酞菁铜阴阳离子分子沉积(MD)膜润湿性研究

酞菁及其衍生物等大环平面分子具有良好的化学稳定性和优异的光电性能 [1,2 ] ,利用酞菁进行模拟生物光合作用的研究 ,以期实现新的光电转换技术 ,近年来已引起人们的广泛重视[3～ 5] .分子沉积(MD)超薄膜[6～ 8] 是以阴阳离子间静电相互作用为成膜驱动力 ,通过相反离子体系的单层交替沉积制备的层状有序超薄膜 .分子沉积技术广泛应用在固体表面改性和生物传感技术等领域 ,沉积分子的物理化学性质是影响其应用的主要因素 .本文通过紫外 -可见光谱跟踪了酞菁铜阴阳离子 MD膜的均匀沉积 ,并根据酞菁 MD膜表面接触角的变化 ,探讨分子端基的…     

Preparation and characterization of 5,10,15,20‐tetraphenylporphyrin Langmuir films for gas chemsensor applications

In this work is reported the preparation and characterization of 5,10,15,20‐tetraphenylporphyrin (H₂TPP) films at the water‐air interfaces. The surface pressure‐area isotherms (π‐A) and UV‐Vis spectroscopy were used to investigate the effect of the spreading methods and parameters on the porphyrin monolayer formation. Also, Langmuir‐Blodgett (LB) and Langmuir‐Schaefer (LS) films were deposited onto glass substrates in order to study the conformation changes in porphyrin molecular packing. Quartz crystal microbalance (QCM) was utilized as the active solid substrate for the development of the NO₂ gas sensor based on the H₂TPP molecular films. The results of π‐A curves have clearly shown the significant contribution of the preparation methods and processing parameters on the conformation of porphyrin molecular films. The UV‐Vis spectroscopy results using polarized absorption dichroism have indicated different molecular packing for porphyrin films deposited by LB and LS methods, with relative tilted angles of 50° ± 5° and 35° ± 5°, respectively. Moreover, the QCM response has given strong evidence that H₂TPP porphyrin molecular films have performed as NO₂ chemsensor. Copyright © 2011 John Wiley & Sons, Ltd.     

5,10,15,20-四-(4-N,N,N-二甲基十六烷基氨基苯基)卟啉LB膜结构的研究

研究了两亲性卟啉5,10,15,20-四-(4-N,N,N-二甲基十六烷基氨基苯基)卟啉(TDMC₁₆PP)在气/液界面上的成膜性能,制备了其多层LB膜。用UV-Vis吸收光谱、荧光光谱、偏振UV-Vis吸收光谱和小角X射线衍射对LB膜进行了测试表征。结果表明:两亲性卟啉TDMC₁₆PP具有良好的成膜性能,其LB膜性质稳定,有较好的结构均匀性和周期性。在LB膜内,脂肪链并不是直立的,卟啉大环平面与基片平面成42.5°排列。     

四(2,4-二特戊基苯氧基)酞菁铜LB膜的制备及结构表征

酞菁类化合物具有良好的热稳定性和化学稳定性,已被广泛应用于光敏,气敏,及分子电子器件等领域。用LB方法对酞菁类化合物进行分子组装,用光谱等手段对其膜结构进行表征已引起人们的重视。本文作者之一合成了具有良好LB成膜特性的四(2,4-二特戊基苯     

Multi-electron transfer in composite phthalocyanine thin films: structure and electrochromic properties

Both sequentially deposited double-layered and codeposited composite thin films were prepared by using two kinds of phthalocyanines. The structure and the electrochromic property of these thin films were compared with those of simple phthalocyanine films. The structures of the films were analyzed by scanning electron microscopy (SEM), X-ray diffrction (XRD) and electron spin resonance (ESR) spectra. From the viewpoint of morphology and crystallinity, codeposited thin films have the same structure as the simple one, having sharp peaks at ca. 2θ=7.0° in the XRD pattern and narrow crystal grains in SEM photographs. ESR measurements have revealed that phthalocyanine molecules disperse very well in the codeposited thin films in a molecular level in comparison with the physical mixture of phthalocyanine powders. This high dispersibility of the molecules in the codeposited thin films can play a role to improve the reversibility in the electrochromism. Thus, the reversibility of the phthalocyanine, which shows irreversible electrochromism in the simple film form, can be improved by the codeposition with another phthalocyanine with reversible electrochromism. In contrast, sequentially deposted double-layered thin film gives completely different results. The electrochromism of the double-layered film depends on the property of the simple phthalocyanine thin film which is in contact with the substrate.     

表面增强拉曼光谱研究基于轴向配位键结合的金属卟啉自组装膜

选择一种金属卟啉有机物(5-对-烷氧基苯基-10,15,20-三苯基卟啉羟基稀土化合物, HoOH)和4,4'-联吡啶(44BPY)作为自组装膜的基本构筑单元, 利用金属配位作用, 成功地将HoOH单分子膜组装到44BPY修饰的银表面. 采用紫外-可见吸收光谱、表面增强拉曼光谱研究了金属卟啉自组装膜的形成并且探索其结构和取向的变化. 结果表明, 底层的44BPY通过4位的N原子垂直吸附到银表面, 另一端的吡啶环上的N原子与HoOH的金属中心配位形成化学键. 从而在44BPY长轴向方向上将HoOH连接到44BPY自组装膜上, 并形成了新的交替膜. 之后, 底层的44BPY取向发生变化, 更向基底倾斜, 而上层的HoOH的分子平面则近乎平行于基底.     

卟啉和酞菁修饰的单壁碳纳米管的合成及光谱性质

利用5-(4-氨基苯基)-10,15,20-三(3,5-二辛氧基苯基)卟啉和2,9,16-三叔丁基-23-氨基锌(Ⅱ)酞菁通过酰胺键连接方式同时对单壁碳纳米管进行共价修饰, 通过红外光谱、拉曼光谱、X射线光电子能谱和透射电镜对所得碳纳米管复合物进行了表征, 证实了其结构. 紫外-可见吸收光谱和荧光光谱分析表明, 光活性分子卟啉和酞菁均与单壁碳纳米管之间存在较强的电子效应. 经卟啉和酞菁共同修饰的单壁碳纳米管复合物比卟啉和酞菁单独修饰的碳纳米管复合物的吸光范围更宽, 而且分散性较好(309 mg/L), 是潜在的光电转换材料.     

Photoalignment of liquid crystals by a covalently attached self-assembled ultrathin film

In this paper, the polyanion-containing cinnamoyl group (PACSS-CF3) was self-assembled with diazoresin (DR) to form a kind of stable covalent ultrathin film by irradiation with 365?nm UV light. The photoalignment properties of the DR/PACSS-CF₃ covalent film were investigated. The covalent film was found to have anisotropy after irradiation by 297?nm linearly polarised ultraviolet light (LPUVL), and could induce uniform alignment of liquid crystals (LCs). The pretilt angle of the LC was 2.5°. The stability of the film was enhanced by the covalent bonds. The films were thermally stable to 180°C. Polarised UV-Vis spectroscopy was utilised to investigate the photochemical process of the covalent film. It was found that cinnamoyl moieties parallel to the polarisation direction of the LPUVL were consumed by the photoreaction faster than those perpendicular to the polarisation direction. It can be concluded that the selective photoreaction induced the anisotropy of the films. The anisotropic films induced the homogeneous alignment of LC.     

Photovoltaic Behaviour of Titanyl Phthalocyanine Thin Films and Titania Bilayer Films

Summary: Titanyl phthalocyanine (TiOPc) thin films were prepared using evaporation and surface polymerization by ion-assisted deposition (SPIAD) in a vacuum deposition system. These films were characterized by means of ultraviolet and X-ray photoelectron spectroscopy as well as UV/Vis absorption spectroscopy. Valence band and elemental content indicated that phthalocyanine electronic and chemical structures were largely preserved during SPIAD. Further, bilayer thin films of titania (TiO₂) and SPIAD TiOPc were prepared. TiO₂ film was deposited by reactive magnetron sputtering of TiO₂ target. Study of the structured samples was focused on the optical and electrical properties of the composite films. The films were characterized by non-contact photovoltage measurements and UV-Vis spectroscopy. These results suggest there is a possibility to use these bilayer thin films in photovoltaic solar cells, however further experiments to improve conductivity of the films will be required.     

卟啉/酞菁配合物修饰钙钛矿太阳能电池研究

为解决资源短缺和环境污染问题,太阳能电池应用研究引起了广泛的科学关注。在过去的十年间,钙钛矿太阳能电池作为一种新型的电池技术得到了快速发展,逐渐成为目前商业化硅基太阳能电池最有力的竞争对手之一。然而,钙钛矿薄膜在低温溶液制备过程中不可避免地形成缺陷,这些缺陷是严重制约钙钛矿太阳能电池光电转化效率与长期运行稳定性得到进一步提高的主要因素。利用功能化有机分子钝化钙钛矿薄膜表面及晶界处缺陷是提升电池性能及稳定性的有效手段。卟啉/酞菁金属配合物具有良好的稳定性和优异的光电特性,利用卟啉/酞菁金属配合物修饰钙钛矿薄膜是提高钙钛矿太阳能电池性能和稳定性的有效方法之一。本文综述了卟啉/酞菁金属配合物界面调控实现高效稳定钙钛矿太阳能电池组装的研究进展,并对其存在的问题及今后可能的发展方向进行了总结与展望。     

Preparation and characterization of thin films of monomeric and polymeric octacyanophthalocyanines

Thin films were prepared on substrates, cleavage surface of KCl single crystal, and metallic copper, by reaction of 1,2,4,5-tetracyanobenzene with the substrate at various temperatures. The films were characterized by elemental analysis, IR, and UV/VIS spectroscopies. The films were observed by scanning electron microscopy. The films produced on copper at temperatures between 300 and 400°C consisted of copper octacyanophthalocyanine and its polymer with ladder structure. The ratio of polymer to monomer increased with elevating the reaction temperature. The films were composed of ribbon-like crystals. The film produced on copper above 450°C was composed of an amorphous and continuous layer of polymeric copper phthalocyanine. The film produced on KCl at temperatures between 250 and 350°C consisted of potassium octacyanophthalocyanine and its polymer with ladder structure. The film produced on KCl above 450°C was polymeric potassium phthalocyanine. Those films contained more metal content than that required stoichiometrical.     

单冠醚取代不对称酞菁LB膜的制备和表征

酞菁化合物有序聚集体已成为材料化学中的研究热点［１,２］,在酞菁分子中引入冠醚会大大改善酞菁化合物的气敏性,在提高响应速度和重复性的同时,其响应温度可降到室温［３,４］．研究冠醚酞菁气敏性质的通常方法是将其制成浇铸膜［４］,这种膜是无序的．膜中分子的...     

Dye degradation studies of Mo‐doped TiO2 thin films developed by reactive sputtering

TiO₂ thin films with various Mo concentrations have been deposited on glass and n‐type silicon (100) substrates by this radio‐frequency (RF) reactive magnetron sputtering at 400°C substrate temperature. The crystal structure, surface morphology, composition, and elemental oxidation states of the films have been analyzed by using X‐ray diffraction, field emission scanning electron microscopy, atomic force microscopy, and X‐ray photoelectron spectroscopy, respectively. Ultraviolet‐visible spectroscopy has been used to investigate the degradation, transmittance, and absorption properties of doped and undoped TiO₂ films. The photocatalytic degradation activity of the films was evaluated by using methylene blue under a light intensity of 100 mW cm⁻². The X‐ray diffraction patterns show the presence of anatase phase of TiO₂ in the developed films. X‐ray photoelectron spectroscopy studies have confirmed that Mo is present only as Mo⁶⁺ ions in all films. The Mo/TiO₂ band gap decreases from ~3.3 to 3.1 eV with increasing Mo dopant concentrations. Dye degradation of ~60% is observed in Mo/TiO₂ samples, which is much higher than that of pure TiO₂.     

Carbon film growth on iron substrates by a CVD method

Carbon film coatings have been produced by a hot‐wall chemical vapor deposition (CVD) method under moderate conditions from pyrolysis of a mixture of propane and argon on an Fe(110) substrate at temperatures of 800–900 °C for different deposition times. The effects of temperature and reaction time on the growth of the carbon films were studied. Field‐emission scanning electron microscopy (FESEM), Raman microscopy, Auger electron spectroscopy (AES) and x‐ray diffraction methods have been performed to study the surface morphologies, growth features and microstructures of the carbon film coatings. The FESEM analyses indicated that carbon films on an Fe substrate consisted of flat‐layer and filamentous morphologies. Raman and AES analyses showed that the carbon initially was crystalline but the degree of disorder in the top layer of the carbon film increased with increasing deposition temperature. High‐resolution transmission electron microscopy studies are also in agreement with Raman results. The same trend was observed when the deposition time was increased from 5 to 30 min. Copyright © 2005 John Wiley & Sons, Ltd.     

具有相反电荷取代基的卟啉和酞菁异聚体荧光光谱的研究

用荧光光谱的方法研究了由水溶性的中位-四-[对-(N,N,N-三甲基苯基)铵基]卟啉的碘化物和2,6,9,15-四(4'-磺酸基)镓酞菁形成的超分子体系,在水溶液中阴离子酞菁与阳离子卟啉能形成杂聚集体。荧光光谱滴定的结果表明:聚集体为杂二聚体,形成平衡常数为1.17×10⁸L/mol。说明了卟啉-酞菁杂二聚体是非常稳定的。没有观察到聚集体的荧光发射。     

Electrochemical properties of protoporphyrin IX zinc(II) films

The electrochemical properties of protoporphyrin IX zinc(II) (ZnPP) films on indium-tin oxide (ITO) substrate have been studied for three types of films with different arrangements, which were an adsorbed film of ZnPP and LB films of ZnPP and its hybrid with hexadecyltrimethylammonium bromide. Cyclic voltammetry (CV) measurement showed that, as the adsorbed amount of ZnPP increases, an irreversible oxidation peak of ZnPP film is intensified. This reveals that electrochemical properties depend on the adsorbed amount rather than the orientation of porphyrin molecules. It was also supported from CV measurement and ultraviolet-visible absorption spectroscopy that porphyrins adsorbed on ITO substrate were desorbed after the single scan of potential. Additionally, photoresponse of these ZnPP films was investigated by photocurrent measurement. The photocurrent generation is due to carboxylic acid moieties but not ZnPP macrocycles.     

用紫外光谱和X射线光电子能谱研究金属卟啉自组装膜

金属卟啉化合物由于具有丰富的电子结构和特殊的物理化学性质,因而在光电材料、分子器件和非线性光学等领域具有广阔的应用前景．有机硅可用于提高高分子化合物在氧化物基底表面的附着力;在气相和液相色谱中可作为固定相;在生物传感器中可用于蛋白质的固定．     

Dispersion of functional tetraphenylporphyrin-ligated metal into ultra-thin flexible acrylate films. 1. Preparation of thin films

As functional metal complexes, copper phthalocyanine (CuPc) and Cobalt (II) meso-tetraphenylporphyrin (CoTPP) were chosen to prepare metal complex/polymer hybrid thin films which were prepared by metal complex sublimation and reactive monomer evaporation onto the glass substrate in the bell jar reactor in vacuum conditions. The polarized transmission micrograph images show that the film deposited at 80 °C contains uniformly dispersed tiny grains and the film deposited at 30 °C is amorphous and homogeneous. As the deposition rate increases, the crystalline clusters were found and were dispersed uniformly. Those crystalline clusters are not to be developed by recrystallization process. Deposited metal complex/acrylate hybrid thin films were in situ photopolymerized. The kinetics of photopolymerization was investigated by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). The thickness of the films was about 200 nm. The reactive monomer acts as a solvent to avoid the recrystallization of metal complexes and to have two-compositional continuous phase. The percent of metal complex can be adjusted up to 60% by controlling the metal complex sublimation rate. A good achievement in the uniformity and continuity of the film matrix has been made and the recrystallization of metal complex in the hybrid films has not been observed.     

具有不同取代链长的卟啉衍生物LB膜的结构研究

本文研究了三种羧酸取代的四苯基卟啉衍生物在空气/Cd^2^+水溶液界面上所形成的单层膜及LB膜。这三种卟啉衍生物中, 一种没有脂链, 另外两种具有不同长度的脂链。由π-A等温线得到的平均表观分子面积相差很大。紫外-可见光谱表明, LB膜中卟啉的Soret吸收带相对于溶液的吸收均红移, 但红移程度不同。LB膜的偏振紫外-可见光谱表明, LB膜中三种卟啉衍生物的卟啉环具有基本一致的取向。运用亚相降低法得到了三种卟啉衍生物单层LB膜, 其紫外-可见光谱与用垂直提拉法得到的LB膜的紫外-可见光谱具有一致的特征。这些结果表明: 卟啉衍生物有无取代链及取代链长的不同对平均表观分子面积的大小和膜中环间的距离有影响, 但对环的取向没有影响。环的取向由环本身及环上的亲水取代基来确定。气/液界面上三种卟啉衍生物的单层膜中环也具有一致的取向, 且与LB膜中环的取向相差不大。提拉不会对膜中环的取向及膜的结构造成大的改变。     

Effects of Co-addition of DBS and PEG on Wetting Performance of TiO_2 Film

Nanocrystalline anatase TiO2 films with indium tin oxide(ITO) coated glass as the film substrate were fabricated through spin-coating technique. The TiO2 pastes were prepared with sodium dodecylbenzenesulfonate(DBS) modified TiO2 nanocrystals, synthesized by sol-hydrothermal processes in advance, together with different amounts of polyethylene glycol(PEG) macromolecules. The as-prepared films were mainly characterized by ultraviolet-visible (UV-Vis) spectroscopy, field emission scanning electron microscopy(...