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Preventing Corrosion of Aluminum Metal with Nanometer-Thick Films of Al2O3 Capped with TiO2 for Ultraviolet Plasmonics

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 Added by Jerome Wenger
 Publication date 2021
  fields Physics
and research's language is English




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Extending plasmonics into the ultraviolet range imposes the use of aluminum to achieve the best optical performance. However, water corrosion is a major limiting issue for UV aluminum plasmonics, as this phenomenon occurs significantly faster in presence of UV light, even at low laser powers of a few microwatts. Here we assess the performance of nanometer-thick layers of various metal oxides deposited by atomic layer deposition (ALD) and plasma-enhanced chemical vapor deposition (PECVD) on top of aluminum nanoapertures to protect the metal against UV photocorrosion. The combination of a 5 nm Al2O3 layer covered by a 5 nm TiO2 capping provides the best resistance performance, while a single 10 nm layer of SiO2 or HfO2 is a good alternative. We also report the influence of the laser wavelength, the laser operation mode and the pH of the solution. Properly choosing these conditions significantly extends the range of optical powers for which the aluminum nanostructures can be used. As application, we demonstrate the label-free detection of streptavidin proteins with improved signal to noise ratio. Our approach is also beneficial to promote the long-term stability of the aluminum nanostructures. Finding the appropriate nanoscale protection against aluminum corrosion is the key to enable the development of UV plasmonic applications in chemistry and biology.

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Ultraviolet (UV) plasmonics aims at combining the strong absorption bands of molecules in the UV range with the intense electromagnetic fields of plasmonic nanostructures to promote surface-enhanced spectroscopy and catalysis. Currently, aluminum is the most widely used metal for UV plasmonics, and is generally assumed to be remarkably stable thanks to its natural alumina layer passivating the metal surface. However, we find here that under 266 nm UV illumination, aluminum can undergo a dramatic photocorrosion in water within a few tens of seconds and even at low average UV powers. This aluminum instability in water environments critically limits the UV plasmonics applications. We show that the aluminum photocorrosion is related to the nonlinear absorption by water in the UV range leading to the production of hydroxyl radicals. Different corrosion protection approaches are tested using scavengers for reactive oxygen species and polymer layers deposited on top of the aluminum structures. Using optimized protection, we achieve a ten-fold increase in the available UV power range leading to no visible photocorrosion effects. This technique is crucial to achieve stable use of aluminum nanostructures for UV plasmonics in aqueous solutions.
Magnetic insulators such as yttrium iron garnet, Y3Fe5O12, with extremely low magnetic damping have opened the door for low power spin-orbitronics due to their low energy dissipation and efficient spin current generation and transmission. We demonstrate reliable and efficient epitaxial growth and nanopatterning of Y3Fe5O12 thin-film based nanostructures on insulating Gd3Ga5O12 substrates. In particular, our fabrication process is compatible with conventional sputtering and liftoff, and does not require aggressive ion milling which may be detrimental to the oxide thin films. Structural and magnetic properties indicate good qualities, in particular low magnetic damping of both films and patterned structures. The dynamic magnetic properties of the nanostructures are systematically investigated as a function of the lateral dimension. By comparing to ferromagnetic nanowire structures, a distinct edge mode in addition to the main mode is identified by both experiments and simulations, which also exhbits cross-over with the main mode upon varying the width of the wires. The non-linear evolution of dynamic modes over nanostructural dimensions highlights the important role of size confinement to their material properties in magnetic devices where Y3Fe5O12 nanostructures serve as the key functional component.
The development of metamaterials, data processing circuits and sensors for the visible and UV parts of the spectrum is hampered by the lack of low-loss media supporting plasmonic excitations and drives the intense search for plasmonic materials beyond noble metals. By studying plasmonic nanostructures fabricated on the surface of topological insulator $mbox{Bi}_{1.5}mbox{Sb}_{0.5}mbox{Te}_{1.8}mbox{Se}_{1.2}$ we found that it is orders of magnitude better plasmonic material than gold and silver in the blue-UV range. Metamaterial fabricated from $mbox{Bi}_{1.5}mbox{Sb}_{0.5}mbox{Te}_{1.8}mbox{Se}_{1.2}$ show plasmonic resonances from 350 nm to 550 nm while surface gratings exhibit cathodoluminescent peaks from 230 nm to 1050 nm. The negative permittivity underpinning plasmonic response is attributed to the combination of bulk interband transitions and surface contribution of the topologically protected states. The importance of our result is in the identification of new mechanisms of negative permittivity in semiconductors where visible-range plasmonics can be directly integrated with electronics.
Metal-insulator transition features as a transformation, from a highly charge conductive state to another state where charge conductivity is greatly suppressed when decreasing the temperature. Here we demonstrate two consecutive transitions in NdNiO3 films with CoFe2O4 capping, in which the metal-insulator transition occurs at 85 K, followed by an unprecedented insulator-metal transition below 40 K. The emerging insulator-metal transition associated with a weak antiferromagnetic behavior is observed in 20 unit cell-thick NdNiO3 with more than 5 unit cell CoFe2O4 capping. Differently, the NdNiO3 films with thinner CoFe2O4 capping only exhibit metal-insulator transition at 85 K, accompanied by a strong antiferromagnetic state below 40 K. Charge transfer from Co to Ni, instead of from Fe to Ni, formulates the ferromagnetic interaction between Ni-Ni and Ni-Co atoms, thus suppressing the antiferromagnetic feature and producing metallic conductive behavior. Furthermore, a phase diagram for the metal-insulator-metal transition in this system is drawn.
Epitaxial growth of single crystalline noble metals on dielectric substrates has received tremendous attention recently due to their technological potentials as low loss plasmonic materials. Currently there are two different growth approaches, each with its strengths and weaknesses. One adopts a sophisticated molecular beam epitaxial procedure to grow atomically smooth epitaxial Ag films. However, the procedure is rather slow and becomes impractical to grow films with thickness > 50 nm. Another approach adopts a growth process using rapid e-beam deposition which is capable of growing single crystalline Ag films in the thick regime (> 300 nm). However, the rapid growth procedure makes it difficult to control film thickness precisely, i.e., the method is not applicable to growing thin epitaxial films. Here we report a universal approach to grow atomically smooth epitaxial Ag films with precise thickness control from a few monolayers to the optically thick regime, overcoming the limitations of the two aforementioned methods. In addition, we develop an in-situ growth of aluminum oxide as the capping layer which exhibits excellent properties protecting the epitaxial Ag films. The performance of the epitaxial Ag films as a function of the film thickness is investigated by directly measuring the propagation length of the surface plasmon polaritons (SPPs) as well as their device performance to support a waveguide plasmonic nanolaser in infrared incorporating an InGaAsP quantum well as the gain media.
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