基于p-6P异质诱导生长酞菁铜薄膜的NO2传感器

为实现室温下低浓度NO₂气体检测,制作了p-六联苯(p-6P)诱导层的酞菁铜有机薄膜传感器。利用原子力显微镜(AFM)研究了不同沉积速率下p-6P薄膜的生长规律,慢速沉积提供足够的分子扩散时间,利于薄膜横向生长,形成高度低、尺寸大的晶畴。在p-6P薄膜上生长了酞菁铜薄膜,可以清晰看到晶畴上酞菁铜薄膜的有序排列。利用X射线衍射(XRD)仪,阐明了p-6P对酞菁铜薄膜具有很好的诱导效应。通过对比不同沉积速率p-6P薄膜诱导的酞菁铜传感器性能,发现慢速沉积诱导层的酞菁铜器件有高的响应强度和低的回复时间。异质诱导生长的酞菁铜传感器响应强度是直接生长在二氧化硅上的酞菁铜传感器的2倍,回复时间是3.2 min,对浓度为1.0 × 10^-5的NO₂气体灵敏。     

酞菁铜旋涂薄膜的制备与气敏性能研究

本文制备了2,9,16,23-四异丙氧基和2,9,16,23-四对甲基苯氧基2种酞菁铜(CuPc(OC₃H₇-i)₄, CuPc(OC₇H₇)₄,简称为烷氧基酞菁铜和苯氧基酞菁铜),并在基片上成功制得了二者的旋涂膜。利用AFM(Atomic force microscope)、UV-Vis和FTIR对薄膜的表面形貌和谱学性质进行了分析。结果表明,以一定的旋转速度进行涂膜,可以获得较为均匀的酞菁铜薄膜,并且2种取代基团的酞菁表面形貌有着较为明显的差别。在室温下测试了2种酞菁薄膜对甲醇和乙醇气体的敏感性能,结果显示薄膜对测试的醇类有较高的灵敏度,对乙醇的灵敏度要大于甲醇,在同种测试气氛下苯氧基酞菁铜薄膜的气敏性能要高于烷氧基酞菁铜薄膜。2种薄膜对浓度为30 μL·L^-1乙醇气体的响应和恢复时间分别在30 s和60 s内。     

四-4-(烷氧基-羰基)酞菁铜(Ⅱ)的合成、结构及其成膜性

本文合成了两种新型取代酞菁铜(Ⅱ)配合物:四-4-(戊氧基-羰基)酞菁铜(Ⅱ)(A)和四-4-(癸氧基-羰基)酞菁铜(Ⅱ)(B),并通过元素分析、ESR、~1H-NMR和FT-IR进行了表征.用可见光谱研究了它们在氯仿溶液中的聚集形式;用X-ray粉末衍射方法研究了配合物的固相堆积排列结构.两种配合物的氯仿溶液在亚相(水)上的π-A曲线表明,它们均有明显的“气”“液”“固”变化过程;并能在不同的表面压力区间形成较好的单分子层和多分子层膜.     

双异质诱导层对红荧烯薄膜晶体管性能的影响

在二氧化硅衬底上依次真空沉积p-六联苯(p-6P)和酞菁铜(CuPc)构成双异质诱导层,研究了不同衬底温度下双异质诱导层对红荧烯薄膜形貌的影响,以及红荧烯分子在双异质诱导层上的生长过程.分析发现,第二诱导层酞菁铜的局部有序性对红荧烯薄膜的结晶度有直接影响.随着衬底温度的升高,酞菁铜薄膜有序区域面积增大,红荧烯的棒状晶粒也逐渐增大.当酞菁铜和红荧烯的衬底温度均为90℃,红荧烯蒸镀厚度为20 nm时,红荧烯薄膜形成高度有序、内部连接及具有特定方向的棒状晶畴.利用X射线衍射(XRD)和透射电子显微镜(TEM)分析了红荧烯薄膜的晶体结构,发现经过双异质诱导后的红荧烯薄膜转变为多晶形态.另外,红荧烯薄膜晶体管性能也明显提高,开态电流提高了约3个数量级,迁移率提高了30倍,阈值电压降低了20 V.     

α-和β-四烷氧取代酞菁的合成及性能研究

利用3-烷氧取代邻苯二腈和4-烷氧取代邻苯二腈与相应的金属盐反应制备了两大系列(α-和β-)四烷氧取代酞菁.讨论了温度对中间体烷氧取代邻苯二腈合成的影响,探讨了酞菁的两种环合方法,并对β-烷氧酞菁的环合历程进行了初步的考察.研究了不同取代位置和酞菁的最大吸收波长之间的关系,结果表明, α-取代烷氧取代酞菁导致λmax红移值较大,而相应β位取代情况下红移值较小,说明给电子基团在α位对酞菁骨架的π共轭结构微扰作用比β位大.同时研究了溶解度及热失重与酞菁结构的关系.     

四取代羧基酞菁锌与白蛋白共价结合物的制备与光谱性质

通过成酰胺键的方式制备了一系列含羧基酞菁和白蛋白(牛血清白蛋白(BSA),人血清白蛋白(HSA))之间的共价结合物,所涉及到的酞菁分别是α-四(4-羧基苯氧基)酞菁锌(1)和α-四[4-(2-羧基乙基)苯氧基]酞菁锌(3),以及它们相应的β位四取代酞菁锌(化合物2和4).比较了游离酞菁以及它们的白蛋白结合物在磷酸盐缓冲溶液(PBS)中的光谱性质.结果表明,当酞菁被共价固定于白蛋白大分子上之后,展现出比游离酞菁更明显的单体特征吸收,而且结合物中的酞菁光谱特征不受体系pH值变化的影响.羧基在酞菁环上的取代位置,对酞菁与白蛋白结合前后的光谱转变幅度有影响,α位取代比β位取代更有利于光谱的变化.化合物1和3的白蛋白共价结合物在PBS溶液中甚至呈现出单体形式为主的光谱特征,Q带最大吸收波长分别位于697和706nm附近.     

酞菁氯化铟的固相合成及光敏性能

以尿素、邻苯二甲酸酐、钼酸铵和四水合三氯化铟为原料, 乙酸钠为催化剂, 采用固相法合成酞菁氯化铟, 并用元素分析、UV-Vis、IR和XRD进行了表征. 考察了反应物配比、催化剂、反应温度和时间对产率的影响, 寻找出最佳制备条件为n(尿素)∶n(邻苯二甲酸酐)∶n(三氯化铟)=14∶4.5∶1, 以乙酸钠为催化剂, 130 ℃下恒温0.5 h, 在220 ℃下反应4 h后, 用88％(质量分数)浓硫酸提纯. 研究了酞菁氯化铟光敏电阻薄膜的光敏性能, 结果表明, 当用0.2 g酞菁氯化铟和0.6 g PVB制备光敏电阻薄膜时, 分散介质丁酮-环己酮的最佳用量为36 mL, 其电阻灵敏度保持在1.50×10⁸以上, 积分灵敏度保持在30 μA/(lx·V)以上. 研究结果表明, 酞菁氯化铟光敏电阻薄膜具有很好的光敏性能.     

CuInS2：两步电沉积制备及性能

采用恒电位沉积法制备铜铟合金预制膜,并存管式炉中通过固态源蒸发硫化预制膜得到CuInS:薄膜.通过扫描电镜(SEM)、能量色散谱仪(EDS)和X射线衍射仪(XRD)对CuInS2薄膜的表而形貌、截面厚度、成分组成和薄膜的组织结构进行了研究,并利用紫外可见光吸收谱仪(UV-Vis)研究了不同硫化温度对CuInS:薄膜的形貌及其光学吸收性质的影响.结果表明:不同的退火温度能够影响CuInS:薄膜的表面形貌以及带隙的大小,从而影响其光学吸收特性.     

酞菁键合硅胶的制备及分离取代酞菁异构体

制备和表征了一种新的酞菁键合硅胶，三-β-(辛巯基)-β-(磺酰胺基)-酞菁铜键合硅胶。研究了该键合酞菁硅胶作为HPLC固定相的基本色谱性能。实验结果表明，该固定相可以分离四-α-(2，2，4-三甲基-3-戊氧基)酞菁(铜、镍)的4种异构体，也可以观察到四-α-(2，2，4-三甲基-3-戊氧基)无金属酞菁的4种异构体，而商业C₁₈(VERTEX Eurospher)却只能观察到两组峰，表明这种酞菁键合硅胶固定相在分析、分离一些取代酞菁异构体方面比商业C₁₈具有更好的分离效果。     

铟酞菁/聚甲基丙烯酸甲酯复合物固体光限幅器性能

将在溶液中表现出优良非线性光学和光限幅性能的铟酞菁及其二聚物嵌入到非光学活性的聚甲基丙烯酸甲酯(PMMA)中, 用传统的旋转涂膜法制备得到具有较高光学质量的复合物薄膜, 用开孔Z-扫描方法在532 nm 处研究了复合物薄膜材料的线性光学和非线性光学性能. 结果表明, 无论是铟酞菁单体还是轴向氧桥联的铟酞菁二聚物, 其PMMA复合材料的光限幅性能均显著优于相应的酞菁分子在溶液中的光限幅性能.     

Phthalocyanine and polystyrene film nanocomposites

The organic solvent was shown to determine the structure of copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (CuPc) in the CuPc-polystyrene composite during the formation of the latter. The structure and morphology of the resulting nanocomposite films was studied by atomic force and transmission electron microscopy. Different physical structures of CuPc formed in different solvents (cyclohexane, toluene, chloroform, and trichloroethylene).     

Electrophoretic deposition of phthalocyanine in organic solutions containing trifluoroacetic acid

The absorption spectra of copper phthalocyanine (CuPc) 1,2-dichloroethane (DCE) solutions containing trifluoroacetic acid (TFAA) shows that the number of protons coordinating to the CuPc molecule was 1 and 2 for the first and second proton adducts, respectively, which indicates the formations of CuPcH(+) and CuPcH(2)(2+). This CuPc molecule may act as a catalyst to dissociate TFAA into trifluoroacetate anion (A(-)) and H(+) and form the proton adducts. The electrical conductivity dependence of the solution on CuPc concentration also supports this mechanism. A dense film of CuPc was deposited on an indium tin oxide cathode plate by electrophoresis of the solution. Similar dense films of a wide variety of phthalocyanines (MPc; M = Cu, H(2), Fe, Ni, Zn, Pb, VO) were also deposited using this method. Similar films of CuPc were also formed using dichloromethane (DCM) and 1,1,1-trichloroethane (TCE) in place of DCE. Depositions are ascribed to the migration of positively charged monomers (i.e., protonated MPc). Scanning electron microscopy revealed that these films are composed of fibrous crystallites, size of which was found to increase with the electrophoresis time, the strength of the applied electrical field and the concentration of CuPc in the bath. The influence of the dielectric constant of the organic solvent on the film growth is discussed.     

溶剂对SEBS/PMMA共混物薄膜形态的影响

采用原子力显微镜研究了聚（苯乙烯嵌-乙烯／丁烯嵌-苯乙烯）（SEBS）和聚甲基丙烯酸甲酯（PMMA）共混物不同溶剂旋转涂膜的表面形态和相分离行为。结果表明,用共混物的氯仿溶液旋转涂膜,可见明显的共混物的宏观相分离和SEBS的微观相分离形态。改变选择性溶剂可使旋涂膜具有不同的均匀度和形态结构,其相区的尺寸和形状相差甚大,有海岛型、网状、双连续状结构。AFM显示用环己烷／丁酮混合溶剂旋转涂膜,共混物的相分离最为彻底;用选择性溶剂氯仿时次之,但有明显的相分离;对SEBS和PMMA均无选择性的单一溶剂或混合溶剂则无明显相分离。     

Polyimide-polydimethylsiloxane copolymers containing nitrile groups

A novel series of nitrile-containing polyimide-polydimethylsiloxane copolymers was prepared by polycondensation reaction of 4,4′-oxydiphthalic anhydride with a mixture of an aromatic diamine, namely 2,6-bis(3-aminophenoxy)benzonitrile, and bis(aminopropyl)oligodimethylsiloxane of controlled molecular weight, in different ratios. The polymers were easily soluble in polar organic solvents, such as N-methylpyrrolidone, N,N-dimethylformamide as well as in less polar solvents such as chloroform, and can be cast from solution into thin flexible films. The inherent viscosity was in the range of 0.43-0.55 dL/g. The polymers showed good thermal stability, the decomposition temperature being above 430 °C. They exhibited a glass transition temperature in the range of 149-219 °C, with reasonable interval between glass transition temperature and decomposition temperature. The surface morphology was investigated by scanning electron microscopy. The water dynamic contact angles were measured by tensiometric method. The free surface energy was evaluated based on Owens and Wendt equation. A composite film based on a polyimide-polydimethylsiloxane copolymer and pyrite ash powder has been prepared and its nanoactuation has been investigated.     

Effects of evaporation velocity and film thickness on poly(3‐hexylthiophene) thin films processed from aggregate dispersions in binary solvent mixtures

Aggregate dispersions of P3HT in two series of solvent mixtures, chloroform:dichloromethane and toluene:dichloromethane, are used to study the impact of the evaporation velocity and film thickness on the P3HT films processed using two spin‐coating speeds (1000 rpm and 2000 rpm). The structural order and surface morphology were investigated with UV/Vis absorption spectroscopy and atomic force microscopy techniques. There is no evidence that the characteristics of the liquid phase P3HT dispersions impact the structures of the films, which is in agreement with a previous study of drop cast P3HT films that were dried over much longer time periods. An association is observed between the extent of aggregation in the liquid phase and the thickness and surface roughness parameters of the films. However, the structural order does not correlate with the thickness of the films, which was previously reported for polymer films processed from amorphous polymer solutions in pure organic solvents. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 330–343     

Self-organization of polystyrenes into ordered microstructured films and their replication by soft lithography

We report on the formation of ordered arrays of micrometric holes on the surface of polystyrene (PS) films cast from volatile solvents in the presence of humidity at different temperatures. The formation mechanism is investigated for PS having different molecular weights, polydispersities, and carboxylic terminations. Among the chosen materials, a highly regular honeycomb microstructured morphology is obtained on the surface of films prepared with dicarboxy-terminated PS with = 100,000. Experiments and observations on film formation indicate that polar groups are playing a fundamental role in this process. Tuning the surface tension by means of polar terminations allows the film morphology to be modified and in particular the preparation of two- or three-dimensional microstructured films. Finally, we show how these structures can be replicated by soft lithography and then used in the fields of photonic crystals and organic electronics.     

Controlling the size of poly(hydroxybutyrate-co-hydroxyvalerate) nanoparticles prepared by emulsification–diffusion technique using ethanol as surface agent

Poly(hydroxybutyrate-co-hydroxyvalerate) (PHBHV) nanospheres and oily nanocapsules were prepared by emulsification–diffusion technique. Controlled particle sizes were obtained employing binary mixtures of solvents (chloroform:ethanol) in the organic phase. Ethanol was chosen because of its dipole–dipole interaction with chloroform and its hydrogen bond with water. The smallest particles (from 253 to 493 nm) were obtained using a mixture of solvents composed of 70% ethanol and 30% chloroform (v/v) in the organic phase, while the largest particles (from 896 to 1568 nm) were obtained using chloroform exclusively. Independently of the organic phase composition, the nanoparticles showed unimodal distributions. Optical microscopy showed that the size of the primary emulsion droplets of the nanosphere formulations decreased with increasing ethanol concentrations in the organic phase. A simple empirical equation was developed correlating the nanoparticle diameters with the surface tension gradient coefficient multiplied by the ethanol molar concentration in the organic phase. The strategy showed that the control of the nanoparticle diameters, using emulsification–diffusion technique, could be achieved by adjusting the surface tension of the organic phase.     

Evaporation‐Induced Ordered Honeycomb Structures of Gold Nanoparticles at the Air/Water Interface

The breath figure method was used to prepare dodecanethiol‐capped gold nanoparticle macroporous structures with pore diameters from 1.7 to 3.5 μm on an air/water interface. A two‐step procedure is proposed for the fabrication of these macroporous structures, by forming a surfactant monolayer on water, and drop‐casting a gold nanoparticle dispersion in chloroform onto the surfactant monolayer. The self‐assembled films are easily transferred from the water surface onto different substrates and were characterized by TEM, SEM, and AFM. Ordered honeycomb structures with different pore arrays (perforated monolayer films, hexagonal networks and alveoli‐like porous films) were obtained. The change in morphology is concentration dependent, and deformed structures with elliptic honeycomb networks are also observed. In addition, honeycomb films using gold nanoparticles stabilized by a weakly bound ligand (dioctadecyldimethylammonium chloride) were formed by the same technique. These films have potential as substrates for surface‐enhanced Raman spectroscopy.