Plan-view preparation of TEM specimens from thin films using adhesive tape

A simple plan-view sample preparation technique for transmission electron microscopy (TEM) specimens is proposed for thin films by tearing-off the film with adhesive tape. The demand for very thin samples is highest for nanostructured materials where the structure of 2-5 nm sized features (grains) needs to be resolved; therefore, overlapping of nanometer-sized features should be avoided. The method provides thin areas at the fracture edges of plan-view specimens with thickness in the range of the grain size in the film allowing for artifact free high-resolution TEM imaging. Nanostructured materials typically fracture between the grains providing areas with the thickness of the grain size. Besides the swiftness of the method, the samples are free of surface amorphization artifacts, which can occur in ion beam milling up to 1 nm depth even at low energy ion bombardment. The thin film tear-off technique is demonstrated on a CuMn alloy thin film with grain size of 2 nm.     

Wetting-dewetting transition line in thin polymer films

Thin polymeric films are increasingly being utilized in diverse technological applications, and it is crucial to have a reliable method to characterize the stability of these films against dewetting. The parameter space that influences the dewetting of thin polymer films is wide (molecular mass, temperature, film thickness, substrate interaction) and a combinatorial method of investigation is suitable. We thus construct a combinatorial library of observations for polystyrene (PS) films cast on substrates having orthogonal temperature and surface energy gradients and perform a series of measurements for a range of molecular masses (1800 g/mol < M < 35 000 g/mol) and film thicknesses h (30 nm < h < 40 nm) to explore these primary parameter axes. We were able to obtain a near-universal scaling curve describing a wetting-dewetting transition line for polystyrene films of fixed thickness by introducing reduced temperature and surface energy variables dependent on M. Our observations also indicate that the apparent polymer surface tension gamma(p) becomes appreciably modified in thin polymer films from its bulk counterpart for films thinner than about 100-200 nm, so that bulk gamma(p) measurements cannot be used to estimate the stability of ultrathin films. Both of these observations are potentially fundamental for the control of thin film stability in applications where film dewetting can compromise film function.     

High‐Throughput Synthesis and Screening of Combinatorial Heterogeneous Catalyst Libraries

In less than one minute the catalytic activity and selectivity of a single catalyst was measured in combinatorial libraries of ternary Rh‐Pd‐Pt‐Cu alloys. Only slightly more than two hours were needed to complete a library with 136 elements. The elements of the libraries (ca. 2–4 μg of material) are contained in a two‐dimensional array synthesized by a thin‐film technique. The analysis was performed by a scanning mass spectrometer (see picture).     

Imaging thin films of nanoporous low-k dielectrics: comparison between ultramicrotomy and focused ion beam preparations for transmission electron microscopy.

Ultramicrotomy, the technique of cutting nanometers-thin slices of material using a diamond knife, was applied to prepare transmission electron microscope (TEM) specimens of nanoporous poly(methylsilsesquioxane) (PMSSQ) thin films. This technique was compared to focused ion beam (FIB) cross-section preparation to address possible artifacts resulting from deformation of nanoporous microstructure during the sample preparation. It was found that ultramicrotomy is a successful TEM specimen preparation method for nanoporous PMSSQ thin films when combined with low-energy ion milling as a final step. A thick, sacrificial carbon coating was identified as a method of reducing defects from the FIB process which included film shrinkage and pore deformation.     

In Situ Electrodeposition of an Asymmetric Sol–Gel Membrane Based on an Octadecyltrimethoxysilane Langmuir Film

The unique properties of Langmuir film formation were utilized in assembling a thin skin of an asymmetric membrane. An octadecyltrimethoxysilane (ODTMS) Langmuir monolayer was formed at the air–water interface and served as the substrate for growing a bulky sol–gel polymer in situ. The latter was based on the electrochemical deposition of tetramethoxysilane dissolved in the water subphase by means of horizontal touch electrochemistry. The resultant asymmetric layer that consisted of a thin hydrophobic ODTMS Langmuir film connected to a bulk hydrophilic sol–gel network was studied in situ and ex situ by using various techniques, such as cyclic voltammetry, electrochemical impedance spectroscopy (EIS), scanning electron microscopy, transmission electron microscopy (TEM), and goniometry. We found that a porous hydrophilic film grew on top of a hydrophobic layer as was evident from TEM, contact angle, and EIS analyses. The film thickness and film permeability could be controlled by changing the deposition conditions such as the potential window applied and its duration. Hence, this method offers an alternative approach for assembling asymmetric films for various applications     

三聚噻吩的表面光电压谱研究

采用表面光电压和电场诱导表面光电压技术研究了三聚噻吩在外电场作用下的电子运动行为,结合三聚噻吩的UV光谱、极化子概念以及前线轨道理论,指认了三聚噻吩能级跃迁性质,即380nm附近的峰为带－带跃迁峰,477,465和600nm附近的峰是与单极化子有关的电子跃迁;而在770和990nm附近的峰则是与双极化子有关的电子跃迁峰。     

Use of Transmission Electron Microscopy in Combinatorial Studies of Functional Oxides

Summary: The principles of combinatorial methodology are based on high‐throughput properties measurements (HTPM) of multiple compositions in combinatorial libraries, and are recently being increasingly applied in materials research. Nevertheless, the authors' view is that the involvement of detailed but time‐consuming investigation using transmission electron microscopy (TEM) should be an important part of combinatorial materials research. In this paper we present three examples from our combinatorial studies where the TEM investigation was essential in obtaining a detailed picture of microstructures and their relationship with the physical properties. In the study of microwave dielectrics such as BaTiO₃‐SrTiO₃, TEM provides essential information on the type and distribution of defects in the deposited films. In the case of the wide‐band semiconductor ZnO‐MgO, the distribution and morphology of the phases were studied and related to the measured electronic properties. Study of the manganates LaMnO₃‐CaMnO₃ with colossal magneto‐resistive properties showed an anisotropic distribution of the structural domains and the morphology of the film. The distribution of the domains and the absence of epitaxial stresses found are essential in the interpretation of magnetic measurements.

Cross‐sectional TEM (dark field) micrograph taken with the reflection of h‐(Zn,Mg)O at x = 0.5.     

High-throughput bioassay-guided fractionation: a technique for rapidly assigning observed activity to individual components of combinatorial libraries,screened in HTS bioassays

In this paper, we describe an automated, high-throughput analytical tool for the unambiguous characterization of the active component(s) of a combinatorially derived reaction mixture. We call this technique high-throughput bioassay-guided fractionation (BGF). The novel aspects of this communication are the systematization of the BGF concept, the application of BGF to combinatorial chemistry, and the high-throughput nature of the identification technique. The identification of the active component in a well mixture is an essential step for subsequent resynthesis or isolation of the active component(s) or for removal of intractable wells from further consideration. We believe the technique described is also applicable to any mixture library, provided the expected component (or components) of each well is (are) known. Example mixture libraries would include collections of synthetic chemicals and collections of purified natural products. The mixture need not come from libraries produced using parallel synthesis. The BGF tool described herein allows full utilization of highly diverse combinatorial libraries, thereby obviating costly up-front purification or extensive prescreening characterization efforts.     

Sonochemical preparation of photochromic nanocomposite thin film based on polyoxometalates well dispersed in polyacrylamide

Novel photochromic nanocomposite thin film containing phosphotungstic acid entrapped in polyacrylamide was prepared using ultrasound technique. TEM image revealed that the polyoxometalates nanoparticles with narrow size distribution were finely dispersed in polymer matrix. IR spectra showed that the Keggin geometry of polyoxometalates was still preserved inside the composite film and strong Coulombic interaction was built between heteropolyoxometalates and polyacrylamide via hydrogen bond. It was found that the thermal stability of the hybrid film was lower than that of pure polymer but the film was stable enough for photochromic application from the TG-DTA curves. The transparent film changed from colorless to blue under UV irradiation and showed reversible photochromism. The bleaching process occurred when the film was in contact with air or O₂ in the dark. The photoreduced process was in accordance with radical mechanism.     

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…     

Traceless liquid phase synthesis of piperazinediones

Liquid phase combinatorial synthesis (LPCS) of piperazinediones by the use of soluble polymer support is explored to generate libraries. Proline anchored polyethylene glycol monomethyl ether (PEG) underwent dipeptide formation with different Fmoc-amino acids in the presence of dicyclohexyl carbodiimide (DCC). Deprotection of Fmoc accompanied with the cleavage from polymer support with cyclization of dipeptide to piperazinediones offers a facile and effective way to prepare diverse combinatorial libraries. Excellent yields and purities were achieved by simple wash and precipitation method.     

Quantitative Analysis of Thin Specimens in the TEM Using a ϕ(ρ<Emphasis Type="Italic">z</Emphasis>)-Model

X-ray microanalysis using Transmission Electron Microscopy (TEM) offers the possibility to perform quantitative analysis with high spatial resolution. Unfortunately, the accuracy is limited and the preparation of the very thin specimens and thin film standards, needed for the analysis and calibration, is rather difficult. To calculate the composition from the measured X-ray intensities, a peak-ratio method is usually applied, based on the well-known thin film approach proposed by Cliff and Lorimer in 1972.In the present paper we propose an entirely different approach, in which the composition is calculated using a full matrix correction method based upon a (z) procedure. Nowadays, such correction models are commonly used in bulk EPMA measurements up to 40kV. The validity of the model under TEM conditions was checked by performing bulk analyses on AlNi and AlTi samples and thin film analyses on an AlNi TEM specimen. Using this method, both thin and thick specimens as well as light elements can be analysed, without having to prepare thin film standards. No major changes to the TEM set-up or simplifications to the model are needed, only an accurate beam current meter is required. As an example of the possibilities, a linescan analysis was made on a GaAs specimen with GaAs/Ti interface, using only bulk standards. Finally, a comparison of our analysis method with other available thin film methods is included in this article.     

Recovery of anionic surfactant by RO process. Part II. Fabrication of thin film composite membranes by interfacial reaction

A new technique has been established to fabricate thin film composite membranes, by which a hydrophilic polymer could be coated in thin film on a hydrophobic support membrane. The new technique was composed of two steps: dispersion of a reactant to the hydrophilic polymer in the hydrophobic support membrane and interfacial reaction between the reactant and the hydrophilic polymer to produce thin film of the hydrophilic polymer on the support membrane. Composite membranes in which a thin film of sodium alginate is coated on a polysulfone support membrane were prepared by the new technique for the reverse osmosis separation of anionic surfactant–water mixture. Two methods were employed to fabricate a thin film of sodium alginate on the support membrane: (1) dispersion of the crosslinking agent, CaCl₂ alone in the support membrane and (2) dispersion of CaCl₂ in the support membrane with help of PVA which adheres fast to the support membrane. The formation mechanism of the thin layer was suggested schematically on each method. Both the methods could produce successively a thin layer of SA on the support membrane. Especially, method (2) gave a strong bonding of the thin layer on the support because of the large contact area with the support through the PVA layer which sticks fast to the SA layer. From the SEM pictures and permeation experiments, the method (2) was confirmed to be better to produce a defect-free thin film of SA on the support membrane.     

Plasma Deposition of Polymeric Thin Films on Organic Corrosion-Inhibiting Paint Pigments: A Novel Method to Achieve Slow Release

Slow release of corrosion-inhibitive paint pigments is a great challenge to the paint industry, because of the urgent need to replace chromate-containing pigments. Unfortunately, most effective corrosion inhibitors are too soluble for use in paints. In this paper, we present a novel method to modify selected water-soluble organic inhibitor particles to achieve the purpose of slow release. A plasma polymerization technique was used to deposit an ultrathin polymer film on the surface of the inhibitor particles. Infrared spectroscopy (FTIR), time-of-flight secondary ion mass spectroscopy (TOFSIMS), scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM/EDX), transmission electron microscopy (TEM), and contact angle data confirmed the successful deposition of the polymer thin film on the inhibitor particles. Using immersion tests and electrochemical techniques, we have demonstrated that the encapsulated water-soluble inhibitor can slowly release into the environment to protect a metal as needed. This technique is a feasible and promising method to promote the replacement of chromate pigments in paints.     

The influence of nanoparticle fillers on the morphology of a spin-cast thin film polymer blend

Polymer/nanoparticle composite films are receiving growing attention thanks to their potential for application in ultra-thin electronic and optical devices. Polymer blend demixing has been shown to be a suitable technique for the structuring of polymer thin films and the patterning of nanoparticles (NP) within them. In this work we show that the morphology of thin polymer films made by spin-casting a polymer blend solution containing NP fillers on a surface depends strongly on the concentration of NP fillers. More specifically, polystyrene/polymethylmethacrylate (PS/PMMA) films formed from a toluene solution, and which demix following a nucleation and growth mechanism, were studied. It was found that both the height and the surface density of PMMA domains increased as the concentration of CoPt:Cu NPs in the film was increased. We find that similar effects are induced in a NP-free PS/PMMA demixed film upon increasing the molecular weight of the PS molecules. This suggests that under certain conditions the NPs and the polymer molecules in the blend do not behave as separate species but form aggregates.     

Efficient split synthesis for targeted libraries

We propose a new approach for fabricating more sophisticated combinatorial chemistry libraries via split synthesis and evaluate its potential through extensive simulation. Our algorithmically intensive method promises to reduce the time and materials costs of synthesizing libraries which are (1) too large to synthesize economically by sequential or parallel synthesis, (2) too long or irregular for conventional split synthesis generation techniques, and (3) not used in sufficient quantity to justify the setup costs of array makers. It also encourages the design of more focused and interesting libraries than are typically constructed using split synthesis. Our algorithms automate the design of efficient synthesis procedures for motif-based libraries which are too complex to design by hand. Our software allows the user to select the most desirable tradeoff between minimizing the number of steps in the synthesis process and containing the combinatorial explosion of the number of compounds synthesized.     

Preparation and infrared/raman classification of 630 spectroscopically encoded styrene copolymers

The barcoded resins (BCRs) were introduced recently as a platform for encoded combinatorial chemistry. One of the main challenges yet to be overcome is the demonstration that a large number of BCRs could be generated and classified with high confidence. Here, we describe the synthesis and classification of 630 polystyrene-based copolymers prepared from the combinatorial association of 15 spectroscopically active styrene monomers. Each of the 630 copolymers displayed a unique vibrational fingerprint (infrared and Raman), which was converted into a spectral vector. To each of the 630 copolymers, a vector of the known (reference) composition was assigned. Unknown (prediction) vectors were decoded using multivariate data analysis. From the inner product of the reference and prediction vectors, a correlation map comparing 396 900 copolymer pairs (630 x 630) was generated. In 100% of the cases, the highest correlation was obtained for polymer pairs in which the reference and prediction vectors correspond to copolymers prepared from identical styrene monomers, thus demonstrating the high reliability of this encoding strategy. We have also established that the spectroscopic barcodes generated from the Raman and infrared spectra are independent of the copolymers' morphology (beaded versus bulk polymers). Besides the demonstration of the generality of the polymer barcoding strategy, the analytical methods developed here could in principle be extended to the investigation of the composition and purity of any other synthetic polymer and biopolymer library, or even scaffold-based combinatorial libraries.     

固态组合化学及其在材料科学中的应用

概述了固态组合化学的概念及其在新材料开发中的应用 ,着重阐述了材料化合物薄膜库的组合制备方法和筛选技术的特点 ,简述了固态组合化学技术在超导、巨磁阻、磷光、催化剂、沸石等新材料开发中的应用以及固态组合化学现有技术中的困难和今后的发展方向     

Large uniform-sized polymer beads for use as solid-phase supports prepared by ascension polymerization

Large uniform-sized polymer beads are desirable for "one-bead-one-compound" applications in the combinatorial synthesis of compound libraries. We have developed a technique for the preparation of large polymer spheres with narrow size distributions. Uniform-sized poly(styrene-co-divinylbenzene) beads with diameters in excess of 1 mm have been prepared by free radical polymerization in an ascension process through a heated column. The size of the beads can be adjusted by the diameter of the injection needle and the injection speed. The resin beads can be made porous by the incorporation of a porogen during the preparation; they reach a specific surface area in excess of 200 m(2)/g. The mechanical properties of the spheres and their use in organic synthesis have been studied.     

Mass spectrometry and combinatorial chemistry: a short outline.

The rapid evolution of combinatorial chemistry in recent years has led to a dramatic improvement in synthetic capabilities. The goal is to accelerate the discovery of molecules showing affinity against a target, such as an enzyme or a receptor, through the simultaneous synthesis of a great number of structurally diverse compounds. This is done by generating combinatorial libraries containing as many as hundreds or thousands of compounds. The need to test all these compounds led to the development of high-throughput screening (HTS) techniques, and also high-throughput analytical techniques capable of assessing the occurrence, structure and purity of the products. In order to be applied effectively to the characterization of combinatorial libraries, an analytical technique must be adequately sensitive (to analyse samples which are typically produced in nanomole amounts or less), fast, affordable and easy to automate (to minimize analysis time and operator intervention). Although no method alone can meet all the analytical challenges underlying this task, the recent progress in mass spectrometric (MS) instrumentation renders this technique an essential tool for scientists working in this area. We describe here relevant aspects of the use of MS in combinatorial technologies, such as current methods of characterization, purification and screening of libraries. Some examples from our laboratory deal with the analysis of pooled oligomeric libraries containing n x 324(n = 1, 2) compounds, using both on-line high-performance liquid chromatography/MS with an ion trap mass spectrometer, and direct infusion into a triple quadrupole instrument. In the first approach, MS and product ion MS/MS with automatic selection of the precursor were performed in one run, allowing library confirmation and structural elucidation of unexpected by-products. The second approach used MS scans to characterize the entire library and also precursor ion and neutral loss scans to detect selectively components with given structural characteristics.