Selective Metal‐vapor Deposition on Organic Surfaces

Selective metal‐vapor deposition signifies that metal‐vapor atoms are deposited on a hard organic surface, but not on a soft (low glass transition temperature, low T_g) surface. In this paper, we introduce the origin, extension, and applications of selective metal‐vapor deposition. An amorphous photochromic diarylethene film shows light‐controlled selective metal‐vapor deposition, which is caused by a large T_g change based on photoisomerization, but various organic surfaces, including organic crystal and polymers, can be utilized for achieving selective metal‐vapor deposition. Various applications of selective metal‐vapor deposition, including cathode patterning of organic light‐emitting devices, micro‐thin‐film fuses, multifunctional diffraction gratings, in‐plane electrical bistability for memory devices, and metal‐vapor integration, have been demonstrated.     

Organic Semiconductor/Gold Interface Interactions: From Physisorption on Planar Surfaces to Chemical Reactions with Metal Nanoparticles

The interaction of gold nanoparticles (AuNPs) with prototypical organic semiconductors used in optoelectronics, namely, tris(8‐hydroxyquinoline)aluminium (Alq₃) and 4,4‐bis[N‐(1‐naphthyl)‐N‐phenylamino]diphenyl (α‐NPD), is investigated in situ by X‐ray photoelectron spectroscopy (XPS). These AuNPs‐on‐molecule experiments are compared with the reversed molecule‐on‐Au cases. The molecules‐on‐Au systems show only weak interactions, and the evolution of the XP spectra is dominated by final‐state effects. In contrast, in the AuNPs‐on‐molecules cases, both initial‐state effects and final‐state effects occur. Spectral features arising for both molecules and metal indicate charge transfer and the formation of organometallic complexes (initial‐state effects). The energy shift in the metal emission underlines the size‐induced nanometric nature of the molecule/Au interaction (final‐state effects). Consequently, the chemical interaction between metals and organic semiconductors likely depends strongly on the deposition sequence in general.     

A Novel Thin‐Film Copper Array Based on an Organic/Inorganic Sensor Hybrid: Microfabrication,Potentiometric Characterization,and Flow‐Injection Analysis Application

A first step towards the microfabrication of a thin‐film array based on an organic/inorganic sensor hybrid has been realized. The inorganic microsensor part incorporates a sensor membrane based on a chalcogenide glass material (Cu‐Ag‐As‐Se) prepared by pulsed laser deposition technique (PLD) combined with an PVC organic membrane‐based organic microsensor part that includes an o‐xylyene bis(N,N‐diisobutyl‐dithiocarbamate) ionophore. Both types of materials have been electrochemically evaluated as sensing materials for copper(II) ions. The integrated hybrid sensor array based on these sensing materials provides a linear Nernstian response covering the range 1×10^?6–1×10^?1 mol L^?1 of copper(II) ion concentration with a fast, reliable and reproducible response. The merit offered by the new type of thin‐film hybrid array includes the high selectivity feature of the organic membrane‐based thin‐film microsensor part in addition to the high stability of the inorganic thin‐film microsensor part. Moreover, the thin‐film sensor hybrid has been successfully applied in flow‐injection analysis (FIA) for the determination of copper(II) ions using a miniaturized home‐made flow‐through cell. Realization of the organic/inorganic thin‐film sensor hybrid array facilitates the development of a promising sophisticated electronic tongue for recognition and classification of various liquid media.     

Chemisorption,Morphology, and Structure of a n‐Type Perylene Diimide Derivative at the Interface with Gold: Influence on Devices from Thin Films to Single Molecules

We have investigated thin films of a perylene diimide derivative with a cyano‐functionalized core (PDI‐8CN₂) deposited on Au(111) single crystals from the monolayer to the multilayer regime. We found that PDI‐8CN₂ is chemisorbed on gold. The molecules experience a thickness‐dependent reorientation, and a 2D growth mode with molecular stepped terraces is achieved adopting low deposition rates. The obtained results are discussed in terms of their impact on field effect devices, also clarifying why the use of substrate/contact treatments, decoupling PDI‐8CN₂ molecules from the substrate/contacts, is beneficial for such devices. Our results also suggest that perylene diimide derivatives with CN bay‐functionalization are very promising candidates for single‐molecule electronic devices.     

Enhanced carrier-transfer in multi-layered organic thin film: Application to electrochromism and electroluminescence

Multi-layered organic thin films were prepared by stepwise vapor deposition of planar molecules with delocalized π-electrons on indium tin oxide (ITO) glass or KCl crystalline surface. The order of the deposition of π-planar molecules with different redox potential can control enhancement or inhibition of the hole or electron transfer according to the concept of “sequential potential field”, or a potential cascade by the organization of redox components. This concept is here applied to electrochromic or electroluminescent devices composed of multi-layered organic thin films.     

Modeling disordered morphologies in organic semiconductors

Organic thin film devices are investigated for many diverse applications, including light emitting diodes, organic photovoltaic and organic field effect transistors. Modeling of their properties on the basis of their detailed molecular structure requires generation of representative morphologies, many of which are amorphous. Because time‐scales for the formation of the molecular structure are slow, we have developed a linear‐scaling single molecule deposition protocol which generates morphologies by simulation of vapor deposition of molecular films. We have applied this protocol to systems comprising argon, buckminsterfullerene, N,N‐Di(naphthalene‐1‐yl)‐N,N'‐diphenyl‐benzidine, mer‐tris(8‐hydroxy‐quinoline)aluminum(III), and phenyl‐C₆₁‐butyric acid methyl ester, with and without postdeposition relaxation of the individually deposited molecules. The proposed single molecule deposition protocol leads to formation of highly ordered morphologies in argon and buckminsterfullerene systems when postdeposition relaxation is used to locally anneal the configuration in the vicinity of the newly deposited molecule. The other systems formed disordered amorphous morphologies and the postdeposition local relaxation step has only a small effect on the characteristics of the disordered morphology in comparison to the materials forming crystals. © 2013 Wiley Periodicals, Inc.     

Determination of Complex Small‐Molecule Structures Using Molecular Alignment Simulation

Correct structural assignment of small molecules and natural products is critical for drug discovery and organic chemistry. Anisotropy‐based NMR spectroscopy is a powerful tool for the structural assignment of organic molecules, but it relies on the utilization of a medium that disrupts the isotropic motion of molecules in organic solvents. Here, we establish a quantitative correlation between the atomic structure of the alignment medium, the molecular structure of the small molecule, and molecule‐specific anisotropic NMR parameters. The quantitative correlation uses an accurate three‐dimensional molecular alignment model that predicts residual dipolar couplings of small molecules aligned by poly(γ‐benzyl‐l ‐glutamate). The technique facilitates reliable determination of the correct stereoisomer and enables unequivocal, rapid determination of complex molecular structures from extremely sparse NMR data.     

Quantitative analysis of an organic thin film by XPS,AFM and FT‐IR

We report the characterization of Firpic (iridium(III)bis[4,6‐di‐fluorophenyl]‐pyridinato‐N,C²,]picolinate) organic thin film prepared by vacuum deposition to provide a systematic route to organic film quantification. To analyze the characteristics of thin Firpic films on a Si substrate, various techniques such as XPS, Fourier transform infra‐red (FT‐IR) spectrometer, and atomic force microscopy (AFM) are utilized. The Firpic films remain stable without surface morphological or compositional change during deposition and after exposure to X‐ray irradiation or atmospheric environment, for which qualities these films are believed to be an ideal platform as a pure organic thin film. The monotonic increases in FT‐IR and XPS intensities with film thickness are matching well with each other. In particular, from the XPS intensity analysis, the relative atomic sensitivity factors of the present system, electron attenuation length, and molecular density in the organic thin film can be evaluated. Copyright © 2011 John Wiley & Sons, Ltd.     

Study of the first nucleation steps of thin films by XPS inelastic peak shape analysis

The initial steps in the formation of thin films have been investigated by analysis of the peak shape (both inelastic background and elastic contributions) of X‐ray photoelectron spectra. Surface coverage and averaged height of the deposited particles have been estimated for several overlayers (nanometre range) after successive deposition cycles. This study has permitted the assessment of the type of nucleation and growth mechanisms of the films. The experiments have been carried out in situ in the preparation chamber of an XPS spectrometer. To check the performance of the method, several materials (i.e. cerium oxide, vanadium oxide and cadmium sulfide) have been deposited on different substrates using a variety of preparation procedures (i.e. thermal evaporation, ion beam assisted deposition and plasma enhanced chemical vapour deposition). It is shown that the first deposited nuclei of the films are usually formed by three‐dimensional particles whose heights and degree of surface coverage depend on the chemical characteristics of the growing thin film and substrate materials, as well as the deposition procedure. It is concluded that XPS peak shape analysis can be satisfactorily used as a general method to characterize morphologically the first nanometric moieties that nucleate a thin film. Copyright © 2006 John Wiley & Sons, Ltd.     

Molecular adsorption and the chemistry of plasma-deposited thin organic films: Deposition of oligomers of ethylene glycol

Weakly ionized, radio-frequency, glow-discharge plasmas formed from methyl ether or the vapors of a series of dimethyl oligo(ethylene glycol) precursors (general formula: H-(CH₂OCH₂)_n-H;n=1 to 4) were used to deposit organic thin films on polytetrafluoroethylene. X-ray photoelecton spectroscopy (XPS) and static secondary ion mass spectrometry (SIMS) of the thin films were used to infer the importance of adsorption of molecular species from the plasma onto the surface of the growing, organic film during deposition. Films were prepared by plasma deposition of each precursor at similar deposition conditions (i.e., equal plasma power (W), precursor flow rate (F), and deposition duration), and at conditions such that the specific energy (energy/mass) of the discharge (assumed to be constrained byW/FM, whereM=molecular weight of the precursor) was constant. At constantW/FM conditions, two levels of plasma power (and, hence, twoFM levels) and three substrate temperatures were examined. By controlling the energy of the discharge (W/FM) and the substrate temperature, these experiments enabled the study of effects of the size and the vapor pressure of the precursor on the film chemistry. The atomic % of oxygen in the film surface, estimated by XPS, and the intensity of theC-O peak in the XPS C_ls spectra of the films, were used as indicators of the degree of incorporation of precursor moieties into the plasma-deposited films. Analysis of films by SIMS suggested that these two measures obtained from XPS were good indicators of the degree of retention in the deposited films of functional groups from the precursors. The XPS and SIMS data suggest that adsorption of intact precursor molecules or fragments of precursor molecules during deposition can have a significant effect on film chemistry. Plasma deposition of low vapor pressure precursors provides a convenient way of producing thin films with predictable chemistry and a high level of retention of functional groups from the precursor.     

In situ ion beam sputter deposition and X‐ray photoelectron spectroscopy (XPS) of multiple thin layers under computer control for combinatorial materials synthesis

Deposition of ultra‐thin layers under computer control is a frequent requirement in studies of novel sensors, materials screening, heterogeneous catalysis, the probing of band offsets near semiconductor junctions and many other applications. Often large‐area samples are produced by magnetron sputtering from multiple targets or by atomic layer deposition (ALD). Samples can then be transferred to an analytical chamber for checking by X‐ray photoelectron spectroscopy (XPS) or other surface‐sensitive spectroscopies. The ‘wafer‐scale’ nature of these tools is often greater than is required in combinatorial studies, where a few square centimetres or even millimetres of sample is sufficient for each composition to be tested. The large size leads to increased capital cost, problems of registration as samples are transferred between deposition and analysis, and often makes the use of precious metals as sputter targets prohibitively expensive. Instead we have modified a commercial sample block designed to perform angle‐resolved XPS in a commercial XPS instrument. This now allows ion‐beam sputter deposition from up to six different targets under complete computer control. Ion beam deposition is an attractive technology for depositing ultra‐thin layers of great purity under ultra‐high vacuum conditions, but is generally a very expensive technology. Our new sample block allows ion beam sputtering using the ion gun normally used for sputter depth‐profiling of samples, greatly reducing the cost and allowing deposition to be done (and checked by XPS) in situ in a single instrument. Precious metals are deposited cheaply and efficiently by ion‐beam sputtering from thin metal foils. Samples can then be removed, studied and exposed to reactants or surface treatments before being returned to the XPS to examine and quantify the effects. Copyright © 2016 The Authors Surface and Interface Analysis Published by John Wiley & Sons Ltd.     

Formation and spectra of clathrate hydrates of methanol and methanol-ether mixtures

Infrared spectra of mixed clathrate hydrates, with either ethylene oxide (EO) or tetrahydrofuran (THF) and methanol molecules as the guest species, have been obtained from thin films prepared by vapor deposition of D₂O mixtures in the 115–130 K range. Although methanol acts as a suppressant to the direct vapor deposition of a type I clathrate with EO, nearly complete conversion of 115 K amorphous codeposits, to the crystalline mixed clathrate, occurs upon warming near 150 K. By contrast, the type II clathrate of THF shows an increased crystalline quality when methanol is included in the vapor deposits of the mixed clathrate hydrate at 130 K. The observation of the O---D stretch-mode band of weakly bonded CD₃OD near 2575 cm⁻¹ is part of the evidence that the methanol molecules are encaged. However, as shown theoretically by Tanaka, the clathrate hydrates of methanol, even when mixed with an ether help gas, are not stable structures but form at low temperatures because of kinetic factors, only to decompose in the 140–160 K range. Attempts to prepare a simple type I or type II clathrate hydrate of methanol have produced mixed results. Limited amounts of clathrate hydrate form during deposition but annealing does not result in complete conversion to crystalline clathrates, particularly for host : guest ratios of 17 : 1.     

Complexes in polymers IV. FTIR microscopic characterization of thin organic polymer films containing embedded transition-metal carbonyl complexes

Thin films of polystyrene (PS), poly(methyl methacrylate) (PMMA) and polystyrene-polyacrylonitrile copolymer (PS-AN), containing various embedded transition-metal complexes, have been studied by FTIR microscopy. The spatial distributions of the transition-metal carbonyl complexes throughout the thin organic polymer films have been determined by a two-dimensional IR mapping procedure. The spectral variations observed in the distribution of the metal carbonyls throughout the different polymer films are discussed. The IR data show that the technique used to prepare the organometallic-embedded thin films (viz. freeze-drying of solutions followed by hot mechanical pressing of the residues) does in general lead to homogeneous films which may eventually find industrial application, e.g. as membrane sensors for small molecules.     

3,4,5,6‐Tetrafluorophenylnitren‐2‐yl: A Ground‐State Quartet Triradical

The photochemistry of 2‐iodo‐3,4,5,6‐tetrafluorophenyl azide ( 7 d ) has been investigated in argon and neon matrices at 4 K, and the products characterized by IR and EPR spectroscopy. The primary photochemical step is loss of a nitrogen molecule and formation of phenyl nitrene 1 d . Further irradiation with UV or visible light results in mixtures of 1 d with azirine 5 d ′, ketenimine 6 d ′, nitreno radical 2 d , and azirinyl radical 9 . The relative amounts of these products strongly depend on the matrix and on the irradiation conditions. Nitreno radical 2 d with a quartet ground state was characterized by EPR spectroscopy. Electronic structure calculations in combination with the experimental results allow for a detailed understanding of the properties of this unusual new type of organic high‐spin molecules.     

Synthesis of Prebiotic Glycerol in Interstellar Ices

Contemporary mechanisms for the spontaneous formation of glycerol have not been able to explain its existence on early Earth. The exogenous origin and delivery of organic molecules to early Earth presents an alternative route to their terrestrial in situ formation since biorelevant molecules like amino acids, carboxylic acids, and alkylphosphonic acids have been recovered from carbonaceous chondrites. Reported herein is the first in situ identification of glycerol, the key building block of all cellular membranes, formed by exposure of methanol‐based — interstellar model ices to ionizing radiation in the form of energetic electrons. These results provide compelling evidence that the radiation‐induced formation of glycerol in low‐temperature interstellar model ices is facile. Synthesized on interstellar grains and eventually incorporated into the “building material” of solar systems, biorelevant molecules such as glycerol could have been dispensed to habitable planets such as early Earth by comets and meteorites.     

ATR-SEIRAS study of the adsorption of acetate anions at chemically deposited silver thin film electrodes

The adsorption of acetate anions at silver thin film electrodes has been studied by in-situ infrared spectroscopy experiments with a Kretschmann internal reflection configuration. Stable silver thin films were chemically deposited on germanium substrates. Ex-situ STM images show mean grain sizes ranging from ca. 20 to 90 nm for deposition times between 2 and 20 min, respectively. The thickness of the silver film, measured by AFM, is typically around 10 nm for a deposition time of 10 min and increases up to 50 nm for a deposition time of 20 min. Roughness factors around 2.3 have been obtained for the silver films from the charge involved in lead underpotential deposition (UPD). A noticeable enhancement of the infrared absorption of adsorbed species (SEIRA effect) is observed when the silver films are used as electrodes under internal total reflection conditions. Maximum intensities of the adsorbate bands were observed for a deposition time of 10 min and an angle of incidence around 65 degrees . The potential-dependent infrared spectra of acetate and interfacial water are consistent with previously proposed models involving the existence of weakly hydrogen-bonded water molecules at potentials below the potential of zero charge and the reorientation of water molecules at potentials above the potential of zero charge. Results reported in this work suggest a weak interaction between acetate and water molecules adsorbed at the silver thin film electrodes.     

Molecular ME‐ToF‐SIMS yield as a function of DHB matrix layer thicknesses obtained from brain sections coated by sublimation/deposition techniques

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) can be used to image biological samples with nanometer‐scale resolution, albeit with the drawback that it often cannot detect large molecular signals. One way to increase secondary ion molecular yield is to chemically modify the surface in the so‐called matrix‐enhanced SIMS (ME‐SIMS) approach, which is based on embedding analyte molecules in low‐weight organic matrices. In this study, a solvent‐free sample preparation technique was employed using sublimation/deposition for coating a mouse brain section with a thin layer of a 2,5‐dihydroxybenzoic acid (DHB) matrix. Using this preparation technique, signal enhancements of up to a factor of 18 could be detected. It was found that the matrix layer thickness plays an important role in the efficiency of yield enhancement. Also, a complex influence of the matrix layer on various signals was observed. Copyright © 2015 John Wiley & Sons, Ltd.     

Thin‐layer chromatography combined with surface‐enhanced Raman scattering for rapid detection of benzidine and 4‐aminobiphenyl in migration from food contact materials based on gold nanoparticle doped metal‐organic framework

In this work, a rapid and sensitive thin‐layer chromatography combined with surface‐enhanced Raman spectroscopy method was established for rapid detection of benzidine and 4‐aminobiphenyl in migration from food contact materials based on Au nanoparticle doped metal‐organic framework. Benzidine and 4‐aminobiphenyl were firstly separated by thin‐layer chromatography to solve the limitation of their overlapping Raman peaks. Then the target molecules were monitored by adding AuNPs/MIL‐101(Cr) on the sample spots. Under the optimum conditions, the concentration of benzidine and 4‐aminobiphenyl can be quantitatively measured in the range of 2.0‐20.0 and1.0‐15.0 μg/L, respectively with good linear relationship, and the limits of detection were 0.21 and 0.23 μg/L, respectively. Furthermore, the developed method was applied to analyze benzidine and 4‐aminobiphenyl in migration of different food contact materials. The recoveries of benzidine and 4‐aminobiphenyl for migration of food contact materials, including paper cups, polypropylene food containers, and polyethylene glycol terephthalate bottles, were 80.6‐116.0 and 80.7‐118% with relative standard deviations of 1.1‐9.1 and 3.1‐9.9%, respectively. Surface‐enhanced Raman scattering detection was performed conveniently in the on‐plate mode without additional elution process. The method shows great potential in rapid monitoring of hazardous substances with overlapping characteristic Raman peaks in food contact materials.     

Generation of paramagnetic hybrid inorganic/organic thin films

There is a growing interest in developing advanced materials for thin film applications in biology, electronics, photonics and engineering. We report the development of hybrid inorganic/organic thin films containing nickel, iron and cobalt paramagnetic materials. By etching the resist in oxygen plasma after processing, most of the organic component of the resist was removed. The elemental chemical composition of the films was confirmed by energy dispersive X‐ray spectroscopy. This process can potentially lead to patterning paramagnetic thin films containing paramagnetic materials by following standard photolithography protocols, obviating the need for a wet or vacuum metal deposition. Copyright © 2010 John Wiley & Sons, Ltd.