In this article nanosphere lithography (NSL) is demonstrated to be a materials general fabrication process for the production of periodic particle array (PPA) surfaces having nanometer scale features. A variety of PPA surfaces have been prepared using identical single-layer (SL) and double-layer (DL) NSL masks made by self-assembly of polymer nanospheres with diameter, D=264 nm, and varying both the substrate material S and the particle material M. In the examples shown here, S was an insulator, semiconductor, or metal and M was a metal, inorganic ionic insulator, or an organic π-electron semiconductor. PPA structural characterization and determination of nanoparticle metrics was accomplished with atomic force microscopy. This is the first demonstration of nanometer scale PPA surfaces formed from molecular materials.

No abstract

Polymeric membranes that contain a collection of monodisperse gold nanotubules, with inside diameters of molecular dimensions (less than 1 nanometer), were used in a simple membrane-permeation experiment to cleanly separate small molecules on the basis of molecular size. For example, when such a membrane was presented with an aqueous feed solution containing pyridine (molecular weight 79) and quinine (molecular weight 324), only the smaller pyridine molecule was transported through the nanotubules and into a receiver solution on the other side of the membrane.

Nanosphere lithography (NSL) is an inexpensive, inherently parallel, high-throughput, and materials-general nanofabrication technique capable of producing well-ordered 2D periodic particle arrays of nanoparticles. This paper focuses on the synthesis of size-tunable silver nanoparticle arrays by nanosphere lithography and their structural characterization by atomic force microscopy (AFM). The in-plane diameter, a, of Ag nanoparticles was tuned from 21 to 126 nm by systematic variation of the nanosphere diameter, D. Similarly, the out-of-plane height, b, was tuned from 4 to 47 nm by varying the mass thickness, d m, of the Ag overlayer. Experimental measurements of a, b, and interparticle spacing d ip of many individual nanoparticles as a function of D and d m were carried out using AFM. These studies show (i) b = d m, (ii) d ip accurately corresponds to predictions based on the nanosphere mask geometry, (iii) a, after correction for AFM tip convolution, is governed only by the mask geometry and the standard deviation, σD, of the nanosphere diameter, and (iv) line-of-sight deposition is strictly operative. Furthermore, we have established that nanosphere lithography can fabricate nanoparticles that contain only ca. 4 × 104 atoms and are in the size range of a surface-confined cluster.

The surface roughness and nanometer scale structure of Ag films used for surface-enhanced Raman scattering (SERS) are characterized using atomic force microscopy (AFM). Two important types of thin film based SERS-active surface have been examined in this study: (1) Ag island films (AgIF's) on smooth, insulating substrates and (2) thick Ag films evaporated over both preroughened and smooth substrates. AFM is demonstrated to be capable of quantitatively defining the three-dimensional (3D) structure of these roughened surfaces. The effects of mass thickness, d, , and thermal annealing on the nanostructure of AgIF's are studied in detail. Particle size histograms are calculated from the AFM images for both "as-deposited" and annealed IF's with d,,,= 1.8 and 3.5 nm. Quantitative measurements of the SERS enhancement factor (EF) are coupled with the AFM data and interpreted within the framework of the electromagnetic theory of SERS. AFM images for thick evaporated Ag films over a monolayer of polymer nanospheres (AgFON) shows the clear presence of "random substructure roughness" reducing their utility as controlled roughness surfaces. Similar roughness structures are observed for thick evaporated Ag films on smooth, insulating substrates. Nevertheless, AgFON surfaces are demonstrated to be among the most strongly enhancing thin film based surfaces ever studied with EF's comparable to those found for electrochemically roughened surfaces. Applications of FON surfaces to ultrahigh sensitivity SERS, anti-Stokes detected SERS, and surfaceenhanced hyper-Raman spectroscopy (SEHRS) are reported.