Evaporated gold island films have been the subject of studies dealing with a variety of spectroscopic and sensing applications. Development of these and other applications requires film stability as well as tunability of the morphology and optical properties of the island films. In the present work, ultrathin, island-type gold films were prepared by evaporation of 1.0-15.0 nm (nominal thickness) gold at a rate of 0.005-0.012 nm s -1 onto glass substrates modified with 3-mercaptopropyl trimethoxysilane (MPTS), the latter used to improve the Au adhesion to the glass. The morphology of the films, either unannealed or annealed (20 h at 200 °C), was studied using atomic force microscopy (AFM) and high-resolution scanning electron microscopy (HR-SEM). The information provided by the two imaging techniques is complementary, giving a good estimate of the shape of the islands and its variation with film thickness and annealing. The optical properties of the films were examined using transmission UV-vis spectroscopy, showing a strong dependence of the localized Au surface plasmon (SP) band on the morphology of the island films. The imaging and spectroscopy indicate a gradual transition from isolated islands to a continuous film upon increasing the Au thickness.

Gold nanoisland films displaying localized surface plasmon resonance optical response were constructed by evaporation on glass and annealing. The surface plasmon distance sensitivity and refractive index sensitivity (RIS) for island films of different nominal thicknesses and morphologies were investigated using layer-by-layer polyelectrolyte multilayer assembly. Since the polymer forms a conformal coating on the Au islands and the glass substrate between islands, the relative sensitivity of the optical response to adsorption on and between islands was evaluated. The RIS was also determined independently using a series of solvents. An apparent discrepancy between the behavior of the RIS for wavelength shift and intensity change is resolved by considering the different physical nature of the two quantities, leading to the use of a new variable, that is, RIS (for intensity change) normalized to the surface density of islands. In the present system the surface plasmon decay length and RIS are shown to be directly correlated; both parameters increase with increasing average island size. This result implies that a higher RIS is not always beneficial for sensing; maximizing the transducer optical response requires the interrelated RIS and decay length to be optimized with respect to the dimensions of the studied analyte-receptor system. It is shown that, as a rule, transducers comprising larger islands furnish better overall sensitivity for thicker adlayers, whereas thinner adlayers produce a larger response when sensed using transducers comprising smaller islands, despite the lower RIS of the latter.

The growing interest in recent years in gold island films prepared by vapor deposition on transparent substrates is largely attributed to the prominent localized surface plasmon (SP) extinction associated with nanostructured metal films. In the present study, two types of evaporated Au island films were investigated: (i) Au films (2.5, 5.0, and 7.5 nm nominal thickness) evaporated on silanized glass and annealed 20 h at a temperature <250 °C; (ii) Au films (7.5 and 10 nm nominal thickness) evaporated on unmodified glass and annealed 10 h at 550 or 600 °C. The 3D morphology of the Au islands was analyzed using high-resolution scanning electron microscopy (HRSEM), crosssectional transmission electron microscopy (TEM), and atomic force microscopy (AFM) crosssectional profilometry. Annealing at high temperatures, close to the glass transition temperature of the substrate, results in wetting of the Au islands by the glass and partial island embedding. The mechanism of morphology evolution during annealing changes from island coalescence and coarsening (low nominal thicknesses) to dewetting of percolated films (higher nominal thicknesses). The aspect ratio of more than 90% of the islands in annealed films is <1.5; therefore, splitting of the SP band to transversal and longitudinal components is not observed. The bulk refractive index sensitivity (RIS), in terms of SP wavelength shift and plasmon intensity change (PIC) per refractive index unit (RIU) change of the medium, was determined by measuring UV-vis spectra of Au island films in a series of methanol/chloroform mixtures. The RIS values for SP wavelength shift (RIS λ ) and PIC (RIS ext ) are 66-153 nm/RIU and 0.2-0.81 abs.u./RIU, respectively. The RIS shows a strong dependence on the wavelength of the SP maximum extinction, i.e., a higher RIS is measured for Au island films exhibiting a SP band at longer wavelengths. Partial thermal embedding of the Au islands in the glass substrate stabilizes the systems but lowers the RIS. The results presented may be useful for tuning the morphology and optical response of Au island films.

Probing the structure of material layers just a few nanometres thick requires analytical techniques with high depth sensitivity. X-ray photoelectron spectroscopy (XPS) provides one such method, but obtaining vertically resolved structural information from the raw data is not straightforward. There are several XPS depth-profiling methods, including ion etching, angle-resolved XPS (ref. 2) and Tougaard's approach, but all suffer various limitations. Here we report a simple, non-destructive XPS depth-profiling method that yields accurate depth information with nanometre resolution. We demonstrate the technique using self-assembled multilayers on gold surfaces; the former contain 'marker' monolayers that have been inserted at predetermined depths. A controllable potential gradient is established vertically through the sample by charging the surface of the dielectric overlayer with an electron flood gun. The local potential is probed by measuring XPS line shifts, which correlate directly with the vertical position of atoms. We term the method 'controlled surface charging' and expect it to be generally applicable to a large variety of mesoscopic heterostructures.