Steven J. Barcelo

Melamine Sensing in Milk Products by Using Surface Enhanced Raman Scattering

Simple and rapid detection of trace amounts of melamine in milk products has been achieved with a portable sensor system based on surface-enhanced Raman scattering (SERS). The sensor system comprised high-performance gold nanofinger SERS sensor chips and a custom-built prototype portable Raman spectrometer. Compared to the FDA procedure and previously reported studies that were limited to laboratory settings, our sampling and analytical methods are simple (with one sampling step), less time-consuming, and cost-effective. We found the limit of detection (LOD) of the melamine is 120 parts per trillion (ppt) in water and 100 parts per billion (ppb) in infant formula, which are well below the FDAs tolerance level of 1 ppm in infant formula.

Fabrication of deterministic nanostructure assemblies with sub-nanometer spacing using a nanoimprinting transfer technique.

Deterministic patterning or assembly of nanoparticles often requires complex processes that are not easily incorporated into system architectures of arbitrary design. We have developed a technique to fabricate deterministic nanoparticle assemblies using simple and inexpensive nanoimprinting equipment and procedures. First, a metal film is evaporated onto flexible polymer pillars made by nanoimprinting. The resulting metal caps on top of the pillars can be pulled into assemblies of arbitrary design by collapsing the pillars in a well-controlled manner. The nanoparticle assemblies are then transferred from the pillars onto a new substrate via nanoimprinting with the aid of either cold welding or chemical bonding. Using this technique, a variety of patterned nanoparticle assemblies of Au and Ag with a critical dimension less than 2 nm were fabricated and transferred to silicon-, glass-, and metal-coated substrates. Separating the nanostructure assembly from the final architecture removes significant design constraints from devices incorporating nanoparticle assemblies. The application of this process as a technique for generating surface-enhanced Raman spectroscopy substrates is presented.

SERS-based pesticide detection by using nanofinger sensors.

Simple, sensitive, and rapid detection of trace levels of extensively used and highly toxic pesticides are in urgent demand for public health. Surface-enhanced Raman scattering (SERS)-based sensor was designed to achieve ultrasensitive and simple pesticide sensing. We developed a portable sensor system composed of high performance and reliable gold nanofinger sensor strips and a custom-built portable Raman spectrometer. Compared to the general procedure and previously reported studies that are limited to laboratory settings, our analytical method is simple, sensitive, rapid, and cost-effective. Based on the SERS results, the chemical interaction of two pesticides, chlorpyrifos (CPF) and thiabendazole (TBZ), with gold nanofingers was studied to determine a fingerprint for each pesticide. The portable SERS-sensor system was successfully demonstrated to detect CPF and TBZ pesticides within 15 min with a detection limit of 35 ppt in drinking water and 7 ppb on apple skin, respectively.

Nanosphere lithography based technique for fabrication of large area well ordered metal particle arrays

Nanosphere lithography is an effective technique for high throughput fabrication of well-ordered patterns, but expanding the method to large area coverage of nanoparticles less than 300 nm in diameter while maintaining good order has proven challenging. Here we demonstrate a nanosphere lithography based technique for fabricating large area, wellordered arrays of hemispherical metal particles which pushes the limits of these size constraints. First, large area monolayers of polystyrene (PS) nanospheres are assembled at an air-water interface and then transferred to a submerged substrate. The submerged substrate is supported at a 10° angle so that the water draining speed can be used to control the transfer rate, which is essential for hydrophobic substrates such as the polymer-coated glass used in our work. A double liftoff procedure was used to transfer the PS pattern to a silver particle array on an arbitrary substrate, achieving tunable control over the final metal particle diameter and spacing in the range of 50-150 nm and 100-200 nm, respectively. Additional control over particle shape and diameter can be obtained by modifying the substrate surface energy. For example, depositing silver on ITO-coated glass rather than a more hydrophilic clean glass substrate leads to a more hemispherical particle shape and a diameter reduction of 20%. Peak wavelength-selective reflection greater than 70% and total extinction greater than 90% were measured. The intensity, position and bandwidth of the main plasmon resonance of the arrays were shown to have minimal angle dependence up to at least 30° off normal.

Nanoimprint lithography for nanodevice fabrication

Nanoimprint lithography (NIL) is a compelling technique for low cost nanoscale device fabrication. The precise and repeatable replication of nanoscale patterns from a single high resolution patterning step makes the NIL technique much more versatile than other expensive techniques such as e-beam or even helium ion beam lithography. Furthermore, the use of mechanical deformation during the NIL process enables grayscale lithography with only a single patterning step, not achievable with any other conventional lithography techniques. These strengths enable the fabrication of unique nanoscale devices by NIL for a variety of applications including optics, plasmonics and even biotechnology. Recent advances in throughput and yield in NIL processes demonstrate the potential of being adopted for mainstream semiconductor device fabrication as well.

Deterministic nanoparticle assemblies: from substrate to solution

The deterministic assembly of metallic nanoparticles is an exciting field with many potential benefits. Many promising techniques have been developed, but challenges remain, particularly for the assembly of larger nanoparticles which often have more interesting plasmonic properties. Here we present a scalable process combining the strengths of top down and bottom up fabrication to generate deterministic 2D assemblies of metallic nanoparticles and demonstrate their stable transfer to solution. Scanning electron and high-resolution transmission electron microscopy studies of these assemblies suggested the formation of nanobridges between touching nanoparticles that hold them together so as to maintain the integrity of the assembly throughout the transfer process. The application of these nanoparticle assemblies as solution-based surface-enhanced Raman scattering (SERS) materials is demonstrated by trapping analyte molecules in the nanoparticle gaps during assembly, yielding uniformly high enhancement factors at all stages of the fabrication process.

TEM study of nanofinger structures for surface enhanced Raman scattering

Chemical sensing applications utilizing surface enhanced Raman spectroscopy (SERS) have drawn significant attention recently. However, developing a reliable, high performance SERS platform remains a challenge. A novel SERS substrate based on nanofingers was successfully demonstrated to provide large enhancement reliably and showed great promise for practical applications. Capillary forces bring the gold caps on the nanofingers into close proximity upon exposure to a solution containing molecules of interest, trapping molecules within the gaps and producing greatly enhanced Raman signals. Transmission electron microscopy (TEM) was used to characterize the structure of the nanofingers, in particular the gaps between finger tips to improve the fundamental understanding of the structural-performance relationship.