Efficient synthesis of an aldehyde‐capped polythiophene containing fluorinated electron‐withdrawing groups

To incorporate an acceptor type polythiophene segment onto a supramolecular block copolymer for potential light harvesting applications, effective synthetic routes for the end‐functionalized and acceptor‐substituted polythiophenes are critical. The Ullmann coupling reaction can be utilized to obtain electron‐deficient polythiophenes and to attach terminal thiophene units that carry functional groups. In this article, the reactions involving a 2,5‐dibromothiophene monomer containing an electron‐withdrawing fluorinated ester and 5‐bromo‐2‐thiophenecarboxaldehyde (the end‐capper) were studied in detail. It was found that the Ullmann coupling reaction of the dibromide is very fast (completed in a few minutes) and the terminal bromine group does not survive long under the reaction condition. These findings lead to the development of an effective procedure for aldehyde end‐capping of electron‐deficient polythiophenes. Polymers with molecular weights around 4000 Da are routinely obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 41–47, 2007     

Organometallic chemistry related to applications for microelectronics in Japan

This is meant to be a brief overview of the developments of research activities in Japan on organometallic compounds related to their use in electronic and optoelectronic devices. The importance of organometallic compounds in the deposition of metal and semiconductor films for the fabrication of many electronic and opto-electronic devices cannot be exaggerated. Their scope has now extended to thin-film electronic ceramics and high-temperature oxide superconductors. A variety of organometallic compounds have been used as source materials in many types of processing procedures, such as metal–organic chemical vapor deposition (MOCVD), metalorganic vapor-phase epitaxy (MOVPE), metal–organic molecular-beam epitaxy (MOMBE), etc. Deposited materials include silicon, Group III–V and II–VI compound semiconductors, metals, superconducting oxides and other inorganic materials. Organometallic compounds are utilized as such in many electronic and optoelectronic devices; examples are conducting and semiconducting materials, photovoltaic, photochromic, electrochromic and nonlinear optical materials. This review consists of two parts: (I) research related to the fabrication of semiconductor, metal and inorganic materials; and (II) research related to the direct use of organometallic materials and basic fundamental research.     

新型高色纯度弱电流猝灭性蓝色有机发光器件

以ADN为基质,分别以不同掺杂剂制备了四种蓝色有机发光器件,器件结构为:CuPc(12 nm)/NPB(40 nm)/AND∶Dopant(50 nm)/Alq(12 nm)/LiF(4 nm)/Al。掺杂剂有:BCzVB(amino-substituted distyrylarylenederivatives)、TBPe、BCzVBi和DSA-ph四种。研究了最佳掺杂浓度以及器件的亮度、电流密度、效率和色坐标等电学特性和光学特性。其中掺杂BCzVB制备了色纯度高、低电流猝灭性的蓝色有机发光器件,色坐标达到x=0.146,y=0.162,最大亮度为11600 cd/m2(15 V),电流效率为2.8 cd/A,流明效率为1.79 lm/W;以ADN为基质,分别以TBPe、BCzVBi和DSA-ph为掺杂剂,制备了另外三种对比器件。器件ADN∶TBPe色坐标为x=0.162,y=0.222(蓝绿光),效率随电流的增加而降低很快;器件ADN∶BczVBi有较好的色纯度(色坐标:x=0.164,y=0.146),但电流效率较低:2.03 cd/A,效率随电流的增加降低幅度也较快。器件ADN∶DSA-ph效率较高为8 cd/A,效率随电流增加变化幅度不大,但色纯度比较差(x=0.153,y=0.306),适合于做白色有机发光器件。     

折射率连续周期分布一维光子晶体的带隙分析

微分传输矩阵法(DTMM)可以解析求解一维非均匀介质中的波动方程。用该方法,对几种折射率连续且周期分布的一维光子晶体进行了带隙分析。结果表明,折射率连续变化的一维周期结构也具有明显的带隙特征,折射率变化越平缓,光带隙的宽度越小。对于折射率正弦变化的一维光子晶体,其折射率变化得越剧烈,光子晶体的中心频率越小,带隙越宽;同时,折射率的平均值越大,中心频率越小,带隙越窄。由于材料的物理特性都是连续变化的,同样可以把结构推广到一维周期性功能梯度材料。     

铟封前后透射式GaAs光电阴极光谱响应特性的测试与分析

利用自行研制的光谱响应测试仪工程化样机,对透射式GaAs光电阴极在高温激活结束、低温激活结束以及铟封成管后的光谱响应特性进行了测试。结果显示,铟封后阴极整个响应波段的光谱响应下降,长波响应受到最显著的影响,表现为800~815 nm之间长波响应大幅度衰减,截止波长和峰值波长向短波移动,峰值响应和积分灵敏度减小,最终的光谱响应曲线变得平坦。阴极参量的计算结果反映铟封后阴极的表面逸出几率降低,说明铟封引起阴极表面激活层发生变化,使得能量较低的长波段光生电子不容易逸出,阴极长波响应和灵敏度随之降低。进一步分析了铟封过程中影响阴极表面激活层的因素。     

多棱锥镜产生多光束干涉场的理论和实验研究

提出了一种使用多棱锥镜和多棱台镜产生多束相干光形成二维和三维光学格子的方法。理论分析和数值模拟了多束轴对称平面波干涉产生的二维及三维点阵结构的特性,得到了光场分布随光束数增加的关系,发现随着干涉光数目的增加,干涉场会复杂变化,当棱锥棱数足够多近似于一个圆锥时,干涉场会变为同心圆结构的贝塞尔光束的场分布。实验上使用多棱锥和多棱台镜进行了多光束干涉实验,得到了多束轴对称平面波干涉形成的光学格子,将数值模拟与实验结果进行了比较,二者完全吻合。     

双缺陷模一维光子晶体的双光子吸收增强研究

采用真空镀膜工艺制备了具有762 nm和800 nm双缺陷模的含两个CdS缺陷层的TiO2/SiO2一维光子晶体,运用抽运探测技术测量了其双光子吸收。对于两个缺陷模,双光子吸收均得到很大的增强,其中缺陷模为800nm时的双光子吸收系数307 cm/GW要大于缺陷模为762 nm时的116 cm/GW,分别为单层CdS薄膜的48倍和18倍。这种双光子吸收的增强是由于光局域化导致一维光子晶体缺陷层内的电场强度增大而形成的。通过传输矩阵法计算了一维光子晶体的内部场强,发现800 nm波长光入射时缺陷层内的电场强度要大于762 nm波长光入射时的电场强度值。     

Optimizing Optoelectronic Properties of Pyrimidine‐Based TADF Emitters by Changing the Substituent for Organic Light‐Emitting Diodes with External Quantum Efficiency Close to 25 % and Slow Efficiency Roll‐Off

A series of green butterfly‐shaped thermally activated delayed fluorescence (TADF) emitters, namely PXZPM , PXZMePM , and PXZPhPM , are developed by integrating an electron‐donor (D) phenoxazine unit and electron‐acceptor (A) 2‐substituted pyrimidine moiety into one molecule via a phenyl‐bridge π linkage to form a D –π–A–π–D configuration. Changing the substituent at pyrimidine unit in these emitters can finely tune their emissive characteristics, thermal properties, and energy gaps between the singlet and triplet states while maintaining frontier molecular orbital levels, and thereby optimizing their optoelectronic properties. Employing these TADF emitters results in a green fluorescent organic light‐emitting diode (OLED) that exhibits a peak forward‐viewing external quantum efficiency (EQE) close to 25 % and a slow efficiency roll‐off characteristic at high luminance.     

声子色散和磁场对极性晶体中极化子自陷能的影响

利用线性组合算符和幺正变换相结合的方法,研究了声子色散和磁场对极性晶体中极化子振动频率和自陷能的影响.计及纵光学(LO)声子色散,在抛物近似下导出了极性晶体中极化子自陷能随电子-纵光学声子耦合常数、回旋共振频率和声子色散系数之间的变化关系.数值计算结果表明极化子自陷能随电子-纵光学声子耦合常数、回旋共振频率和声子色散系数的增大而增大.