Raman spectroscopy of smithsonite

Raman spectroscopy at both 298 and 77 K has been used to study a series of selected natural smithsonites from different origins. An intense sharp band at 1092 cm⁻¹ is assigned to the CO₃²⁻ symmetric stretching vibration. Impurities of hydrozincite are identified by a band around 1060 cm⁻¹. An additional band at 1088 cm⁻¹ which is observed in the 298 K spectra but not in the 77 K spectra is attributed to a CO₃²⁻ hot band. Raman spectra of smithsonite show a single band in the 1405–1409 cm⁻¹ range assigned to the ν₃ (CO₃)²⁻ antisymmetric stretching mode. The observation of additional bands for the ν₃^g modes for some smithsonites is significant in that it shows distortion of the ZnO₆ octahedron. No ν₂ bending modes are observed for smithsonite. A single band at 730 cm⁻¹ is assigned to the ν₄ in phase bending mode. Multiple bands be attributed to the structural distortion are observed for the carbonate ν₄ in phase bending modes in the Raman spectrum of hydrozincite with bands at 733, 707 and 636 cm⁻¹. An intense band at 304 cm⁻¹ is attributed to the ZnO symmetric stretching vibration. Copyright © 2007 John Wiley & Sons, Ltd.     

Vibrational spectra,X‐ray and molecular structure of 1H‐ and 3H‐imidazo[4,5‐b]pyridine and their methyl derivatives: DFT quantum chemical calculations

Molecular structure, vibrational energy levels and potential energy distribution of 1H‐imidazo[4,5‐b]pyridine, 3H‐imidazo[4,5‐b]pyridine, 5‐methyl‐1H‐imidazo[4,5‐b]pyridine, 6‐methyl‐1H‐imidazo[4,5‐b]pyridine and 7‐methyl‐3H‐imidazo[4,5‐b]pyridine were determined using density functional theory (DFT) at the B3LYP/6‐31G(d,p) level. The optimised bond lengths and bond angles are in good agreement with the X‐ray data of 5‐methyl‐1H‐imidazo[4,5‐b]pyridine obtained in the present work (Pbca space group; a = 8.660(2), b = 11.078(2), c = 11.078(3) Å, Z = 8). The N⁺H group plays the role of a proton donor in a medium strong hydrogen bond of the type N H…N, linking the N‐atom of the pyridine with the adjacent molecule related by the symmetry operation: 1/2 − x, y − 1/2, z(N…N = 2.869(25) Å). The presence of hydrogen bond is confirmed by appearance in the IR spectra of a very broad and strong contour in the 2000–3100 cm⁻¹ range. The place of substitution of the methyl group at the pyridine ring influences the proton position of the NH group at the imidazole unit. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of an aliphatic spacer group on the adsorption mechanism on the colloidal silver surface of L‐proline phosphonodipeptides

A comparative study of molecular structures of five L ‐proline (L ‐Pro) phosphonodipeptides: L ‐Pro‐NH‐C(Me,Me)‐PO₃H₂ (P1), L ‐Pro‐NH‐C(Me,iPr)‐PO₃H₂ (P2), L ‐Pro‐L ‐NH‐CH(iBu)‐PO₃H₂ (P3), L ‐Pro‐L ‐NH‐CH(PA)‐PO₃H₂ (P4) and L ‐Pro‐L ‐NH‐CH(BA)‐PO₃H₂ (P5) has been carried out using Raman and absorption infrared techniques of molecular spectroscopy. The interpretation of the obtained spectra has been supported by density functional theory calculations (DFT) at the B3LYP; 6–31 + + G** level using Gaussian 2003 software. The surface‐enhanced Raman scattering (SERS) on Ag‐sol in aqueous solutions of these phosphonopeptides has also been investigated. The surface geometry of these molecules on a silver colloidal surface has been determined by observing the position and relative intensity changes of the Pro ring, amide, phosphonate and so‐called spacer (−R) groups vibrations of the enhanced bands in their SERS spectra. Results show that P4 and P5 adsorb onto the silver as anionic molecules mainly via the amide bond (∼1630, ∼1533, ∼1248, ∼800 and ∼565 cm⁻¹), Pro ring (∼956, ∼907 and ∼876 cm⁻¹) and carboxylate group (∼1395 and ∼909 cm⁻¹). Coadsorption of the imine nitrogen atom and PO group with the silver surface, possibly by formation of a weaker interaction with the metal, is also suggested by the enhancement of the bands at 1158 and 1248 cm⁻¹. P1, P2 and P3 show two orientations of their main chain on the silver surface resulting from different interactions of the  C CH₃,  NH and  CONH fragments with this surface. Bonding to the Ag surface occurs mainly through the imino atom (1166 cm⁻¹) for P2, while for P1 and P3 it occurs via the methyl group(s) (1194–1208 cm⁻¹). The amide group functionality (CONH) is practically not involved in the adsorption process for P1 and P2, whereas the C_s P bonds do assist in the adsorption. Copyright © 2008 John Wiley & Sons, Ltd.     

Time-resolved spectroscopy of freestanding GaN layers grown by halide vapour phase epitaxy

Freestanding GaN layers of various thicknesses grown by HVPE have been studied by time-resolved spectroscopy combined with structural and electrical measurements. We have observed an increase of the PL lifetime with increasing layer thickness; however, a saturation of the recombination times has been detected for the GaN layers thicker than 400 μm. We explain the observed thickness-dependent behavior of the decay times by competition of two nonradiative mechanisms; namely, for layers with thickness less than 400 μm the main nonradiative channel is related to the structural defects, while in thicker layers the recombination decay time is limited by impurities and/or vacancies.     

微纳米尺度红外光热膨胀效应及新型光热驱动方法研究

介绍了一种新型的基于非对称结构的光热微型驱动器.驱动器由两个宽细不同的薄悬臂组成.当红外激光照射在悬臂上时,宽窄悬臂的比表面积不同,导致其温度升高和伸长量不同,从而使驱动器产生偏转.建立了驱动器的热力学模型,并给出了偏转量的计算公式.使用准分子激光加工系统制作了一个长750μm的微驱动器样机,红外激光(998nm)作为驱动源,利用自制的控制监控系统进行了可行性试验,观察并测量了驱动器偏转量与红外激光功率的关系.结果表明,本驱动器在16mW的红外激光的驱动下,即可产生258μm的偏转量.利用光热膨胀的方法 关键词： 光热膨胀 非对称结构 微驱动器 红外激光     

Synthesis and Characterization of Pyrene‐Centered Starburst Oligofluorenes

A series of starburst materials ( T1 – T3 ) based on a pyrene core with four oligofluorene arms of different length have been synthesized and characterized. The starburst materials show good film forming ability and sky blue fluorescence. Electroluminescent devices take on a stable blue emission and the device performance increases with an increase in arm length. The single‐layered device made of T3 has a maximum brightness of over 2 700 cd · m⁻² and a maximum current efficiency of 1.75 cd · A⁻¹, which is among the best in starburst material devices. The morphology of T1 – T3 has been studied by atomic force microscopy. The starburst oligofluorenes with different arm lengths show a distinctive texture, which indicates the size dependent morphology of the starburst materials.

     

m面GaN平面内结构和光学各向异性研究

采用金属有机物化学气相淀积方法在铝酸锂LiAlO₂衬底上外延生长m面GaN薄膜.X射线衍射测量的结果表明所得薄膜具有较理想的m面晶体取向,并对其各向异性的应变进行了计算,摇摆曲线的测量发现样品存在明显的面内结构各向异性.采用偏振光致发光研究材料的面内光学各向异性,发现随着偏振角度的改变,发光峰的峰位和强度均有明显变化,并用对称性破缺导致价带子带劈裂的理论对结果进行了解释. 关键词： m面GaN 结构各向异性 偏振光致发光     

Si／SiNx／SiO2多层膜的光致发光

采用射频磁控溅射法,制备了具有强光致可见发光的纳米Si/SiNx/SiO2多层膜,利用傅立叶红外吸收(FTIR)谱,光致发光(PL)谱对其进行了研究。用260nm光激发得到的PL谱中观察到高强度的392nm(3.2eV)和670nm(1.9eV)光致发光峰,分析认为它们分别来自于缺陷态≡Si-到价带顶和从导带底到缺陷态≡Si-的辐射跃迁而产生的光致激发辐射复合发光。PL谱中只有370nm(3.4eV)处发光峰的峰位会受退火温度的影响,结合FTIR谱认为370nm发光与低价氧化物—SiOx(x<2.0)结合体有密不可分的关系。当SiO2层的厚度增大时,发光强度有所增强,800℃退火后出现最强发光,认为具有较大SiO2层厚度的Si/SiNx/SiO2结构多层膜更有利于退火后形成Si—N网络,能够得到更高效的光致发光。用量子限制-发光中心(QCLC)模型解释了可能的发光机制,并建立了发光的能隙态(EGS)模型。     

MOCVD生长InxGa1-xN合金微观结构和光学特性

利用发光光谱、X射线衍射(XRD)、原子力显微(AFM)等实验方法对MOCVD生长的InxGa1-xN合金进行了研究。原子力显微图样表明样品表面出现纳米尺度为微岛状结构。样品PL和PLE谱表明,其主要吸收峰位于波长为365,474nm,发光峰的位置位于波长为545,493nm处,其中545nm发光峰半高宽较493nm发光峰宽,这两个峰分别起源于In(Ga)N浸润层和InGaN层发光,浸润层局域化激子和岛状微观结构弛豫特性是产生发光峰Stokes移动的重要原因。     

生长温度和结构参数对InGaAs／GaAs量子阱光学特性的影响

研究了不同生长温度下制备的In0.15Ga0.85As/GaAs应变量子阱的PL谱,结果表明,生长温度越高,In偏析和In-Ga互混越严重,同时,导致更多的In脱附,PL谱发光峰蓝移。对不同In含量的和不同InGaAs厚度的InGaAs/GaAs量子阱进行PL谱测试,分析表明In含量<0.2,生长温度低于560℃时,In含量和InGaAs层量子阱的厚度对In偏析、脱附和In-Ga互混基本没有影响。