Benjamin D. Wiltshire

Amphiphobic surfaces from functionalized TiO2 nanotube arrays

Vertically-oriented, self-organized TiO2 nanotube arrays (TNAs) are a highly ordered n-type semiconducting nanoarchitecture with a wide range of potential applications. We generated low energy surfaces repellent to a broad spectrum of liquids by functionalizing TNAs using monolayers of two different fluorinated hydrocarbon molecules: perfluorononanoic acid (PFNA) and 1H, 1H′, 2H, 2H′-perfluorodecyl phosphonic acid (PFDPA). Nanotubes of two different outer diameters (50 nm and 130 nm) were studied and their wetting behavior analyzed in liquids belonging to different solvent classes to infer the nature of the wetting states. We show that the wetting behavior of perfluorinated monolayer-functionalized TNAs in polar liquids is explained by fakir or Cassie-states whilst the wetting behavior of bare nanotubes in every liquid is explained by Wenzel-type states. On the other hand, a transition between the Cassie and Wenzel states due to closed pores in the TNA architecture dictates the wetting behavior of functionalized TNAs in apolar liquids. The wetting behavior of functionalized TNAs is understood considering the synergistic effect of geometric and chemical surface modification. PFDPA-functionalized TNAs were found to be resilient to 24 hours of exposure to water and ethylene glycol at a static fluid pressure of 0.105 MPa, and are one step closer towards the realization of a mechanically robust omniphobic surface. At the same time, an understanding of wetting behavior will be useful in the design and optimization of a wide range of interface-sensitive devices such as metal oxide nanotube/nanopore array based sensors, implants, flow-through membranes, photocatalysts and heterojunction solar cells.

Halide perovskite solar cells using monocrystalline TiO2 nanorod arrays as electron transport layers: impact of nanorod morphology

This is the first report of a 17.6% champion efficiency solar cell architecture comprising monocrystalline TiO2 nanorods (TNRs) coupled with perovskite, and formed using facile solution processing without non-routine surface conditioning. Vertically oriented TNR ensembles are desirable as electron transporting layers (ETLs) in halide perovskite solar cells (HPSCs) because of potential advantages such as vectorial electron percolation pathways to balance the longer hole diffusion lengths in certain halide perovskite semiconductors, ease of incorporating nanophotonic enhancements, and optimization between a high contact surface area for charge transfer (good) versus high interfacial recombination (bad). These advantages arise from the tunable morphology of hydrothermally grown rutile TNRs, which is a strong function of the growth conditions. Fluorescence lifetime imaging microscopy of the HPSCs demonstrated a stronger quenching of the perovskite PL when using TNRs as compared to mesoporous/compact TiO2 thin films. Due to increased interfacial contact area between the ETL and perovskite with easier pore filling, charge separation efficiency is dramatically enhanced. Additionally, solid-state impedance spectroscopy results strongly suggested the suppression of interfacial charge recombination between TNRs and perovskite layer, compared to other ETLs. The optimal ETL morphology in this study was found to consist of an array of TNRs ∼300 nm in length and ∼40 nm in width. This work highlights the potential of TNR ETLs to achieve high performance solution-processed HPSCs.

Heterojunctions of mixed phase TiO2 nanotubes with Cu, CuPt, and Pt nanoparticles: interfacial band alignment and visible light photoelectrochemical activity

Anodically formed, vertically oriented, self-organized cylindrical TiO2 nanotube arrays composed of the anatase phase undergo an interesting morphological and phase transition upon flame annealing to square-shaped nanotubes composed of both anatase and rutile phases. This is the first report on heterojunctions consisting of metal nanoparticles (NPs) deposited on square-shaped TiO2 nanotube arrays (STNAs) with mixed rutile and anatase phase content. A simple photochemical deposition process was used to form Cu, CuPt, and Pt NPs on the STNAs, and an enhancement in the visible light photoelectrochemical water splitting performance for the NP-decorated STNAs was observed over the bare STNAs. Under narrow band illumination by visible photons at 410 nm and 505 nm, Cu NP-decorated STNAs performed the best, producing photocurrents 80% higher and 50 times higher than bare STNAs, respectively. Probing the energy level structure at the NP-STNA interface using ultraviolet photoelectron spectroscopy revealed Schottky barrier formation in the NP-decorated STNAs, which assists in separating the photogenerated charge carriers, as also confirmed by longer charge carrier lifetimes in NP-decorated STNAs. While all the NP-decorated STNAs showed enhanced visible light absorption compared to the bare STNAs, only the Cu NPs exhibited a clear plasmonic behavior with an extinction cross section that peaked at 550 nm.

Optical anisotropy in vertically oriented TiO2 nanotube arrays

Nanofabricated optically anisotropic uniaxial thin films with deep submicron feature sizes are emerging as potential platforms for low-loss all-dielectric metamaterials, and for Dyakonov surface wave-based subwavelength optical confinement and guiding at interfaces with isotropic media. In this context, we investigate the optical properties of one such uniaxial platform, namely self-organized titania nanotube arrays (TNTAs) grown by the bottom-up nanofabrication process of electrochemical anodization on silicon wafer substrates, and subsequently annealed at different temperatures, i.e. 500 °C and 750 °C. We performed detailed quantitative analysis of the structure of the TNTAs using x-ray diffraction and Raman spectroscopy, which revealed a measurable phonon confinement in TNTAs annealed at 500 °C. Variable angle spectroscopic ellipsometry was used to investigate the optical anisotropy in two kinds of TNTAs-those constituted by anatase-phase and those containing a mixture of anatase and rutile phases. Both kinds of TNTAs were found to have positive birefringence (Δn) exceeding 0.06 in the spectral region of interest while mixed phase TNTAs exhibited Δn as high as 0.15. The experimentally measured anisotropy in the refractive index of the TNTAs was compared with the predictions of two different effective medium approximations incorporating the uniaxial geometry. The measured value of Δn for TNTAs exceeded that of bulk anatase single crystals, indicating the potential of nanostructured dielectrics to outperform dielectric crystals of the same material with respect to the magnitude of the achievable directional refractive index contrast.

Reduced Ensemble Plasmon Line Widths and Enhanced Two-Photon Luminescence in Anodically Formed High Surface Area Au–TiO2 3D Nanocomposites

Localized surface plasmon resonances (LSPR) in TiO2 nanorod and nanotube arrays decorated by gold nanoparticles can be exploited to improve photocatalytic activity, enhance nonlinear optical coefficients, and increase light harvesting in solar cells. However, the LSPR typically has a low quality factor, and the resonance is often obscured by the Urbach tail of the TiO2 band gap absorption. Attempts to increase the LSPR extinction intensity by increasing the density of gold nanoparticles on the surface of the TiO2 nanostructures invariably produce peak broadening due to the effects of either agglomeration or polydispersity. We present a new class of hybrid nanostructures containing gold nanoparticles (NPs) partially embedded in nanoporous/nanotubular TiO2 by performing the anodization of cosputtered Ti-Au thin films containing a relatively high ratio of Au:Ti. Our method of anodizing thin film stacks containing alternate layers of Ti and TiAu results in very distinctive LSPR peaks with quality factors as high as 6.9 and ensemble line widths as small as 0.33 eV even in the presence of an Urbach tail. Unusual features in the anodization of such films are observed and explained, including oscillatory current transients and the observation of coherent heterointerfaces between the Au NPs and anatase TiO2. We further show that such a plasmonic NP-embedded nanotube structure dramatically outperforms a plasmonic NP-decorated anodic nanotube structure in terms of the extinction coefficient, and achieves a strongly enhanced two-photon fluorescence due to the high density of gold nanoparticles in the composite film and the plasmonic local field enhancement.

Ultraviolet sensing using a TiO2 nanotube integrated high resolution planar microwave resonator device

This paper presents a unique integrated UV light sensing concept and introduces a device with a detection limit of 1.96 nW cm-2. The combination of a high quality factor, a microwave planar resonator (Q ∼ 50 000) with a semiconducting nanomaterial enables a revolutionary potential paradigm for photodetection of low light intensities and small form factors. The presenting device employs a high-resolution microwave microstrip resonator as the signal transducer to convert the variant dielectric properties (permittivity and conductivity) of the nanotube membrane into electrical signals such as the resonant frequency, quality factor and resonant amplitude. The microwave resonator has an active feedback loop to improve the initial quality factor of the resonator from 200 to 50 000 and leads to boosting of the sensing resolution by orders of magnitude. Anatase TiO2 nanotubes are assembled on the surface of the microwave resonator. Upon exposure to UV light, electron-hole pair generation, trapping and recombination in the nanotubes are exploited as a unique signature to quantify the UV light intensity. The change of dielectric properties of the nanotube membrane is monitored using the underlying active microwave resonator. The proposed concept enables the detection and monitoring of UV light at high resolution, with very small exposure power and integrated form factors.

Composition-Tunable Formamidinium Lead Mixed Halide Perovskites via Solvent-Free Mechanochemical Synthesis: Decoding the Pb Environments Using Solid-State NMR Spectroscopy

Mixed-halide lead perovskites are becoming of paramount interest in the optoelectronic and photovoltaic research fields, offering band gap tunability, improved efficiency, and enhanced stability compared to their single halide counterparts. Formamidinium-based mixed halide perovskites (FA-MHPs) are critical to obtaining optimum solar cell performance. Here, we report a solvent-free mechanochemical synthesis (MCS) method to prepare FA-MHPs, starting with their parent compounds (FAPbX3; X = Cl, Br, I), achieving compositions not previously accessible through the solvent synthesis (SS) technique. By probing local Pb environments in MCS FA-MHPs using solid-state nuclear magnetic resonance spectroscopy, along with powder X-ray diffraction for long-range crystallinity and reflectance measurements to determine the optical band gap, we show that MCS FA-MHPs form atomic-level solid solutions between Cl/Br and Br/I MHPs. Our results pave the way for advanced methods in atomic-level structural understanding while offering a one-pot synthetic approach to prepare MHPs with superior control of stoichiometry.

Distinguishing between Deep Trapping Transients of Electrons and Holes in TiO2 Nanotube Arrays Using Planar Microwave Resonator Sensor

A large signal direct current (DC) bias and a small signal microwave bias were simultaneously applied to TiO2 nanotube membranes mounted on a planar microwave resonator. The DC bias modulated the electron concentration in the TiO2 nanotubes and was varied between 0 and 120 V in this study. Transients immediately following the application and removal of DC bias were measured by monitoring the S-parameters of the resonator as a function of time. The DC bias stimulated Poole-Frenkel-type trap-mediated electrical injection of excess carriers into TiO2 nanotubes, which resulted in a near-constant resonant frequency but a pronounced decrease in the microwave amplitude due to free electron absorption. When ultraviolet illumination and DC bias were both present and then stepwise removed, the resonant frequency shifted due to trapping-mediated change in the dielectric constant of the nanotube membranes. Characteristic lifetimes of 60-80, 300-800, and ∼3000 s were present regardless of whether light or bias was applied and were also observed in the presence of a hole scavenger, which we attributed to oxygen adsorption and deep electron traps, whereas another characteristic lifetime >8000 s was only present when illumination was applied, and is attributed to the presence of hole traps.

The Wetting Behavior of TiO2 Nanotube Arrays With Perfluorinated Surface Functionalization

A facile electrochemical anodization method was used for producing hierarchically textured surfaces based on TiO2 nanotubes in two different configurations. It was found that perfluoro-functionalized TiO2 nanotubes exhibit high static contact angles for a variety of liquids such as apolar, polar aprotic and polar protic solvents. Wenzel and Cassie-Baxter theories were applied for theoretical contact angle calculations for the present study. By using Cassie theories, it is shown that a drop of polar liquid was in a fakir or Cassie-Baxter (CB) state on perfluoro-functionalized nanotube surfaces. The fakir state prevents spreading of the liquid on the surface. On the other hand, the wetting of non-polar liquids such as hexane is characterized by either Wenzel states or transition states characterized by partial imbibition that lie in between the CB and Wenzel states.Copyright