 关键词： 晶体 钨酸锌 受激拉曼散射 闪烁体     

Er3+离子掺杂钡镓锗玻璃上转换发光机理研究

研究了Er³⁺离子掺杂钡镓锗玻璃的吸收光谱、拉曼光谱和上转换光谱.分析了Er³⁺离子在钡镓锗玻璃中的上转换发光机理.结果表明：玻璃的最大声子能量为828cm^-1，紫外截止波长为275nm.采用800nm和980nmLD激发玻璃样品，在室温下观察到强烈的上转换绿光和红光发射.随着Er³⁺离子浓度的增加，绿光发光强度先增加后减小，而红光发光强度呈单调递增趋势.能量分析表明：800nmLD激发产生的绿光主要源于Er³⁺离子4I_13/2能级的激发态吸收过程；红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程.980nmLD激发产生的绿光主要源于Er³⁺离子4I_11/2能级之间的能量转移过程；而红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程和4I_13/2能级的激发态吸收过程.通过量子效率分析，发现采用800nmLD激发Er³⁺离子掺杂浓度为1mol% 的样品时，上转换绿光发光效率最高. 关键词： 上转换发光机理 3+离子掺杂')" href="#">Er³⁺离子掺杂 钡镓锗玻璃     

Enhancement of upconversion luminescence of YAlO3:Er3+ by Gd3+ doping

The upconversion luminescences of YAlO3:Er3+ phosphor co-doping with different Gd3+ concentrations are investigated under the excitation of 980- and 532-nm diode lasers. A near ultraviolet upconversion emission at 410 nm is observed in YAlO3 under 532-nm excitation. Moreover, the inactive Gd3+ ions can improve the upconversion intensity efficiently in a certain range of concentration. Under 980-nm excitation, the visible upconversion emissions at 546 and 646 nm are enhanced by about 10 and 8 times at the Gd3+ concentration of 40%, respectively. The upconversion emission at 410 nm under 532-nm excitation is also enhanced by 7 times. The substitution of Gd3+ ions for Y3+ sites changes the local symmetry of Er3+, leading to the improvement of upconversion efficiency.     

Photoluminescence of SrGa2S4:Sn,Re(=Ce, Gd) phosphors

The photoluminescence (PL) spectra, PL excitation spectra, color coordinates, and X-ray diffraction spectra are reported for SrGa₂S₄:Sn,Re(=Ce and Gd, respectively) phosphors. By mixing SrGa₂S₄:Sn,Ce phosphors with different Ce³⁺ concentrations, white emissions can be obtained under the excitation of a 340-nm UV LED. Emissions in the green to yellow color range can be obtained from SrGa₂S₄:Sn,Gd phosphors. The rare earth ions enhance the green emission band, which peaks at 534 nm, instead of the yellow one. The origin of this enhancement is discussed. The resonant energy transfer rates are estimated in the cases from Ce³⁺ to the green and yellow centers of Sn²⁺ and between the yellow centers and the green centers.     

Polarized SSXANES study of spin ordering in ferromagnetic and paramagnetic phases of La1.2Sr1.65Ca0.15Mn2O7

Spin-selected polarized X-ray absorption near-edge structures (SSXANES) at the Mn K-edge from a bilayer La_1.2Sr_1.65Ca_0.15Mn₂O₇ single crystal have been studied with high resolution, both in the ferromagnetic (15 K) as well as paramagnetic phase (300 K). The orientation-dependent SSXANES spectra show unmistakable temperature dependence as the system makes the ferromagnetic to paramagnetic phase transition. The pre-edge structures are too intense to be ascribed to weak quadrupole transitions and are interpreted in terms of hybridization of Mn 3d orbitals with O2p and Mn 4p orbitals over and above similar onsite hybridization. The results also indicate possible existence of a small local (time-frozen) ferromagnetic ordering in the macroscopically disordered state. Need for further experimental and theoretical work on the SSXANES spectra from the bilayer system is emphasized.     

硫酸镁微液滴水和重水交换动力学的微区拉曼研究

本文利用微区拉曼技术,研究硫酸镁液滴水和重水交换的动力学.在低湿度时,由接触离子对连接形成的链状结构使硫酸镁液滴表面形成胶态结构,阻碍其与环境之间的水交换,造成表面和内部的结构差异.拉曼光谱的高空间分辨能力为观测这一特殊的表面结构提供了便利.沉积在聚四氟乙烯疏水基底上的硫酸镁重水液滴呈球形,可以实现对液滴表面和中心的两...     

热处理对钙钛矿锰氧化物La_(0.95)Sr_(0.05)MnO_3离子价态和磁结构的影响

对于磁性氧化物的磁有序,传统的观点用超交换相互作用(SE)和双交换相互作用(DE)模型进行解释,其出发点都建立在全部氧离子是-2价的基础上.例如,对于LaMnO_3,认为其中的La和Mn都处于+3价,用SE模型解释相邻Mn~(3+)离子间的反铁磁序;当以二价的Sr离子替代一部分La离子后,认为等量的Mn~(3+)离子变为Mn~(4+)离子,用DE模型解释相邻Mn~(3+)和Mn~(4+)离子间的铁磁序.然而,事实上在氧化物中存在一部分负一价氧离子.Cohen[Nature 358 136]利用密度泛函理论计算了BaTiO_3的价电子态密度,结果得到只有Ba离子的化合价与传统观点相同,为+2价;而Ti和0分别为+2.89价和-1.63价,不是传统观点的+4价和-2价,但是与多年来关于氧化物电离度的研究[Rev.Mod.Phys.42 317]和X射线光电子谱(XPS)的研究结果相符合.本文经过不同热处理条件制备了名义成分为La_(0.95)Sr_(0.05)MnO_3的三个样品,通过对样品的XPS分析,发现样品中不存在Mn~(4+)离子,只存在Mn2+和Mn~(3+)离子,平均价态随热处理程序的增加而升高.尽管三个样品有相同的晶体结构,但磁矩明显不同.对于这样的性能,不能用SE和DE模型解释其磁结构.利用本课题组最近在研究尖晶石结构铁氧体磁有序过程中提出的O 2p巡游电子模型解释了这种现象,利用样品在10 K的磁矩估算出的Mn离子平均价态变化趋势与XPS分析结果一致.O 2p巡游电子模型的出发点建立在氧化物中存在一部分负一价氧离子的基础上,这是其与SE和DE模型的根本区别.     

N2O+离子A2Σ+电子态的光解动力学研究

用一束波长为360.55nm的激光，通过N2O分子的（3+1）共振多光子电离（REMPI）过程制备纯净且布居完全处于X2Π(000)态的母体离子N2O+，然后用另一束波长在275—328nm范围内的可调谐激光将制备的N2O+离子激发至预解离电子态A2Σ+.实验发现，由于解离碎片NO+所具有的一定的反冲速度，其TOF质谱峰明显比N2O+母体宽.通过分析NO+碎片TOF质谱峰形状，得到了解离产物的总平均平动能〈ET〉；通过考察〈ET〉随光解能量的变化，发现光解能量在32000cm-1附近约250cm-1的变化 关键词： N2O+离子A2Σ+态 TOF质谱峰 预解离机理     

锂离子电池相关材料的Raman光谱学研究

锂离子电池是目前综合性能最好的可充电池。本文总结我们实验室用Raman光谱学研究锂离子电池相关材料的一些结果 ,包括聚合物电解质的微结构和离子输运机制 ,低温热解碳负极材料的结构表征和锂离子在其中的嵌入 /脱出机理 ,元素替代引起正极材料LiMn2 O4的结构变化以及在充放电过程中电极 /电解质界面形成的钝化层的性质及其对电池性能的影响     

Mossbauer, Raman and X-ray diffraction studies of superparamagnetic NiFe2O4 nanoparticles prepared by sol-gel auto-combustion method

Superparamagnetic nickel ferrite single phase nanoparticles with the average crystallite size of ∼9 nm have been synthesized at a low temperature (220 °C) by the sol-gel auto-combustion method. In the present study the as prepared powder was further calcined at different temperatures for 4 h, resulting in nanoparticles of larger size. The nanoparticles exhibited superparamagnetic behavior and changes in cation distribution as revealed by the Mossbauer, Raman and X-ray diffraction studies. The Mossbauer spectra collected at 5 K and under 5 T applied magnetic field showed mixed spinel structure and canted spin order for the nanoparticles, whereas there is collinear spin order with inverse spinel structure for larger particles. The vibrational spectra of the nanoparticles showed a redshift and broadening in the Raman line shape due to confinement effects.