聚(ε-己内酯)薄膜结晶形貌及分子取向研究

用匀胶机通过溶液铸膜方法在硅片和铝箔基板上分别制备具有不同厚度的聚(ε-己内酯)(PCL)薄膜. 通过原子力显微镜(AFM)和偏光衰减全反射傅里叶红外光谱(ATR-FTIR)对薄膜中PCL的结晶形貌、 片晶生长方式及分子链取向进行了研究. AFM结果表明, 在200 nm或更厚的薄膜中, PCL主要以侧立(edge-on)片晶的方式生长; 对于厚度小于200 nm的薄膜, PCL片晶更倾向于以平躺(flat-on)的方式生长. 这种片晶生长方式的改变在硅片和铝箔基板上都表现出同样的倾向. 此外, 在15 nm或更薄的薄膜中, PCL结晶由通常的球晶结构变为树枝状晶体. 偏光ATR-FTIR结果表明, 当膜厚小于200 nm时, 薄膜结晶中PCL分子链沿垂直于基板表面方向取向, 并且膜越薄, 取向程度越高, 与AFM的观测结果一致.     

Structures and electrical properties of ferroelectric copolymer ultrathin films

Ultrathin films of ferroelectric copolymer vinylidenefluoride and trifluoroethylene, P(VDF-TrFE), were successfully obtained by spin-coating and their nanoscale structures and electrical properties were studied utilizing atomic force microscopy (AFM). We succeeded in obtaining ultrathin copolymer films on graphite whose thickness ranged from 1 nm to several tens of nanometers by controlling concentration of copolymer solutions in methylethylketone. We found that ultrathin films thinner than 4 nm showed layered structures whose layer thickness was about 0.5 nm. On the other hand, films thicker than 4 nm formed typical edge-on lamellar crystal structures. Furthermore, we investigated surface potential distribution and piezoelectric property by AFM-based techniques and discussed interaction between electrical dipoles in the molecular chains and graphite substrate.     

Thickness-dependent molecular chain and lamellar crystal orientation in ultrathin poly(di-n-hexylsilane) films

The molecular chain and lamellar crystal orientation in ultrathin films (thickness < 100 nm) of poly-(di-n-hexylsilane) (PDHS) on silicon wafer substrates have been investigated by using transmission electronic microscopy, wide-angle X-ray diffraction, atomic force microscopy, and UV absorption spectroscopy. PDHS showed a film thickness-dependent molecular chain and lamellar crystal orientation. Lamellar crystals grew preferentially in flat-on orientation in the monolayer ultrathin films of PDHS, i.e., the silicon backbones were oriented along the surface-normal direction. By contrast, the orientation of lamellar crystals was preferentially edge-on in ultrathin films thicker than ca. 13 nm, i.e., the silicon backbones were oriented parallel to the substrate surface. We interpret the different orientations of molecular chain and lamellar crystal as due to the reduction of the entropy of the polymer chain near the substrate surface and the particularity of the crystallographic (001) plane of flat-on lamellae, respectively. A remarkable influence of the orientations of the silicon backbone on the UV absorption of these PDHS ultrathin films was observed due to the one-dimensional nature of sigma-electrons delocalized along the silicon backbone. With the silicon backbones perpendicular or parallel to the surface of the substrate, the UV absorbance increased or decreased with an increase of the angle between the incident UV beam direction and direction normal to the thin film, respectively.     

左旋聚乳酸/聚(ε-己内酯)共混物在取向聚乙烯基底上的附生结晶行为

利用电子显微镜结合电子衍射研究了左旋聚乳酸/聚(ε-己内酯)(PLLA/PCL)共混物在取向聚乙烯(PE)基底上的结晶行为.纯PLLA在取向PE基底上能够附生结晶,主要形成分子链相互垂直的片晶结构.PCL在PE基质上也能发生附生结晶,导致两者分子链平行.PLLA/PCL共混物在取向PE基底上结晶的形态结构依赖于共混组成.在PLLA含量大于95 wt%时,PCL不影响PLLA与PE的附生结晶行为.当PCL含量增加至10 wt%时,PLLA在PE上的附生结晶行为受到了一定程度的影响.当PCL含量超过40 wt%时,PLLA在PE上的附生结晶被抑制,取而代之是PCL在PE取向基质上附生结晶,产生两者分子链平行的取向片晶.另外,在PLLA含量在50 wt%~30 wt%之间时,体系产生明显的微相分离,微相分离并不影响PCL与PE的附生结晶,在PCL的富集区仍然发生平行链附生结晶,而PLLA的富集区结构变得模糊.当PLLA含量少于20 wt%时,微相分离不明显,少量PLLA应该分散在PCL片晶间的非晶区.     

聚甲基丙烯酸甲酯单分子膜的原子力学显微镜研究

报道了利用原子力显微镜（ＡＦＭ）技术对聚甲基丙烯酸甲酯（ＰＭＭＡ）单分子膜进行分子结构水平的观察研究．由ＡＰＭ图像中得到的ＰＭＭＡ单体所占面积与用π－Ａ曲线中换算出液面上ＰＭＭＡＬａｕｇｍｕｉｒ膜中单体的面积符合得很好．从ＡＦＭ图像中可见ＰＭＭＡＬＢ膜中ＰＭＭＡ的线型碳链是与档板（ｂａｒｒｉｅｒ）平行的紧密排列，与ＬＢ提膜方向相垂直．并由此对ＰＭＭＡＬＢ膜的形成过程进行分析．此外，还观察到了在Ｓｉ基底上ＰＭＭＡ直链的卷绕伸直排列形态，初步分析了其形成原因．     

Epitaxial growth of low molecular weight polypropylene from vapor phase

Polypropylene was evaporated on the (001) cleavage faces of alkali halide single crystals, NaCl, KCl, KBr, and KI, under a vacuum of 10^?5 torr. Films evaporated on the substrate were found to be composed of low molecular weight polypropylene with a narrow molecular weight distribution. The polypropylene film evaporated on the substrate maintained at 100°C, was composed of rod-like crystals of α form, the (010) plane of which was parallel to the (001) plane of alkali halide and their long axes were oriented in the (110) direction of the substrate. When the substrate was kept above 150°C, the film included three crystalline forms, α, γ, and δ forms. Fiber-like crystals of the α form lay parallel to the (110) direction of NaCl. In the initial stage of growth, lamellar crystals were observed in the film. The lamellar (001) plane lay flat in the film and branching occurred on the (010) lateral faces. Both the γ-form and the (predominately) new δ-form crystals were observed in the same area of the film prepared at temperatures above 150°C.     

Layer-by-layer electrostatic assembly with a control over orientation of molecules: anisotropy of electrical conductivity and dielectric properties

While forming layer-by-layer (LbL) electrostatic assembly of a magnetic organic molecule, namely, nickel phthalocyanine (NiPc), we apply a magnetic field. The field orients the magnetic moment of the molecules on a monolayer along the direction of magnetic field. Such an orientation of the molecules is then electrostatically immobilized with a monolayer of a polycation. By repeating the dipping cycle, we form LbL films with planar NiPc molecules facing a particular direction. With NiPc's moment perpendicular to the molecular plane, two types of LbL films were formed: (a) NiPc's molecular plane parallel to the substrate (moment is perpendicular) and (b) molecules perpendicular to the substrate and facing one particular direction, the direction of magnetic field. Such films, with the molecules lying either (a) parallel or (b) perpendicular to the substrate, provide unique systems to study anisotropy of optical, dielectric, and electrical characteristics in these planar organic molecules. The latter film responds to the polarization of incident beam in electronic absorption spectroscopy. Here we show methods to obtain an orientation of molecules in LbL films and study anisotropy of dielectric constant and conductivity of the molecules in ultrathin films.     

Lamellar orientation in thin films of symmetric semicrytalline polystyrene-b-poly(ethylene-co-butene) block copolymers: effects of molar mass, temperature of solvent evaporation, and annealing

Orientation of the lamellar microdomains in thin films of three symmetric polystyrene-b-poly(ethylene-co-butylene) block copolymers (S65E155, S156E358, and S199E452) on mica was investigated via atomic force microscopy (AFM), grazing incidence X-ray diffraction (GIXRD) and X-ray photoelectron spectroscopy (XPS). The results show that lamellar orientation in the SxEy block copolymers greatly depends on the molar mass of the block copolymers, the temperature of solvent evaporation, and annealing. The nascent thin film of the low molar mass block copolymer, S65E155, shows a multilayered structure parallel to the mica surface with the PS block at both polymer/mica and polymer/air interfaces, but the high molar mass block copolymers, S156E358 and S199E452, exhibit a structure with lamellar microdomains perpendicular to the mica surface. When the solvent is evaporated at a lower temperature, the crystallization rate is fast and a two-dimensional spherulite structure with the lamellar microdomains perpendicular to the mica surface is observed. Annealing of all the thin films with lamellar microdomains perpendicular to the mica surface leads to morphological transformation into a multilayered structure parallel to the mica surface. In all SxEy thin films on mica, the stems of PE crystals are always perpendicular to the interface between the lamellar PE and PS microdomains. A mechanism is proposed for the formation of different microdomain orientations in the thin films of semicrystalline block copolymers. When the thin film is prepared from a homogeneous solution, microdomains perpendicular to the substrate surface are formed rapidly for strongly segregated block copolymers or at a lower crystallization temperature and kinetically trapped by the strong segregation strength or solidification of crystallization, while for weakly segregated block copolymers or at slower crystallization rate, the orientation of the microdomains is dominated by surface selectivity.     

Effect of Film Thickness on the Columnar Packing Structures of Discotic Supramolecules in Thin Films

The effects of film thickness on the columnar packing structure of discotic supramolecules in a thin supported film have been investigated by grazing‐incidence small‐angle X‐ray scattering technique using magnetically aligned cobalt octa(n‐decylthio)porphyrazine (CoS10) films on octadecyltrichlorosilane (OTS)‐functionalized substrates as model systems. Magnetically aligned CoS10 films with a range of film thicknesses (49–845 nm) form uniaxially oriented ‘edge‐on’ columnar superstructures with their columnar directors perpendicular to the applied magnetic field. However, the orientational ordering of the columnar packing in the plane perpendicular to the applied magnetic field is strongly dependent on the film thickness. While being damped by the elasticity of the side chains of CoS10, the strong interfacial interaction at the film‐substrate interface propagates up to 50–100 nm from the substrate, maintaining the orientation of columnar packing in the plane perpendicular to the applied magnetic field. When the distance from the film‐substrate interface becomes larger than about 100 nm, symmetric tilting of columnar layer orientation, which saturates at 11.5°, occurs due to longitudinal edge dislocations induced by accumulated elastic deformation.     

Ordered arrays of organometallic iridium complexes with long alkyl chains on graphite

Iridium(III) fac-tris(2-phenylpyridine) fac-[Ir(ppy)3] complexes equipped with long alkyl chains were prepared to examine their capability to form organized arrays on the surface of highly oriented pyrolytic graphite (HOPG). The molecules form lamellar arrays at the 1-phenyloctane/HOPG interface. From the analysis of the STM images, it was concluded that the molecules align with alkyl chains being interdigitated. Similar lamellar arrays were also obtained at the air/HOPG interface upon drop-casting of toluene solutions. The lamellar structure at the molecular level leads to rectangular two-dimensional crystalline domains a few hundred nanometers long (nanoslips). Infrared external reflection spectroscopy suggested that the adsorbed alkyl chains adopt the trans-zigzag conformation in the nanoslip, although the orientations of the zigzag plane of the alkyl groups are mixed. Cyclic voltammetry indicates fast electron transfer between the adsorbed molecules and the substrate and significant intermolecular electronic interactions. It was found that annealing at high temperatures is an effective method to prepare ordered assemblies more than a few micrometer scale (microslips). The orientations of the nanoslips prepared from the racemic mixture exhibited an apparent 12-fold symmetry, while its optically active enantiomer resulted in more irregular domains with a six-fold symmetry, implying an important role of chirality on packing at the molecular level and on the orientation of the domains at larger scales. When drop-cast from more concentrated solutions than a few hundreds of micromolar, multilayers were obtained, in which the alkyl chains in the molecules are more or less perpendicular to the surface. This structure can be transformed into the nanoslips upon standing.     

MORPHOLOGICAL STUDY ON THE ORIENTED CHITOSAN FILM OBTAINED FROM PRE-SHEARED LIQUID CRYSTALLINE SOLUTION IN DICHLOROACETIC ACID

The oriented chitosan films obtained from pre-sheared liquid crystalline chitosan/dichloroacetic acid (DCA)solutions were studied by means of polarized optical microscopy (POM), scanning electron microscopy (SEM), infra-reddichroism technique and wide angle X-ray diffraction (WAXD). The shear induced band texture in the film was found tocorrespond to the sinusoidal fibrillar microstructure along the shearing direction on the basis of POM and SEM observations.The sinusoidal fibril was found to be lying within the film plane. The model of chitosan molecular orientation in the pre-sheared film with band texture can be established assuming that the main chain orients in the shearing direction and the sidegroup is perpendicular to the shearing direction. The WAXD azimuthal scanning at 2θ= 20° indicates that the (002) planeorients perpendicular to the shearing direction.     

Dense passivating poly(ethylene glycol) films on indium tin oxide substrates

We describe the formation and characterization of surface-passivating poly(ethylene glycol) (PEG) films on indium tin oxide (ITO) glass substrates. PEG chains with a molecular weight of 2000 and 5000 D were covalently attached to the substrates in a systematic approach using different coupling schemes. The coupling strategies included the direct grafting with PEG-silane, PEG-methacrylate, and PEG-bis(amine), as well as the two-step functionalization with aldehyde-bearing silane films and subsequent coupling with PEG-bis(amine). Elemental analysis by X-ray photoelectron spectroscopy (XPS) confirmed the successful surface modification, and XPS and ellipsometry provided values for film thicknesses. XPS and ellipsometry thickness values were almost identical for PEG-silane films but differed by up to 400% for the other PEG layers, suggesting a homogeneous layer for PEG-silane but an inhomogeneous distribution for other PEG coatings on the molecularly rough ITO substrates. Atomic force microscopy (AFM) and water contact angle goniometry confirmed the different degrees of surface homogeneity of the polymer films, with PEG-silane reducing the AFM rms surface roughness by 50% and the water contact angle hysteresis by 75% compared to uncoated ITO. The ability of the PEG layers to passivate the substrate against the nonspecific adsorption of biopolymers was tested using fluorescence-labeled immunoglobulin G and DNA oligonucleotides in combination with fluorescence microscopy. The results indicate a positive relationship between film density and homogeneity on one hand and the ability to passivate against biopolymer adhesion on the other hand. The most homogeneous layers prepared with PEG-silane reduced the nonspecific adsorption of fluorescence-labeled DNA by a factor of 300 compared to uncoated ITO. In addition, the study finds that the ratio of film thicknesses derived by ellipsometry and XPS is a useful parameter to quantify the structural integrity of PEG layers on molecularly rough ITO surfaces. The findings may be applied to characterize PEG or other polymeric films on similarly coarse substrates.     

Growth of organic n-conductors on thin polymer films for use in organic field effect transistors

Thin films of different polymers - poly(styrene) (PS), poly(methylmethacrylate) (PMMA), poly(vinylcarbazole) (PVCz), poly(vinylchloride) (PVC) and poly(vinylidene fluoride) (PVDF) - were deposited by spin-coating or by vapor deposition. On these polymers, thin films of (hexadecafluorophthalocyaninato)-oxovanadium (F₁₆PcVO) were prepared by physical vapor deposition. The growth of these films was monitored in situ by optical spectroscopy. The optical absorbance spectra were analyzed based on the coupling of transition dipoles to obtain information on the intermolecular arrangement of chromophores in the films. In all of these samples, the molecules are oriented with their molecular plane preferentially perpendicular to the substrate surface. This gives the desired overlap of the π-systems for electric conductance parallel to the substrate. Differences in the interactions were detected when deposition temperatures below or above the glass transition temperature of a given polymer were compared. The morphology of the polymer films and the deposited semiconductors were investigated by atomic force microscopy and scanning electron microscopy. The influence of the chosen substrate on the film structure is determined. The optical and electric properties of the films could thereby be influenced and the applicability of such films as active layers in organic thin film transistors is discussed.     

Substrate-induced anisotropy of c-axis textured NaxCoO2 thin films

Na_xCoO₂ [x = 0.51, 0.54, and 0.59] thin films have been grown on SrTiO₃ (100)-oriented single crystals with a 5° vicinal cut towards [010] by pulsed laser deposition. We analysed the films by X-ray diffractometry, atomic force microscopy (AFM), and dc-transport measurements. X-ray diffraction patterns of the films show single phase and c-axis textured growth with the film plane closely aligned to the [001]-direction of 5° miscut SrTiO₃ (001) substrates. In addition to the structural analysis of these films we performed transport measurements along and perpendicular to the substrate tilt direction and determined the resistivity anisotropy as a function of temperature. The results enable the development of a strategy for the fabrication of Na_xCoO₂ based thermoelectric thin film devices.     

聚亚苯基苯并二噻唑的X射线衍射研究

本文用X射线衍射研究了聚亚苯基苯并二噻唑(PBT)薄膜的结构特征。衍射结果表明PBT在液晶态成膜具有高的取向度,分子链在垂直于取向方向呈有序的二维周期排列,沿取向方向分子链相互间无序平行排列。热处理可明显提高PBT的有序度,即在垂直于取向方向分子链的二维排列更规整,晶格畸变减小,而取向方向分子链中苯杂环呈群集排列,出现三维有序的衍射斑点,测其群集结构平面的法线与取向方向夹角为29°。     

结晶性间同立构1,2-聚丁二烯的单晶结构

近十几年来 ,结晶性间同立构 1 ,2 -聚丁二烯引起人们的广泛关注 ,但绝大多数研究工作集中在聚合物的制备、物理性质和应用方面[1～ 3] ,对于其结晶行为和晶体结构则未见报道 .原因是间同立构 1 ,2 -聚丁二烯分子侧链含有大量的双键 ,在较高温度下很容易交联 ,特别是高间规度的聚合物 ,由于其熔融温度高 (>2 0 0℃ )则更易产生交联 ,这给结晶行为和结构研究带来很大困难 .结晶性间同立构 1 ,2 -聚丁二烯的晶体结构为平面锯齿链正交堆砌 ,Pacm空间群[4 ] .我们曾报道了结晶性间同立构 1 ,2 -聚丁二烯的合成和溶液浇铸膜的板条状结构[5] ,本…     

Columnar self-assembly and alignment of planar carbenium ions in Langmuir-Blodgett films

Structural and optical properties of multilayer Langmuir-Blodgett (LB) films of two amphiphilic carbenium salts 2-didecylamino-6,10-bis(dimethylamino)-4,8,12-trioxatriangulenium hexafluorophosphate (ATOTA-1) and 2,6-bis(decylmethylamino)-10-dimethylamino-4,8,12-trioxatriangulenium hexafluorophosphate (ATOTA-2) are described. The LB films were prepared on lipophilic glass by standard vertical dipping. Grazing incidence X-ray diffraction (GIXD) measurements show that the planar organic cores, in spite of their positive charge, form closely packed columns with a repeating distance of ～3.45 ?. Specular X-ray reflectivity (SXR) reveals the LB multilayers to consist of Y-type bilayers with thickness 31 ? for ATOTA-1 and 41 ? for ATOTA-2. This significant difference is ascribed to the different packing motifs of the alkyl chains in the two LB films. GIXD and polarized UV-vis absorption and emission spectroscopy show that the columnar aggregates in the LB films are oriented along the dipping direction. This alignment is attributed to shear effects during LB transfer. The main absorption band of the LB films is blue-shifted compared to that in solution, while the fluorescence is red-shifted by more than 100 nm. These findings suggest the presence of H-aggregates in agreement with the cofacial packing derived from the X-ray measurements. Polarized absorption spectroscopy with variable angle of incidence was used to resolve two perpendicular optical transitions in the visible range, one at 460 nm polarized perpendicular to the columnar direction, in the plane of the film, and one at 420 nm polarized along the film normal.     

NO2 gas detection by Langmuir-Blodgett films of copper phthalocyanine multilayer structures

Copper (II) phthalocyanine derivatives with four alkyl chains were synthesized. Langmuir-Blodgett (LB) films of the following two compounds were deposited: Cu(II)[tetrakis(3,3-dimethyl-butoxycarbonyl)] phthalocyanine and Cu(II)[tetrakis(n-butoxycarbonyl)] phthalocyanine. Moreover, LB films from a 1:1 mixture of the two compounds were prepared. All isotherms and optical data were consistent with the molecules being stacked nearly edge-on to the substrate, with the molecular faces having a preferred orientation perpendicular to the dipping direction. The dynamic response characteristics of the electrical conductance of the LB films to different NO₂ concentrations in dry air are described. A relationship has been observed between the anisotropic molecular orientation and the electrical conductivity parallel to the substrate.     

Photoinduced electron transfer in Langmuir-Blodgett monolayers of porphyrin-fullerene dyads

A series of electron donor-acceptor (DA) dyads, composed of a porphyrin donor and a fullerene acceptor covalently linked with two molecular chains, were used to fabricate solid molecular films with the Langmuir-Blodgett (LB) technique. By means of the LB technique, the DA molecules can be oriented perpendicular to the plane of the substrate. In DHD6ee and its zinc derivative hydrophilic groups are attached to the phenyl moieties in the porphyrin end of the molecule; while in the other three dyads, TBD6a, TBD6hp, and TBD4hp, the hydrophilic groups are in the fullerene end of the molecule. This makes it possible to alternate the orientation of the molecules in two opposite directions with respect to the air-water interface and to fabricate molecular assemblies in which the direction of the primary photoinduced vectorial electron transfer can be controlled both by the deposition direction of the LB monolayer and by the selection of the used DA molecule. This was proved by the time-resolved Maxwell displacement charge measurements. The spectroscopic properties of the DA films were studied with the steady-state absorption and fluorescence methods. In addition, the time correlated single photon counting technique was used to determine the fluorescence properties of the dyad films.     

Templating α-helical poly(L-lysine)/polyanion complexes by nanostructured uniaxially oriented ultrathin polyethylene films

We report a templating effect of uniaxially oriented melt-drawn polyethylene (MD-PE) films on α-helical poly(L-lysine)/poly(styrenesulfonate) (α-PLL/PSS) complexes deposited by the layer-by-layer (LBL) method. The melt-drawing process induced an MD-PE fiber texture consisting of nanoscale lamellar crystals embedded in amorphous regions on the MD-PE film surface whereby the common crystallographic c axis is the PE molecular chain direction parallel to the uniaxial melt-drawing direction. The MD-PE film and the α-PLL/PSS deposit were analyzed by atomic force microscopy (AFM) and in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) using polarized light as a complementary method. Both methods revealed that α-PLL/PSS complexes adsorbed at the MD-PE surface were anisotropic and preferentially oriented perpendicular to the crystallographic c direction of the MD-PE film. Quantitatively, from AFM image analysis and ATR-FTIR dichroism of the amide II band of the α-PLL, mean cone opening angles of 12-18° for both rodlike α-PLL and the anisotropic α-PLL/PSS complexes with respect to the PE lamellae width direction were obtained. A model for the preferred alignment of α-PLL along the protruding PE lamellae is discussed, which is based on possible hydrophobic driving forces for the minimization of surface free energy at molecular and supermolecular topographic steps of the PE surface followed by electrostatic interactions between the interconnecting PSS and the α-PLL during layer-by-layer adsorption. This study elucidates the requirements and mechanisms involved in orienting biomolecules and may open up a path for designing templates to induce directed protein adsorption and cell growth by oriented polypeptide- or protein-modified PE surfaces.