Temperature stability of thin film refractory plasmonic materials.

Materials such as W, TiN, and SrRuO3 (SRO) have been suggested as promising alternatives to Au and Ag in plasmonic applications owing to their stability at high operational temperatures. However, investigation of the reproducibility of the optical properties after thermal cycling between room and elevated temperatures is so far lacking. Here, thin films of W, Mo, Ti, TiN, TiON, Ag, Au, SrRuO3 and SrNbO3 are investigated to assess their viability for robust refractory plasmonic applications. These results are further compared to the performance of SrMoO3 reported in literature. Films ranging in thickness from 50 to 105 nm are deposited on MgO, SrTiO3 and Si substrates by e-beam evaporation, RF magnetron sputtering and pulsed laser deposition, prior to characterisation by means of AFM, XRD, spectroscopic ellipsometry, and DC resistivity. Measurements are conducted before and after annealing in air at temperatures ranging from 300 to 1000° C for one hour, to establish the maximum cycling temperature and potential longevity at elevated temperatures for each material. It is found that SrRuO3 retains metallic behaviour after annealing at 800° C, while SrNbO3 undergoes a phase transition resulting in a loss of metallic behaviour after annealing at 400° C. Importantly, the optical properties of TiN and TiON are degraded as a result of oxidation and show a loss of metallic behaviour after annealing at 500° C, while the same is not observed in Au until annealing at 600° C. Nevertheless, both TiN and TiON may be better suited than Au or SRO for high temperature applications operating under vacuum conditions.

Coupled Electronic and Magnetic Phase Transition in the Infinite-Layer Phase LaSrNiRuO4.

Topochemical reduction of the ordered double perovskite LaSrNiRuO6 with CaH2 yields LaSrNiRuO4, an extended oxide phase containing infinite sheets of apex-linked, square-planar Ni(1+)O4 and Ru(2+)O4 units ordered in a checkerboard arrangement. At room temperature the localized Ni(1+) (d(9), S = (1)/2) and Ru(2+) (d(6), S = 1) centers behave paramagnetically. However, on cooling below 250 K the system undergoes a cooperative phase transition in which the nickel spins align ferromagnetically, while the ruthenium cations appear to undergo a change in spin configuration to a diamagnetic spin state. Features of the low-temperature crystal structure suggest a symmetry lowering Jahn-Teller distortion could be responsible for the observed diamagnetism of the ruthenium centers.

Crystalline AuNP-Decorated Strontium Niobate Thin Films: Strain-Controlled AuNP Morphologies and Optical Properties for Plasmonic Applications.

Gold nanoparticle (AuNP) decoration is a commonly used method to enhance the optical responses in many applications such as photocatalysis, biosensing, solar cells, etc. The morphology and structure of AuNPs are essential factors determining the functionality of the sample. However, tailoring the growth mechanism of AuNPs on an identical surface is not straightforward. In this study, AuNPs were deposited on the surface of a perovskite thin film, strontium niobate (SNO), using pulsed laser deposition (PLD). AuNPs exhibited a dramatic variation in their growth mechanisms, depending on whether they were deposited on SNO thin films grown on magnesium oxide (SNO/MgO) or strontium titanate (SNO/STO) substrates. On SNO/MgO, the Au aggregates form large NPs with an average size of up to 3500 nm2. These AuNPs are triangular with sharp edges and corners. The out-of-plane direction of growth is favored, and the surface coverage ratio by AuNPs is low. When deposited on SNO/STO, the average size of AuNPs is much smaller, i.e., ∼250 nm2. This reduction in the average size is accompanied by an increase in the number density of NPs. AuNPs on SNO/STO have a round shape and high coverage ratio. Such an impact from the substrate selection on the AuNP structure is significant when the sandwiched SNO film is below 80 nm thickness and is weakened for 200 nm of SNO films. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize all samples. Strain analysis was used to explain the growth mechanism of AuNPs. The average height of AuNPs was measured by using atomic force microscopy (AFM). Ellipsometry in the visible-near-infrared (vis-NIR) region was used to characterize the optical response of all samples. AuNP-decorated SNO/MgO and SNO/STO thin films exhibit different optical properties, with only gold-decorated SNO/MgO samples showing a size-dependent epsilon-near-zero behavior of nanoparticles. These results provide an additional route to control the structure of AuNPs. They can be used for various plasmonic applications like the design and development of strain-engineered gold-nanoparticle-decorated devices for surface-enhanced Raman spectroscopy (SERS) and photocatalysis.

Optimizing Hot Electron Harvesting at Planar Metal-Semiconductor Interfaces with Titanium Oxynitride Thin Films.

Understanding metal-semiconductor interfaces is critical to the advancement of photocatalysis and sub-bandgap solar energy harvesting where electrons in the metal can be excited by sub-bandgap photons and extracted into the semiconductor. In this work, we compare the electron extraction efficiency across Au/TiO2 and titanium oxynitride (TiON)/TiO2-x interfaces, where in the latter case the spontaneously forming oxide layer (TiO2-x) creates a metal-semiconductor contact. Time-resolved pump-probe spectroscopy is used to study the electron recombination rates in both cases. Unlike the nanosecond recombination lifetimes in Au/TiO2, we find a bottleneck in the electron relaxation in the TiON system, which we explain using a trap-mediated recombination model. Using this model, we investigate the tunability of the relaxation dynamics with oxygen content in the parent film. The optimized film (TiO0.5N0.5) exhibits the highest carrier extraction efficiency (NFC ≈ 2.8 × 1019 m-3), slowest trapping, and an appreciable hot electron population reaching the surface oxide (NHE ≈ 1.6 × 1018 m-3). Our results demonstrate the productive role oxygen can play in enhancing electron harvesting and prolonging electron lifetimes, providing an optimized metal-semiconductor interface using only the native oxide of titanium oxynitride.

Enhancing Structural Properties and Performance of Graphene-Based Devices Using Self-Assembled HMDS Monolayers.

The performance of graphene devices is often limited by defects and impurities induced during device fabrication. Polymer residue left on the surface of graphene after photoresist processing can increase electron scattering and hinder electron transport. Furthermore, exposing graphene to plasma-based processing such as sputtering of metallization layers can increase the defect density in graphene and alter the device performance. Therefore, the preservation of the high-quality surface of graphene during thin-film deposition and device manufacturing is essential for many electronic applications. Here, we show that the use of self-assembled monolayers (SAMs) of hexamethyldisilazane (HMDS) as a buffer layer during the device fabrication of graphene can significantly reduce damage, improve the quality of graphene, and enhance device performance. The role of HMDS has been systematically investigated using surface analysis techniques and electrical measurements. The benefits of HMDS treatment include a significant reduction in defect density compared with as-treated graphene and more than a 2-fold reduction of contact resistance. This surface treatment is simple and offers a practical route for improving graphene device interfaces, which is important for the integration of graphene into functional devices such as electronics and sensor devices.

Complementary Metal-Oxide-Semiconductor Compatible Deposition of Nanoscale Transition-Metal Nitride Thin Films for Plasmonic Applications.

Transition-metal nitrides have received significant interest for use within plasmonic and optoelectronic devices because of their tunability and environmental stability. However, the deposition temperature remains a significant barrier to widespread adoption through the integration of transition-metal nitrides as plasmonic materials within complementary metal-oxide-semiconductor (CMOS) fabrication processes. Binary, ternary, and layered plasmonic transition-metal nitride thin films based on titanium and niobium nitride are deposited using high-power impulse magnetron sputtering (HIPIMS) technology. The increased plasma densities achieved in the HIPIMS process allow thin films with high plasmonic quality to be deposited at CMOS-compatible temperatures of less than 300 °C. Thin films are deposited on a range of industrially relevant substrates and display-tunable plasma frequencies in the ultraviolet to visible spectral ranges. Strain-mediated tunability is discovered in layered films compared to that in ternary films. The thin film quality, combined with the scalability of the deposition process, indicates that HIPIMS deposition of nitride films is an industrially viable technique and can pave the way toward the fabrication of next-generation plasmonic and optoelectronic devices.