Preparation of Copper Phthalocyanine Crystals Using Solvothermal Synthesis
有机光电材料
Design, Fabrication, and Performance Investigation of OrganicOptoelectronic DevicesChong-an DiABSTRACTOrganic optoelectronic materials and devices, which is also called …plastic electronics‟, att rached focus attention in past decade due to their potential application in large area and low cost flexible displays, solid-state lighting, radio frequency identification (RFID) cards and electronic papers etc. As important parts of organic optoelectronic devices, organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic light-emitting transistors (OLEFTs) have made great achievements. The performance of these optoelectronic devices depends not only on the properties of the organic semiconductors involved, but is also dramatically affected by the properties of other functional layers and the nature of the interfaces present. Therefore, interface engineering, a novel approach towards high-performance OFETs, is a vital task for organic optoelectronic devices. Electrode/organic interfaces, dielectric/organic interfaces, organic/organic interfaces and organic/atmosphere interfaces are the three frequently reported interfaces in organic devices. In this dissertation, a systematic research has been carried out centering on the interface engineering of organic optoelectronic devices. With investigation of interface phenomenon and effective interface modification, dramatic decrease of power consumption and cost, obvious ehancement of device performance and improvement of stability are achieved. The main results are obtained as follows:1: Exploration of novel anode modification approach for OLEDs to reduce the power consumption and enhance the efficiency.Power consumption and light emitting property are the key parameters for the real application of organic light-emitting diodes. In fact, modification of electrodes is a widely applied approach to improve device performance of OLEDs since it can optimize the devices performance without change of organic functional materials. We demonstrated that the improvement of interface contact between ITO anode and organic semiconductor layer can be realized by the introduction of ultrathinhexadecafluoro copper phthalocyanine (F16CuPc) layer. Besides, The modification brings on formation of dipole layer on the ITO surface, which in turn leads to workfunction enhancement of ITO anode and dramatic decrease of hole injection barrier. With device design and optimization, we fabricated high performance low-operation voltage single-layer, double-layer and multi-layer OLEDs with tris(8-quinolinolato)aluminum (Alq3) as emissive layer. For the single layer Alq3 devices, the modification of the anode results in the significant enhancement in the current efficiency by about 30 times. The operation voltage decrease obviously for double layer devices, with minimum turn-on voltage of 2.6 V. As for multilayer OLEDs, the maximum current efficiency up to 7.63 cd/A and low turn-on voltage of 2.89 V are obtained by improving carrier density in the combination zone and optimization of carrier balance. The performance is one of the best one for OLEDs with Alq3 light emitting layer（Patent Number:ZL 200510126485.X; Di CA, et al. Appl. Phys. Lett. 2007, 90, 133508；Di CA, et al. Appl. Phys. Lett. 2006, 89, 033502）.2: Development of novel organic light-emitting transistor structure and realization of light emission under ambient atmosphere.Organic light-emitting transistor is a highly integrated organic optoelectronic devices since both field-effect and light emitting can be realized in the same channel simultaneously. With optimized photolithograph techniques, we fabricated OFETs with Au and Al serves as source and drain electrode, respectively. Then, the laterally arranged heterojunction structures are achieved by successively inclined deposition of the field-effect and light-emitting materials. It has been observed that introduction of Au-Al source-drain electrodes and laterally arranged heterojunction structures result in enhancement of electron injection and improved carrier density of both holes and electrons. Besides, the designed device structure offers an ideal and widely applicable one to realize effective integration of field-effect property and light emission. It is because the two kind of organic semiconductors could take full use of their own advantages. We fabricated both small molecular and polymer based OLEFTs with pentacene, Alq3and TPA-PPV, respectively（Patent Number: ZL 200610089448.0；ZL 200510130758.8; Di CA, et al. Appl. Phys. Lett. 2006, 88, 121907；Di CA, et al.Adv. Funct. Mater. 2007, 17, 1567.）. The results constitute first demonstration of organic light-emitting transistor under ambient atmosphere（Cicoira, F. et al. Adv. Funct. Mater. 2007, 17, 3421；Cicoira, F. et al. J. Mater. Chem. 2008, 18, 158）.3: Exploration of novel approach to fabricate high performance low-cost OFETs.Low cost plays dominant role in determining the further development of OFETs. Source-drain electrodes are important parts in OFETs. Gold has been the most widely applied source–drain electrode for OFETs to date, due to its high conductivity, good stability, and formation of excellentcontact with many p-type organic semiconductors. However, the high cost of gold is an adverse factor in practical applications. On the other hand, low-cost electrodes such as Cu and Ag, are unsuitable for most p-type OFETs due to their relatively low workfunction. We provide a simple method to modify the bottom contact Cu or Ag electrodes with organic charge transfer compounds (Cu-TCNQ or Ag-TCNQ). The modification enhanced the workfunction of electrodes and improved the electrode/organic semiconductor contact which results in dramatic improvement of carrier injection. Therefore, we fabricated low cost Cu or Ag based OFETs with device performance comparable with the one of Au based OFETs. Besides, we investigated the influence of electrode morphology on the device performance by the formation of nanosized Cu electrodes. It has been discovered that introduction of source-drain electrodes with proper roughness is helpful to reduce the contact resistance. Fabrication of OFETs based on many organic semiconductors proved that it is a universal approach to improve the performance of bottom contact devices（Patent Number: 200610089591.X；Di CA, et al. J. Am. Chem. Soc. 2006, 128, 16418; Di CA, et al. Phys. Chem. Phys. Chem.2008, 10, 2302 (Front Cover)）. The result possess potential application in the patterning of organic crystals and construction of corresponding devices（Di CA et al. Chem. Mater. 2009, 21, 4873）.4: Discovery and investigation of high performance top contact OFETs with Cu electrodes. The typical OFET electrode structure, with a bottom gate, can be divided into top-contact and bottom-contact configurations. With varied electrode deposition sequence, the OFETs with different electrode structure required different modification techniques and exhibit varied device performance. Top-contact OFETs usually have a good electrode/organic layer contact and exhibit high device performance. We discovered that many organic semiconductors based OFETs with Cu top-contact electrodes show comparable device performance with the one of Au top-contact devices. The most excellent performance up to 0.8 cm2V-1s-1 can be obtained for pentacene FETs with Cu top-contact. The high performance is result from good electrode/organic layer contact and the formation of Cu x O during the electrode deposition process or device storage in air. The spontaneous formed Cu x O possess matched energy level with many organic semiconductors and bring on improved device performance (Patent Application Number: 200710118153.6；Di CA, et al. Adv. Mater. 2008, 20, 1286.). The results thus provide an effective way towards high performance low cost top-contact OFETs (High-tech Materials Alert, 2008, 25, 9).5: Development of novel graphene patterning method and its applications in OFETs. Graphene, single or few layer of two dimensional graphite, received great interest among condensed physics and material sciences due to its unusual and stable structure. We developed a novel vapor deposition method with ethanol as the carbon source to fabricate patterned gragheneusing the patterned copper or silver and demonstrated its application in OFETs. The patterned graphene exhibit good contact with organic semiconductors, with low carrier injection barrier for p-type OFETs and can serve as excellent source-drain electrodes for OFETs. The pentacene based bottom-contact devices with channel length of 5 m can reach high mobility of 0.53 cm2V-1s-1 which is one of the best result for pentacene bottom contact devices with bare SiO2 dielectric layer (Patent Application Number: 200710177814.2; Di CA, et al.Adv. Mater. 2008, 20, 3289). The result demonstrates novel approach to fabricate patterned graphene and open a new application of graphene in OFETs (NPG, Asia Materials, /asia-materials/highlight.php?id=291；Pang, SP et al. Adv. Mater. 2009, 21, 3488；Cao Y, et al. Adv. Funct. Mater. 2009, 19, 2743). The result is the first experimental step towards integrating graphene and conjugated organics （Burghard, M. et al. Adv. Mater. 2009, 21，2586.）.6: Discovery of relationship between the device stability and dielectric/organic layer interfaces and fabrication of high performance pentacene FETs.Device stability, a hot topic in the organic optoelectronic device field, is widely believed to be related to the properties of organic semiconductors. Pentacene is the most widely investigated organic semiconductor for OFETs. However, poor device stability is the key shortcomings that impede its real application. We discovered that the device stability of pentacene OFETs in air is strongly related to the properties of dielectric layers. The device performance of pentacene FETs with bare SiO2 can maintain for 7 months. By the investigation of relationship between the device stability and dielectric layer surface energy, we suggest the pentacene aggregation and phase transfer should be responsible for the device performance degradation for devices with low surface energy dielectric layer (OTS modified SiO2). We obtained high performance pentancene FETs with high mobility up to 1.8 cm2V-1s-1 and excellent stability by the optimization of dielectric layer（Di CA, et al. Phys. Chem. Chem. Phys. 2009, 11, 7268.）.In summary, centering on investigation of interface phenomenon, we fabricated high performance OLEDs, OFETs and OLEFTs by the device design and optimization. Also, a series of novel interface approaches were explored to improving the device performance and stability, lowering the the fabrication cost and power consumption (Di CA, et al.J. Phys. Chem. B 2007, 111, 14083(Feature Article, Front Cover), Di CA, et al. Acc. Chem. Res. 2009，42，1573). These results might boost further development of organic optoelectronic devices towards real applications.Key words: organic light-emitting diodes, organic field-effect transistors, organiclight-emitting transistors, interface, electrode modification中文摘要被称为“塑料电子学”的有机光电材料与器件因其在大面积和低成本的柔性显示、平板照明、射频标签和电子纸等方面的广阔应用前景在过去二十年中备受关注。
鳕鱼皮胶原蛋白肽铜螯合物的制备条件
鳕鱼皮胶原蛋白肽铜螯合物的制备条件陈晓刚;陈忻【摘要】为提高鳕鱼皮的附加值，采用正交试验法探讨鳕鱼皮胶原蛋白肽与硫酸铜螯合反应条件，制备鳕鱼皮胶原蛋白肽铜。
结果表明：制备鳕鱼皮胶原蛋白肽螯合铜的最佳条件是胶原蛋白肽与硫酸铜的质量比为3．5∶1，pH 7．0，反应温度50℃，反应时间40 min，该条件下铜离子的螯合率为34．35％。
%The preparation conditions of copper chelate from collagen peptide of cod skin were optimized by the orthogonal design to improve addition value of cod skin.The copper chelation rate from collagen peptide of cod skin under the optimum preparation conditions of 3.5:1 of collagenpeptide/copper sulfate ratio,pH 7.0,50℃ and for 40 min can re ach 34.35%.【期刊名称】《贵州农业科学》【年(卷),期】2015(000)001【总页数】5页(P154-158)【关键词】鳕鱼皮;胶原蛋白肽;铜螯合物;制备条件【作者】陈晓刚;陈忻【作者单位】佛山科学技术学院理学院化学与化工系，广东佛山 528000;佛山科学技术学院理学院化学与化工系，广东佛山 528000【正文语种】中文【中图分类】S986.5;TS254铜是动物体所必需的微量元素之一，在动物体内参与血红蛋白的合成和某些氧化酶的合成与激活。
铜的缺乏会影响动物对铁的利用，从而产生贫血[1]。
铜是饲养动物必需的微量元素，有重要的营养生理功能，同时对动物的免疫系统及抗氧化应激也有强烈影响。
4,4'-联吡啶铜(Ⅱ)配合物的合成及其晶体结构
4,4'-联吡啶铜(Ⅱ)配合物的合成及其晶体结构覃妍;肖瑜;黄浦;朱芸;易茗【摘要】采用溶液法合成了一维链状4,4'-联吡啶铜配合物{[Cu2(OOCCH3)4(4,4-bpy)]·(CHaCN)}n(4,4-bpy=4,4'-联吡啶),经单晶X射线衍射测定其晶体结构.此晶体属单斜晶系,空间群C2/c.晶胞参数:a=2.311 67(5)nm,b =1.40023(2)nm,c=1.531 03(4)nm,β=108.205(2)°,V=4.707 69(17)nm3,F(000) =2 288,Z=8,D.=1.582 g/em3,μ=1.850mm-1,R1=0.033 6,ωoR2=0.093 5.晶体结构分析表明,配合物中心Cu2形成了变形的几何四方锥CuNO4构型,Cu2通过4个乙酸根桥连形成双核单元,双核单元再通过4,4'-联吡啶N原子桥联成一维链状,经分子间范德华力作用构造出了三维超分子网.%The title complex was synthesized in the reaction by 4,4'-bipyridine and cupric acetate in acetonitrile DMF solution.The crystal structure was determined by single crystal X-ray diffraction.The crystal structure of the title complex belongs to the monoclinic system with space group C2/c and cell parameters:a=2.311 67 (5) nm,b=1.40023(2) nm,c=1.531 03(4)nm,β=108.205(2)°,V=4.707 69(17) nm3,F(000)=2 288,Z =8,Dc =1.582g/cm3,μ =1.850 mm-1,R1 =0.033 6,ωR2 =0.093 5.The Cu(Ⅱ) was coordinated by four oxygen atoms from OOCCH3 groups and one nitrogen atom from 4,4'-bipyridine,and formed a distorted square pyramidal geometrical configuration.The complex formed a dimer through OOCCH3 bridges which constructed a one dimensional chain.The 1D chain further formed 3D network through the van der Waals force.【期刊名称】《桂林理工大学学报》【年(卷),期】2016(036)004【总页数】5页(P799-803)【关键词】4,4'-联吡啶;铜配合物;晶体结构【作者】覃妍;肖瑜;黄浦;朱芸;易茗【作者单位】桂林理工大学广西岩溶地区水污染控制与用水安全保障协同创新中心,广西桂林541004;桂林理工大学广西岩溶地区水污染控制与用水安全保障协同创新中心,广西桂林541004;桂林理工大学广西岩溶地区水污染控制与用水安全保障协同创新中心,广西桂林541004;桂林理工大学广西岩溶地区水污染控制与用水安全保障协同创新中心,广西桂林541004;桂林理工大学广西岩溶地区水污染控制与用水安全保障协同创新中心,广西桂林541004【正文语种】中文【中图分类】O614.12配位聚合物通常是指金属离子和小分子配体通过自组装形成的、具有高度规整的无限网络结构的配合物［1］。
以小分子型诱导剂液相还原制备铜纳米片
以小分子型诱导剂液相还原制备铜纳米片张晓杰;方斌;袁双龙【摘要】在次亚磷酸钠-硫酸铜溶液的反应体系中加入小分子型诱导剂,制备了高径厚比的铜纳米片,并将其分散于丙烯酸/环氧复合树脂中制成导电胶.通过X射线衍射(XRD)、扫描电子显微镜(SEM)表征铜纳米片的结构与形貌,采用电阻测试仪测定导电胶的导电性能,研究了诱导剂种类及浓度、反应体系的pH值对铜纳米片形貌的影响,并分析了铜纳米片的形成过程.结果表明:诱导剂胸腺嘧啶的加入及合适的pH是制备铜纳米片的关键;胸腺嘧啶的浓度及pH过低或过高时,均会导致产物中片状铜粉比例减少,颗粒状铜粉比例增加.获得高质量的铜纳米片的最佳条件为:胸腺嘧啶的浓度1.5 mmol/L,pH 1.5,反应时间2h.此条件下所得的铜纳米片表面平整,厚度为50～100 nm,直径约为15 μm,以此铜纳米片制得的导电胶比球磨法片状铜粉制成的导电胶有着更好的导电性.【期刊名称】《北京化工大学学报（自然科学版）》【年(卷),期】2018(045)004【总页数】6页(P41-46)【关键词】铜纳米片;胸腺嘧啶;导电性【作者】张晓杰;方斌;袁双龙【作者单位】华东理工大学材料科学与工程学院,上海200237;华东理工大学材料科学与工程学院,上海200237;华东理工大学材料科学与工程学院,上海200237【正文语种】中文【中图分类】TB383引言导电银浆、导电银胶在电子行业中应用广泛[1]，其组分中最重要的成分是银粉，尤其是片状银粉。
使用价格低廉的铜粉代替银粉一直是工业上追求的目标，但是由于铜粉极易氧化，导致这种替代很难实现。
随着应用技术的发展，使用铜来代替银的可能性开始增加。
而片状铜粉作为导电填料，一般要求其具有厚度薄、直径大、分散性好等特点。
目前，工业上制备片状铜粉的方法是机械球磨法[2]，所制备出的铜粉厚度在0.02～2 μm，粒径在0.2～50 μm，径厚比(直径与厚度比值)小于等于20，且在球磨粉碎过程中由于硬球对金属粉末的多次撞击、研磨和压合，会不可避免地出现团聚和尺寸分布宽等缺陷[3]。
酞菁铜相对原子质量
酞菁铜相对原子质量引言酞菁铜（CuPc）是一种有机金属配合物，它具有广泛的应用领域，包括化学传感器、有机光电器件和催化剂等。
相对原子质量是描述元素质量的重要指标之一，对于研究酞菁铜的性质和应用具有重要意义。
本文将探讨酞菁铜的相对原子质量及其相关内容。
酞菁铜的化学式和结构酞菁铜的化学式为CuPc，它是由铜原子与四个酞菁分子形成的二维平面结构。
酞菁分子是由四个吡咯烷基团环形排列而成，中间的铜原子与这四个酞菁分子的氮原子形成配位键。
相对原子质量的定义相对原子质量是指一个元素原子质量与碳-12同位素相对质量之比。
根据国际纯粹与应用化学联合会（IUPAC）的规定，相对原子质量是以碳-12同位素为标准的。
碳-12被定义为原子质量单位的基准，其相对原子质量被定义为12。
其他元素的相对原子质量则是相对于碳-12的比值。
酞菁铜的相对原子质量计算要计算酞菁铜的相对原子质量，首先需要知道其中铜和碳、氢、氮等元素的相对原子质量。
根据国际纯粹与应用化学联合会的数据，铜的相对原子质量为63.55，碳的相对原子质量为12.01，氢的相对原子质量为1.008，氮的相对原子质量为14.01。
计算酞菁铜的相对原子质量时，需要考虑其中每个元素的原子数目。
根据酞菁铜的化学式CuPc，其中包含一个铜原子和16个碳原子、4个氮原子、8个氢原子。
根据相对原子质量的定义，酞菁铜的相对原子质量可通过如下公式计算：相对原子质量 = (铜的相对原子质量× 铜的原子数目 + 碳的相对原子质量×碳的原子数目 + 氮的相对原子质量× 氮的原子数目 + 氢的相对原子质量× 氢的原子数目) / 总原子数目代入相关数值可得：相对原子质量= (63.55 × 1 + 12.01 × 16 +14.01 × 4 + 1.008 × 8) / 29 = 430.628因此，酞菁铜的相对原子质量约为430.628。
季戊四醇油酸酯膜厚测量及薄膜润滑研究
摘要 ： 运 用光 干 涉法相对光 强原理 ， 通 过 纳 米级 润 滑膜 厚度 测量 仪 测 量 了不 同温度 、 不 同栽荷 下
纳米 间隙 中环 境友好 润滑 剂季 戊四醇 油酸 酯的 油膜厚 度 。探 究 了膜厚 与速 度 、 载荷 、 温度 之 间的
关系， 观察了薄膜润滑现象。结果表明： 在对数坐标 系下， 膜厚与速度具有一定的线性 关系， 在速 度较 高 时， 线性 关 系更 强 ， 润 滑剂具 有 流体 效 应 。载荷 对 膜 厚 的影 响 远 小 于速 度 对 膜 厚 的影 响 ， 温度对膜厚的影响主要表现在温度越 高时， 润滑剂的黏度越低 ， 润滑剂的膜厚越薄。 关键词 ： 纳米级； 季戊四醇油酸酯； 薄膜润滑 中图分类号 ： Ｔ ＨＩ １ ７ ． ２ 文献标 志码 ： Ａ 文 章编号 ： ２ ０ ９ ５— ５ ０ ９ Ｘ（ ２ ０ １ ５ ） ０ ６— ０ ０ ７ ５— ０ ４ 纳米摩擦学作 为超精密仪器与微机 系统发展 的基 础 ， 近年来 受 到越来 越多 的关 注 。 自 Ｒ ｅ ｙ ｎ ｏ ｌ ｄ ｓ
２ ０ １ ５年 ６月 第４ ４卷 第 ６期
机械设计与制造工程
Ｍａ ｃ ｈ ｉ ｎ ｅ Ｄｅ ｓ ｉ ｇ ｎ ａ ｎ ｄ Ｍａ ｎ ｕ ｆ ａ ｃ ｔ ｕ ｒ ｉ ｎ ｇ Ｅｎ ｇ ｉ ｎ ｅ ｅ ｒ ｉ ｎ ｇ
Ｊ ｕ ｎ ． ２ ０ １ ５ Ｖｏ １ ． ４ ４ Ｎｏ ． ６
季戊 四醇 油酸酯 （ ｐ ｅ ｎ ｔ ａ ｅ ｒ ｙ ｔ ｈ ｒ ｉ ｔ ｏ ｌ ｏ ｌ ｅ ａ ｔ ｅ ） 作为 一种 环
流 体特 性 、 尺寸效 应 与其 膜 厚有 着密 切 的联 系 ， 因 此 对润 滑剂膜 厚进 行测量 ， 对 于揭示 润滑剂 流体规
氨基甲酸酯键的N取代
Circuit Simulation for the Dielectric Responses of the Composites of Copper Phthalocyanine Oligomers and Sulfonated Polyurethanes by Separating the Structural ElementsJUAN ZHANG,1DAN ZHU,1,2MASARU MATSUO 11Graduate School of Humanities and Sciences,Faculty of Human Life and Environment,Nara Women’s University,Nara 630-8263,Japan2Jiangsu Key Laboratory of Biofunctional Materials,College of Chemistry and Environment Science,Nanjing Normal University,Nanjing 210097,People’s Republic of ChinaReceived 14January 2009;revised 3March 2009;accepted 29March 2009DOI:10.1002/polb.21720Published online in Wiley InterScience ().ABSTRACT:The copper phthalocyanine (CuPc)oligomer with high dielectric constantwas synthesized by the solution method.The FT-IR and X-ray diffraction results revealed its chemical structure.The high dielectric constant of CuPc was proved to result from the free movement of charge carriers along the conjugated orbitals.The com-posites of CuPc and sulfonated polyurethane (PUI)were prepared and the contents of CuPc in the composites were varied from 10to 50wt %.The dielectric performance was greatly enhanced for the composite compared with that of average polymers.Different from the behaviors appeared in a common composite with conductive fillers,there is no percolation phenomenon observed in the CuPc/PUI composite,and the dielectric con-stants of CuPc/PUI composites decreased with the increase in the CuPc content,which is assumed to due to the strong electrostatic interactions between CuPc and PUI.Con-sidering the many-body interactions within the bulk sample and the contact effect between the bulk sample and the metallic electrode,an equivalent circuit was estab-lished to simulate the dielectric behaviors of the composites and computational curve fit-ting was done.The results were in good agreement,indicating that the dielectric responses of the composites come from both the extrinsic and the intrinsic contributions.The extrinsic was associated with the Maxwell-Wagner relaxation at the interface between the electrode and the bulk sample,and the intrinsic was associated with the huge dipoles provided by the mobile charges within the CuPc grains and the interaction among them in the bulk composites.A circuit model concerning the universal dielectric response was proposed in describing the intrinsic contribution,which quantitatively verified the strong interaction among the dipoles with the relaxation time,representingthe aggregated structure of CuPc when its content was high in the composites.VC 2009Wiley Periodicals,Inc.J Polym Sci Part B:Polym Phys 47:1146–1155,2009Keywords:composites;dielectric properties;equivalent circuit;phthalocyanines;simulationsINTRODUCTIONElectroactive polymers (EAPs)are of great inter-est for a wide range of exciting applications,suchas electromechanical and dielectric devices,Journal of Polymer Science:Part B:Polymer Physics,Vol.47,1146–1155(2009)VC 2009Wiley Periodicals,Inc.Correspondence to:D.Zhu (E-mail:zhudan1013@)or M.Matsuo (E-mail:m-matsuo@cc.nara-wu.ac.jp)1146because of their many attractive features,such as light weight,high mechanicalflexibility,and con-formability.1–4To satisfy the requirement for a high-performance electro-mechanical material,a high-dielectric constant is demanded to generate a high elastic energy under low appliedfield.5,6There are two major categories of EAPs depending on their mode of activation mecha-nism,that is,electronic and ionic categories,met-allophthalocyanines are assigned to the latter. Electricfield or Coulomb forces generally drive electronic EAPs,whereas the primary driver for ionic EAPs is the mobility or diffusion of ions. Since the discovery of their semiconductivity in 1948,7metallophthalocyanines have become one of the most interesting classes of organic semicon-ductors,because they are planar,highly aromatic, symmetrical,and thermally stable compounds.8 Metallophthalocyanine polymers can be synthe-sized through metal–metal bonding or covalent bonding between the phthalocyanine rings and the extent of conjugation and delocalization can be enhanced by polymerization,leading to their unusual electrical properties,which have attracted considerable attention in recent years.9 Copper-phthalocyanine(CuPc),which has a high dielectric constant at room temperature due to the nomadic polarization mechanism(delocalized electrons lead to the space charge phenomenon),10 is a promising material for dielectric application. Nevertheless,they are brittle and difficult to pro-cess,11leading to an appeal to an appropriate polymer matrix which is easy to obtain and be processed to prepare a composite with high dielec-tric constant.In2000,an organic polymeric composite based on CuPc oligomers and poly(vinylideneflu-oride-trifluoroethylene)[P(VDF-TrFE)]copolymer, which obtained huge dielectric constant,was found by H.Xu et al.12Whereas,in their research, the CuPc content has reached as high as55%for a composite with satisfactory dielectric properties. Hence,we dedicate tofind a better polymer ma-trix to fabricate a composite with high dielectric constant and low dielectric percolation threshold. The excellent dispersive condition of the CuPc is desired,and the ionized polyurethane(PUI), which is a material with polar group and possibly obtaining dipolar interactions and good miscibility with CuPc,provides the idea on solving this prob-lem.PUI molecules obtain high polarity and intrinsic dielectric constant than other polymers, which may be expected that the CuPc with car-boxylic acid functional groups will be easier and more complete to disperse in a matrix of PUI, obtaining a satisfactory polymer composite in physical properties.Therefore,the polymer com-posites of CuPc and PUI have been prepared and their dielectric properties have been characterized and analyzed from the view of micro-structures.The investigation on the dielectric properties provides a potential tool to illuminate the rela-tionship between the micro-structure and the macroscopic physical properties in a heteroge-neous system.The particular chemical structures of variousfillers can provide their different in-trinsic dielectric constant and affect their disper-sion in a polymer matrix,resulting in the differ-ent dielectric behaviors for the composites based on the same matrix and the differentfillers.Fur-thermore,the dielectric behaviors are strongly affected by the charge distribution and by the sta-tistical thermal motions of its polar groups.Espe-cially the study of relaxation process constitutes a powerful approach for obtaining information about the nature and types of molecular motions and the dispersion mode offillers that are affected by chemical compositions,molecular structure, morphology,etc.13In addition,the establishment of equivalent circuit,as well as the application of mathematical simulation,will reasonably and precisely elucidate the mechanism and origin of the dielectric behaviors of the heterogeneous composites.In our experiment,the CuPc oligomers were synthesized by the solution method and charac-terized by structural analysis to verify their highly planar-conjugated structure,which can provide a large delocalized orbital for electron delocalization,thus leading to a huge intrinsic dielectric constant.CuPc is selected as reinforce-mentfillers to fabricate its composites with PUI matrix.Though they obtain the polarization mechanism as other conjugated polymers,such as polyaniline and polyacene quinone radical poly-mers,they show the unique dielectric reinforce-ment effect and the mechanism on their compo-sites.The interfacial status in the CuPc/PUI com-posites is investigated,and the relationship between the microscopic hetero-structures and the physical properties is studied.An equivalent circuit has been established to explore the origin and the character of the dielectric behaviors of the composites.Thefitting results,which are in good agreement with the experimental data, reveal that there are two contributions to the dielectric properties,the intrinsic contribution based on the bulk sample and the extrinsicDIELECTRIC BEHAVIORS OF COPPER PHTHALOCYANINE OLIGOMERS1147Journal of Polymer Science:Part B:Polymer PhysicsDOI10.1002/polbcontribution from the contact effect between thesample and the electrode.EXPERIMENTALMaterialsPyromellitic dianhydride(PMA)was purchasedfrom Shanghai Chemical Reagent Co.,Pellethane50,a condensate of methylene diphenyl-diisocya-nate(MDI),poly(tetramethyl glycol)(PTMO,MW ¼1000),and1,4-butanediol(BD)with a molar ra-tio3.3/2.3/1.0,was purchased from Dow Chemi-cals.Sodium hydride and1,3-propane sultone(97%)were from Aldrich Chemical Company,theother reagents were commercial chemicals. SynthesisSynthesis of Copper-Phthalocyanine OligomerThe CuPc oligomer was synthesized by the solu-tion method.11Copper sulfate pentahydrate,PMA,urea,ammonium chloride and ammoniummolybdate calculated according to an appropriatemolar ratio were ground together and then placedin a three-neckedflask equipped with thermome-ter,condenser,and mechanical stirrer.Nitroben-zene was used as solvent,and the temperature of reaction solution was increased slowly from the room temperature and then maintained at180–185 C for12h.The as-synthesized solid materi-als wasfinely ground and washed with methanol to remove nitrobenzene completely.The powder was boiled in2M hydrochloric acid saturated with sodium chloride for several minutes andfiltered after cooling to room temperature.The product was neutralized by2M sodium hydroxide solution containing sodium chloride at90 C until the am-monia was completely gotten rid of.The precipi-tate was solved in2M hydrochloric acid and then centrifugated.After centrifugation,the product was dried at room temperature under vacuum. The synthesis route of CuPc oligomer is displayed in Scheme1.Synthesis of PUIThe synthesis route of PUI displays in Scheme2. Reaction was performed in a three-neckedflask equipped with condenser,drying tube,thermome-ter,magnetic stirrer,and nitrogen inlet.Theflask wasflamed outside while swept by nitrogenforScheme2.The synthesis route of the sulfonated PUI.1148ZHANG,ZHU,AND MATSUOJournal of Polymer Science:Part B:Polymer PhysicsDOI10.1002/polbanhydrous circumstance.Pellethane was dis-solved in anhydrous N,N-dimethyl-formamide (DMF),and then cooled to aboutÀ5 C with a salt-ice bath.Calculated amount of sodium hydride was added intoflask with vigorous stir-ring and reacted for1h until all of the sodium hydride had been consumed to obtain a greenish-yellow solution.Previously calculated propane sultone was added to the metallated polyurethane reaction mixture and continued to react at about 0 C for0.5h.The ice-salt bath was removed,and stirring was continued for another0.5h at room temperature,and then at50–60 C for another 1h.Followed by addition of toluene and removal of the excessive solvent,the reaction mixture was precipitated.Then the precipitates were washed by water and dried in vacuum for48h to obtain thefinal product.Preparation of CuPc/PUI Composite FilmsThe compositefilms of CuPc/PUI were prepared by solution casting.The solution of PUI in DMF was prepared,and the CuPc particles were dis-persed in the prepared PUI solution under ultra-sonic treating for2h.The compositefilms were obtained by a solution-casting method and dried in air at60 C for12h,followed by vacuum dry-ing at60 C for24h to completely evaporate the remnant solvent.The thicknesses of all thefilms were about100–200l m.CharacterizationAll samples were completely dried in a vacuum desiccant for24h at room temperature to get rid of the residual solvent before testing.The FT-IR spectrum was taken by the Fourier transform infrared spectrophotometer of Bruker Vector-22 FT-IR with the standard laser spectrum of 632.8nm.Samples were ground,mixed with po-tassium bromide,and compressed to pellets for testing.X-ray measurements were performed by a 12-kW rotating-anode X-ray generator(Shimadzu XD-3AX)with a point focusing,and the mono-chromatic Cu K a radiation(wavelength of0.1542 nm)was used.Samples tested were in powder form for CuPc,as well as in thefilm forms for PUI and the composites.Corrections of X-ray diffrac-tion intensity were made for air scattering,back-ground noise,polarization and absorption.The measurement for the content of the carbox-ylic radicals in CuPc was performed by the poten-tiometrictitration and back titration.The content of the copper in CuPc was measured by induc-tively coupled plasma atomic emission spectrome-try(ICP Jarrell-Ash J-A1100),the potassium salts solution of CuPc was prepared for testing.The dielectric spectra were recorded by the Im-pedance Analyzer(HP4194A/RT)from Agilent Co. Before the measurements,the samples were hot-pressed under80 C for10min,and then vacuum evaporated with Au electrode by an Ion Coater, Hitachi Eiko IB-3with the coating area of 4.9mm2.The measuring voltage was0.5V, and the frequency was in the range from100Hz to10MHz.RESULTS AND DISCUSSIONThe FT-IR spectrum of CuPc oligomer is shown in Figure1.The broad absorption band from3500to 3000cmÀ1is assigned to the O A H stretching vibration in carboxylic acid,then combining the strong C A O stretching vibration around 1710cmÀ1,the existence of carboxylic acid func-tional groups can be verified.A mild absorption band observed around920cmÀ1can be attributed to the metal-ligand vibration resulting from bond-ing between the copper atom and the nitrogen atoms in the four surrounding isoindole rings,14,15 which is the most important characteristic of met-allophthalocyanines.Another absorption band around810cmÀ1is also assigned to the metal-ligand vibration.16–18In addition,the absorption bands observed around1628,1580,1508,1456, and1096cmÀ1are assigned to phthalocyanine skeletal vibration,namely,the C A C or C A N stretching deformation in the large conjugated plane of CuPc.The absorption bands observed around1135and731cmÀ1correspond to the C A H in-plane bending deformation and the C A H out-of-plane bending deformation of the periph-eral benzene rings of CuPcmolecule, Figure1.The FT-IR spectrum of CuPc oligomer.DIELECTRIC BEHAVIORS OF COPPER PHTHALOCYANINE OLIGOMERS1149Journal of Polymer Science:Part B:Polymer PhysicsDOI10.1002/polbrespectively .19,20The results are coincident with the established values reported.21–24The content of carboxylic acid functional groups in CuPc obtained from the back titration is 24.48wt %,a little lower than the value of 25.40wt %from the theoretical calculation in which CuPc oligomer is regarded as a homopoly-mer of tetramers.Actually ,it is impossible to obtain the tetramers only from the synthetic pro-cess,and the dimers,trimers even multimers are also possibly synthesized at the same ly,the CuPc tetramer oligomer obtained is mixed with a small amount of various unimers of other degree of polymerization,resulting in the deviation from the theoretical value.Although the experimental result is very close to the theoretical value,it indicates that the CuPc oligomers obtained are mostly the tetramers.Moreover,the condensation reaction between few carboxylic acid groups possibly occurs,leading to a decrease of the content of the carboxylic acid functional groups.In contrast,the result of element analysis dem-onstrates that the copper content in CuPc oligomer is 6.08%,which is 81.94%of the theoreti-cal value of 7.42%.The deviation of the copper content from the theoretical value may be due to the partial demetallization of the copper from the phthalocyanine rings during the synthetic plex formation takes place between cop-per and chloride ions during HCl-washing and the copper salt is separated out leaving behind the metal-free phthalocyanine macrocyclic struc-ture,10,14resulting in the decrease of the copper content in CuPc.The dielectric constant of CuPcoligomer is significantly affected by its copper con-tent,the dielectric constant will decrease dramati-cally after treatment by HCl.10Figure 2shows the wide-angle X-ray diffraction intensity curves taken for CuPc oligomer.Based on the Bragg formula,for CuPc,the interplanar spacings corresponding to the diffraction peaks situated around 2h ¼9.1,10.3,26.9,and 28.3oare given as 9.72,8.59,3.31,and 3.15A˚,respec-tively ,which verify the crystalline structures of CuPc.25–28The strong reflection from the crystalplane with lattice space of 3.31A˚in distance,is a typical peak observed from the planar structures of carbon or graphite,29,30implying that CuPc obtains the highly conjugated structure based on the stacking of the graphite-like planes.In addi-tion,the strong diffraction peak around 28.3 is assigned to the second-order reflection (004),due to the existence of copper atom which can make the extra contribution to the scattering.31The results from X-ray indicate that Cu atoms and the four surrounding isoindole nitrogen atoms must all lie strictly in one plane,and Cu atoms are bound by covalent bond to the four isoindole nitro-gen atoms.31The whole CuPc molecule obtains the extended conjugated structure in a plane,which can provide huge p -associated orbital for electron delocalization.The existence of copper allows a further increase of the delocalization due to the bridge bonding.Thus a large polarization occurs,providing a high dielectric constant to the intrinsic CuPc.The frequency dependence of bulk dielectric constant and loss tangent of CuPc oligomers at room temperature are shown in Figure 3.The dielectric constant of CuPc can reach 7Â105at the frequency of 100Hz,and gradually dropstoFigure 3.The frequency dependence of the dielec-tric behavior of CuPc oligomer.1150ZHANG,ZHU,AND MATSUOJournal of Polymer Science:Part B:Polymer PhysicsDOI 10.1002/polb200at107Hz.The strong dielectric dispersion at low frequency is characteristic for a charge carrier system.The high dielectric constant in CuPc is due to a kind of colossal polarization,termed as ‘‘nomadic polarization’’by Pohl.32–34In a molecu-lar view,there are large amounts of charge car-riers in CuPc created intrinsically by naturally dissociation of the conjugated polymers.These mobile charges would move freely along extended regions provided by the associated p-orbital with near-zero resistance,and are ultimately limited by a boundary.Those conjugated planar or stacked‘‘huge molecular orbital(MO)poly-mers.’’32will form a collection of highly polarized polarons,35thereby exhibit high bulk permittivity under the external electricfield.In CuPc or its composite in this article,the most contributions to the dielectric constant at the low frequencies are those huge polarons,that is,the grains of CuPc.For CuPc,there are two reasons to cause the dielectric losses at the frequencies in our mea-surement range.One is the conduction loss from the movement of charges along the huge delocal-ized conjugated orbitals,which consumes the elec-trical energy.The other is the relaxation loss pro-duced under the process of polarization because of the hindrance to the movements of the polarons, including atoms,groups,and the whole molecules, resulting in the energy consumption in overcom-ing the internal viscous resistance during the ori-entation of the polarons.Both the dielectric constant and loss tangent of CuPc decrease with the increasing frequency, which is attributed to the fact that the polarons with large dipole moments provides an increase in the dielectric constant for CuPc.Meanwhile,it also provides an increase in the dielectric loss tan-gent due to the enhanced electronic conductance and the enhanced hindrance from the interaction between the polarons.Because both the nomadic polarization and the displacement of the electrons are proportional to the size of the polarons or the delocalized regions,the dielectric loss tangent increases with the increase of the dielectric con-stant,as shown in Figure3.On the basis of the above structural discussion, CuPc oligomers have high bulk dielectric constant and their polarization mechanism is the same as that of other conjugated organic semiconductors. Hence,to explore the dielectric reinforcement effect and mechanism of the PUI composites with CuPc,we fabricated the CuPc/PUI composites in which CuPc was used asfillers and thefiller con-tents varying from10to50%.The change of the dielectric constants of CuPc/PUI composites ver-sus the CuPc content is shown in Figure4.As observed from Figure4,the dielectric con-stants of CuPc/PUI composites decrease with increasing CuPc contents.It lies in the fact that CuPc obtains a lot of carboxylic groups,which can form a strong electrostatic force with the ionic groups in PUI,thus improving the dispersion of CuPc in PUI,so that the dielectric constant of the composite is high even in low content of CuPc. The lower the CuPc content is,the better disper-sion of CuPc in PUI is.With CuPc content increasing,the CuPc particles get close to each other and aggregate,which result in the enhance-ment of the interaction among the charges in the neighboring grains of CuPc.It is the long-range free moving of those charges that provide the huge permittivity of the bulk composite,so with the aggregation of CuPc and with the retarding of the charge mobility,the dielectric constants decrease.The aggregation of CuPc can be observed from X-ray diffraction spectra as shown in Figure5.PUI displays an amorphous phase and there is no detectable crystalline phase in PUI matrix due to the mergence of the hard segment and soft segment of polyurethane after ionization.While for CuPc/PUI composite with 25wt%CuPc content,there exists a diffraction peak around2h%27 which is due to CuPc crys-tal,indicating that CuPc has formed obvious aggregates when its content is25wt%.Figure6shows the frequency dependence of the dielectric behaviors for CuPc/PUI composites with various weight ratios of CuPc.A step-like increase in the dielectric constant towardlowerfrequencies is accompanied by a corresponding loss peak.Such Debye-like dipolar relaxation is mainly accounted for a large dielectric response at low frequency and the behavior can be explained by the contact effect.36It is of common sense that if the electron work function in a metal is different with that in a semiconductor,a thin layer which is made of mo-bile electron carriers will appear in the semicon-ductor close to the junction.This depletion layer acts as a high capacitance in parallel with a large resistor,connected in series to the bulk sample.For CuPc/PUI composite with 10wt %CuPc con-tent,the composites are semiconductive and the depletion regions may be formed at the interface between the composites and the metallic electro-des,leading to Maxwell-Wagner-type relaxations and giant dielectric constant at low frequency.In addition,as discussed above,CuPc particles get close to each other and aggregate with increasing the CuPc content,leading to the decrease of the concentration of space charges on the interface between the bulk sample and the electrodes.Meanwhile,the aggregation of CuPc particles makes it difficult for the huge dipoles formed or orientated to follow the change of the applied field,because of the enhanced hindrance to the orientation of the dipoles from the neighboring circumstance,that is,the interaction among the charges within the neighboring grains of CuPc.Therefore,with the CuPc content increasing,the relaxation peaks move towards low frequencies and the intensities of relaxation decrease.Besides the extrinsic contribution from the con-tact effect,the intrinsic dielectric response attrib-uted to the bulk sample also contributes to the total dielectric behaviors.Considering the many-body interactions within the huge dipoles of the CuPc grains,the intrinsic dielectric response is addressed by the sum of DC conductivity ,fre-quency dependent AC conductivity and the infi-nite dielectric constant e 1at high frequency.According to the theory of the universal dielectric response by Jonscher,37the intrinsic contribution of the bulk sample can be described by:e 0intrinsic ¼tan n p 2 r0e 0x n À1þe 1(1)where x ¼2p f is angular frequency,r 0x n is the universal dielectric response (UDR)used for fre-quency dependence AC conductivity ,e 0is vaccum permittivity,and n is an exponential factor with the value between 0and 1.Considering the extrinsic contribution from the contact region,which is Debye-likerelaxation,Figure 6.The frequency dependence of (a)the dielectric constant and (b)loss tangent for CuPc/PUI composites with different weightratios.Figure 5.The X-ray diffraction spectra of PUI and CuPc/PUI composite with 25wt %CuPc content.1152ZHANG,ZHU,AND MATSUOJournal of Polymer Science:Part B:Polymer PhysicsDOI 10.1002/polbthe totally dielectric response can be exhibited as follows 36,38:e 0¼tan n p 2 r 0e 0x n À1þe 1þe c Àe 11þx 2s 2(2)The first and second terms on the right hand sideof the equation represent the response of the bulk sample at low and high frequency,and the last term represents the contribution of contact region.e c is the dielectric constant of contact region and s is the relaxation time which is single without distribution.The equivalent circuit and the fitting results are shown in Figure 7,the solid curve well fits the experiment data by eq 2and the dot line demon-strates the intrinsic response of the bulk sample.The values of the corresponding parameters obtained from the fit are listed in Table 1.The relax-ation time s is a parameter describing how fast a micro-system will get to new equilibrium with the change of the external circumstance.In most occa-sions,s represents the extent that the dipole is impeded in the orientation,or the extent that the charges are constrained in movement,that is,the interaction of nearby circumstance to the dipole.With increasing the CuPc content,the aggregation of CuPc makes the grains get close to each other,it makes the formation of the huge dipole more and more difficult in keeping up with the change of the applied field as for the enhanced interactions from the nearby charges in the neighboring dipoles,lead-ing to the increase in the relaxationtime.CONCLUSIONSThe CuPc oligomer with high bulk dielectric con-stant was synthesized by the solution method. The FT-IR and X-ray diffraction spectra were measured to characterize the chemical structure of CuPc,and it demonstrated that the origin of the high dielectric constant as well as its polariza-tion mechanism was the free movement of charge carriers along the conjugated orbitals.The CuPc/ PUI composites were prepared with CuPc con-tents varied from10to50%,demonstrating a characteristic reinforcement on the dielectric properties of the polymer.Different from the obvious percolation behavior observed for the composites of other condcutivefillers,the dielec-tric constants of CuPc/PUI composites decreased with the increase of the CuPc content,due to the fact that the strong electrostatic interactions between the carboxylic groups in CuPc and the ionic groups in PUI improves the dispersion of CuPc in the low content of CuPc,whereas the aggregation of CuPc at high content results in the decrease of the dielectric constant.Considering the many-body interactions within the bulk sample,as well as the contact effect between the bulk sample and the metallic elec-trode,an equivalent circuit was established to simulate the dielectric behaviors of the compo-sites.Thefitting results were in good agreement with the experimental data and indicated that the dielectric responses of the composites did come from two contributions.One was the extrinsic associated with the Maxwell-Wagner-type relaxa-tion at the interface between the electrode and the bulk sample,and the other,the intrinsic one was from the highly polarized CuPc grains that acted as huge dipoles in the composite.In describ-ing the intrinsic contribution,we used a model containing a universal dielectric response,repre-senting the unique aggregated structure of CuPc in the composites.It was verified by the relaxa-tion time that the interactions among CuPc dipoles increase with the increasing contents of CuPc.REFERENCES AND NOTES1.Zhang,Q.M.;Li,H.F.;Poh,M.;Xia,F.;Cheng,Z.Y.;Xu,H.S.;Huang, C.Nature2002,419, 284–287.2.Bar-Cohen,Y.J Spacer Rockets2002,39,822–827.3.Herbert,J.M.Ferroelectric Transducers and Sen-sors;Gordon and Breach Science Publishers:New York,1982.4.Dias,C.J.;Das-Gupta,D.K.IEEE Trans DielectrElectr Insul1996,5,706–734.5.Zhang,Q.M.;Bharti,V.;Zhao,X.Science1998,280,2101–2104.6.Bai,Y.;Cheng,Z.Y.;Bharti,V.;Xu,H.;Zhang,Q.M.Appl Phys Lett2000,76,3804–3806.7.Eley,D.D.Nature1948,162,8198.Moser,F.A.;Thomas,A.L.Phthalocyanine Com-pounds;Reinhold Publishing Corp.:New York, 1963.9.Meier,H.;Albrecht,W.;Zimmerhackl, E.PolymBull1985,13,43–50.10.Nalwa,H.S.;Dalton,L.R.;Vasudevan,P.EurPolym J1985,21,943–947.11.Achar, B.N.;Fohlem,G.M.;Parker,J. A.JPolym Sci Part A:Polym Chem1982,20,1785–1790.12.Xu,H.S.;Bai,Y.;Bharti,V.;Cheng,Z.Y.J ApplPolym Sci2001,82,70–75.13.Rellick,G.S.;Runt,J.J Polym Sci Part B:PolymPhys1986,24,279–302.14.Nalwa,H.S.;Vasudevan,P.J Mater Sci Lett1983,2,77–79.15.Kobayashi,T.;Kurokawa,F.;Uyeda,N.;Suito,E.Spectrochim Acta A Mol Biomol Spectrosc1970, 26,1305–1311.16.Janczak,J.Pol J Chem1998,72,1871–1878.Table1.The Corresponding Parameters from the Simulation ResultsCuPcContent(wt%)n r0(S/m)e1e c s(s)100.3738 2.958Â10À613 2.587Â1047Â10À5200.3609 2.879Â10À615 2.251Â1049Â10À5300.3321 2.504Â10À617 2.009Â104 3.5Â10À4400.3306 2.010Â10À618 1.905Â104 4.1Â10À4500.316 1.050Â10À624 1.785Â104 1.3Â10À31154ZHANG,ZHU,AND MATSUOJournal of Polymer Science:Part B:Polymer PhysicsDOI10.1002/polb。
弹性模量测定的实验研究
式中的比例系数 E 称为该材料的弹性模量． 钢丝的 2 d 为钢丝的直径． 因此 截面积为 A = πd / 4 ， 4 FL FL = ， 2 AΔ L πd Δ L 式中 F = mg（ 所挂重物的重力） ， 即 E =
*
（ 2）
图1
实验装置示意图
Fig． 1 The instrument of experiment
（ 上接第 262 页） ［ 24］ WANG H， YIP C T， CHEUNG K Y， et al． Titania － nanotube － array photovoltaic cells［ J］ ． Appl Phys Lett， 2006 ， 89 ： 023 508． ［ 25］ WANG M L， HUANG C G， CAO Y G， et al． The effects of shell characteristics on the current － voltage behaviors of dye － sensitized solar cells based on ZnO / TiO2 core / J］ ． Appl Phys Lett， 2009 ， 94 ： 263 506． shell arrays［ ［ 26］ WANG H， OEY C C， DJURISIC A B， et al． Titania bicontinuous network structures for solar cell applications ［ J］ ． Appl Phys Lett， 2005 ， 87 ： 023 507． ［ 27］ OEY C C， DJURISIC A B， WANG H， et al． Polymer － TiO2 solar cells： TiO2 interconnected network for improved cell performance［ J］ ． Nanotechnology， 2006 ， 17 ： 706． ［ 28］ WATKINS P K， WALKER A B， VERSCHOOR G L B． Dynamical monte carlo modelling of organic solar cells： the dependence of internal quantum efficiency on morphology［ J］ ． Nano Lett， 2005 ， 5 （ 9 ） ： 1 8141 818． ［ 29］ MARSH R A， GROVES C， GREENHAM N C． A microscopic model for the behavior of nanostructured organic ． J Appl Phys， 2007 ， 101 ： photovoltaic devices ［J］ 083 509． ［ 30］ YANG F ， FORREST S R． Photocurrent generation in nanostructured organic solar cells［ J］ ． ACS Nano， 2008 ， 2 （ 5 ） ： 1 0221 032．