Normal and surface-enhanced Raman spectroscopy of nitroazobenzene submonolayers and multilayers on carbon and silver surfaces

Raman and ultraviolet-visible (UV-Vis) absorption spectra were obtained for nitroazobenzene (NAB) chemisorbed on smooth and rough silver, and they were compared to published spectra for NAB on sp(2) hybridized pyrolyzed photoresist film (PPF) surfaces. High signal-to-noise ratio Raman spectra were obtained for 4.5 nm thick NAB films on PPF and smooth Ag due to significant enhancement of the NAB scattering relative to that observed in solution. The UV-Vis spectra of chemisorbed NAB exhibited a significant shift toward longer wavelength, thus bringing the NAB absorption closer to the 514.5 nm laser wavelength. The red shift was larger for PPF than for smooth Ag, consistent with the approximately 5x stronger Raman signal obtained on PPF. Deposition of Ag onto quartz without a chromium adhesion layer produced a rough Ag surface that enhanced the Raman spectrum of chemisorbed NAB by a factor of approximately 1000, as expected for roughened Ag due to electromagnetic field enhancement. The strong Raman signal permitted observation of NAB at low coverage and revealed changes in the NAB spectrum as the film progressed from submonolayer to multilayer thicknesses. Finally, deposition of Ag onto PPF/NAB samples through a metal grid produced Ag squares on top of the NAB, which enhanced the Raman scattering of the NAB layer by a factor of approximately 100. Deposition of a final conducting film on the Ag squares should permit in situ observation of a wide range of molecules in operating molecular electronic junctions.     

Characterization of carbon/nitroazobenzene/titanium molecular electronic junctions with photoelectron and Raman spectroscopy

Molecular junctions consisting of nitroazobenzene (NAB) chemisorbed to a substrate of pyrolyzed photoresist film (PPF) and a top contact of vapor-deposited titanium were examined with Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The thickness of the NAB layer varied from submonolayer to 4.5 nm, and a thin (1-3 nm) overlayer of Ti was deposited by electron beam deposition. Without Ti, the NAB surface Raman spectrum was sufficiently strong to observe previously unreported modes in the 500-1000-cm(-1) region, and the 1000-1700-cm(-1) region was sufficiently strong to observe the effects of metal deposition. Upon Ti deposition, the intensities of NAB modes associated with the nitro group decreased significantly, and the XPS indicated formation of a Ti-N bond. For the thicker NAB layers (1.9 and 4.5 nm), the intensities of the NO(2) Raman modes partially recovered over a several-day period, but they remain depressed or absent in the submonolayer sample. The results indicate a reaction between condensing Ti atoms and the terminal NO(2) group, probably to form a Ti-nitroso linkage between NAB and Ti. The result is a molecular junction with covalent bonding at both ends in the form of a C-C bond between PPF and NAB and a Ti-N bond to the top contact. The structural implications of the current results are interpreted in the context of recently reported functioning PPF/NAB/Ti molecular electronic junctions. In particular, the reaction between Ti and the nitro group appears to prevent short circuits resulting from incursion of Ti into the NAB layer.     

Raman spectroscopic determination of the structure and orientation of organic monolayers chemisorbed on carbon electrode surfaces

Azobenzene (AB) and 4-nitroazobenzene (NAB) were covalently bonded to carbon surfaces by electrochemical reduction of their diazonium derivatives. The N(1s) features of XPS spectra of modified surfaces had intensities expected for monolayer coverage. However, the Raman spectra were significantly more intense than expected, implying an increase in scattering cross section upon chemisorption. A likely explanation is resonance enhancement of the carbon/adsorbate chromophore analogous to that reported earlier for dinitrophenylhydrazine (DNPH) chemisorption. Vibrational assignments indicate that the C-C vibration between azobenzene and the carbon surface is in the 1240-1280 cm(-1) region, and this conclusion is supported by spectra obtained from [(13)C]graphite. Observation of depolarization ratios for 4-nitroazobenzene and DNPH on graphite edge plane indicate that NAB is able to rotate about the NAB/carbon C-C bond, while chemisorbed DNPH is not. The partial multiple bond character of the DNPH linkage to graphite is consistent with the observation that the DNPH π system remains parallel to the graphitic planes.     

Mono- and multilayer formation by diazonium reduction on carbon surfaces monitored with atomic force microscopy "scratching"

Contact mode atomic force microscopy (AFM) was used to intentionally scratch a monolayer deposited on a pyrolyzed photoresist film (PPF). The force was set to completely remove the monolayer but not to damage the underlying PPF surface. A line profile determined across the scratch with tapping mode AFM permitted determination of the monolayer thickness from the depth of the scratch. A statistical process was devised to avoid user bias in determining the monolayer thickness and was used to determine the thickness as a function of derivatization parameters. PPF surfaces modified by reduction of diazonium ions of stilbene, biphenyl, nitrobiphenyl, terphenyl, and nitroazobenzene (NAB) were scratched and their modification layer thicknesses determined. For single-scan derivatizations of 1 mM diazonium ions to -0.6 V versus Ag+/Ag, the biphenyl and stilbene monolayers exhibited thicknesses close to those expected for true monolayers. However, more extensive derivatization resulted in multilayers up to 6.3 nm thick for the case of NAB. Such multilayers imply that electrons are transmitted through the growing film during diazonium reduction, despite the fact that electron tunneling would not be expected to be operative over such long distances. The results are consistent with a conductance increase in the growing film, which yields a partially conductive layer that can support further diazonium ion reduction and additional layer growth.     

Electroanalytical performance of carbon films with near-atomic flatness

Physicochemical and electrochemical characterization of carbon films obtained by pyrolyzing a commercially available photoresist has been performed. Photoresist spin-coated on to a silicon wafer was pyrolyzed at 1,000 degrees C in a reducing atmosphere (95% nitrogen and 5% hydrogen) to produce conducting carbon films. The pyrolyzed photoresist films (PPF) show unusual surface properties compared to other carbon electrodes. The surfaces are nearly atomically smooth with a root-mean-square roughness of <0.5 nm. PPF have a very low background current and oxygen/carbon atomic ratio compared to conventional glassy carbon and show relatively weak adsorption of methylene blue and anthraquinone-2,6-disulfonate. The low oxygen/carbon ratio and the relative stability of PPF indicate that surfaces may be partially hydrogen terminated. The pyrolyzed films were compared to glassy carbon (GC) heat treated under the same conditions as pyrolysis to evaluate the electroanalytical utility of PPF. Heterogeneous electron-transfer kinetics of various redox systems were evaluated. For Ru(NH3)6(3+/2+), Fe(CN)6(3-/4-), and chlorpromazine, fresh PPF surfaces show electron-transfer rates similar to those on GC, but for redox systems such as Fe3+/2+, ascorbic acid, dopamine, and oxygen, the kinetics on PPF are slower. Very weak interactions between the PPF surface and these redox systems lead to their slow electron-transfer kinetics. Electrochemical anodization results in a simultaneous increase in background current, adsorption, and electron-transfer kinetics. The PPF surfaces can be chemically modified via diazonium ion reduction to yield a covalently attached monolayer. Such a modification could help in the preparation of low-cost, high-volume analyte-specific electrodes for diverse electroanalytical applications. Overall, pyrolysis of the photoresist yields an electrode surface with properties similar to a very smooth version of glassy carbon, with some important differences in surface chemistry.     

Structural,morphological, optical and electrical properties of CdS thin films simultaneously doped with magnesium and chlorine

CdS thin films simultaneously doped with Mg and Cl at different doping concentrations (0, 2, 4, 6 and 8 at%) were prepared on glass substrates by spray pyrolysis technique using perfume atomizer at 400 °C. The effect of Mg and Cl doping concentration on the structural, morphological, optical and electrical properties of the deposited films were investigated using X-ray diffraction (XRD), scanning electron microscopy, UV–Vis spectroscopy and dc electrical measurements, respectively. XRD analysis showed that the undoped and doped CdS films exhibit hexagonal structure with a preferential orientation along the (0 0 2) plane. The 2θ angle position of the (0 0 2) peak of the doped films was shifted towards a higher angle with increasing Mg and Cl concentration. The UV–Vis–NIR absorption spectra of Mg and Cl doped thin films are measured and classical Tauc approach was employed to estimate their band gap energies. The increase in band gap energy from 2.46 to 2.73 eV with the reduction in crystallite size supports quantum size effect. Raman spectra implied that more defects existed in the doped samples. Electrical studies showed that all the films have resistivity in the order of 10¹ Ω-cm and the CdS film with 6 at% Mg and Cl concentration has a minimum resistivity of 1.332 × 10¹ Ω-cm.     

Aligned silver nanorod arrays as substrates for surface-enhanced infrared absorption spectroscopy

Preferentially aligned silver nanorod arrays prepared by oblique angle vapor deposition were evaluated as substrates for surface-enhanced infrared absorption (SEIRA) spectroscopy. These nanorod arrays have an irregular surface lattice and are composed of tilted, cylindrically shaped nanorods that have an average length of 868 nm +/- 95 nm and an average diameter of 99 nm +/- 29 nm. The overall enhancement factor for chemisorbed organic films of para-nitrobenzoic acid (PNBA) deposited onto the Ag nanorod arrays analyzed by external reflection SEIRA was calculated to be 31 +/- 9 compared to infrared reflection-absorption spectroscopy (IRRAS) obtained from a 500 nm Ag film substrate. This enhancement is attributed to the unique optical properties of the nanorod arrays as well as the increased surface area provided by the nanorod substrate. SEIRA reflection-absorbance intensity was observed with both p- and s-polarized incident radiation with angles of incidence ranging from 25 degrees to 80 degrees . The largest intensity was achieved with p-polarization and incident angles larger than 75 degrees . Polarization-dependent ultraviolet/visible/near-infrared (UV/Vis/NIR) spectra of the nanorod arrays demonstrate that the red-shifted surface plasmon peaks of the elongated nanorods may be partially responsible for the observed SEIRA response. The SEIRA detection limit for the Ag nanorod arrays was estimated to be 0.08 ng/cm(2). Surface-enhanced Raman scattering (SERS) and SEIRA analysis of chemisorbed PNBA utilizing the same nanorod substrate is demonstrated.     

Ultraviolet-visible spectroelectrochemistry of chemisorbed molecular layers on optically transparent carbon electrodes

Pyrolysis of diluted commercial photoresist spun onto quartz slides yields optically transparent graphitic films. Transparent carbon electrodes approximately 6 nm thick can be reproducibly prepared, with a maximum absorbance in the ultraviolet-visible (UV-vis) range of 0.25 at 270 nm. These electrodes are sufficiently conductive for electrochemistry, enabling modification of the surface via diazonium ion reduction and spectroelectrochemistry. Good quality ultraviolet-visible absorption spectra of covalently bonded molecular layers of nitroazobenzene, nitrobiphenyl, and azobenzene, with thicknesses of 1.4-4 nm, were obtained after subtracting the spectrum of the unmodified substrate. The spectra of all three molecules immobilized on the carbon surface showed red shifts of the absorption maxima relative to a solution of free molecules, indicating substantial electronic interactions between chemisorbed molecules and the Pi system of the substrate and/or intermolecular coupling. Spectroelectrochemical measurements show that reduction of free and chemisorbed molecules produce new absorption features in the 500-800 nm range; these spectral changes are partially reversible upon repeated potential cycling. Finally, density functional calculations correlate the new bands to the formation of anion radical or "methide" species that have more extensive electron delocalization than the parent molecules. The results from this work are useful for linking structural transformations in molecular layers "buried" under conductive top contacts in a type of molecular junction to changes in the electronic properties of the junction.     

Fabrication and characterization of silicon quantum dots in Si-rich silicon carbide films

Amorphous Si-rich silicon carbide films were prepared by magnetron co-sputtering and subsequently annealed at 900-1100 degrees C. After annealing at 1100 degrees C, this configuration of silicon quantum dots embedded in amorphous silicon carbide formed. X-ray photoelectron spectroscopy was used to study the chemical modulation of the films. The formation and orientation of silicon quantum dots were characterized by glancing angle X-ray diffraction, which shows that the ratio of silicon and carbon significantly influences the species of quantum dots. High-resolution transmission electron microscopy investigations directly demonstrated that the formation of silicon quantum dots is heavily dependent on the annealing temperatures and the ratio of silicon and carbide. Only the temperature of about 1100 degrees C is enough for the formation of high-density and small-size silicon quantum dots due to phase separation and thermal crystallization. Deconvolution of the first order Raman spectra shows the existence of a lower frequency peak in the range 500-505 cm(-1) corresponding to silicon quantum dots with different atom ratio of silicon and carbon.     

Regeneration of pyrolyzed photoresist film by heat treatment

A simple, time-, and cost-effective procedure is described for regenerating film-modified or deactivated pyrolyzed photoresist film (PPF) surfaces. Heating for 30 min at 545 ± 25 °C in argon at a flow rate of 1 L min(-1) removes covalently bound thin organic films, attached via electrografting from aryldiazonium salt solutions. The heat-treated surfaces exhibit improved electrochemical characteristics compared to those prior to modification and can be reused for solution-based electrochemical measurements and for electrografting. The same treatment reactivates PPF electrodes that have been deactivated by exposure to adsorbates from air or solution. X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and water contact angle measurements establish that the regeneration procedure does not lead to significant changes in oxygen content, roughness, or hydrophobicity of PPF surfaces. XPS measurements also confirm the complete removal of covalently attached organic films after heat treatment but reveal a specific interaction between grafted nitrophenyl films and PPF which results in a small amount of N incorporation in the surface.     

Adsorption characteristics of 4,4′-bipyridine molecules on gold nanosphere films studied by surface-enhanced Raman scattering

We have measured and compared the surface-enhanced Raman scattering (SERS) spectra of 4,4′-bipyridine (bpy) molecules deposited (adsorbed) on the films of gold nanospheres (NSs, mean diameter 35 ± 5 nm), as prepared by the salting-out method using NaClO₄ and NaOH. The bpy-deposited (adsorbed) films were prepared by casting an aliquot of the bpy-ethanol solutions in different concentrations (less and above the monolayer converge on the gold surface), or on immersion of the NS films into the concentrated bpy solution. The enhancement of the SERS spectra of bpy was larger for the NS film prepared from NaClO₄ than that from NaOH. But, the SERS intensity was independent of the concentration of the bpy solution. The changes in the intensities and the shapes of the SERS spectra were distinctly observed on immersion of the bpy-deposited (adsorbed) NS films into pure ethanol, and these spectral changes were prominent for the NS film prepared from NaClO₄. This must be attributed to considerably coalesced structures of the NS film prepared from NaClO₄. From the comparison of the intensity changes before and after immersion into ethanol, it is suggested that the vertical orientation of the bpy molecules adsorbed on the NS films changes into the flat orientation with respect to the surface of the gold nanoparticles at the solid-liquid interface, on immersion of the film into pure ethanol.     

A study of pyrolysis of polymethylsiloxanes by Fourier transform infrared

This paper is dedicated to a comparative study of pyrolysis of decamethylcyclopentasiloxane and hexamethyldisiloxane, widely used as precursors for CVD of silicon dioxide films. The pyrolysis process was carried out in a hot-wall horizontal tube reactor made from quartz within the temperature range 25-1000 degrees C. FTIR spectroscopy has been used for the analysis of gaseous reaction products in the exhaust line of the reactor. It has been found that transformation of DMPSO was initiated by the open ring in the precursor molecules with its further transformation to linear biradicals followed by the chain's growth due to radical reactions. HMDSO transformation is connected with separation of silanon, silyl and methyl radicals with following multi-type interactions of siloxane radicals and formation of non-rigorously organized three-dimensional molecules.     

Grain refinement in low SFE and particle-containing nickel aluminium bronze during severe plastic deformation at elevated temperatures

The influence of particle size and morphology on grain refinement in low stacking fault energy(SFE)alloys was studied by comparing the grain structures in single-and multi-phase Al-bronze(AB)alloys following equal channel angular pressing(ECAP)between 350 and 500℃.In particular,nickel aluminium bronze(NAB)was chosen as it contained both coarse and fine rounded particles,as well as a lamellar phase which evolved during ECAP.Grain refinement in the single-phase alloy was achieved through dynamic recrystallisation initiated at deformed twin boundaries.By contrast,different mechanisms were observed in the particle-containing NAB.Recrystallisation around the coarse κⅡ particles(～5 μm)was promoted through particle stimulated nucleation(PSN),whereas recrystallisation in the region of the fine κⅣ(～0.4μm)was delayed due to the activation of secondary slip.Grain refinement in areas of the lamellar κⅢ showed significant variation,depending on the lamellar orientation relative to the shear plane of ECAP.As the lamellae deformed,numerous high angle grain boundaries were generated between fragments and served as nucleation sites for recrystallisation,while PSN occurred around spheroidised lamellae.The spreading of the κⅢ particles by ECAP then enhanced the total area of recrystallised grains.     

The effects of incident angle on C-axis orientation in sputtered Co-Cr films

The effects of the incident angle of the sputtered atoms on the crystallographic orientation in the Co-Cr films have been investigated in detail. Specimen films 1000 - 2000 Å thick were prepared by the Facing Targets Sputtering (FTS) system. The specially designed mask was used for collecting only the sputtered particles with the quasi-coherent incidence to the substrate. When the films are prepared at relatively low argon gas pressures, the effect of incident angle is not so apparent and the well c-axis oriented films can be obtained for the incident angle below 45°. This result indicate that the surface diffusion may be dominant over the incident angle for attaining the desired crystallographic orientation in the films when they are prepared at low working gas pressures. Owing to the unique target/substrate layout, the plasma-free FTS system with low working gas pressures may have much larger flexibilities for preparing the well c-axis oriented Co-Cr films as compared with the conventional sputtering systems or the vacuum evaporation one.     

Structural analysis of porphyrin multilayer films on ITO assembled using copper(I)-catalyzed azide-alkyne cycloaddition by ATR IR

We report the use of grazing-angle attenuated total reflectance (GATR) IR and polarized UV-vis to determine the molecular structure of porphyrin based molecular multilayer films grown in a layer-by-layer (LbL) fashion using copper-catalyzed azide-alkyne cycloaddition (CuAAC). The molecular orientation and bonding motif present in multilayer films of this type could impact their photophysical and electrochemical properties as well as potential applications. Multilayer films of M(II) 5,10,15,20-tetra(4-ethynylphenyl)porphyrin (1 M = Zn, 2 M = Cu) and azido based linkers 3-5 were used to fabricate the films on ITO substrates. Electrochemically determined coverage of films containing 2 match the trends observed in the absorbance. GATR-IR spectral analysis of the films indicate that CuAAC reactivity is leading to 1,4-triazole linked multilayers with increasing porphyrin and linker IR characteristic peaks. Films grown using all azido-linkers (3-5) display an oscillating trend in azide IR intensity suggesting that the surface bound azido group reacts with 1 and that further layering can occur through additional reaction with linkers, regenerating the azide surface. Films containing linker 5 in particular show an overall increase in azide content suggesting that only two of the three available groups react during multilayer fabrication, causing an overall buildup of azide content in the film. Films of 1 with linker 3 and 5 showed an average porphyrin plane angle of 46.4° with respect to the substrate as determined by GATR FT-IR. Polarized UV-vis absorbance measurements correlate well with the growth angle calculated by IR. The orientation of the porphyrin plane within the multilayer structures suggests that the CuAAC-LbL process results in a film with a trans bonding motif.     

Influence of RF power on structural,morphology, electrical,composition and optical properties of Al-doped ZnO films deposited by RF magnetron sputtering

In this study, influence of RF power on the structural, morphology, electrical, composition and optical properties of Al-doped ZnO (ZnO:Al) films deposited by RF magnetron sputtering have been investigated. Films were systematically and carefully investigated by using variety of characterization techniques such as low angle X-ray diffraction, UV–visible spectroscopy, Raman spectroscopy, Hall measurement, X-ray photoelectron spectroscopy, field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy etc. Low angle X-ray diffraction analysis showed that the films are polycrystalline with hexagonal wurtzite structure and which was further confirmed by Raman spectroscopy analysis. Its preferred orientation shifts from (102) to (002) with increase in RF power. The average grain size was found in the range of 15–21 nm over the entire range of RF power studied. The FE-SEM analysis showed that grain size and surface roughness of ZnO:Al films increase in with increase in RF power. The UV–visible spectroscopy analysis revealed that all films exhibit transmittance >85 % in the visible region. The optical band gap increases from 3.37 to 3.85 eV when RF power increased from 75 to 225 W. Hall measurements showed that the minimum resistivity has been achieved for the film deposited at 200 W. The improvement in the electrical properties may attribute to increase in the carrier concentration and Hall mobility. Based on the experimental results, the RF power of 200 W appears to be an optimum sputtering power for the growth of ZnO:Al films. At this optimum sputtering power ZnO:Al films having minimum resistivity (8.61 × 10^?4 Ω-cm), highly optically transparent (~87 %) were obtained at low substrate temperature (60 °C) at moderately high deposition rate (22.5 nm/min). These films can be suitable for the application in the flexible electronic devices such as TCO layer on LEDs, solar cells, TFT-LCDs and touch panels.     

Preparation and characterization of an electrogenerated chemiluminescence sensor by electrochemical grafting of 4-nitrophenyl diazonium salts onto a glass carbon electrode

An ECL sensor was fabricated by immobilization of a tris(2,2'-bipyridyl)ruthenium (II) complex (Ru(bpy)3(2+)) to an amine group-modified GC electrode (NH2-GC electrode). Here, the NH2-GC electrode was prepared by electrochemical reduction of a nitro group-modified GC electrode in 0.1 M KCl ethanol solution under H2 gas, which was followed by electrochemical grafting of 4-nitrophenyl diazonium salts in 0.1 M NBu4BF4 acetonitrile solution onto the GC electrode. The prepared ECL sensor was successfully confirmed via cyclic voltammetry, contact angle, scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), and ECL spectrometry. The contact angle for the surface of the GC electrode, NO2-GC electrode, and NH2-GC electrod was 88.4 degrees, 67.4 degrees, and 52.4 degrees, respectively. The stability of the ECL sensor was investigated under continuous cyclic potential scanning for 55 cycles and the ECL intensity remained at 55%. The prepared ECL electrode can be expected to immobilize enzymes for preparation of the ECL biosensor to detect target molecules.     

Heat Treatment of Thin Carbon Films Grown by Ion Beam Sputtering Using an Impulse Electron Beam

We report on a new process to make thin carbon films using ion beam sputtering (Ar and H₂ mixture) from a graphite target followed by impulse electron beam on the sputter deposited film. The thin carbon films studied by x-ray diffraction showed a preferred orientation of carbon chains perpendicular to the substrate surface. The IR and Raman spectroscopic data have been interpreted as indicating the formation of polyyne and cumulene structures in the thin carbon films.     

真空还原制备的VO2热致相变薄膜Raman光谱和红外光谱研究

报道了利用真空还原制备的VO2薄膜的红外透射光谱和Raman光谱,并进行370－900nm波段的光透射测试以及900nm波长的热滞回线特性测试,表明所制备VO2薄膜具有优良的热致相变光学特性,结晶状态不同的薄膜其Raman谱位置有明显改变,室温时的红外光谱表现出较好的红外振动特性。讨论了薄膜结晶状态对Raman位移的影响以及VO2薄膜的红外光谱。     

Fourier transform Raman spectroscopy of thin films

Conventional Raman measurements of dyes in the visible region exhibit resonant effects which enhance the Raman scattering cross-section of the chromophores by several orders of magnitude but make scattering from other parts of the molecules, such as the hydrocarbon chains, unobservable. Taking advantage of the benefits inherent to Fourier transform (FT) spectroscopy, Raman spectra can now be measured routinely with an FT IR spectrometer and a continuous wave Nd:YAG laser. By coupling the laser excitation into a thin film waveguide, we have recently observed FT Raman spectra of a thin film of polystyrene. The advantages of using integrated optics with FT Raman spectroscopy for Langmuir-Blodgett films of dye molecules are also discussed.