聚(2-甲氧基-5-辛氧基)对苯乙炔/Y_2O_3:Eu~(3+)纳米复合材料的光致电子转移效应

采用原位脱氯化氢缩合聚合法制备了聚(2-甲氧基-5-辛氧基)对苯乙炔/Y_2O_3:E~(3+)(PMOCOPV/Y_2 O_3:Eu~(3+))纳米复合材料。红外光谱证实了在Y_2O_3:Eu~(3+)表面的包覆层为PMOCOPV。紫外-可见吸收光谱表明与PMOCOPV相比,PMOCOPV/Y_2O_3:Eu~(3+)的最大吸收峰发生红移且强度提高。荧光光谱研究表明PMOCOPV/Y_2O_3:Eu~(3+)的最大发射波长发生红移且强度提高,荧光寿命得到增强,Y_2O_3:Eu~(3+)与PMOCOPV之间形成了光致电子转移体系,使得π电子离域程度增加,并且导致荧光量子效率提高。根据E_g与入射光子能量hv的关系,拟合了PMOCOPV/Y_2O_3:Eu~(3+)薄膜的光学禁带宽度,发现E_g减小。采用简并四波混频方法测试它们的三阶非线性极化率x~((3)),结果发现与PMOCOPV相比,PMOCOPV/Y_2O_3:Eu~(3+)纳米复合体的非线性光学响应逐渐增强,进一步说明PMOCOPV与Y_2O_3:Eu~(3+)之间形成了分子间光致电子转移体系,产生了复杂的分子间离域π电子非线性运动。     

聚(2,5-二丁氧基)对苯乙炔/多壁碳纳米管复合材料的制备和性能研究

通过原位聚合法制备了聚（2,5-二丁氧基）对苯乙炔/多壁碳纳米管（PDBOPV/MWCNTs）复合材料.红外光谱和拉曼光谱证实了在MWCNTs表面的包覆层为PDBOPV.高分辨透射电子显微镜观察发现,PDBOPV/MWCNTs复合材料直径为35—45 nm,其中PDBOPV包覆层厚度约为15 nm.紫外—可见吸收光谱表明随着MWCNTs含量的增加,PDBOPV/MWCNTs的吸收发生红移且强度提高.荧光光谱研究表明随着MWCNTs含量的增加,PDBOPV/MWCNTs的最大发射波长发生蓝移且强度减小,MWCNTs与PDBOPV之间形成了光致电子转移体系,使得π电子离域程度增加,并且导致荧光量子效率降低.根据E_g与入射光子能量hν的关系,拟合了PDBOPV/MWCNTs薄膜的光学禁带宽度,发现随着MWCNTs的增加,E_g逐步减小.采用简并四波混频方法测试它们的三阶非线性极化率χ^（3）,结果发现随着MWCNTs含量的增加,PDBOPV/MWCNTs复合体的非线性光学响应逐渐增强,这说明PDBOPV与MWCNTs之间形成了分子间光致电子转移体系,产生了复杂的分子间π-π电子非线性运动. 关键词： 聚（2 5-二丁氧基）对苯乙炔 多壁碳纳米管 复合材料 光致发光     

聚(2,5－二丁氧基对苯乙炔)电致发光性能的研究

本文对以聚(2,5-二丁氧基对苯乙炔)为发光层的聚合物电致发光二极管的电致发光性能和影响其性能的因素进行了研究。其发光峰值波长为590um,起亮电压为12V,最大亮度可达112cd/m2.热处理温度和时间影响其发光强度和峰值波长,一般以200℃,真空处理3.5h为宜。还原气氛(N2+H2)下的热处理有利于电致发光性能的提高。器件在空气中具有一定的使用寿命。其量子效率可达0.16%光子/电子。并研究了器件制备工艺对性能的影响,初步探讨了聚合物电致发光机理。     

聚（2，5－二丁氧基对苯乙炔）电致发光性能的研究

本文对以聚（２，５－二丁氧基对苯乙炔）为发光层的聚合物电致发光二极管的电致发光性能和影响其性能的因素进行了研究．其发光峰值波长为５９０ｕｍ，起亮电压为１２Ｖ，最大亮度可达１１２ｃｄ／ｍ２．热处理温度和时间影响其发光强度和峰值波长，一般以２００℃，真空处理３．５ｈ为宜．还原气氛（Ｎ２＋Ｈ２）下的热处理有利于电致发光性能的提高．器件在空气中具有一定的使用寿命．其量子效率可达０．１６％光子／电子．并研究了器件制备工艺对性能的影响，初步探讨了聚合物电致发光机理．     

聚(2-甲氧基-5-辛氧基)对苯乙炔/单壁碳纳米管复合材料的光致发光特性

采用原位聚合法在无水四氢呋喃(THF)溶液中制备了聚(2-甲氧基-5-辛氧基)对苯乙炔(MOPPV)/单壁碳纳米管(SWNTs)复合材料。通过对该复合材料的红外光谱、X射线衍射、透射电镜、扫描电镜等的研究,证实SWNTs已聚合到MOPPV上且被MOPPV紧密有效地包覆,形成了纳米线网状结构。通过紫外-可见(UV-Vis)吸收光谱和光致发光(PL)谱发现:随着SWNTs掺杂量的增加,该复合材料的吸收强度逐渐增强且最大吸收峰出现红移,其发光强度呈现先升高后降低的趋势,发光峰蓝移。当SWNTs掺杂质量分数为3.85%时,复合材料的发光强度最大,此时最大发光峰位较纯MOPPV蓝移8 nm。研究结果表明:在MOPPV中掺入一定量的SWNTs,能有效地增强复合材料的光致发光强度。     

辛氧基取代苯-吡啶共聚物的发光性能

辛氧基苯-吡啶共聚物在氯仿、四氢呋喃、环己烷等常用有机溶剂中显示了很好的溶解性。报道了辛氧基苯-吡啶三种共聚物旋涂膜和稀氯仿溶液的光吸收和光发射性能,电化学循环伏安法测定能带结构的结果及液氮条件下(77K)简单发光器件ITO/Polymer/Mg:In(10:1)的电致发光性能。三种聚合物都具有很好的光学活性,显示蓝色光致发光和电致发光特性,三种器件显示了非常好的整流特性,且发光色纯度较好。三种聚合物π^*     

各种烷氧基取代聚对苯乙炔的合成和发光性能研究

利用脱氯缩合聚合法合成了聚（2－甲氧基－5－丁氧基）对苯乙炔（PMOBOPV），聚（2－甲氧基－5－辛氧基）对苯乙炔（PMOCOPV）和聚（2－丁氧基－5－丁氧基）对苯乙炔（PDBOPV），聚（2－辛氧基－5－辛氧基）对苯乙炔（PD－COPV）4种发光材料。对反应体系的浓度，酸碱度，反应温度及时间等工艺条件和路线进行了细致的研究。结果表明：反应物的纯度，含量对合成产物的产率和性能有较大的影响；碱性是影响脱氯缩合反应的关键因素，而反应温度和时间对缩合反应影响则相对较小，在一定温度下当反应时间达到一定阶段后其转化率基本不变，对合成材料的化学结构，物理性能和发光特性进行了表征和检测。结果显示：非对称烷氧基取代PPV具有良好的溶解性，成膜性和稳定性；而对称性烷氧基取代PPV的溶解性和成膜性相对较差。以PMOBOPV为发光材料，采用旋涂工艺制作出单层和双层发光器件，并对器件的电致和光致发光性能进行了研究。     

碳纳米管掺杂对聚合物聚(2-甲氧基-5-辛氧基)对苯乙炔-PbSe量子点复合材料性能的影响

基于碳纳米管的良好导电性、激子传输性能和量子点聚合物复合材料高的光电转换性能, 采用原位缩合法制备了聚合物聚(2-甲氧基-5-辛氧基)-对苯乙炔(MOPPV)功能化碳纳米管(SWNT)-PbSe量子点复合材料, 通过对复合材料的X射线衍射、透射电子显微镜和紫外可见吸收光谱研究, 发现MOPPV, SWNT与PbSe量子点可以有效地复合, 且SWNT与MOPPV形成网状结构; PbSe量子点尺寸为5.75 nm, 其可均匀地分散在MOPPV-SWNT基体中形成包覆或镶嵌结构, 并发生了光诱导电荷转移.通过对复合材料的光电性能研究发现, 当MOPPV, SWNT, PbSe三者的质量比为1: 0.3 : 1 时其光电性能最好, 开路电压为0.556 V, 短路电流为2.133 mA, 填充因子为34.48%, 转换效率为0.452%, 与聚合物MOPPV-PbSe量子点复合材料材料相比, 光电性能提高了2–3倍. 关键词： 量子点 碳纳米管 复合材料 转换效率     

聚对苯撑乙炔咔唑薄膜对TNT挥发物的检测

以3, 6-二溴-9-辛基咔唑和2, 5-二戊烷氧基-1, 4-二乙炔基苯为单体,通过Pd催化的Sonogashira偶联反应合成了聚对苯撑乙炔咔唑衍生物PPECz。PPECz的溶液和固体薄膜都具有较好的发光性能,并且均对2, 4, 6-三硝基甲苯(TNT)有明显的响应。在常温常压条件下,微量(40 μg)的TNT挥发物在60 s内就能使聚合物PPECz薄膜的荧光强度被猝灭56%,可作为一种潜在的硝基苯类爆炸物的荧光检测材料。     

聚对苯乙炔的能带结构和关联能计算

在考虑电子-电子相互作用情况下,对基态非简并聚合物聚对苯乙炔（PPV）的长程关联能进行了理论计算,并用长程关联能对带隙进行修正,最后讨论了长程关联能对带隙的影响。在对PPV链的计算中发现,长程关联能先会随着链长N的增加而减小,但当链长大于10后长程关联能会达到饱和。在链长为20个单元的PPV计算中,长程关联能的修正会降低由Hartree-Fock(HF)方法所得的能隙宽度。修正后的能隙宽度能很好的接近实验结果。     

Magnetic Field-Effect on Photoluminescence of Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) Nanoparticles in a Poly[vinyl butyral] Matrix

Abstract

In this work the magnetic field effects (MFE) on the photoluminescence of MEH-PPV film and nanoparticles were obtained using the MFE technique with continuous-wave photoexcitation. The analysis of the MFE dependence for the MEH-PPV film gave a HWHM (half-width at half maximum) ～ 65?mT and a total MFE value about 102.8% at 200?mT whereas the MFE dependence of the MEH-PPV nanoparticles showed significant broadening, with their HWHM ～ 280?mT and a total MFE value of 99% at 550?mT. By a simple theoretical model based on rate equations, the mechanism of the negative magnetic field effect was explained. The observed negative effect was the result of the dominant singlet exciton formation rate in the MEH-PPV nanoparticles. For explaining this negative effect the enhanced triplet-triplet annihilation due to confinement of triplet excitons in the nanoparticles and singlet molecular oxygen-triplet exciton annihilation were proposed.     

π-electron density dependence of third-order optical nonlinearities in poly(1,4-phenylene vinylene) derivatives

The third-order nonlinear optical properties of poly(1,4-phenylene vinylene) (PPV), poly(2-bromo-1,4-phenylene vinylene) (BrPPV) and poly(2-chloro-1,4-phenylene vinylene) (ClPPV) were studied by forward degenerate four-wave mixing (DFWM). They have large and ultrafast third-order optical nonlinear responses, which mainly arise from the distortion of the large π-conjugated electronic charge distribution in the backbone. It was found that there was a significant contribution to π-electron density and thus χ⁽³⁾ values from the substituents at the phenylene ring.     

(Ta_2O_5)_(1-x)(TiO_2)_x陶瓷结构相变研究

采用固相反应技术制备了x分别为 0 0 5、0 0 8和 0 1 1的 (Ta2 O5) 1-x(TiO2 ) x 陶瓷 ;在室温至 6 0 0℃范围内 ,测量了这些陶瓷样品的拉曼光谱随温度的变化。随着温度的升高 ,拉曼光谱中位于 35～38cm- 1的最低频移的声子模发生软化 ,并随之发生结构相变。拉曼光谱和实验结果都表明 :组分x分别为0 0 5、0 0 8和 0 1 1的 (Ta2 O5) 1-x(TiO2 ) x 陶瓷分别在 36 0、4 5 0和 5 4 0℃发生了由三斜至单斜相的结构相变。上述结论得到了 (Ta2 O5) 0 92 (TiO2 ) 0 0 8单晶热膨胀系数测量数据的支持。     

烷氧基取代聚对苯乙炔三阶非线性光学性能

通过双醚化反应、氯甲基化反应以及在强碱性条件下进行的脱氯化氢反应制备聚（2-甲氧基-5-丁氧基）对苯乙炔（PMOBOPV）、聚（2-甲氧基-5-己氧基）对苯乙炔（PMOHOPV）、聚（2,5-二丁氧基）对苯乙炔（PDBOPV）和聚（2,5-二己氧基）对苯乙炔（PDHOPV）等四种可溶性聚对苯乙炔（PPV）衍生物,通过紫外-可见吸收光谱对产物分子结构进行表征.结果显示,PMOBOPV、PMOHOPV、PDBOPV和PDHOPV的共轭π电子发生π → π* 跃迁的吸收峰分别位于491 nm、495nm、504nm和510nm处,相应的光学禁带宽度分别为2.23eV、2.18eV、2.12eV和2.07eV.利用简并四波混频技术测量PPV衍生物的三阶非线性光学性能,探讨了分子结构对PPV衍生物三阶非线性极化率（χ(3)）的影响.研究发现,激发波长为532 nm时,PMOBOPV、PMOHOPV、PDBOPV和PDHOPV的共振χ(3)值分别为3.45×10－10、5.13×10－10、7.15×10－10和9.61×10－10 esu;激发波长为1064 nm时,它们的非共振χ(3)值分别为1.09×10－11、1.42×10－11、1.62×10－11和2.14×10－11 esu.     

激光烧结(Ta_2O_5)_(1-x)(TiO_2)_x陶瓷的拉曼光谱研究

简介了激光快速烧结陶瓷技术;测量了采用激光快速烧结技术和传统电炉烧结技术制备的(Ta2O5)1-x(TiO2)x陶瓷的相对介电常数和介电损耗;分析了这两类试样的激光拉曼光谱和粉末XRD谱;发现:(Ta2O5)1-x(TiO2)x陶瓷经激光快速烧结后产生了新相,从而导致相对介电常数大幅度提高。     

Synthesis and Fluorescence Properties of Lanthanide (III) Perchlorate Complexes with Bis(benzoylmethyl) Sulfoxide

A ligand with two carbonyl groups and one sulfinyl group has been synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, ¹H NMR and UV spectra. The results indicated that the composition of these complexes is REL₅(ClO₄)₃·3H₂O (RE = La(III), Pr(III), Eu(III), Tb(III), Yb(III), L = C₆H₅COCH₂SOCH₂COC₆H₅). The fluorescent spectra illustrate that both the Tb (III) and Eu (III) complexes display characteristic metal-centered fluorescence in solid state, indicating the ligand favors energy transfer to the excitation state energy level of them. However, the Tb (III) complex displays more effective luminescence than the Eu (III) complex, which is attributed to especial effectively in transferring energy from the average triplet energy level of the ligands (T) onto the excited state (⁵D₄) of Tb (III) than that (⁵D₀) of Eu (III), showing a good antenna effect for Tb(III) luminescence. The phosphorescence spectra and the relationship between fluorescence lifetimes and fluorescence intensities were also discussed.     

A Novel Porphyrin-Labeled Poly(N-Isopropylacrylamide): Spectral and Luminescent Properties

A novel water-soluble tetraarylporphyrin-containing polymer has been synthesized by the reaction of bromoalkyl-containing poly(N-isopropylacrylamide) with 5-(4-pyridyl)-10,15,20-tri(4-methoxyphenyl)porphyrin. Some physicochemical properties of the obtained polymers are reported. It has been shown that a strong interaction between the porphyrin units takes place in liquid aqueous medium at temperatures below the lower critical solution temperature (LCST). This phenomenon results in considerable broadening of the Soret band in the absorption spectrum and in strong quenching of fluorescence. Higher than LCST fluorescence enhancement is observed.     

Spectroscopic properties and photophysics of the synthesized compound 5-nitro-benzo[b]thiophene-2-carboxylic acid in non-polar/polar media and in the presence of TiO2 nanoparticles

The present work investigates by electrochemical and steady-state and time-resolved spectroscopic methods a synthesized compound 5-nitro-benzo[b]thiophene-2-carboxylic acid (5NBTC), both in normal solvents and in the presence of TiO₂ nanoparticles to reveal the nature of the photophysical processes involved. From the present experimental observations it is inferred that both in the ground state and the excited electronic state S₁, there exists a strong binding between -COOH functionality of 5NBTC and TiO₂ nanoparticles. However, the rupture of this binding in the presence of excess TiO₂, as apparent from the steady-state and time-resolved spectroscopic measurements, is responsible for the increase in radiative transitions. Formations of aggregations of TiO₂ nanoparticles at higher concentrations appear the cause of such rupturing. The redox potential measurements by cyclic voltammetry and theoretical computations by time-dependent density functional theory (TD-DFT) with B3LYP/6-311 G(d, p) basis function implemented in the Gaussian package confirm the electron accepting nature of 5NBTC and hence no electron transfer is possible between the organic compound and TiO₂ nanoparticles. It is most likely that the interaction model between 5NBTC and TiO₂ nanoparticles should be that the -COOH group of 5NBTC molecule coordinates either directly or through a hydrogen bond to the TiO₂ surface.     

铕(Ⅲ)-2-(5-溴-2-吡啶偶氮)-5-二乙氨基苯酚-溴化十六烷基三甲铵显色反应的研究

研究了铕 ( ) - 5 - Br- PADAP- CTMAB体系的显色反应和光度性质 ,并探讨了其最佳的光度分析条件。在 p H =5 .0的 HAc- Na Ac缓冲溶液中 ,有表面活性剂 CTMAB存在的条件下 ,Eu( )与 5 - Br-PADAP形成了配位比为 1∶ 2的深红色络合物。配合物的最大吸收峰位于 5 98nm,表观摩尔吸光系数为1.5 9× 10 5L· mol-1· cm-1,铕含量在 0— 10μg/ 2 5 m L范围内符合比耳定律。加标回收实验结果令人满意。