Stability of monomolecular films of archaebacterial tetraether lipids on silicon wafers: a comparison of physisorbed and chemisorbed monolayers

The monomolecular organisation of symmetric, chemically modified tetraether lipids caldarchaeol-PO(4) was studied using Langmuir film balance, ellipsometry, and atomic force microscopy (AFM). Solid silicon wafer substrates were modified to hydrophobic, hydrophilic, and amino-silanised surfaces; and Langmuir-Blodgett (LB)-films were transferred onto each. LB-caldarchaeol-PO(4) films were subjected to further rinsing with organic solvent and additional physical treatments, to compare their resistance and stability on chemisorbed (amino-silanised) and physisorbed (hydrophobic and hydrophilic) surfaces. The resistance and stability of these monolayer films was characterized by ellipsometry and AFM, and film thickness was determined using ellipsometry. AFM was also employed to observe surface morphology. Monolayer films on hydrophobic surfaces were found to be more resistant to rinsing with organic solvent and additional physical treatments than monolayer films on either amino-silanised or hydrophilic surfaces. The hydrophobic effect with hydrophobic surfaces appears to support the formation of stronger caldarchaeol-PO(4) films on silicon wafer substrates, with increased resistance and stability.     

荧光素衍生物LB膜对TiO2电极的光敏化作用

合成了三种荧光素长碳链衍生物，通过LB技术将它们组装成单分子薄膜，修饰在用溶胶-凝胶法制备的TiO2透明电极上，研究了这些LB膜的结构和特性及它对TiO2的光增感作用．并对其光敏化机理作了阐述．     

Thin films of functionalized amorphous silica for immunosensors application

Within the framework of the development of an optical immunosensor, the sol-gel process has been used to prepare a thin film of amorphous silica, deposited by spin coating on a gold-coated glass slide, and possessing chemically active functional groups (SH, NH₂...). After activation of the sol-gel film in aqueous buffers by a bifunctional coupling agent, biological molecules such as antibodies could be covalently bonded on or inside the sol-gel film. Therefore, the behavior in aqueous solutions of the functionalized silica thin films has been analysed by Surface Plasmon Resonance (SPR) and guided wave propagation. Results show a modification of the thickness and of the refractive index of the silica film. Pore size range has been deduced by the infiltration of different molecular weight dextran molecules diluted in water into the sol-gel material. Immunosassays have demonstrated biological activity of antibodies which are covalently linked to or entraped in the sol-gel film.     

Microcrystalline domains of monolayer and multilayer BDN-SA Langmuir–Blodgett films

Monolayer and multilayer BDN(Bis(4-diethyannodithiobenzil)nickel)-SA(stearyl alcohol) LB (Langmuir–Blodgett) films were prepared and the characteristics of microcrystalline domains were studied using UV–vis.–NIR and AFM. The results indicate that BDN-SA LB films consist of numerous ball-like microcrystalline domains at size scales from a few tens to a few hundreds of nm. AFM images of a multilayer LB film show that well-ordered molecular arrangements exist on the surface of domains which resemble a mosaic structure. The relationship between the mean size of the domain of a BDN-SA LB film with the thickness of the film was also shown.     

Spectroellipsometric Characterization of Multilayer Sol-Gel Fe2O3 Films

Multilayer Fe₂O₃ films were deposited by the sol-gel method on glass substrates using three successive deposition procedures. The films were thermally treated for 1 h at 300°C.The optical and microstructural properties of these films were investigated by spectroscopic ellipsometry (SE) in the 500–1000 nm range. The optical gap was found by fitting the dispersion of the film refractive index (n) with the Wemple-DiDomenico (WDD) formula.The ellipsometric measurements showed also that the Fe₂O₃ films are anisotropic. The birefringence values (n) of the sol-gel films (0.05–0.08) are smaller than the large values of the Fe₂O₃ (which are around 0.28) but increase with the crystalization of the films. AFM mesurements showed that the films treated at 300°C start to crystallize.     

Photoconductive properties of organic-inorganic hybrid films of layered perovskite-type niobate

A hybrid film of layered niobate and an organic amphiphile was prepared by the Langmuir-Blodgett (LB) method. Trimethylammonium-exchanged perovskite-type niobates ((CH(3))(3)NHSr(2)Nb(3)O(10)) were exfoliative to form an aqueous suspension. A monolayer of octadecylamine was produced on such an aqueous dispersion as a template for a hybrid film. A hybrid film was transferred as a Y-type LB film onto a hydrophilic glass plate or an ITO substrate. The structure of a deposited film was investigated with X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and atomic force microscopy (AFM) measurements, indicating a layer-by-layer structure with a single or double sheet of niobate as an inorganic composite. From the cyclic voltammogram on an ITO electrode modified with the Y-type 10 layered film, the lower edge of the conduction band of a niobate layer was determined to be - 0.6 V (vs Ag/AgCl). ac impedance and dc measurements were carried out on 1, 5, and 10-layered LB films (2 mm (electrode spacing) x 8 mm (width)) with aluminum electrodes. The freshly deposited samples behaved as an insulator under the illumination of 280 nm light (2.04 x 10(16) quanta s(-1)). Photoconductivities appeared, however, when they were preirradiated with a 150 W Xe lamp (ca. 2 x 10(18) quanta s(-1)) for 0.5-8.5 h. The process was denoted as photomodification. From the FT-IR and XRD results, it was deduced that the photomodification of LB films caused the decomposition of organic templates (octadecylammonium) accompanied by the collapse of layer-by-layer structures. dc analyses on the 5- and 10-layered films after photomodification also showed that they behaved as a photosemiconductor under UV light illumination.     

长链香豆素LB膜对n-Si/Ni液结上的光致电荷转移的影响

本文研究了由硬脂酸香豆素制得的LB膜对n-Si/Ni电极性能的修饰作用.该LB膜沉积方式是Z型的,成膜之后吸收蓝移(由343nm移至325nm).在60mW·cm^-2溴钨灯光照下,n-Si/Ni/3LB/Fe(CN) /Pt电池的光电转换效率增大了一倍,稳定性亦有明显改善.交流阻抗测量表明,光照使n-Si/Ni/3LB电极的电解电阻大大减小,实验结果表明,硬脂酸香豆素LB膜对n-Si/Ni电极上的光致电荷传递过程的修饰作用是良好的.     

Surface plasmon resonance on the LB monolayer of solvent-soluble silicon phthalocyanine

Thin films of bis-(p-chlorophenoxy) (tetra-4-nitrophthalocyaninato)silicon, TNPcSi(OPhCl-p)₂, were prepared by using Langmir-Blodgett techniques and the morphology of the film was investigated by AFM (atomic force microscope) analysis. It has been found that the LB films were successfully transferred onto substrates like mica, gold deposited glass, and pure glass with domains aggregated on the substrates. Surface plasmon resonance has been used to investigate the interaction between sulfur dioxide and a monolayer of TNPcSi(OPhCl-p)₂ LB film. It has been found that the monolayer of LB film transferred onto gold deposited glass gave a 0.55° shift of resonant angle and an additional 0.45° shift of resonant angle after exposion in sulfur dioxide\atomospheric ambient for twenty minute. The UV–visible absorption spectrum of the LB films of TNPcSi(OPhCl-p)₂ showed that there is chemical changes in the film after the exposure to the sulfur dioxide ambient. This work has shown a promising application as an optical gas sensor.     

原子力显微镜研究APS化单晶硅衬底及单层MD膜表面

原子力显微镜研究ＡＰＳ化单晶硅衬底及单层ＭＤ膜表面张希，高芒来，王力彦，沈家骢（吉林大学化学系，长春，１３００２３）关键词原子力显微镜，ＡＰＳ修饰表面，分子沉积膜以静电相互作用为成膜推动力的各种功能体系分子沉积（ＭＤ）超薄膜已有报道［１￣４］．对ＭＤ...     

Morphological investigation of hybrid Langmuir-Blodgett films of arachidic acid with a hydrotalcite/dendrimer nanocomposite

A hydrotalcite clay/dendrimer nanocomposite prepared by the ionic exchange process was adsorbed from suspension of the nanocomposite on a Langmuir monolayer of arachidic acid at the air/water interface, followed by compressing and transferring onto an arachidic acid monolayer Langmuir-Blodgett (LB) film on mica. For comparison, the hydrotalcite-adsorbed hybrid film was also prepared. The morphology of hydrotalcite and the nanocomposite studied by transmission electron microscopy indicated the layered structures with respectively 1.2 +/- 0.3 and 3.2 +/- 0.5 nm repeating distances. The hybrid Langmuir films displayed the occupied surface area of 0.24 nm2 for both hydrotalcite and the nanocomposite. The formation of hybrid Langmuir films was confirmed by Brewster angle microscopy. Atomic force microscopic images of hybrid LB films revealed the formation of plateau domains with the height difference of 6 nm for hydrotalcite and 12 nm for the nanocomposite and the presence of dendrimers adsorbed on the clay surface of the nanocomposite.     

Surface chemistry studies of (CdSe)ZnS quantum dots at the air-water interface

Trioctylphosphine oxide- (TOPO-) capped (CdSe)ZnS quantum dots (QDs) were prepared through a stepwise synthesis. The surface chemistry behavior of the QDs at the air-water interface was carefully examined by various physical measurements. The surface pressure-area isotherm of the Langmuir film of the QDs gave an average diameter of 4.4 nm, which matched very well with the value determined by transmission electron microscopy (TEM) measurements if the thickness of the TOPO cap was counted. The stability of the Langmuir film of the QDs was tested by two different methods, compression/decompression cycling and kinetic measurements, both of which indicated that TOPO-capped (CdSe)ZnS QDs can form stable Langmuir films at the air-water interface. Epifluorescence microscopy revealed the two-dimensional aggregation of the QDs in Langmuir films during the early stage of the compression process. However, at high surface pressures, the Langmuir film of QDs was more homogeneous and was capable of being deposited on a hydrophobic quartz slide by the Langmuir-Blodgett (LB) film technique. Photoluminescence (PL) spectroscopy was utilized to characterize the LB films. The PL intensity of the LB film of QDs at the first emission maximum was found to increase linearly with increasing number of layers deposited onto the hydrophobic quartz slide, which implied a homogeneous deposition of the Langmuir film of QDs at surface pressures greater than 20 mN.m(-1).     

Structural and thermal study of CuInSe2 films

Ternary copper indium Di-selenide (CISe) thin film has been deposited by spin-coating on non-conducting glass slide substrates and a solution prepared by the sol-gel process. At room temperature, correspondingly, CuCl2·2H2O, InCl3·3H2O, and H2SeO3 were employed as precursor source chemicals for Cu, In, and Se ions. The dark brown films adhered effectively to the glass substrates. Energy dispersive X-ray analysis is utilized to assess the thin film's chemical composition, which revealed that the film was close to the stoichiometric ratio and proved the proper elemental composition. The thin film's tetragonal unit cell structure was validated by XRD analysis, and all of the derived lattice parameters (a = 5.8512 A and c = 11.7268 A) are excellent consistent with the previous results. Scherrer's formula yields a crystallite size of 5.94 nm. SEM microtopography of the film surface revealed that the film is homogeneous on the substrate surface, and AFM revealed that the film has a spike-like morphology. UV–Vis spectroscopy was performed in the 300–1400 nm region. The obtained values of the absorption coefficient and band gap are 1.2eV. The thermal analysis is carried out by TGA.     

不含亲水基团的偶氮苯衍生物L-B膜的制备和性质研究

本文合成了具有一定结构特点的偶氮苯的衍生物, 以元素分析和^1HNMR鉴定了B产物的组成和结构。采用L-B技术制备了其多层L-B膜, 以紫外可见光谱研究了膜中分子的聚集状态和膜的纵向均匀性; 以偏振紫外确定了膜中分子偶氮基的取向; L-B膜的小角度X射线衍射结果表明膜具有层状有序的周期性结构。     

A multiscale structural study of nanoparticle films prepared by the Langmuir–Blodgett technique

Arrays of magnetic nanoparticles (NPs) represent a very interesting challenge toward the development of new devices for magnetic applications such as data storage and spintronic. The final properties of such assemblies depending essentially on the spatial arrangement of NPs, it is of first importance to investigate precisely their structure. Here, the structure of monolayer and multilayer films of magnetic iron oxide NPs assembled by the Langmuir–Blodgett (LB) technique has been studied by usual techniques such as SEM, AFM and ellipsometry and by a new and an easy to process enhanced optical technique: the Surface Enhancement Ellipsometry Contrast (SEEC) microscopy. This technique is based on the use of a new generation of microscope slides used as substrates which allow the strong enhancement of the sample contrast to a point where it becomes possible to visualize the structure of monolayer and multilayer films at the nanoscale with a conventional optical microscope. The SEEC microscopy is demonstrated to be complementary to usual characterization techniques to study the structure of NPs films, especially for films containing very small nanosized NPs which are more difficult to analyze by usual techniques. While the film structure is investigated with lateral resolution of microns, the layer thickness is analyzed at the nanoscale (with a precision of 0.3 nm) with a close fit to the experimental measurements on local (AFM) and on larger (ellipsometry) areas. This technique presents the advantage to visualize directly the topography of NPs assemblies on very large areas by extracting information such as the height profile, the film roughness and generating 3D images.     

Preparation and characterization of thin films of SiO(x) on gold substrates for surface plasmon resonance studies

We report here on the fabrication and characterization of stable thin films of amorphous silica (SiO(x)) deposited on glass slides coated with a 5 nm adhesion layer of titanium and 50 nm of gold, using the plasma-enhanced chemical vapor deposition (PECVD) technique. The resulting surfaces were characterized using atomic force microscopy (AFM), ellipsometry, contact angle measurements, and surface plasmon resonance (SPR). AFM analysis indicates that homogeneous films of silica with low roughness were formed on the gold surface. The deposited silica films showed excellent stability in different solvents and in piranha solution. There was no significant variation in the thickness or in the SPR signal after these harsh treatments. The Au/SiO(x) interfaces were investigated for their potential applications as new surface plasmon resonance sensor chips. Silica films with thicknesses up to 40 nm allowed visualization of the surface plasmon effect, while thicker films resulted in the loss of the SPR characteristics. SPR allowed further the determination of the silica thickness and was compared to ellipsometric results. Chemical treatment of the SiO(x) film with piranha solution led to the generation of silanol surface groups that have been coupled with a trichlorosilane.     

Study of Langmuir and Langmuir-Blodgett films of odorant-binding protein/amphiphile for odorant biosensors

To make ultrathin films for the fabrication of artificial olfactory systems, odorant biosensors, we have investigated mixed Langmuir and Langmuir-Blodgett films of odorant-binding protein/amphiphile. Under optimized experimental conditions (phosphate buffer solution, pH 7.5, OBP-1F concentration of 4 mg L(-1), target pressure 35 mN m(-1)), the mixed monolayer at the air/water interface is very stable and has been efficiently transferred onto gold supports, which were previously functionalized by self-assembled monolayers (SAMs) with 1-octadecanethiol (ODT). Atomic force microscopy and electrochemical impedance spectroscopy were used to characterize mixed Langmuir-Blodgett (LB) films before and after contact with a specific odorant molecule, isoamyl acetate. AFM phase images show a higher contrast after contact with the odorant molecule due to the new structure of the OBP-1F/ODA LB film. Non-Faradaic electrochemical spectroscopy (EIS) is used to quantify the effect of the odorant based on the electrical properties of the OBP-1F/ODA LB film, as its resistance strongly decreases from 1.18 MOmega (before contact) to 25 kOmega (after contact).     

有机HTDIOO分子LB膜结构的AFM研究

利用原子力显微镜（AFM）对有机分子HTDIOO单层和多层LB膜结构进行了观察·实验结果表明，针尖与LB膜表面分子间的相互作用力会对成像的膜结构有影响．当悬臂针尖与LB膜表面分子的相互作用力较大时，针尖会扰动HTDIOO分子在单层LB膜中的有序排列．HTDIOO单层LB膜具有有序结构；而在多层LB膜中，HTDIOO分子则聚集在一起形成了一定的畴结构．     

有机HTDIOO分子LB膜结构的AFM研究

利用原子力显微镜（ＡＦＭ）对有机分子ＨＴＤＩＯＯ单层和多层ＬＢ膜结构进行了观察。实验结果表明，针尖与ＬＢ膜表面分子间的相互作用力会对成像的膜结构有影响。当悬臂针尖与ＬＢ膜表面分子的相互作用力较大时，针尖会扰动ＨＴＤＩＯＯ分子在单层ＬＢ膜中的有序排列。ＨＴＤＩＯＯ单层ＬＢ膜具有有序结构；而在多层ＬＢ膜中，ＨＴＤＩＯＯ分子则聚集在一起形成了一定的畴结构。     

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.     

Structural, optical and photoelectric properties of ZnO:In and Mg x Zn1 −x O nanofilms prepared by sol-gel method

The photochromic sol-gel hybrid materials containing cyanoazobenzene chromophores were described. These materials were obtained by copolycondensation of the functionalized triethoxysilane and tetraethoxysilane precursor. They were deposited on glass substrates via spin coating and casting techniques to provide thin transparent films. The UV-vis spectroscopy showed reversibility of the trans-cis photoisomerization of the chromophoric fragments. The reversible change of refractive index of the films on illumination with white light was determined by ellipsometry. The difference of real part of the refractive index of the sample was in the range 0.0053–0.0075. Formation of diffraction grating was achieved by two beam coupling arrangement using a 532 nm laser. The diffraction efficiency for the first order diffraction was in the range of 2–3.5%. The kinetics of photochromic grating recording and erasing was described by biexponential function approach.