Structural investigation of n-hexadecanoic acid multilayers on mica surface: Atomic force microscopy study

The structure of n-hexadecanoic acid (HA) multilayers formed by spreading an ethanol solution containing this molecule onto a freshly cleaved mica surface has been studied by atomic force microscopy (AFM). AFM images of multilayers obtained with different coating time showed that HA molecules first formed some sporadic domains on mica surface. With the proceeding of the coating process, these domains gradually enlarged and coalesced, until formed a continuous film finally. It was observed that HA molecules were always adsorbed on mica surface with tilted even-numbered layers structure. The height of the repeated tilted bilayer film was measured to be approximately 3.8 ± 0.2 nm, which implied a ∼60° tilt molecular conformation of the HA bilayers on mica surface. Phase image confirmed that the HA multilayers terminated with the hydrophilic carboxylic acid groups. The formation mechanism of the HA multilayers was discussed in detail. Thus, resulted hydrophilic surfaces are of special interest for further study in biological or man-made member systems.     

Morphology of compressed dipalmitoyl phosphatidylcholine monolayers investigated by atomic force microscopy

The effectiveness of a substitute of natural lung surfactants on replacement therapy strongly depends on the stability of the monolayer of those substitute molecules. An atomic force microscope is utilized to investigate the microstructure of the films of the major components of natural lung surfactants, dipalmitoyl phosphatidylcholine—DPPC, which are transferred to mica substrates by the Langmuir-Blodgett film technique. A concave deformation structure was first observed for DPPC in solid phase. The depth of the concave domain was about 6 nm and was remarkably uniform. For a collapsed DPPC monolayer, the surface film consists of a granular convex multilayer structure and a disc-like concave structure. Dynamic cyclic compression-expansion experiments indicate that the formation of the concave domain is a reversible process while the process for convex multilayer formation is irreversible. This gives direct evidence that convex grain is the collapsed structure of DPPC monolayer and the concave shallow disc corresponds to the elastic deformation of a DPPC solid film. Results of atomic force microscopy indicate that the nucleation and growth model instead of the fracture model can better describe the collapse behavior of a DPPC monolayer.     

Needles and clusters of zinc porphyrin molecules on mica

Molecular monolayers of zinc porphyrins deposited from a liquid solution on mica substrates have been characterised using atomic force microscopy (AFM). At room temperature, needle-shaped single layer porphyrin islands are formed due to an anisotropic growth rate. The average island size depends on the concentration of the porphyrin solution, but the length to width aspect ratio is rather independent of the island size. Annealing the porphyrin monolayers to 450 K leads to the reduction of the size of the monolayer islands in two different ways depending on the heating rate. With slow heating rate, the island size was found to shrink by losing molecules from the edge of the island. With high heating rate, nanoscale molecular clusters were found to form.     

AFM studies on Langmuir-Blodgett films of cholesterol

The Langmuir monolayer of cholesterol at the air-water interface exhibits a condensed phase in which the cholesterol molecules are aligned normal to the water surface. We have transferred the monolayer from water surface to different substrates by Langmuir-Blodgett (LB) technique and have studied their assembly by atomic force microscope (AFM). Our studies reveal that the aggregation of cholesterol molecules on hydrophobic surfaces leads to interesting structures. The cholesterol molecules assemble into a uniform film, elongated domains and uniformly distributed torus-shaped domains (doughnuts) for one, two and four cycles of deposition, respectively. Beyond four cycles, the molecules adsorb and desorb by an equal amount resulting in no further deposition. The formation of uniformly distributed doughnuts can be attributed to the hydrophobic interaction and reorganization of the molecules due to successive adsorption and desorption during deposition cycles. Our studies on hydrophilic surfaces show that cholesterol cannot form more than one layer of deposition.PACS: 68.47.Pe Langmuir-Blodgett films on solids; polymers on surfaces; biological molecules on surfaces - 68.37.Ps Atomic force microscopy (AFM) - 68.43.Mn Adsorption/desorption kinetics     

Thin PTCDA films on Si(0 0 1): 1. Growth mode

We have studied the interface and thin film formation of the organic molecular semiconductor 3,4,9,10 perylene tetracarboxylic dianhydride (PTCDA) on clean and on hydrogen passivated Si(0 0 1) surfaces. The studies were made by means of high resolution X-ray photoelectron spectroscopy (HRXPS), near edge X-ray absorption fine structure (NEXAFS), low energy electron diffraction (LEED), and atomic force microscopy (AFM). On the passivated surface the LEED pattern is somewhat diffuse but reveals that the molecules grow in several ordered domains with equivalent orientations to the substrate. NEXAFS shows that the molecules are lying flat on the substrate. The Si 2p XPS line shape is not affected when the film is deposited so it can be concluded that the interaction at the interface between PTCDA and the substrate is weak. The evolution of the film formation appears to be homogeneous for the first monolayer with a nearly complete coverage of flat lying molecules based on the XPS attenuation. For layer thickness of 0.5-2 monolayers (ML) the molecules start to form islands, attracting the molecules in between, leaving the substrate partly uncovered. For thicker films there is a Stranski-Krastanov growth mode with thick islands and a monolayer thick film in between. For the clean surface the ordering of the film is much lower and angle resolved photoelectron spectroscopy (ARPES) of the molecular orbitals have only a small dependence of the emission angle. NEXAFS shows that the molecules do not lie flat on the surface and also reveal a chemical interaction at the interface.     

原子力显微镜扫描成像DNA分子

采用Mg2+处理DNA、APTES或戊二醛修饰云母表面、DNA拉直方法制备了λ-DNA及DNA-组蛋白复合物样品.室温下原子力显微镜以轻敲模式在空气中扫描样品成像.实验结果表明:AFM扫描成像的效果与样品的制备方法有关,同时也受操作因素影响.     

Enhanced surface evolution induced by the molecular desorption in dodecanethiol self-assembled monolayer on Au(1 1 1)

The evolution of the surface structure in dodecanethiol self-assembled monolayer on Au(1 1 1) substrate has been studied with ultra high vacuum scanning tunneling microscopy at several temperatures. The structure of substrate Au(1 1 1) surface changed suddenly at a temperature of 110 °C. The enhanced mobility of the substrate gold atoms at this temperature is attributed to the desorption of the dodecanethiol molecules.     

Controlled assembly of DNA nanostructures on silanized silicon and mica surfaces for future molecular devices

In order to establish key technology for future molecular devices, we have explored the assembly behaviour of λ-deoxyribonucleic acid (DNA) molecules adsorbed on silanized mica and silanized oxide silicon surfaces by using atomic force microscopy (AFM). AFM experiments show that λ-DNA molecules can be hardly adsorbed on untreated mica and oxidized silicon surfaces, but can be strongly adsorbed onto aminosilanized mica and oxidized silicon surfaces. Importantly, DNA molecules can be assembled into linear DNA alignment, and can also self-assemble into various network structures on the silanized surfaces. Our experimental observations have demonstrated the feasibility of assembling DNA-based nanostructures by varying surface chemistry of substrates, and offer useful clues in constructing DNA-based nanodevices for nanoelectronics and biomolecular computation as well as quantum computation.     

The epitaxial sexiphenyl (0 0 1) monolayer on TiO2(1 1 0): A grazing incidence X-ray diffraction study

A para-sexiphenyl monolayer of near up-right standing molecules (nominal thickness of 30 Å) is investigated in-situ by X-ray diffraction using synchrotron radiation and ex-situ by atomic force microscopy. A terrace like morphology is observed, the step height between the terraces is approximately one molecular length. The monolayer terraces, larger than 20 μm in size, are extended along the [0 0 1] direction of the TiO₂(1 1 0) substrate i.e. along the Ti-O rows of the reconstructed substrate surface. The structure of the monolayer and its epitaxial relationship to the substrate is determined by grazing incidence X-ray diffraction. Extremely sharp diffraction peaks reveal high crystalline order within the monolayer, which was found to have the bulk structure of sexiphenyl. The monolayer terraces are epitaxially oriented with the (0 0 1) plane parallel to the substrate surface (out-of-plane order). Four epitaxial relationships are observed. This in-plane alignment is determined by the arrangement of the terminal phenyl rings of the sexiphenyl molecules parallel to the oxygen rows of the substrate.     

Synthesis of ZnS nanoparticles on a solid surface: Atomic force microscopy study

In this work, zinc sulfide (ZnS) nanoparticles had been synthesized on DNA network/mica and mica surface, respectively. The synthesis was carried out by first dropping a mixture of zinc acetate and DNA on a mica surface for the formation of the DNA networks or zinc acetate solution on a mica surface, and subsequently transferring the sample into a heated thiourea solution. The Zn²⁺ adsorbed on DNA network/mica or mica surface would react with S²⁻ produced from thiourea and form ZnS nanoparticles on these surfaces. X-ray diffraction and atomic force microscopy (AFM) were used to characterize the ZnS nanoparticles in detail. AFM results showed that ZnS nanoparticles distributed uniformly on the mica surface and deposited preferentially on DNA networks. It was also found that the size and density of ZnS nanoparticles could be effectively controlled by adjusting reaction temperature and the concentration of Zn²⁺ or DNA. The possible growth mechanisms have been discussed in detail.     

Influence of surface temperature and surface modifications on the initial layer growth of para-hexaphenyl on mica (0 0 1)

Ultra-thin films of para-hexaphenyl (6P) were prepared on muscovite mica (0 0 1) utilizing organic molecular beam deposition (OMBD) under well defined ultra high vacuum (UHV) conditions. The 6P growth characteristics were studied as a function of substrate temperature and substrate surface conditions. For the initial state of layer growth, thermal desorption spectroscopy (TDS) was used to verify the existence of a wetting layer. In this monomolecular continuous wetting layer, the molecules lie flat on the surface and are rather strongly bonded. For thicker films, in-situ X-ray photoelectron spectroscopy (XPS) in combination with (TDS) was applied to reveal the kinetics of the layer growth. Ex-situ atomic-force microscopy (AFM) was used to determine the film morphology. In particular, the influence of surface modifications (carbon contamination, sputtering) on 6P layer growth was investigated. XPS and low energy electron diffraction (LEED) were used to characterize the mica surface before the film deposition. TDS and AFM revealed a considerable change in film growth, from a needle-like island growth of flat laying molecules on top of the wetting layer (for the air cleaved mica) to terrace-like film growth of standing molecules, without a wetting layer (after surface modifications).     

First self-assembly study of large π-conjugated corrole dimers on solid substrates

Our study focus on β,β′-doubly linked corrole dimers (CDs) on mica and Au(1 1 1) surface using samples prepared by the synthetic method described by Osuka group appeared on recent publication [S. Hiroto, K. Furukawa, H. Shinokubo, A. Osuka, J. Am. Chem. Soc. 128 (2006) 12380]. Atomic force microscopy (AFM) and scanning tunneling microscopy (STM) were used to investigate the self-assembled structure of corrole dimers adsorbed on mica and Au(1 1 1) surfaces respectively at room temperature in air. The CDs adopt a dissimilar adsorption modality due to the different surface free energy of the different substrates. These types of molecular layers provide a useful platform for the study of surface and interface phenomena outside a vacuum system. It is potentially useful for practical fabrication of molecular devices because of the simplicity of the sample preparation and the stability of the interface in ambient conditions.     

Grafting onto poly(ethylene terephthalate) driven by 172 nm UV light

The reactivity of the surface of poly(ethylene terephthalate) (PET) film under 172 nm UV irradiation (xenon excimer lamp) towards nitrogen-borne 1-octene, n-nonane and heptafluorodecene vapor was investigated. Materials receiving from 0 to 24 J/cm² of UV were examined by X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (ToF/SIMS), water and mineral oil contact angle measurement and atomic force microscopy (AFM). A uniform nanoscale layer developed on PET surface attributed to the grafting reaction between photolytically-produced polymer radicals and vapor phase molecules.     

Molecular depth profiling and imaging using cluster ion beams with femtosecond laser postionization

The emergence of cluster ion sources as viable SIMS probes has opened new possibilities for detection of neutral molecules by laser postionization. Previous studies have shown that with atomic bombardment multiphoton ionization using high-power femtosecond pulses leads to photofragmentation. The large amount of photofragmentation can be mostly attributed to high amounts of internal energy imparted to the sputtered molecules during the desorption process. Several pieces of preliminary data suggest that molecules subjected to cluster beam bombardment are desorbed with lower internal energies than those subjected to atomic beam bombardment. Lower energy molecules may then be less likely to photodissociate creating less photofragments in the laser postionization spectra. Here we present data taken from coronene films prepared by physical vapor deposition comparing a 40 keV ion source with a 20 keV Au⁺ ion source, which supports this hypothesis. Furthermore, the depth profiling capabilities of cluster beams may be combined with laser postionization to obtain molecular depth profiles by monitoring the neutral flux. In addition, imaging and depth profiling may be combined with atomic force microscopy (AFM) to provide three-dimensional molecular images.     

A rapid approach to reproducible, atomically flat gold films on mica

A simple and reproducible method for the preparation of gold films on mica with large (typically 0.8-1.0 μm) atomically flat (1 1 1) terraces is described. The procedure involves thin gold film evaporation onto freshly cleaved mica substrates, followed by 1 min annealing at 650 °C under nitrogen. The annealed gold surfaces are compared to those of freshly evaporated gold films on mica using cyclic voltammetry and atomic force microscopy. Our results favorably compare to other published annealing techniques, with minimal equipment and time necessary to reproducibly obtain atomically flat gold terraces.     

Evaluating the surface density and heterogeneity of a dithiobis (succinimidylpropionate) self-assembled monolayer on gold and its coupling with DNA embedded within a matrix

The homogeneity of a self-assembled monolayer (SAM) on a surface is an important parameter which affects the ability of a SAM to fulfill its intended function. As an example, SAMs formed from octanethiols can form an impermeable surface, while SAMs based on a bifunctional coupling reagent can form a surface with uniform reactivity. Exposure of gold nanoparticles or gold surfaces to solutions of dithiobis (succinimidylpropionate) (DSP) gives rise to a surface which can react with DNA. Atomic force microscopy, UV-vis and gel electrophoresis experiments indicate that a self-assembled monolayer of DSP on gold nanoparticles can attenuate aggregation, inhibit the “lying down” of covalently-bound single-stranded (ss) DNA and promote more efficient hybridization. The determination of the point of aggregation after reacting DSP with colloidal gold yields 2.86 × 10⁻¹⁰ mol/cm² or 42% of the value determined from molecular modeling. Cyclic voltammetry experiments validate that DSP on a gold quartz crystal (6.3 × 10⁻¹⁰ mol/cm²) forms a fairly uniform SAM that is within 94% of maximum coverage when compared with results obtained from molecular modeling (6.67 × 10⁻¹⁰ mol/cm²). Surface plasmon resonance experiments indicate that the reaction of a DSP coated gold surface with (ss) DNA yields 2.4 × 10⁻¹² mol/cm² or reaction with about 1% of the available surface area. Subsequent reactions of the DSP surface with the filler, n-boc-1,4-phenylene diamine (n-boc), yield a total surface coverage of 1.8 × 10⁻¹¹ mol/cm². The surrounded (ss) DNA yields a surface with 97% hybridization efficiency toward the complement.     

Investigation of plumes produced by material ablation with two time-delayed femtosecond laser pulses

We experimentally investigated and herewith reported the results of laser ablation of copper and gold with two time-delayed femtosecond laser pulses at 800 nm in vacuum. The ablation plume dynamic was monitored by fast plume imaging and time- and space-resolved optical emission spectroscopy. Optical microscopy was used to follow the ablation depth as a function of the delay between the two laser pulses. Nanoparticles deposition on mica substrates was analysed by atomic force microscopy.We estimate roughly the plume's atomization degree - that is the mass fraction of atomized material over the total ablated mass - from the relative intensities of radiation emitted from atoms and nanoparticles. It is shown that the atomization degree depends critically on the time delay between both laser pulses and on the characteristic time of electron-lattice relaxation. The increase of the atomization degree is accompanied by the decrease of the ablation depth. Atomic force microscopy measurements confirm the partial atomization of nanoparticles, as the analyses of particle deposition on mica substrates show a large decrease of the number of nanoparticles for large delay between the two pulses.     

Hexaphenyl thin films on clean and carbon covered Au(1 1 1) studied with TDS and LEED

The adsorption and growth of ordered para-hexaphenyl (6P) films have been investigated both on clean and partially carbon pre-covered Au(1 1 1) single crystal surfaces by thermal desorption spectroscopy (TDS) and low energy electron diffraction (LEED) under ultra-high vacuum conditions. The existence of a distinct first and second monomolecular 6P layer that clearly separate from the multilayer regime, which comprise lying molecules with respect to the substrate surface, could be inferred from TDS. For both the 6P mono- and multilayer grown on pure Au(1 1 1) the desorption energies have been determined based on experimental TDS data. In particular, for the monolayer regime a coverage dependence of the desorption energy has been found, which is attributed to repulsive interactions between neighbouring 6P molecules adsorbed on the gold surface. The existence of well-ordered film structures could be inferred from LEED for half monolayer and full monolayer thick 6P films. Based on the LEED and TDS data, structural models are presented for these highly ordered organic films. Multi-step dehydrogenation of 6P molecules adsorbed on clean Au(1 1 1) surfaces is reported for temperatures above 650 K together with experimental evidence for the existence of a regular overlayer composed of partially dehydrogenated polycyclic aromatic hydrocarbon (PAH) intermediates. A quite different adsorption/desorption kinetics and film growth has been observed for 6P films grown on carbon pre-covered Au(1 1 1) surfaces.     

Immobilization of immunoglobulin G in a highly oriented manner on a protein-A terminated multilayer system

In this study, we have fabricated a multilayer system consisting of 3-glycidoxypropyldimethylmethoxysilane (GPDS), poly(dimethylsiloxane) bis 3-aminopropyl terminated (PDMS) and protein-A on a silicon wafer surface for oriented immobilization of immunoglobilin G (IgG). The multilayer system with a different component in each layer was characterized by ellipsometry, contact-angle goniometer, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) and fluorescence microscopy. The epoxy-terminated monolayer was formed by the chemisorption of GPDS molecules on the hydroxylated silicon surface. The PDMS film about 4.5 nm thick was produced on the GPDS-monolayer by the chemical reaction between the amine groups at the end of PDMS chain and the epoxy groups of GPDS molecules. By introducing the PDMS chains, the hydrophilic character of GPDS-monolayer decreased. Study of the time dependence of polymer grafting showed that the chemisorption of GPDS is fast, whereas at least 16 h is needed to generate the homogeneous PDMS layer. For immobilization of IgG molecules in a highly oriented manner, protein-A molecules were first chemically bound to an ultrathin (∼4.5 nm) PDMS reactive polymer layer and later used to capture IgG. It was shown that the existence of protein-A in the multilayer system has a strong influence on the binding properties of IgG not only in the efficiency of binding, but also in its specificity. In conclusion, the multilayer system with protein-A has the potential to be further developed into an efficient immunoassay protein chip.