诱导成膜聚合与IPN界面

本文简要介绍了一种新颖的聚合物/聚合物复合薄膜的制备方法——诱导成膜聚合法。即用一种高分子溶液作某一能溶于该溶液的单体的诱导成膜剂,诱导单体成膜。经聚合后,便得到具有IPN界面的聚合物/聚合物层状复合薄膜。     

聚合物辅助设计生长高质量多功能薄膜

随着薄膜材料的日益发展和新型薄膜材料的不断涌现,开发薄膜生长技术对于半导体和光电等科技领域的作用日益突出。本文主要介绍最近发展的聚合物辅助沉积从分子层面上控制生长高质量的薄膜材料。聚合物辅助沉积是一种生长高质量薄膜的化学水性溶液方法,将金属离子与聚合物通过络合、氢键或静电等方式形成一种均匀稳定的前驱体溶液,再经过超滤、成膜和热处理形成高质量的金属氧化物、金属碳化物、金属氮化物、金属单质、金属硫/硒化物等薄膜以及纳米粒子等化合物或复合功能材料。该方法中水溶性的聚合物能通过络合作用抑制金属离子的水解使得溶液稳定,并能精确控制薄膜的组分从而形成高质量的薄膜。该化学溶液方法的提出为科学技术领域提供了一种低成本和大面积制备薄膜的技术路线。本文最后总结和展望了聚合物辅助沉积法未来的挑战和发展方向。     

卟啉四臂星型聚乳酸的制备与表征

利用本体聚合方法,采用辛酸亚锡为催化剂,四氨基苯基卟啉为引发剂,引发丙交酯开环聚合,制备四臂星型聚乳酸功能高分子材料.采用1 H-NMR,FTIR,GPC等对星型聚合物的分子结构、分子量及其分布等进行了研究.利用溶液浇铸成膜方法,制备了聚乳酸薄膜材料;并利用XRD方法,研究了聚乳酸薄膜的结构.研究表明,利用四氨基苯基卟啉为引发剂,合成了以卟啉为核的四臂星型聚合物,其溶液浇铸薄膜具有正交晶系α晶型结构,而线型聚乳酸呈非晶态结构.利用紫外可见吸收光谱研究了星型聚乳酸的光谱性质,结果表明合成聚合物具有锡卟啉的光学特性.     

利用Breath Figure法制备具有Honeycomb结构的有机/无机复合膜

以聚苯乙烯和正硅酸乙酯的有机溶液为铸膜溶液, 利用Breath Figure法制备了PS/SiO2Honeycomb结构复合膜. 采用SEM对复合膜进行了形貌分析, 探讨了聚合物浓度、 PS/TEOS配比、聚合物的结构、溶剂等对膜Honeycomb结构的影响. 研究结果表明, 聚合物浓度在20～50 mg/mL, PS/TEOS质量比大于2∶1的条件下可以制备结构完整的多孔膜, 且制备的Honeycomb结构在0.8 cm2内无缺陷; 采用双羧基封端的聚苯乙烯成膜效果好于单羧基封端的成膜效果; 以氯仿和苯作为溶剂均可以制备完全Honeycomb结构的复合膜, 但以苯为溶剂制备的多孔膜孔径较大. 成膜中TEOS水解不完全, 复合膜中混杂着未完全水解的TEOS以及SiO2. EDS面扫描分析表明, Si和O均匀地分散在复合膜中.     

共轭聚合物材料的有序化,结晶化及器件应用研究

聚合物半导体材料因其可溶液加工的特点在构筑大面积、价廉、柔性有机器件方面引起了人们的广泛兴趣.但是,通常情况下,器件中聚合物半导体薄膜都是通过旋涂方式制备,该薄膜中分子的有序性差而且存在大量的晶界和缺陷,这不利于聚合物半导体材料本征性能的合理评价和高性能聚合物光电器件的制备.因此,如何制备高取向聚合物薄膜一直是该领域研...     

聚芴类共轭聚合物(PFs)从溶液到薄膜凝聚态演变过程中的定量构效关系

聚芴（polyfluorenes，PFs）是一类具有高荧光效率和良好热稳定性的经典蓝光共轭聚合物.本研究组近年来集中于聚芴类共轭聚合物溶液中单链构象-聚集态结构-薄膜凝聚态结构-器件性能间的定量构效关系研究，利用静/动联用激光光散射等表征手段，结合标度率研究方法，对PFs成膜前体溶液复杂的单链和聚集的形态结构进行了系统的研究.结合光谱与电镜等方法，揭示出PFs在溶液中孤立单链、凝聚态结构、β构象及其过渡态结构形成的动力学过程、机理及规律，构建出成膜前体溶液单链构象-薄膜中链构象-器件性能之间的定量构效关系.旨在从高分子本征性质入手，提高其光电效率.本研究不仅对聚芴类高分子，而且对整个共轭聚合物类材料的设计与加工都将具有重要的指导意义.     

聚对苯二甲酸乙二酯的结晶与取向

为了了解PET球晶的拉伸性能与球晶结构的关系以及无定形PET的取向和结晶,我们采取了两条不同的路线来制备样品:(1)先用溶液浇铸成膜的办法制备具有正球晶、负球晶或非常球晶的薄膜,然后进行单轴拉伸。电子显微图象及电子衍射证明,球晶的拉伸性能与C轴和球晶半径方向的夹角有关,夹角愈大拉伸愈困难;(2)先制备无定形的薄膜,然后在玻璃化温度附近进行单轴拉伸以获得C轴取向,再在215℃退火,使之结晶。电子衍射图证明,这样制备的样品具有高度的C轴取向。DSC结果表明,结晶的完善程度远比球晶的为高。     

等离子体聚合法修饰半导体光电极的研究——聚丙烯腈/n-GaAs,n-GaP电极

用导电聚合物修饰光电化学体系中的半导体电极,对于抑制电极的光腐蚀、改善电极特性及赋予其催化功能有明显的效果.在制备聚合物薄膜的几种方法中,等离子体聚合可得到高度交联、均匀、化学稳定性好的超薄膜,且成膜工序简单,已引起重视并取得初步应用。等离子体聚合法修饰导体电极国内外均有报道,但在修饰半导体电极方面的研究甚少。本文探讨了用这种方法在n-GaAs、n-GaP电极上制备聚丙烯腈(PAN)薄膜,并进行     

聚合物主体中纳米CdTe的光致发光与电致发光性质

利用紫外和荧光光谱技术研究了共轭聚合物PPE4+分别在溶液和薄膜中与纳晶CdTe间的能量传递现象。通过静电层层组装技术制备了混杂有纳晶CdTe的PPE4+薄膜发光二极管,并测试了其电致发光性质。结果表明在溶液和薄膜中共轭聚合物PPE4+与纳晶CdTe间均能发生有效的能量转移,而共轭聚合物PPE4+在能量传递过程中起到分子天线的作用。     

有序自组装聚合物纳米结构

采用水辅助方法(water-assisted fabrication method),分别以4-十二烷基苯磺酸掺杂的聚苯胺(PANI-DBSA)和聚2-甲氧基-5-(2′-乙烯基-己氧基)苯乙炔(MEH-PPV)两种功能高聚物为成膜材料,冷凝水滴为模板,利用水滴在聚合物溶液表面的自组装,制备出了两种纳米层次以上的蜂窝状有序多孔聚合物薄膜.通过原子力显微镜和共聚焦荧光显微镜对其形貌、电学性质和荧光图像进行了表征.     

Structural and orientational studies of chiral N-[4(1-pyrene)butyroyl]-phenylalanine in cast film

Cast films of chiral material N-[4(1-pyrene)butyroyl]-l-phenylalanine (Py-l-Phe) and the racemic modification (the 1:1 mixture of Py-l-Phe and Py-d-Phe) have been investigated in the present study. The microscopic structure, molecular orientation and the aggregation in the film have been studied by using ultraviolet-visible (UV-vis) and infrared (IR) spectroscopy. When a cast film is formed from the chloroform solution at room temperature, the J-aggregates of Py-l-Phe and Py-d-Phe are observed by UV-vis spectra. A comparison of Fourier transform infrared (FT-IR) transmission and reflection-absorption (RA) spectroscopy has been applied to reveal the orientation and structural characterization of the cast films. It has been found that the pyrenyl ring in the cast film of Py-l-Phe assumes a nearly vertical orientation with respect to the surface of the solid substrate. And there are two different hydrogen bonding species, cyclic dimer and linear dimer, exist in carboxyl groups in cast films. The detailed analysis of the OH and NH stretching modes of Py-l-Phe and Py-d-Phe allows us to reveal the hydrogen bonds existing in the films.     

阳极氧化TiN薄膜制备N掺杂纳米TiO2薄膜及其可见光活性

室温下通过电泳沉积(EPD)的方法在Ti片表面制备TiN薄膜, 然后对TiN薄膜进行阳极氧化得到N掺杂多孔纳米结构的TiO2薄膜. 利用X射线衍射(XRD), X射线光电子能谱(XPS), 扫描电子显微镜(SEM)及光电化学方法对得到的薄膜进行表征. XRD测试结果表明, 经过阳极氧化并在350 ℃空气气氛中退火1 h的薄膜中存在锐钛矿晶型的TiO2. XPS的结果表明, 样品中的N元素取代部分O, 且N的摩尔分数为0.95%. SEM显示, 经阳极氧化后薄膜表面出现多孔纳米结构. 光电化学测试结果显示, 阳极氧化提高了N掺杂TiO2薄膜在可见光下的光电响应. 经阳极氧化并热处理的薄膜在0 V电位及可见光照射下光电流密度为2.325 μA·cm-2, 而单纯热处理的薄膜在相同条件下光电流密度仅为0.475 μA·cm-2. 阳极氧化得到纳米多孔结构提高了N掺杂纳米TiO2薄膜的表面积, 从而对可见光的响应增大.     

Solvent-induced phase separation in polycarbonate blends PC/TMPC

Compatibility of the polycarbonates of bisphenol A (PC) and tetramethyl bisphenol A (TMPC) was studied in glassy films cast from CH₂Cl₂ at room temperature, and above the glass-transition temperature. Blends with different compositions and of different molecular weights were analyzed by DSC and small-angle neutron scattering (SANS). Solution studies were made with light scattering and microscopy. Some of the blend films were two-phased when cast at room temperature, but all films were one-phased in equilibrium above the glass transition. The SANS data demonstrated that phase separation in the cast films was not caused by inherent incompatibility of PC and TMPC, but was induced by the solvent CH₂Cl₂. The effect is caused by a closed miscibility gap in the ternary solution system PC/TMPC/CH₂Cl₂.     

Swelling-assisted modification of poly(ethylene terephthalate) by methacrylic acid

When a poly(ethylene terephthalate), PET, film is heated in an aqueous solution of methacrylic acid in the presence of hydrogen peroxide as an initiator, it is found that the weight of the film is increased. The amount of methacrylic acid that may be added onto the film is dependent upon the concentration of the monomer, the initiator, and the temperature at which the reaction occurs. Pretreatment of the film with 1,1,2,2,tetrachloroethane causes swelling and the amount of add-on is increased as the swelling level increases. Methacrylic-acid-modified PET films hydrolyze at room temperature in aqueous sodium hydroxide; the rate of hydrolysis is dependent upon the amount of add-on and the concentration of the base. This procedure leads to a chemically induced blend of polymethacrylic acid and poly(ethylene terephthalate), and grafting of the monomer onto the polymer film does not occur. © 1995 John Wiley & Sons, Inc.     

Surface structure and photoluminescence properties of AZO thin films on polymer substrates

Al‐doped zinc oxide (AZO) thin films were deposited on indium tin oxide (ITO) coated polyethylene terephthalate (PET) substrates by radio frequency (RF) magnetron sputtering method at room temperature. The effects of film thickness on the surface structure and the photoluminescence properties of the films were investigated by atomic force microscopy (AFM), secondary ion mass spectroscopy (SIMS) and room temperature photoluminescence (PL). AFM analysis showed that the surface of all films was extremely flat and uniform at nanoscale. Root mean square (RMS) value of the surface roughness which scanned the surface area of 3 µm by 3 µm and grain size increased with increasing the film thickness. Thus, the surface morphology of the films became rough because of the coarse grains. The depth profile of AZO layers was analyzed by SIMS. It was found that the thickness of the AZO layer is almost same with the desired film thickness. The PL intensity of the dominant peak decreased and shifted slightly towards the shorter wavelengths with increasing the film thickness. According to the relationships between luminescence intensity and crystalline characteristics, it was observed that the intensity of the peak decreased by the increased surface area of the grains. Copyright © 2014 John Wiley & Sons, Ltd.     

High‐refractive‐index and high‐barrier‐capable epoxy‐phenoxy‐based barrier film for organic electronics

A barrier film is a fundamental component of the fast growing organic electronic device industry that is necessary to sustain long‐term stability. The barrier film prevents the permeation of environmental moisture and oxygen into the organic electronic device. Superior barrier property is the most crucial characteristic of a barrier film, in addition to a high refractive index. A high‐refractive‐index barrier film has the potential to reduce the refractive‐index mismatch between a device and a protective film, consequently, reducing the energy costs by increasing the light output. In this work, six epoxy and phenoxy resin composite compositions are synthesized separately, each with a different cross‐linker. POL‐TE1/PET and POL‐HD1/PET films show enhanced refractive indexes of 1.726 (at 750 nm) and 1.721 (at 500 nm), allowing only 71.7% and 70.4% permeation, respectively, compared to those of POL/PET, while exhibiting more than 80% transparency and excellent properties. The films are fabricated using a straightforward process, from a solution, at low temperature and under atmospheric conditions, using an applicator and bar coating.     

聚(3-己基)噻吩薄膜中电荷传导的研究

对两种具有相同化学结构的聚(3-己基)噻吩膜进行了电荷传导研究以检验膜的结构对载流子迁移率的影响. 一种膜是由3-己基噻吩单体经电化学合成直接制备的膜(原位生长膜); 另一种膜是将原位生长膜溶于三氯甲烷后重新滴涂而成的(滴涂膜). 研究表明, 虽然两种膜的制备方法不一样, 但在最低(0.02%)和较高(20%～30%)掺杂率下两膜中的载流子迁移率相一致; 然而在中等掺杂率区域, 两膜中的载流子迁移率明显不同. 对于原位生长膜, 载流子迁移率在低掺杂区域几乎保持不变, 当掺杂率大于1%后开始上升; 而在滴涂膜中, 随着掺杂率的增加, 迁移率先下降然后迅速升高. 上述两种迁移率变化特征分别与以前研究中观察到的电化学合成高分子膜和化学合成高分子旋涂或滴涂膜中迁移率的变化特征相一致, 表明了迁移率随掺杂率变化特征的改变是由膜的结构变化而引起的     

One pot,single step,room temperature dielectrophoretic deposition of gold nanoparticles clusters on polyethylene terephthalate substrate

The major challenge of plastic electronics is the deposition of gold nanoparticles (AuNPs) on flexible substrates at room temperature. Here, we show fast, single step, room temperature deposition of AuNPs on polyethylene terephthalate (PET) and biaxially oriented PET (BoPET) substrate by employing dielectrophoresis. The deposition has been carried out using two‐electrode system, with BoPET (or PET) and metallic (Pt or stain steel) mesh, under an AC signal of 20 kHz and 20 V peak‐to‐peak (V_pp) (signal for PET is 6 V_pp and 6 kHz). In this method, we show how to deposit AuNPs on PET‐like insulator by exploiting its polarization capability under an AC signal. The polarization of PET has been confirmed by change in the Raman spectra of the PET film under in situ AC signals. Furthermore, we show that using this dielectrophoretic deposition method, the PET films can be patterned by AuNPs at room temperature without any pre‐ and posttreatment.     

Influence from Thermal Elimination Temperature of Precursor Polymer and Film‐forming Methods on the Photophysics of the Poly(2,5‐didodecyloxy‐p‐phenylenevinylene)

A series of poly(p‐phenylenevinylene)s (PPVs) with good solubility were synthesized from thermal elimination of precursor poly(2,5‐didodecyloxy‐p‐phenylenevinylene) at different temperature via Wessling method. The polymer photophysics were influenced by the thermal elimination condition, which was consistent with NMR and IR characterizations. The additional absorption peak at longer wavelength and the red‐shifted emission maximum both in solution and in film, for PPVs obtained at high elimination temperature, indicated the existence of longer conjugated blocks in these systems. The emission maximum for drop‐cast film (436 nm) for PPV obtained under 200°C (PPV200) was 16 nm blue shifted to the spin‐coated films (452 nm) or 29 nm to the solution (465 nm). The SEM study showed drop‐cast film had the morphology of isolated conjugated particles in the matrix while blurry linear structure was found for spin‐coated film, which was consistent with the photophysics. The discussion about this difference was carried out based on the consideration of the flexibility of the polymer chains and different conjugated length of PPV in different states.     

Some properties of polyvinyl acetate films cast from methanol,acetone and chloroform as solvent

Polyvinyl acetate was cast into films on a clean mercury surface from its solution in either methanol, acetone or chloroform. Some mechanical properties of the films, exposed at 20 °C and 65% r.h., and 45 and 60 °C in air ovens, were studied. They were found to be highly dependent on the solvent used for film casting and the time of exposure of film at each of the temperatures. The initial modulus, yield stress, tensile strength and work to rupture of the polymer films were greater for those cast from acetone than those cast from chloroform, and for all the films these properties increased with exposure time, with an induction period in some cases. The elongation at break decreased with exposure time from an initial value which was higher for the chloroform-cast than the acetone-cast films. Films cast from methanol were found to be too brittle for testing.The results are interpreted on the basis of interactions between the solvent molecules and those of the polymer. Of the three solvents, chloroform produced polyvinyl acetate films with the most constant mechanical properties over the longest period of exposure which depended on the temperature of exposure, decreasing as the temperature increased. Hence chloroform is recommended for casting films of polyvinyl acetate. Methanol is practically unsuitable while acetone could be used where chloroform is not available.