Characterization of novel Ag on TiO2 films for surface-enhanced Raman scattering

Novel Ag on TiO2 films are generated by semiconductor photocatalysis and characterized by ultraviolet-visible (UV/Vis) spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM), as well as assessed for surface-enhanced Raman scattering (SERS) activity. The nature and thickness of the photodeposited Ag, and thus the degree of SERS activity, is controlled by the time of exposure of the TiO2 film to UV light. All such films exhibit the optical characteristics (lambda(max) congruent with 390 nm) of small (< 20 nm) Ag particles, although this feature becomes less prominent as the film becomes thicker. The films comprise quite large (> 40 nm) Ag islands that grow and merge with increasing levels of Ag photodeposition. Tested with a benzotriazole dye probe, the films are SERS active, exhibiting activity similar to that of 6-nm-thick vapor-deposited films. The Ag/TiO2 films exhibit a lower residual standard deviation (approximately 25%) compared with Ag vapor-deposited films (approximately 45%), which is, however, still unacceptable for quantitative work. The sample-to-sample variance could be reduced significantly (< 7%) by spinning the film during the SERS measurement. The Ag/TiO2 films are mechanically robust and resistant to removal and damage by scratching, unlike the Ag vapor-deposited films. The Ag/TiO2 films also exhibit no obvious loss of SERS activity when stored in the dark under otherwise ambient conditions. The possible extension of this simple, effective method of producing Ag films for SERS, to metals other than Ag and to semiconductors other than TiO2, is briefly discussed.     

Preparation of silver nanoparticles by photo-reduction for surface-enhanced Raman scattering

A substrate for surface-enhanced Raman scattering (SERS) has been developed. Based on the surface-catalyzed reduction of Ag⁺ by citrate on the silver nanoparticles surface under light irradiation, small silver seeds on a quartz slide can be enlarged. The optical properties and characteristics of the silver films have been investigated by ultraviolet-visible spectroscopy, scan electron microscope and atomic force microscopy (AFM). The results indicate that the particle size and shape are different at different reduction time. At the first 3 h, some triangular and hexagonal nanoparticles formed; with the reduction proceeding, the shape of the silver particles became irregular and the size became larger. The silver films obtained are very suitable as SERS active substrate. The relationship between SERS intensity and the reduction time has been investigated for 1,4-bis[2-(4-pyridyl)ethenyl]-benzene molecule adsorbed on the silver film. The SERS intensity reached a maximum at 8 h reduction. The AFM measurements indicate that roughness features with an average size of 100 nm are present on the surface, which yielded the strongest SERS signal. Pyridine was used as a probe molecule to investigate the enhancement factor (EF) of the silver films. According to the formalism of Tian and co-workers, the EF of the silver films is estimated to be 3.4 × 10⁵. The silver film that can remain active for more than 50 days would seem to be suitable for various analytical applications.     

Fabricating Au–Ag core-shell composite films for surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) integrates high levels of sensitivity with spectroscopic precision, and thus, has tremendous potential for chemical and biomolecular sensing. The key to the wider application of Raman spectroscopy using roughened metallic surfaces is the development of highly enhancing substrates for analytical purposes, i.e., for better detection sensitivity of trace contaminants and pollutants. Here, we have prepared Au, Ag, AuAg multilayer, and Au@Ag films on glass substrates for SERS-active substrates. The Au@Ag film shows a much stronger SERS signal for trans-bis(4-pyridyl)ethylene (BPE) molecules than those from pure Au, Ag, and AuAg films, indicating the Au@Ag film is more powerful than pure Au, Ag, and AuAg film as SERS active substrates. The enhanced surface Raman scattering signals were attributed to the local field enhancement in the core-shell structure.     

Apatite formation from simulated body fluid on various phases of TiO2 thin films prepared by filtered cathodic vacuum arc deposition

Hydroxyl (OH⁻)-free TiO₂ thin films with amorphous and crystalline phases were deposited onto (100) silicon substrates using filtered cathodic vacuum arc deposition in order to investigate the in vitro apatite formation in simulated body fluid (SBF). The surface morphology, composition and structure of the TiO₂ thin films were characterized. The X-ray photoelectron spectroscopy results confirmed the presence of calcium and phosphorus on all TiO₂ thin film surfaces after immersion in SBF at 37 °C. Fourier transform infra red results showed the presence of carbonated apatite on the surface of these films. Amorphous structured TiO₂ thin film showed poor ability to form apatite on its surface in SBF. Apatite formation was more pronounced on the surfaces of the anatase films in comparison to those of rutile. The carbonated apatite deposition rate increased significantly when the TiO₂ film was illuminated with UV light prior to immersing in the SBF. In particular, the UV-treated anatase and rutile films showed increased rates of carbonated apatite formation on their surfaces in comparison to samples not treated with radiation. The increase in hydrophilicity due to UV treatment appears beneficial for the apatite growth on these surfaces.     

Ag Nanoparticle‐Grafted PAN‐Nanohump Array Films with 3D High‐Density Hot Spots as Flexible and Reliable SERS Substrates

A facile fabrication approach of large‐scale flexible films is reported, with one surface side consisting of Ag‐nanoparticle (Ag‐NP) decorated polyacrylonitrile (PAN) nanohump (denoted as Ag‐NPs@PAN‐nanohump) arrays. This is achieved via molding PAN films with ordered nanohump arrays on one side and then sputtering much smaller Ag‐NPs onto each of the PAN‐nanohumps. Surface‐enhanced Raman scattering (SERS) activity of the Ag‐NPs@PAN‐nanohump array films can be improved by curving the flexible PAN film with ordered nanohump arrays during the Ag‐sputtering process to increase the density of the Ag‐NPs on the sidewalls of the PAN‐nanohumps. More 3D hot spots are thus achieved on a large‐scale. The Ag‐NPs@PAN‐nanohump array films show high SERS activity with good Raman signal reproducibility for Rhodamine 6G probe molecules. To trial their practical application, the Ag‐NPs@PAN‐nanohump array films are employed as SERS substrates for trace detection of trinitrotoluene and a congener of polychlorinated biphenyls. A lower detection limit of 10⁻¹²m and 10⁻⁵m can be achieved, respectively. Furthermore, the flexible Ag‐NPs@PAN‐nanohump array films can also be utilized as swabs to probe traces of methyl parathion on the surface of fruits such as apples. The as‐fabricated SERS substrates therefore have promising potential for applications in rapid safety inspection and environmental protection.     

A new approach to solution-phase gold seeding for SERS substrates

Surface-enhanced Raman scattering (SERS) vastly improves signal-to-noise ratios as compared to traditional Raman scattering, making sensitive assays based upon Raman scattering a reality. However, preparation of highly stable SERS-active gold substrates requires complicated and expensive methodologies and instrumentation. Here, a general and completely solution-phase, seed-based approach is introduced, which is capable of producing gold films for SERS applications on a variety of substrates, not requiring surface modification or functionalization. SERS enhancement factors of ≈10(7) were observed. Moreover, solution-phase gold film deposition on highly complex surfaces, such as protein-coated bioassays, is demonstrated for the first time. Protein bioassays coated with such SERS-active gold films are combined with bioconjugated single-walled carbon nanotube Raman labels, affording highly sensitive detection of the cancer biomarker, carcinoembryonic antigen in serum, with a limit of detection of ≈5 fM (1 pg mL(-1) ).     

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.     

Initiated Chemical Vapor Deposition: A Versatile Tool for Various Device Applications

Advances in device technology have been accompanied by the development of new types of materials and device fabrication methods. Considering device design, initiated chemical vapor deposition (iCVD) inspires innovation as a platform technology that extends the application range of a material or device. iCVD serves as a versatile tool for surface modification using functional thin film. The building of polymeric thin films from vapor phase monomers is highly desirable for the surface modification of thermally sensitive substrates. The precise control of thin film thicknesses can be achieved using iCVD, creating a conformal coating on nano‐, and micro‐structured substrates such as membranes and microfluidics. iCVD allows for the deposition of polymer thin films of high chemical functionality, and thus, substrate surfaces can be functionalized directly from the iCVD polymer film or can selectively gain functionality through chemical reactions between functional groups on the substrate and other reactive molecules. These beneficial aspects of iCVD can spur breakthroughs in device fabrication based on the deposition of robust and functional polymer thin films. This review describes significant implications of and recent progress made in iCVD‐based technologies in three fields: electronic devices, surface engineering, and biomedical applications.

     

Controlled layer-by-layer formation of ultrathin TiO2 on silver island films via a surface sol-gel method for surface-enhanced Raman scattering measurement

A surface sol-gel process has been demonstrated to be an effective method for the surface modification of silver island films as unique SERS substrates for monitoring molecular adsorption on a dielectric titania surface. This layer-by-layer approach allows control of the thickness of the dielectric surface with a monolayer precision on silver surfaces. The enhancement of Raman scattering from adsorbed Rhodamine 6G molecules is inversely proportional to the thickness of the titania film, which is consistent with the decay of electromagnetic enhancement. Despite a reduction in the sensitivity of the film, a substantial improvement in the film was achieved as a result of the enhanced stability of this substrate compared to the silver island film without a TiO(2) coating.     

Growth of thin metallic films on insulating substrates in the presence of electron irradiation

The condensation parameters for Ag and Sb films on amorphous dielectric substrates have been studied under electron irradiation conditions (J = 400 μcm^-2, V_e = 1 kV). With the help of Auger spectroscopy it was shown that the irradiation activated additional condensation centres, whose lifetimes on Sitall substrates were 1 h or more. Optimum doses of irradiation were determined (14 × 10^-3 A s cm^-2).From critical flux measurements for Ag condensation on polymeric surfaces, it was determined that irradiation increased the number of condensation centres by 2–2.5 times without influencing the film formation energy. It was shown that irradiation changed the process of Ag film condensation, causing earlier coalescence.     

Surface-enhanced Raman scattering on uniform transition-metal films: toward a versatile adsorbate vibrational strategy for solid-nonvacuum interfaces?

Procedures are outlined for the electrodeposition of ultrathin films of Pt-group transition metals onto gold that provide intense surface-enhanced Raman scattering (SERS) for adsorbates bound to the overlayers yet (unlike earlier reports) are sufficiently "pinhole-free" to avoid significant spectral and chemical interferences from the underlying substrate. Constant-current electrodeposition of Pd, Rh, Pt, and Ir from perchloric acid and/or phosphate electrolytes yields essentially layer-by-layer growth, so that near-ideal pinhole-free electrochemical and spectral characteristics are achieved for film thickness of ～2 monolayers or more. The desired film uniformity is diagnosed from the voltammetric oxide formation-removal behavior and, especially, from the absence of the characteristic C-O stretching (ν(CO)) SERS band at 2110-2120 cm(-)(1) due to CO binding to Au surface sites. Carbon monoxide is also employed as a surface environment-sensitive adsorbate to probe the electrochemical SERS characteristics as a function of the transition-metal film thickness. The Raman enhancement was observed to decrease by 2-fold every 10-20 ? or so, exhibiting a "spacer distance" dependence that is weaker than (but functionally similar to) recently reported organic insulator films. The practical value of the present films for obtaining rich vibrational spectra for diverse adsorbates on transition metals is pointed out and briefly illustrated for benzonitrile on a Pt film electrode. The more general promise of this overlayer film SERS strategy as a versatile vibrational technique for characterizing other types of chemically important surface materials is also noted.     

Ultraviolet-visible and surface-enhanced Raman scattering spectroscopy studies on self-assembled films of ruthenium phthalocyanine on organic monolayer-modified silver substrates

A self-assembled film of ruthenium phthalocyanine (RuPc) fabricated on a silver substrate pre-modified with a monolayer of 4-mercaptopyridine (PySH) or 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BPENB) was studied by ultraviolet-visible (UV-Vis) and surface enhanced Raman scattering (SERS) spectroscopy. PySH or BPENB was used as a ligand to link RuPc since they not only modify the silver substrate, but also deliver a pyridyl group pointing out from the silver surface. Therefore, we can explore the relationship between the structure and orientation of metallophthalocyanine and the substrate modified by the two kinds of organic-monolayers with the different conjugates and molecular lengths. UV-Vis bands due to the organic-monolayer (PySH or BPENB) modified silver films shift to longer wavelengths and a new band arising from the metallophthlocyanine appears, suggesting the binding of RuPc to PySH/BPENB, as well as the interaction between the marcocycle of RuPc and the ring of PySH/BPENB. Vibrational bands arising from both the RuPc and PySH/BPENB moieties appear clearly in the SERS spectra of the RuPc-PySH/BPENB composite films, indicating that RuPc is successfully assembled on the top of PySH/BPENB film. The shifts and relative intensity changes of bands due to PySH or BPENB in the SERS spectra imply the binding of the metallophthalocyanine to the pyridyl group in the composite films. Furthermore, the comparison of the SERS spectra revealed that the orientations of PySH and BPENB in the two kinds of composite films are different; the BPENB moiety in the RuPc-BPENB composite film is more perpendicular to the silver surface compared with the PySH moiety in the RuPc-PySH composite film.     

Formation and characterization of cobalt oxide layers on polyimide films via surface modification and ion-exchange technique

Polyimide (PI) films with thin cobalt oxide (Co₃O₄) layers on both film sides have been prepared via a surface modification and ion-exchange technique. The method works by hydrolyzing the PI film surfaces in aqueous potassium hydroxide solution and incorporating Co²⁺ into the hydrolyzed layers of PI film via subsequent ion exchange, and followed by thermal treatment in ambient atmosphere. The PI composite films were characterized by Attenuated total reflection-Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffractions, scanning electron microscopy, transmission electron microscopy and thermogravimetric analyses, as well as surface resistance and mechanical measurements. By varying the absorbed cobalt ion content, a series of PI/Co₃O₄ composite films with insulative to semiconductive surfaces were obtained. The room temperature surface resistances of the semiconductive composite films reached to about 10⁷ Ω. The Co₃O₄ particle formed on PI film surfaces was in the range of 10-40 nm. The final composite films maintained the essential mechanical properties and thermal stability of the pristine PI films. The adhesion between surface Co₃O₄ layers and PI matrix was acceptable.     

Improvement of physical properties of IGZO thin films prepared by excimer laser annealing of sol–gel derived precursor films

Indium gallium zinc oxide (IGZO) transparent semiconductor thin films were prepared by KrF excimer laser annealing of sol–gel derived precursor films. Each as-coated film was dried at 150 °C in air and then annealed using excimer laser irradiation. The influence of laser irradiation energy density on surface conditions, optical transmittances, and electrical properties of laser annealed IGZO thin films were investigated, and the physical properties of the excimer laser annealed (ELA) and the thermally annealed (TA) thin films were compared. Experimental results showed that two kinds of surface morphology resulted from excimer laser annealing. Irradiation with a lower energy density (≤250 mJ cm⁻²) produced wavy and irregular surfaces, while irradiation with a higher energy density (≥350 mJ cm⁻²) produced flat and dense surfaces consisting of uniform nano-sized amorphous particles. The explanation for the differences in surface features and film quality is that using laser irradiation energy to form IGZO thin films improves the film density and removes organic constituents. The dried IGZO sol–gel films irradiated with a laser energy density of 350 mJ/cm² had the best physical properties of all the ELA IGZO thin films. The mean resistivity of the ELA 350 thin films (4.48 × 10³ Ω cm) was lower than that of TA thin films (1.39 × 10⁴ Ω cm), and the average optical transmittance in the visible range (90.2%) of the ELA 350 thin films was slightly higher than that of TA thin films (89.7%).     

Synthesis and characterization of cross-linked silicone thin films by pulsed laser ablation deposition (PLAD)

Stable, uniform and cross-linked silicone films have been synthesized by pulsed laser ablation deposition (PLAD) for the first time. A KrF excimer (248 nm) laser was used in the synthesis. The effect of incident energy density on the deposited film chemistry was examined in depth. The surface analysis showed that at low energy densities (100–150 mJ/cm²), smooth, hydrophobic films similar in structure to the starting cross-linked silicone elastomer were obtained. Beyond 200 mJ/cm², hydrophilic films with oxygen contents much higher than the starting polymer were obtained. These films also exhibited a more particulate texture suggesting ablation of particles and/or polymeric clusters from the silicone target. The results demonstrate that the PLAD process may prove valuable for the preparation of cross-linked silicone thin films with tailored properties. Received: 27 June 2001 / Accepted: 17 July 2001     

Preparation of nanoporous TiO2 film with large surface area using aqueous sol with trehalose

The precursor solutions containing TiO₂ sol for nanoporous films were prepared by hydrolyzing titanium(IV) isopropoxide and adding trehalose dihydrate. The porous and thick TiO₂ film was prepared by dip-coating technique on glass substrate and heating at 500 °C. The maximum thickness of the film prepared by one-run dip-coating was ca. 740 nm. The film was composed of nanosized particles (10–20 nm) and pores (7 nm). The specific surface area and porosity of the film were 163 m²/g and 65%, respectively.     

Replication of surfaces of natural leaves for enhanced micro-scale tribological property

In this paper, we report on the replication of surfaces of Lotus and Colocasia leaves onto thin polymeric films using a capillarity-directed soft lithographic technique. The replication was carried out on poly(methyl methacrylate) (PMMA) film spin coated on silicon wafer using poly(dimethyl siloxane) (PDMS) molds. The friction properties of the replicated surfaces were investigated at micro-scale in comparison with those of PMMA thin film and uncoated silicon wafer. The coefficients of friction of the replicated surfaces were almost five times lower than those of the PMMA thin film and four times lower than those of the uncoated silicon wafer. The superior micro-tribological properties of the replicated surfaces could be attributed to the reduced real area of contact projected by the surfaces.     

Ferroelectric polymeric PVDF films prepared by ultrasonic atomization method

Ferroelectric poly (vinylidene fluoride) (PVDF) films were prepared by ultrasonic atomization. Various thickness and surface morphology of PVDF films were obtained by changing the frequency of an ultrasonic atomizer. The films were characterized by atomic force microscope (AFM) and ferroelectric tester. The results showed that there were some improvements in the thickness control and surface smoothness of polymeric PVDF films, which are critical problems for film deposition such as solution casting method. Ferroelectric properties measurement indicated that the films after corona charging displayed typical ferroelectric P–E hysteresis loops, giving a remanent polarization, P _r, of 5 μC/cm² and coercive field, E _c, of 150 MV/m. The maximum film deposition rate was 85 nm/min at the frequency of 6 MHz.     

Broadband coherent anti-Stokes Raman spectroscopy characterization of polymer thin films

Broadband coherent anti-Stokes Raman spectroscopy (CARS) is demonstrated as an effective probe of polymer thin film materials. A simple modification to a 1 kHz broad bandwidth sum frequency generation (SFG) spectrometer permits acquisition of CARS spectra for polymer thin films less than 100 nm thick, a dimension relevant to organic electronic device applications. CARS spectra are compared to the conventional Raman spectra of polystyrene and the resonance-enhanced Raman spectra of poly(3-hexylthiophene). The CARS spectra obtained under these conditions consistently demonstrate enhanced signal-to-noise ratio compared to the spontaneous Raman scattering. The sensitivity of the CARS measurement is limited by the damage threshold of the samples. The dielectic properties of the substrate have a dramatic effect on the detected signal intensity. For ultrathin films, the strongest signals are obtained from fused silica surfaces. Similar to surface-enhanced Raman scattering (SERS), Au also gives a large signal, but contrary to SERS, no surface roughening is necessary.     

Linker-molecule-free gold nanorod layer-by-layer films for surface-enhanced Raman scattering

This paper reports a methodology for synthesizing and ordering gold nanorods into two-dimensional arrays at a water/hexane interface. This preparation method allows the systematic control of the nanoparticle film thickness. An investigation into the thickness-dependent surface-enhanced Raman scattering (SERS) of the adsorbed molecules revealed the nanorod (NR) films to have 1 order of magnitude stronger SERS enhancement than the nanosphere (NS) under similar experimental conditions. The exposed surface areas of the prepared NR and NS films were analyzed using electrochemical methods, and it was found that they had comparable exposed surface areas. Therefore, the order of magnitude difference in the enhancement factor was not due to the differences in surface area but to their intrinsic difference in the optical coupling of each film. The difference was attributed to the high density of junction points with the NR films in comparison with the corresponding NS films. Scanning emission microscopy showed that the NR films have line contacts with each other but the NS films have point contacts, which can explain the difference in SERS intensity between the NR and NS films.