Molecular assembly of artificial photosynthetic antenna core complex on an amino-terminated ITO electrode

Bacterial photosynthetic membrane proteins, light-harvesting antenna complex (LH1), reaction center (RC), and their combined ‘core’ complex (LH1–RC) are functional elements in the primary photosynthetic events, i.e., capturing and transferring light energy and subsequent charge separation. These photosynthetic units (PSUs) isolated from Rhodospirillum rubrum (Rs. rubrum) were assembled onto an ITO electrode modified with 3-aminopropyltriethoxysilane (APS–ITO). The near IR absorption spectra of PSUs on the assembled electrodes were identical to those of solutions, indicating that the LH1 and LH1–RC core complexes were native on the electrode. Photocurrent response of PSUs on the electrode was examined upon illumination of the LH1 complex at 880 nm. The LH1–RC and a mixed assembly of LH1 and RC exhibited photocurrent response, but not LH1 only, consistent with the function of these PSUs, capturing light energy and transferring electron. This result provides useful methodology for building an artificial fabrication of PSUs on the electrode.     

Confinement of polyaniline chains in capillary layers: an ordering effect of the uniaxially aligned surfaces

An ordering effect of uniaxially aligned poly(tetrafluoroethylene) (PTFE) substrates prepared by rubbing on polyaniline (PANI) molecules at the interfaces of PTFE/PANI film and PTFE/PANI solution has been investigated using electronic absorption spectroscopy. It was observed slight dichroism in electronic spectra from only very thin (thickness approximately 20 nm and less) PANI films as well as from PANI solutions of capillary thickness (10 to 30 microm) confined by oriented PTFE surfaces. The ordering effect is discussed in terms of a hydrodynamic flow arising upon sample formation and steric factors at the PTFE surface, which cause uniaxial deformation of the polymer coil on the rubbed PTFE surface.     

Synthesis and electroluminescent properties of naphthalimide derivatives

Naphthalimide derivatives, N-ethyl-4-acetylamino-l ,8-naphthalimide (EAAN) and polymer with N-propyl-4-acetylamino-l,8-naphthalimide (PAAN) side-chain (P-PAAN) were successfully synthesized. Electroluminescent devices of ITO/PVK(120nm)/EAAN(50nm)/Al(150nm) (Ⅰ) and ITO/PVK P-PAAN( 10:1) (50nm)/Al(150nm) (Ⅱ) constructed with EAAN and P-PAAN as the emitting layer were investigated, whereas the single-layer devices of ITO/EAAN or P-PAAN(50nm)/Al(l50nm) (Ⅲ) were not observed to have any e-mission light. The emission results revealed that the exciton recombination formed by positive and negative charge carriers injected from electrodes of devices Ⅰ and Ⅱ was much more balanced than that of devices Ⅲ, which implied that naphthalimide derivatives are a new type of electron-transporting materials with high performance. The electron-transporting properties of naphthalimide derivatives were also elucidated by investigation of the electroluminescent behaviors from both devices of ITO/PPV (80nm)/Al and ITO/P     

Rollable ferroelectric liquid crystal devices monostabilized with molecularly aligned polymer walls and networks

This paper describes a flexible monostabilized ferroelectric liquid crystal (FLC) device using molecularly aligned polymer walls and networks, which are sequentially formed with a two-step photopolymerization-induced phase separation. When ultraviolet (UV) light was irradiated through a photomask onto a heated nematic phase solution of FLC and monomer, monomer molecules that had flowed into the irradiated areas were photopolymerized, and polymer walls aligned along the rubbing direction of the polyimide alignment layers on plastic film substrates were formed. After uniform UV irradiation without a photomask, polymer networks aligned along the rubbing direction were formed in the FLC. The FLC molecules were monostabilized in the rubbing direction by the strong anchoring of the polymer networks. The device, which was sandwiched between crossed polarizers, exhibited a monostable electro-optic characteristic with a high contrast ratio of over 100:1 and a response time of less than 1 ms. The FLC device exhibited spatially uniform operation even when it was rolled up with a radius of curvature of 1.5 cm.     

Synthesis,characterization, and electroluminescence of novel copolyfluorenes and their applications in white light emission

New copolyfluorenes (PC8OF0–PC8OF50) comprised of 9,9‐dioctylfluorene and jacketed units 2,5‐bis[(5‐octyloxy‐phenyl)‐1,3,4‐ oxadiazole]‐1‐(3,5‐dibromophenyl)‐benzene (35C8) were synthesized by palladium‐catalyzed Suzuki coupling reaction. They were characterized by molecular weight determination, ¹H NMR, elemental analysis, DSC, TGA, absorption and emission spectroscopy, and cyclic voltammetry (CV). These copolymers were readily soluble in common organic solvents and exhibited high glass transition temperature and thermal stability.The copolymer films showed absorption peaks from 381 nm to 351 nm, and PL peaks from 432 nm to 421 nm with a blue shift originated from 35C8 units. Both the HOMO energy levels and LUMO levels changed little as the content of 35C8 units increased (?5.59 eV to ?5.48 eV and ?2.60 eV to ?2.49 eV). Electroluminescent devices: ITO/PEDOT:PSS[poly(ethylenedioxythiophene):polystyrenesulfonate]/polymer/Ca (25 nm)/Ag(80 nm) (a), ITO/PEDOT:PSS/polymer/TPBI [1,3,5‐ tris(N‐phenylbenzimidazol‐2‐yl)benzene](15 nm)/Mg:Ag(10:1, wt)/Ag (b), and ITO/ PEDOT:PSS/PVK[Poly(N‐vinylcarbazole)]/polymer/TPBI(15 nm)/Ca(25 nm)/Ag(80 nm) (c) were fabricated to investigate the influence of jacketed contents and device architectures on emission characteristics. The maximum brightness and current efficiency of the PC8OF25 device (5097.8 cd/m² and 0.484 cd/A) surpassed those of the PC8OF0 device (3122.8 cd/m² and 0.416 cd/A). The EL emissions of PC8OF0 – PC8OF50 were pure blue and low‐energy excimer emission bands were successfully suppressed, indicating that these copolymers could be good candidates for blue light‐emitting materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4555–4565, 2009     

Thermally enhanced photoinduced molecular reorientation in a photo-crosslinkable polymer liquid crystal based on polarization triplet energy transfer

Polarization-selective photosensitization and molecular reorientation in photo-crosslinkable polymer liquid crystal (PMCB6M) films, based on polarization-selective triplet energy transfer using LP-365 nm and LP-405 nm light with different photosensitizers, are described. A dramatic improvement in the photoreactivity of the film was observed with a small amount of photosensitizer; and a high degree of molecular reorientation and slantwise reorientation were generated when annealing the resulting films at elevated temperatures. The efficiency of reorientation depended on the photoinduced dichroism of the film.     

Tin oxide coating on polytetrafluoroethylene films in aqueous solutions

Polytetrafluoroethylene (PTFE) films were successfully coated with tin oxide in aqueous solutions. Tin oxide was crystallized in the solution and formed nanocrystal coatings on the polymer films. The coatings consisted of SnO₂ and SnO crystals. They were assemblies of tin oxide nanosheet of about 10 to 50 nm in size and about 5 nm in thickness. The nanocrystal films can be exfoliated from the PTFE substrates. Tin oxide nanocrystal films had a rough liquid surface and a dense substrate‐side surface. Transparency of PTFE films coated with tin oxide was same as that of bare PTFE films in the range from 400 to 800 nm. The PTFE films coated with tin oxide nanocrystals can be pasted on desired substrates. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis,Physical Properties,and Self‐Assembly of A Novel Asymmetric Aroyleneimidazophenazine

The synthesis, physical properties, and self‐assembly of a novel asymmetric aroyleneimidazophenazine (IZ1) is reported. The as‐prepared IZ1 nanowires display an obvious red fluorescence. A heterojunction light‐emitting diode (LED) device with the structure ITO/IZ1 nanowires/p‐SiC/Al (10 nm)/Ti (80 nm)/Al (380 nm)/ITO was fabricated, and electroluminescence emission with two peaks at about 412 nm and 613 nm was detected with a forward bias ranging from 5 to 10 V.     

Synthesis,photophysics, and electroluminescent performance of stable blue‐light‐emitting copoly(9,9‐diarylfluorene)s

A series of fluorene derivatives containing nonsymmetric and bulky aromatic groups at C‐9 position were synthesized and used for the preparation of blue‐light‐emitting copolyfluorenes ( P1 – P4 ) by the Suzuki coupling polycondensation. The copolymers were characterized by molecular weight determination, elemental analysis, differential scanning calorimeter, thermogravimetric analysis, absorption and emission spectroscopy, cyclic voltammetry, and differential pulse voltammetry. Their decomposition temperatures and glass transition temperatures are 423–441 °C and >120 °C, respectively. In film state, the copolyfluorenes exhibit blue photoluminescence at 425–450 nm, which remains almost unchanged after annealing at 200 °C in air for 60 min. Polymer light‐emitting diodes [ITO/PEDOT:PSS/ P1 – P4 /Ca(50 nm)/Al(100 nm)] show stable blue‐light emission under device operation with the CIE co‐ordinates being between (0.16, 0.07) and (0.17, 0.09). The light‐emitting diodes devices from P1 and P3 containing electron‐deficient oxadiazole units display enhanced performance, with the maximum brightness and maximum current efficiency being (4510 cd/m² and 2.40 cd/A) and (2930 cd/m², 1.19 cd/A), respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2821–2834, 2009     

基于纳米CdS对尿酸的光催化氧化和铜(Ⅱ)配合物对氧的电催化还原的燃料电池性能

以纳米硫化镉薄膜修饰的铟锡氧化物电极(CdS/ITO)作光阳极, 铜(Ⅱ)配合物[Cu(phen)(L-Trp)·(H₂O)]⁺(phen=1,10-菲啰啉, L-Trp=L-色氨酸)修饰单壁碳纳米管(SWCNTs)电极作阴极, 构建了光催化尿酸(UA)燃料电池, 并研究了其性能及热处理温度的影响. 结果表明, 在40 ℃以下获得的纳米CdS修饰电极在320~550 nm波长区间显现明显的吸收和光伏响应, 在可见光辐射下能光催化氧化UA; 较高温度的热处理(200~300 ℃)却降低了纳米CdS对UA的光催化氧化活性. [Cu(phen)(L-Trp)(H₂O)]⁺/SWCNTs电极在-0.131 V电位下呈现一对准可逆的氧化还原峰, 并能电催化还原O₂和H₂O₂. 此外, 基于UA在CdS/ITO电极上的光催化氧化及O₂在[Cu(phen)(L-Trp)(H₂O)]⁺/SWCNTs电极上的电催化还原, 组装了UA(0.2 mmol/L)燃料电池, 其在可见光照射(0.18 mW/cm²)下产生0.52 V开路电压, 13.08 μA/cm²短路光电流, 在0.41 V下呈现的最大功率密度为4.10 μW/cm².     

SYNTHESIS AND CHARACTERIZATION OF PHENOTHIAZINE-BASED PPV-TYPE COPOLYMERS CONTAINING FLUORENE AND THIOPHENE MOIETIES

Copolymers of fluorene-co-phenothiazine (P1) and thiophene-co-phenothiazine (P2) were prepared respectively by Wittig reaction. The synthesis, photo-physical and electroluminescent properties of the resulting polymers were analyzed by FT-IR, GPC, 1H-NMR, UV-Vis, Photoluminescence (PL), Electroluminescence (EL) and Cyclic Voltammetry (CV). Their single layer devices with configuration of ITO/polymers/Ca/Al were studied. GPC results revealed the weight-average molecular weight (Mw) was 3.0×103 and 5.4×103, respectively. The device with a single layer structure of ITO/P1/Ca/Al emits green light with the maximum peak at 552nm. However,the device with a single layer structure of ITO/P2/Ca/Al emit red light with the maximum peak at 616nm.     

Synthesis of copolyfluorenes containing green chromophores based on triphenylamine unit and their application in light‐emitting diodes

Two series of new copolyfluorenes ( PFTP, PFTT ) were prepared by the Suzuki coupling reaction from two green‐emitting dibromo monomers (TP‐Br, TT‐Br) based on triphenylamine unit to be applied in white light electroluminescent devices. They were characterized by molecular weight determination, elemental analysis, DSC, TGA, absorption and photoluminescence spectra, and cyclic voltammetry. The estimated actual contents of the TP and TT chromophores were lower than 7.8 mol % and 1.9 mol % for PFTP and PFTT , respectively. In film state both copolyfluorenes showed photoluminescence at 400–470 and 470–600 nm originated from fluorene segments and the chromophores, respectively, due to incomplete energy transfer. Light‐emitting diodes with a structure of ITO/PEDOT:PSS/copolymer/Ca(50 nm)/Al(100 nm) showed major emission at 493–525 nm, plus minor emission at 400–470 nm when chromophore contents were low. The maximum brightness and maximum current efficiency of PFTP2 device were 8370 cd/m² and 1.47 cd/A, whereas those of PFTT1 device were 9440 cd/m² and 1.77 cd/A, respectively. Tri‐wavelength white‐light emission was realized through blending PFTT1 with poly(9,9‐dihexylfluorene) and a red‐emitting iridium complex, in which the maximum brightness and CIE coordinates were 6880 cd/m² and (0.31, 0.33), respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1553–1566, 2009     

Rup_2P表面敏化TiO_2基复合薄膜光致界面电荷转移

采用离子束溅射技术制备出TiO2/ITO、Zn2+掺杂的TiO2(TiO2-Zn)/ITO和TiO2/ZnO/ITO薄膜,采用表面敏化技术和旋转涂膜法,制备出(1,10-邻菲咯啉)2-2-(2-吡啶基)苯咪唑钌混配配合物(Rup2P)表面敏化的TiO2基复合薄膜Rup2P/TiO2/ITO、Rup2P/TiO2-Zn/ITO和Rup2P/TiO2/ZnO/ITO.表面光电压谱(SPS)结果发现:敏化后的TiO2基薄膜在可见区(400-600nm)产生SPS响应;TiO2基薄膜的能带结构不同,其在400-600nm和350nm处的SPS响应的峰高比不同.利用电场诱导表面光电压谱(EFISPS),测定TiO2基薄膜和表面敏化TiO2基复合薄膜各种物理参数,并确定其能带结构.分析可知,表面敏化TiO2基复合薄膜在400-600nm的SPS响应峰主要源于Rup2P分子的中心离子Ru4d能级到配体1,10-邻菲咯啉π*1和2-(2-吡啶基)苯咪唑π*2能级的跃迁;TiO2中Zn2+掺杂能级有利于Ru4d能级到配体π*1和π*2跃迁的光生电子向TiO2-Zn导带的注入;TiO2/ZnO异质结构有利于光生电子向ITO表面的转移,从而导致可见光(400-600nm)SPS响应增强以及光电转换效率的提高.     

超薄层在白色有机电致发光器件中的应用

以DCJTB为掺杂剂, 以BCP为空穴阻挡层, 研究了两种结构的有机电致发光器件ITO/NPB/BCP/Alq3:DCJTB/Alq3/Al(结构A)和ITO/NPB/BCP/Alq3/Alq3:DCJTB/Alq3/Al(结构B)的电致发光光谱. 实验结果显示, 在结构A器件的电致发光光谱中, 绿光的相对发光强度较弱,增加Alq3层的厚度对绿光的相对发光强度的影响也很小; 而在结构B器件的电致发光光谱中, BCP层与掺杂层(Alq3:DCJTB)之间的Alq3薄层对绿光的相对发光强度影响显著, 用很薄的Alq3层就可以得到强的绿光发射. 进一步改变器件结构, 利用有机超薄层就可以得到稳定的白光器件ITO/NPB(50 nm)/BCP(3 nm)/Alq3(3 nm)/Alq3:DCJTB(1%(w))(5 nm)/Alq3(7 nm)/Al. 随着电压的增加(14-18 V), 该器件的色坐标基本保持在(0.33, 0.37)处不动; 在432 mA·cm-2的电流密度下, 该器件的发光亮度可达11521 cd·m-2.     

Photo-dimerization of a chalcone-based side chain polymer for the alignment of ferroelectric liquid crystals

The alignment and optical properties of ferroelectric liquid crystal cells, having alignment films of a chalcone-based side chain polymer treated by linearly polarized UV irradiation were investigated. The long absorption band of the UV/Vis spectra gradually decreased and the FTIR spectra shifted as the irradiation times increased, indicating that cyclo-addition and isomerization reactions of the chalcone-based side chains occurred. UV dichroism demonstrated anisotropic changes in the alignment films, with a maximum at low exposure energy (0.5 J cm^-2). Liquid crystal molecules were aligned perpendicular to the polarization direction of the linearly polarized UV radiation. The azimuthal anchoring energy of liquid crystal E7 on a chalcone-based side chain polymer surface increased with exposure energy. Well aligned defect-free cells and high contrast ratio were achieved with irradiation of longer than 5 min; the geometric conditions for a stable C2 structure may be satisfied at low temperature with slowly cooling.     

Anchoring properties of a nematic liquid crystal on anisotropic hydroxypropylcellulose films

Thin solid films of hydroxypropylcellulose (∼15-30 µm) prepared from liquid crystalline and isotropic aqueous solutions are used as liquid crystal alignment layers. Using the standard nematic liquid crystal 5CB we measured the interface properties of these solid films as a function of the polymer concentration in the aqueous precursor solution, expressed in terms of zenithal and azimuthal anchoring orientations and extrapolation lengths. The hydroxypropylcellulose thin films are found to induce a planar orientation of 5CB independently of the polymer concentration, with the alignment along the polymer backbone. The zenithal anchoring strength is found to be strong and essentially independent of the temperature far from the nematic-isotropic transition, with an extrapolation length ξ_θ≈50 nm. The zenithal anchoring becomes weaker near the nematic-isotropic transition, as expected. The azimuthal anchoring strength is found to be intermediately weak and strongly dependent on the polymer concentration, with an extrapolation length varying from ξ_θ≈250 nm to ξ_ϕ≈500 nm. These films are particularly interesting since their surface topography and morphology may be tuned by varying a few parameters in the film preparation process, such as the polymer concentration in the aqueous solution.     

含二唑的聚(间亚苯乙烯)电致发光二极管

含二唑的聚（间亚苯乙烯）电致发光二极管印寿根李晨曦黄文强何炳林（南开大学吸附分离功能高分子材料国家重点实验室高分子化学研究所天津３０００７１）彭俊彪刘星元李文连（中国科学院长春物理研究所长春１３００２１）关键词电致发光，光电子能谱，聚（间亚苯...     

酞菁锂薄膜的光电流极性研究

利用旋转涂膜法和真空镀膜法制备了以酞菁锂薄膜为工作层的有机光电器件, 结构为氧化铟锡/聚二氧乙基噻吩: 聚对苯乙烯磺酸/酞菁锂/聚偏氟乙稀/铝(ITO/PEDOT: PSS/LiPc/PVDF/Al). 在可见光和近红外脉冲激光照射下, 研究了器件的光电流极性. 在532 nm脉冲激光照射下, 器件的外电路光电流方向从ITO流向铝; 但在1064 nm脉冲激光照射下, 其外电路光电流极性发生反向, 即从铝流向ITO. 酞菁锂薄膜的吸收光谱和X射线衍射谱图显示, 其对可见和近红外光有非常广的吸收, 且为x晶型. 酞菁锂自由基的双极性特性可随入射光波长的变化而改变.     

有机钌螯合物/TiO_2杂化膜修饰电极上Pt纳米团簇的光电流增强效应

利用LB膜技术可控制备了纳米单层和多层的二氧化钛-有机钌螯合物杂化膜,并研究了上述无机-有机杂化膜修饰电极在Pt纳米团簇敏化后的光电流增强效应.实验结果表明:(1)纳米单层TiO2/[Ru(phen)2(dC18bpy)]2+(简称为TiO2-Ru)杂化膜的平均厚度为(3.6±0.5)nm;(2)在光照条件下TiO2-Ru杂化膜能有效催化还原[Pt(NH3)6]4+形成粒径位于20～160nm之间的Pt纳米团簇;(3)Pt纳米团簇的引入消除了金属钌螯合物中配体对电子传递的阻碍作用,改变了电子传递途径,从而有效减少了电子空穴对的复合,提高了Pt纳米团簇敏化的n层杂化膜修饰电极(ITO/(TiO2-Ru)n/Pt)在支持电解质中的光电流.与纳米单层TiO2-Ru杂化膜修饰的ITO电极(ITO/TiO2-Ru)相比,当工作电压为900mV时,ITO/TiO2-Ru/Pt在0.1mol·L-1的NaClO4电解质溶液中和光照(λ360nm)条件下,单位面积的光电流提高了约5倍;(4)ITO/(TiO2-Ru)n/Pt电极光电流的大小与杂化膜的层数密切相关,当TiO2-Ru杂化膜的层数从一层、二层增加到四层时,光电流呈现先升高后下降行为,这表明ITO/(TiO2-Ru)n/Pt电极的电子传递过程直接通过非电活性的二氧化钛纳米单层进行.     

Bright White Organic Light-emitting Device Based on 1,2,3,4,5,6-Hexakis（9,9-diethyl-9H-fluoren-2-yl）benzene

Organic light-emitting devices(OLEDs) with the structure of indium-tin-oxide(ITO)/N,N'-bis-(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine(NPB)/2,9-dimenthyl-4,7-diphenyl-1,10-phenanthroline(BCP)/tris(8-hydroxyquinoline)aluminum(Alq3)/Mg:Ag or that of ITO/NPB/1,2,3,4,5,6-hexakis(9,9-diethyl-9H-fluoren-2-yl)benzene(HKEthFLYPh)/Alq3/Mg:Ag were studied.White light emission was achieved with the two devices when the thicknesses of BCP and HKEthFLYPh were 1.5 nm(device B) and 5 nm(device II),respectively...