Electromagnetic theory predicts that the optimal value of the localized plasmon resonance (LPR) wavelength for the maximal SERS enhancement factor (EF) is half the sum of the laser and Raman wavelengths. For small Raman shifts, the theoretical EF scales as the fourth power of the local field. However, experimental data often disagree with these theoretical conclusions, leaving the question of choosing the optimal plasmon resonance for the maximal SERS signal unresolved. Here, we present experimental data for gold nanorods (AuNRs), gold nanotriangles (AuNTs), and gold nanostars (AuNSTs) simulating 1D, 2D, and 3D plasmonic nanostructures, respectively. The LPR wavelengths were tuned by chemical etching within 580–1020 nm at a constant concentration of the particles. The particles were functionalized with Cy7.5 and NBT, and the dependence of the intensity at 940 cm−1 (Cy7.5) and 1343 cm−1 (NBT) on the LPR wavelength was examined for laser wavelengths of 633 nm and 785 nm. The electromagnetic SERS EFs were calculated by averaging the product of the local field intensities at the laser and Raman wavelengths over the particle surface and their random orientations. The calculated SERS plasmonic profiles were redshifted compared to the laser wavelength. For 785 nm excitation, the calculated EFs were five to seven times higher than those for 633 nm excitation. With AuNR@Cy7.5 and AuNT@ Cy7.5, the experimental SERS was 35-fold stronger than it was with NBT-functionalized particles, but with AuNST@Cy7.5 and AuNST@NBT, the SERS responses were similar. With all nanoparticles tested, the SERS plasmonic profiles after 785 nm excitation were slightly blue-shifted, as compared with the laser wavelength, possibly owing to the inner filter effect. After 633 nm excitation, the SERS profiles were red-shifted, in agreement with EM theory. In all cases, the plasmonic EF profiles were much broadened compared to the calculated ones and did not follow the four-power law.
The results of the research and design of a novel vacuum photosensor with a planar molybdenum blade structure are presented. The advanced prototype implements the principle of an increasing penetrability of the Schottky barrier for the metal–vacuum interfaces under the action of an external strong electrostatic field. Theoretical and experimental substantiation of the photosensor performance in a wide range of wavelengths (from 430 to 680 nm and from 800 to 1064 nm) beyond the threshold of the classical photoelectric effect is given. The finite element method was applied to calculate distribution of the optical and electrostatic fields inside the photosensor structure. The sensor current-to-light response was studied using the periodic pulsed irradiation with the tunable wavelength. It was shown that the nanoscale localization zones of two types are formed near the surface of the blade tip: the zone of an increased concentration of hot electrons localized inside the molybdenum blade, and the zone with an increased strength of the external electrostatic field localized outside the blade. In general, the mutual positions of these zones may not coincide, whereas the position of the first-type localization zone significantly varies with the changes in the wavelength of the irradiating light. This causes features in the spectrum of the quantum yield of the photosensor such as expressed non-monotonic behavior and occurrence of sharp dips. The design of the photosensor that provides matching of the positions for both types of localization zones was proposed; the manufactured prototypes of the designed device were experimentally studied. In the designed photosensor, the ballistic transport of photoelectrons in the vacuum gap with a strong field provides a possibility for the creation of ultra-fast optoelectronic devices, such as modulators, detectors, and generators.
<!-- *** Custom HTML *** --> A mathematical model for the calculation of the optical and thermal properties of an ensemble of gold nanostars with different tip lengths L = 10 to 20 nm in an aqueous environment is proposed. The heating of a nanoparticle ensemble under irradiation by a laser pulse of a nanosecond duration: resonant λ = 808 nm and nonresonant λ = 1064 nm is studied. A significant blue shift of surface plasmon resonance during the formation of a vapor bubble around the nanoparticle was detected and described. Based on the analysis of the kinetics of nanoparticle heating under the action of a laser pulse before and after the formation of a vapor bubble, a theoretical description of the experimentally observed threshold nature of particle photomodification is given. It was found that the laser intensity Im necessary to achieve the melting temperature Tm (photomodification threshold) tends to increase with decreasing nanostar tip length and for an individual nanostar differs by an order of magnitude. However, up to 45% of the nanoparticles are heated to the melting temperature Tm by a single pulse with an intensity only 2.5 times higher than the minimum value of Im. At a wavelength of 1064 nm, Im is ∼6 times higher than at a wavelength of 808 nm.
The main goal of this work was to modify the previously developed blade-type planar structure using plasmonic gold nanostars in order to stimulate photofield emission and provide efficient laser control of the electron current. Localization and enhancement of the field at the tips of gold nanostars provided a significant increase in the tunneling electron current in the experimental sample (both electrical field and photofield emission). Irradiation at a wavelength in the vicinity of the plasmon resonance (red laser) provided a gain in the photoresponse value of up to 5 times compared to irradiation far from the resonance (green laser). The prospects for transition to regimes of structure irradiation by femtosecond laser pulses at the wavelength of surface plasmon resonance, which lead to an increase in the local optical field, are discussed. The kinetics of the energy density of photoinduced hot and thermalized electrons is estimated. The proposed laser-controlled matrix current source is promising for use in X-ray computed tomography systems.
An important direction in the development of X-ray computed tomography sensors in systems with increased scanning speed and spatial resolution is the creation of an array of miniature current sources. In this paper, we describe a new material based on gold nanostars (GNS) embedded in nanoscale diamond-like carbon (DLC) films (thickness of 20 nm) for constructing a pixel current source with photoinduced electron emission. The effect of localized surface plasmon resonance in GNS on optical properties in the wavelength range from UV to near IR, peculiarities of localization of field and thermal sources, generation of high-energy hot electrons, and mechanisms of their transportation in vacuum are investigated. The advantages of the proposed material and the prospects for using X-ray computed tomography in the matrix source are evaluated.