Masud Parvez Arnob

3D Cross‐Point Plasmonic Nanoarchitectures Containing Dense and Regular Hot Spots for Surface‐Enhanced Raman Spectroscopy Analysis

3D stacking of plasmonic nanostructures is achieved using a solvent-assisted nanotransfer printing (S-nTP) technique to provide extremely dense and regular hot spot arrays for highly sensitive surface-enhanced Raman spectroscopy (SERS) analysis. Moreover, hybrid plasmonic nanostructures obtained by printing the nanowires on a continuous metal film or graphene surface show significantly intensified SERS signals due to vertical plasmonic coupling.

Simultaneous Chemical and Refractive Index Sensing in the 1-2.5 μm Near-Infrared Wavelength Range on Nanoporous Gold Disks.

Near-infrared (NIR) absorption spectroscopy provides molecular and chemical information based on overtones and combination bands of the fundamental vibrational modes in the infrared wavelengths. However, the sensitivity of NIR absorption measurement is limited by the generally weak absorption and the relatively poor detector performance compared to other wavelength ranges. To overcome these barriers, we have developed a novel technique to simultaneously obtain chemical and refractive index sensing in 1-2.5 μm NIR wavelength range on nanoporous gold (NPG) disks, which feature high-density plasmonic hot-spots of localized electric field enhancement. For the first time, surface-enhanced near-infrared absorption (SENIRA) spectroscopy has been demonstrated for high sensitivity chemical detection. With a self-assembled monolayer (SAM) of octadecanethiol (ODT), an enhancement factor (EF) of up to ∼10(4) has been demonstrated for the first C-H combination band at 2400 nm using NPG disk with 600 nm diameter. Together with localized surface plasmon resonance (LSPR) extinction spectroscopy, simultaneous sensing of sample refractive index has been achieved for the first time. The performance of this technique has been evaluated using various hydrocarbon compounds and crude oil samples.

3-Dimensional Plasmonic Substrates Based on Chicken Eggshell Bio-Templates for SERS-Based Bio-Sensing

A simple technique is presented to fabricate stable and reproducible plasmonic substrates using chicken eggshell as bio-templates, an otherwise everyday waste material. The 3-dimensional (3D) submicron features on the outer shell (OS), inner shell (IS), and shell membrane (SM) regions are sputter coated with gold and characterized for surface-enhanced Raman scattering (SERS) performance with respect to coating thickness, enhancement factor (EF), hot-spots distribution, and reproducibility. The OS and IS substrates have similar EF (2.6 × 106 and 1.8 × 106, respectively), while the SM provides smaller EF (1.5 × 105) due to its larger characteristic feature size. The variability from them (calculated as relative standard deviation, %RSD) are less than 7, 15, and 9 for the OS, IS, and SM substrates, respectively. Due to the larger EF and better signal reproducibility, the OS region is used for label-free sensing and identification of Escherichia coli and Bacillus subtilis bacteria as an example of the potential SERS applications. It is demonstrated that the detection limit could reach the level of single bacterial cells. The OS and IS regions are also used as templates to fabricate 3D flexible SERS substrates using polydimethylsiloxane and characterized. The simple, low-cost, and green route of fabricating plasmonic substrates represents an innovative alternative approach without the needs for nanofabrication facilities. Coupled with hyperspectral Raman imaging, high-throughput bio-sensing can be carried out at the single pathogen level.

Fabrication of multipoint side-firing optical fiber by laser micro-ablation

A multipoint, side-firing design enables an optical fiber to output light at multiple desired locations along the fiber body. This provides advantages over traditional end-to-end fibers, especially in applications requiring fiber bundles such as brain stimulation or remote sensing. This Letter demonstrates that continuous wave (CW) laser micro-ablation can controllably create conical-shaped cavities, or side windows, for outputting light. The dimensions of these cavities determine the amount of firing light and their firing angle. Experimental data show that a single side window on a 730 μm fiber can deliver more than 8% of the input light. This can be increased to more than 19% on a 65 μm fiber with side windows created using femtosecond laser ablation and chemical etching. Fine control of light distribution along an optical fiber is critical for various biomedical applications such as light-activated drug-release and optogenetics studies.

3D plasmonic nanoarchitecture as an emerging biosensing platform

Md Masud Parvez Arnob1 & Wei-Chuan Shih*,1,2,3,4 1Department of Electrical & Computer Engineering, University of Houston, Houston, TX 77204, USA 2Department of Biomedical Engineering, University of Houston, Houston, TX 77204, USA 3Program of Materials Science & Engineering, University of Houston, Houston, TX 77204, USA 4Department of Chemistry, University of Houston, Houston, TX 77204, USA * Author for correspondence: wshih@uh.edu

Modeling nanoporous gold plasmonic nanoparticles: Calculation of optical properties

Maxwell-Garnett effective medium theory (MG-EMT) has been employed to model disk shaped nanoporous gold nanoparticles (NPG nanoparticles or NPG Disks). Optical properties of these nanoparticles have been calculated using the proposed model via Finite Difference Time Domain (FDTD) method. Calculated optical properties reflect strong dependence on particle dimensions. The resonant extinction wavelength (λRes) can be tuned from ~600 to ~1300 nm by changing the particle diameter from 100 to 500 nm while the thickness is fixed at 75 nm; λRes can be blue shifted from ~600 to ~550 nm by varying the thickness from 25 to 100 nm for 100 nm diameter particles. Among these particle dimensions, the maximum scattering coefficient has been found in 200 nm diameter and 25 nm thick nanoparticles, while the maximum absorption coefficient in 100 nm diameter and 25 nm thick nanoparticles.

New fabrication technique for nanoporous gold nanoparticles (Conference Presentation)

Nanoporous gold nanoparticles (NPG-NP) showcase tunable pore and ligament sizes ranging from nanometers to microns. The nanoporous structure and sub-wavelength nanoparticle shape contribute to its unique LSPR properties. NPG-NP features large specific surface area and high-density plasmonic field enhancement known as “hot-spots”. Hence, NPG-NP has found many applications in nanoplasmonic sensor development. In our recent studies, we have shown that NPG-NP array chip can be utilized for high-sensitivity detection by various enhanced spectroscopic modalities, as photothermal agents, and for disease biomarker detection. To date, array-format, substrate-bound NPGN has been fabricated by either colloidal nanosphere lithography or random nucleation during the sputtering deposition process. Although highly cost-effective, these techniques cannot provide precise control of individual particle size and location. In this paper, we report the development of a new fabrication technique based on electron-beam lithography (EBL). Herein, a customized EBL technique is utilized to pattern larger areas (several square millimeters) of randomly distributed NPGN by careful design of the shot pattern, which limits the writing time to the acceptable level. Since the position, size, and shape of a huge number of features need to be generated and stored individually, memory limitations of this unique EBL technique constitutes an additional challenge, which is normally not present if small areas are to be patterned with features on an ordered lattice. This issue is solved by programmatically generating random feature positions within a simulation cell of carefully chosen size and implementing periodic boundary conditions.

3D plasmonic nanoarchitectures for extreme light concentration

Plasmonic nanomaterials are known to concentrate incident light to their surfaces by collective electron oscillation. Plasmonic hot-spot refers to locations where electromagnetic fields are particularly enhanced relative to the incident field. Traditional plasmonic nanomaterials are 1D (e.g., colloidal nanoparticles) or 2D (lithographically patterned nanostructure arrays) in nature, which typically result in sparse field concentration patterns. To improve efficiency and better utilization of hot-spots, we investigate 3D plasmonic nanoarchitecture where abundant hot-spots are formed in a 3D volumetric fashion, a feature drastically departing from traditional nanostructures.

Surface-enhanced near-infrared absorption (SENIRA) spectroscopy

We present first experimental demonstration of surface-enhanced near-infrared absorption (SENIRA) spectroscopy of molecular overtone and combination bands in the 1–2.5 μm wavelength range. The plasmonic enhancement platform of choice is nanoporous gold (NPG) disks which feature high-density plasmonic hot-spots of localized electric field amplification. With a self-assembled monolayer (SAM) of octadecanethiol (ODT), an enhancement factor (EF) of up to ∼104 has been demonstrated for the 1st C-H overtone at 1725 nm using NPG disk with 600 nm diameter. Together with localized surface plasmon resonance (LSPR) extinction spectroscopy, simultaneous sensing of sample refractive index has been achieved for the first time.

Monolithic nanoporous gold disks with large surface area and high-density plasmonic hot-spots

Plasmonic metal nanostructures have shown great potential in sensing, photovoltaics, imaging and biomedicine, principally due to enhancement of the local electric field by light-excited surface plasmons, the collective oscillation of conduction band electrons. Thin films of nanoporous gold have received a great deal of interest due to the unique 3- dimensional bicontinuous nanostructures with high specific surface area. However, in the form of semi-infinite thin films, nanoporous gold exhibits weak plasmonic extinction and little tunability in the plasmon resonance, because the pore size is much smaller than the wavelength of light. Here we show that by making nanoporous gold in the form of disks of sub-wavelength diameter and sub-100 nm thickness, these limitations can be overcome. Nanoporous gold disks (NPGDs) not only possess large specific surface area but also high-density, internal plasmonic “hot-spots” with impressive electric field enhancement, which greatly promotes plasmon-matter interaction as evidenced by spectral shifts in the surface plasmon resonance. In addition, the plasmonic resonance of NPGD can be easily tuned from 900 to 1850 nm by changing the disk diameter from 300 to 700 nm. The coupling between external and internal nanoarchitecture provides a potential design dimension for plasmonic engineering. The synergy of large specific surface area, high-density hot spots, and tunable plasmonics would profoundly impact applications where plasmonic nanoparticles and non-plasmonic mesoporous nanoparticles are currently employed, e.g., in in-vitro and in-vivo biosensing, molecular imaging, photothermal contrast agents, and molecular cargos.