Nitrogen-doped TiO2 nanotube arrays (N-TNAs) were successfully fabricated by a simple thermal annealing process in ambient N2 gas at 450 °C for 3 h. TNAs with modified morphologies were prepared by a two-step anodization using an aqueous NH4F/ethylene glycol solution. The N-doping concentration (0–9.47 at %) can be varied by controlling N2 gas flow rates between 0 and 500 cc/min during the annealing process. Photocatalytic performance of as-prepared TNAs and N-TNAs was studied by monitoring the methylene blue degradation under visible light (λ ≥ 400 nm) illumination at 120 mW·cm−2. N-TNAs exhibited appreciably enhanced photocatalytic activity as compared to TNAs. The reaction rate constant for N-TNAs (9.47 at % N) reached 0.26 h−1, which was a 125% improvement over that of TNAs (0.115 h−1). The significant enhanced photocatalytic activity of N-TNAs over TNAs is attributed to the synergistic effects of (1) a reduced band gap associated with the introduction of N-doping states to serve as carrier reservoir, and (2) a reduced electron‒hole recombination rate.
Fluorine-doped tin oxide (FTO) thin films were deposited on glass substrates using ultrasonic spray pyrolysis (USP) at a fixed substrate temperature of 400 °C and various Fluorine/Tin (F/Sn) atomic ratios of 0, 0.1, 0.5, and 1.0. Effects of F/Sn atomic ratios on structural-morphological, compositional, electrical, optical, and nanomechanical properties of the FTO thin films were systematically studied. The FTO films exhibited a tetragonal structure with preferred orientations of (110), (200), and (211), and polycrystalline morphology with spear-like or coconut shell-like particles on the surfaces. The presence of F-doping was confirmed by XPS results with clear F1s peaks, and F-concentration was determined to be 0.7% for F/Sn = 0.1 and 5.1% for F/Sn = 0.5. Moreover, the resistivity of FTO films reduced remarkably from 4.1 mΩcm at F/Sn = 0 to 0.7 mΩcm at F/Sn = 1, primarily due to the corresponding increase of carrier concentration from 2 × 1020 cm−3 to 1.2 × 1021 cm−3. The average optical transmittance of the films prepared at F/Sn of 0–0.5 was over 90%, and it decreased to 84.4% for the film prepared at F/Sn = 1. The hardness (H) and Young’s modulus (E) of the FTO films increased when the F/Sn ratios increased from 0 to 0.5, reaching maximum values of H = 12.3 ± 0.4 GPa, E = 131.7 ± 8.0 GPa at F/Sn = 0.5. Meanwhile, the H and E reduced considerably when the F/Sn ratio further increased to 1.0, following the inverse Hall-Petch effect approximately, suggesting that the grain boundary effect played a primary role in manipulating the nanomechanical properties of the FTO films. Furthermore, favorable mechanical properties with large H/Ef and H 3 / E f 2 ratios were found for the FTO film prepared at F/Sn = 0.5, which possessed high crystallinity, large grain size, and compact morphology.
The nanomechanical properties and nanoindentation responses of bismuth selenide (Bi2Se3) thin films are investigated in this study. The Bi2Se3 thin films are deposited on c-plane sapphire substrates using pulsed laser deposition. The microstructural properties of Bi2Se3 thin films are analyzed by means of X-ray diffraction (XRD). The XRD results indicated that Bi2Se3 thin films are exhibited the hexagonal crystal structure with a c-axis preferred growth orientation. Nanoindentation results showed the multiple “pop-ins” displayed in the loading segments of the load-displacement curves, suggesting that the deformation mechanisms in the hexagonal-structured Bi2Se3 films might have been governed by the nucleation and propagation of dislocations. Further, an energetic estimation of nanoindentation-induced dislocation associated with the observed pop-in effects was made using the classical dislocation theory.
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