Laser-machined thin copper films on silicon as physical unclonable functions.

Physical unclonable functions (PUFs) are receiving significant attention with the rise of cryptography and the drive towards creating unique structures for security applications and anti-counterfeiting. Specifically, nanoparticle based PUFs can produce a high degree of randomness through their size, shape, spatial distribution, chemistry, and optical properties, rendering them very difficult to replicate. However, nanoparticle PUFs typically rely on complex preparation procedures involving chemical synthesis in solution, therefore requiring dispersion, and embedding within a host medium for application. We propose laser machining of surfaces as a one-step process for the creation of complex nanoparticle based PUFs by machining 600 nm thick copper films on a silicon substrate to yield a complex spatial and chemical distribution of redeposited copper, silicon, and oxide species. The approaches and material system investigated have potential applications in silicon chip authentication.

Multiphoton laser-induced confined chemical changes in polymer films.

We report ultrafast-laser-induced photochemical, structural, and morphological changes in a polyimide film irradiated at the polymer-glass interface in back-incident geometry. Back-illumination creates locally hot material at the interface leading to a confined photochemical change at the interface and a morphological change through a blister formation. The laser-induced photochemical changes in polyimide resulted in new absorption and luminescence properties in the visible region. The laser-treated polyimide exhibited photoluminescence anisotropy resulting from formation of ordered polymer upon irradiation by linearly polarized ultrashort laser pulses. Confocal fluorescence microscopy resulted in similar observations to the bulk. Reflection-absorption infrared spectroscopy and X-ray photoelectron spectroscopy together indicated confinement of laser-induced chemical changes at the interface.

Visible light driven plasmonic photochemistry on nano-textured silver.

Plasmon assisted generation of silver sulfate from dodecanethiol is demonstrated on a nano-textured silver substrate with a strong surface plasmon resonance in the visible range. The observed photo-physical processes are attributed to hot charge carriers that are generated from the excitation of surface plasmon resonances using 532 nm laser light. Excited charge carriers are responsible for cleaving the alkane chain, and for generating reactive oxygen species which rapidly photooxidize the exposed sulfur atoms. The ability to drive photochemical reactions with photon energies in the visible range rather than in the UV, on nano-textured silver surfaces, will enable researchers to study photochemical transformations for a wide variety of applications. The strong optical absorbance across the visible range, combined with the fact that the substrates can be fabricated over large areas, naturally makes them candidates for solar driven photochemical applications, and for large scale plasmonic reactors.

A platform for colorful solar cells with enhanced absorption.

We demonstrate submicron thick platform integrating amorphous silicon nanowires and thin-films achieving vivid colors in transmission and reflection. The platform nearly doubles the absorption efficiency compared to the starting thin-film without much compromising with color diverseness. The structural colors can be changed over a wide range by changing the diameters of the nanowires while still keeping the absorption efficiency higher than starting thin-film. The optical response of the platform is conceptually understood for different diameters combined with different thin-film thicknesses indicating the presence of leaky waveguide modes and coupled cavity modes. Our proposed platform can enable architectural low price colorful solar cells on transparent substrates.

Resonant photo-thermal modification of vertical gallium arsenide nanowires studied using Raman spectroscopy.

Gallium arsenide nanowires have shown considerable promise for use in applications in which the absorption of light is required. When the nanowires are oriented vertically, a considerable amount of light can be absorbed, leading to significant heating effects. Thus, it is important to understand the threshold power densities that vertical GaAs nanowires can support, and how the nanowire morphology is altered under these conditions. Here, resonant photo-thermal modification of vertical GaAs nanowires was studied using both Raman spectroscopy and electron microscopy techniques. Resonant waveguiding, and subsequent absorption of the excited optical mode reduces the irradiance vertical GaAs nanowires can support relative to horizontal ones, by three orders of magnitude before the onset of structural changes occur. A power density of only 20 W mm(-2) was sufficient to induce local heating in the nanowires, resulting in the formation of arsenic species. Upon further increasing the power, a hollow nanowire morphology was realized. These findings are pertinent to all optical applications and spectroscopic measurements involving vertically oriented GaAs nanowires. Understanding the optical absorption limitations, and the effects of exceeding these limitations will help improve the development of all III-V nanowire devices.

Adjustable optical response of amorphous silicon nanowires integrated with thin films.

We experimentally demonstrate a new optical platform by integrating hydrogenated amorphous silicon nanowire arrays with thin films deposited on transparent substrates like glass. A 535 nm thick thin film is anisotropically etched to fabricate vertical nanowire arrays of 100 nm diameter arranged in a square lattice. Adjusting the nanowire length, and consequently the thin film thickness permits the optical properties of this configuration to be tuned for either transmission filter response or enhanced broadband absorption. Vivid structural colors are also achieved in reflection and transmission. The optical properties of the platform are investigated for three different etch depths. Transmission filter response is achieved for a configuration with nanowires on glass without any thin film. Alternatively, integrating thin film with nanowires increases the absorption efficiency by ∼97% compared to the thin film starting layer and by ∼78% over nanowires on glass. The ability to tune the optical response of this material in this fashion makes it a promising platform for high performance photovoltaics, photodetectors and sensors.

Enhanced photothermal conversion in vertically oriented gallium arsenide nanowire arrays.

The photothermal properties of vertically etched gallium arsenide nanowire arrays are examined using Raman spectroscopy. The nanowires are arranged in square lattices with a constant pitch of 400 nm and diameters ranging from 50 to 155 nm. The arrays were illuminated using a 532 nm laser with an incident energy density of 10 W/mm(2). Nanowire temperatures were highly dependent on the nanowire diameter and were determined by measuring the spectral red-shift for both TO and LO phonons. The highest temperatures were observed for 95 nm diameter nanowires, whose top facets and sidewalls heated up to 600 and 440 K, respectively, and decreased significantly for the smaller or larger diameters studied. The diameter-dependent heating is explained by resonant coupling of the incident laser light into optical modes of the nanowires, resulting in increased absorption. Photothermal activity in a given nanowire diameter can be optimized by proper wavelength selection, as confirmed using computer simulations. This demonstrates that the photothermal properties of GaAs nanowires can be enhanced and tuned by using a photonic lattice structure and that smaller nanowire diameters are not necessarily better to achieve efficient photothermal conversion. The diameter and wavelength dependence of the optical coupling could allow for localized temperature gradients by creating arrays which consist of different diameters.

Color generation and refractive index sensing using diffraction from 2D silicon nanowire arrays.

Tunable structural color generation from vertical silicon nanowires arranged in different square lattices is demonstrated. The generated colors are adjustable using well-defined Bragg diffraction theory, and only depend on the lattice spacing and angles of incidence. Vivid colors spanning from bright red to blue are easily achieved. In keeping with this, a single square lattice of silicon nanowires is also able to produce different colors spanning the entire visible range. It is also shown that the 2D gratings also have a third grating direction when rotated 45 degrees. These simple and elegant solutions to color generation from silicon are used to demonstrate a cost-effective refractive index sensor. The sensor works by measuring color changes resulting from changes in the refractive index of the medium surrounding the nanowires using a trichromatic RGB decomposition. Moreover, the sensor produces linear responses in the trichromatic decomposition values versus the surrounding medium index. An index resolution of 10(-4) is achieved by performing basic image processing on the collected images, without the need for a laser or a spectrometer. Spectral analysis enables an increase in the index resolution of the sensor to a value of 10(-6) , with a sensitivity of 400 nm/RIU.

Temperature and hydration dependence of proton MAS NMR spectra in MCM-41: model based on motion induced chemical shift averaging.

The proton MAS NMR spectra in MCM-41 at low hydration levels (less than hydration amounting to one water molecule per surface hydroxyl group) show complex proton resonance peak structures, with hydroxyl proton resonances seen in dry MCM-41 disappearing as water is introduced into the pores and new peaks appearing, representing water and hydrated silanol groups. Surface hydroxyl group-water molecule chemical exchange and chemical shift averaging brought about by a water molecule visiting different surface hydrogen bonding sites have been proposed as possible causes for the observed spectral changes. In this report a simple model based on chemical shift averaging, due to the making and breaking of hydrogen bonds as water molecules move on the MCM-41 surface, is shown to fully reproduce the NMR spectra, both as a function of hydration and temperature. Surface proton-water proton chemical exchange is not required in this model at low hydration levels.