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Codoping titanium dioxide nanowires with tungsten and carbon for enhanced photoelectrochemical performance

Recent density-functional theory calculations suggest that codoping TiO2 with donor-acceptor pairs is more effective than monodoping for improving photoelectrochemical water-splitting performance because codoping can reduce charge recombination, improve material quality, enhance light absorption and increase solubility limits of dopants. Here we report a novel ex-situ method to codope TiO2 with tungsten and carbon (W, C) by sequentially annealing W-precursor-coated TiO2 nanowires in flame and carbon monoxide gas. The unique advantages of flame annealing are that the high temperature (>1,000 °C) and fast heating rate of flame enable rapid diffusion of W into TiO2 without damaging the nanowire morphology and crystallinity. This is the first experimental demonstration that codoped TiO2:(W, C) nanowires outperform monodoped TiO2:W and TiO2:C and double the saturation photocurrent of undoped TiO2 for photoelectrochemical water splitting. Such significant performance enhancement originates from a greatly improved electrical conductivity and activity for oxygen-evolution reaction due to the synergistic effects of codoping.

Rapid and Controllable Flame Reduction of TiO2 Nanowires for Enhanced Solar Water-Splitting

We report a new flame reduction method to generate controllable amount of oxygen vacancies in TiO2 nanowires that leads to nearly three times improvement in the photoelectrochemical (PEC) water-splitting performance. The flame reduction method has unique advantages of a high temperature (>1000 °C), ultrafast heating rate, tunable reduction environment, and open-atmosphere operation, so it enables rapid formation of oxygen vacancies (less than one minute) without damaging the nanowire morphology and crystallinity and is even applicable to various metal oxides. Significantly, we show that flame reduction greatly improves the saturation photocurrent densities of TiO2 nanowires (2.7 times higher), α-Fe2O3 nanowires (9.4 times higher), ZnO nanowires (2.0 times higher), and BiVO4 thin film (4.3 times higher) in comparison to untreated control samples for PEC water-splitting applications.

Weak Polyion Multilayer-Assisted in Situ Synthesis as a Route toward a Plasmonic Ag/TiO2 Photocatalyst

Nanocrystalline Ag/TiO(2) composite thin films were synthesized using a two-step synthesis methodology: the in situ precipitation of Ag nanoparticles followed by an in situ sol-gel reaction of titanium iso-propoxide in a weak polyion multilayer (PEM) template formed by the layer-by-layer (LbL) self-assembly of poly(acrylic acid) (PAA) and polyallylamine (PAH). Because the PEM template is assembled from weak polyions, it contains nonionized carboxylic groups that are able to react with the inorganics, resulting in the formation of a homogeneous Ag(x)/TiO(2)-PEM precursor film, where the content of Ag is controlled by repeating the Ag loading cycle. The subsequent annealing of the precursor yields nanostructured Ag(x)/TiO(2) films with thicknesses controlled by the PEM template on the nanometer scale. Transmission electron, field-emission scanning electron, and atomic force microscopy methods were employed to evaluate the morphology and growth characteristics of the metallic and semiconductor nanocrystallites in the Ag(x)/TiO(2) composite thin films. The as-formed Ag(x)/TiO(2) composite thin films exhibited UV-visible photoactivity monitored by the decomposition of methylene blue (MB). In the near-UV range, the expected photocatalytic behavior of TiO(2) is greatly enhanced because it is assisted by the near-field amplitudes of the localized surface plasmon resonance (LSPR) of the Ag nanoparticles in the Ag(x)/TiO(2) films.

Cu and CuO/titanate nanobelt based network assemblies for enhanced visible light photocatalysis.

3D network configurations of copper(II) oxide/titanate nanobelt (CuO/TiNBs) and copper/titanate nanobelt (Cu/TiNBs) were formed using a two-step polyelectrolyte-assisted synthesis and assembly approach. The photoactivity of the TiNB/CuO and Cu/TiNB composite networks is significantly enhanced as compared to the activity of 3D structures formed of pristine TiNB. An efficient, UV-vis-light-induced electron transfer at the two-component interface achieved by the intimate coupling of TiNB with p-type semiconducting CuO and plasmonic Cu nanoparticles in composite heterostructures facilitates control over the systems exciton dynamics, which results in highly efficient UV-vis photocatalytic performance of heterostructures. The superior photocatalytic activity of the metal and semiconductor/semiconductor nanocomposite structures in the visible region is discussed, highlighting the role of interfacial electron-charge transfer (IFCT) in semiconductor-semiconductor (CuO/TiNB) and surface plasmon resonance (SPR) of Cu nanoparticles in metal-semiconductor heterostructures.

Plasma processing for crystallization and densification of atomic layer deposition BaTiO3 thin films.

High-k, low leakage thin films are crucial components for dynamic random access memory (DRAM) capacitors with high storage density and a long storage lifetime. In this work, we demonstrate a method to increase the dielectric constant and decrease the leakage current density of atomic layer deposited BaTiO3 thin films at low process temperature (250 °C) using postdeposition remote oxygen plasma treatment. The dielectric constant increased from 51 (as-deposited) to 122 (plasma-treated), and the leakage current density decreased by 1 order of magnitude. We ascribe such improvements to the crystallization and densification of the film induced by high-energy ion bombardments on the film surface during the plasma treatment. Plasma-induced crystallization presented in this work may have an immediate impact on fabricating and manufacturing DRAM capacitors due to its simplicity and compatibility with industrial standard thin film processes.

Enhanced Step Coverage of TiO2 Deposited on High Aspect Ratio Surfaces by Plasma-Enhanced Atomic Layer Deposition

Plasma-enhanced atomic layer deposition (PEALD) provides multiple benefits compared to thermal ALD including lower possible process temperature and a wider palette of possible materials. However, coverage of high aspect ratio (AR) structures is limited due to the recombination rates of the radical plasma species. We study the limits of conformality in 1:30 AR structures for TiO2 based on tetrakis(dimethylamido)titanium (TDMA-Ti) and O2 plasma through variation in plasma exposure and substrate temperature. Extending plasma exposure duration and decreasing substrate temperature within the ALD window both serve to improve the conformality of the deposited film, with coverage >95% achievable. Additionally, the changes in morphology of the TiO2 were examined with crystallites of anatase and brookite found.

Atomic Layer Deposition of Undoped TiO2 Exhibiting p-Type Conductivity

With prominent photocatalytic applications and widespread use in semiconductor devices, TiO2 is one of the most popular metal oxides. However, despite its popularity, it has yet to achieve its full potential due to a lack of effective methods for achieving p-type conductivity. Here, we show that undoped p-type TiO2 films can be fabricated by atomic layer deposition (ALD) and that their electrical properties can be controlled across a wide range using proper postprocessing anneals in various ambient environments. Hole mobilities larger than 400 cm(2)/(V·s) are accessible superseding the use of extrinsic doping, which generally produces orders of magnitude smaller values. Through a combination of analyses and experiments, we provide evidence that this behavior is primarily due to an excess of oxygen in the films. This discovery enables entirely new categories of TiO2 devices and applications, and unlocks the potential to improve existing ones. TiO2 homojunction diodes fabricated completely by ALD are developed as a demonstration of the utility of these techniques and shown to exhibit useful rectifying characteristics even with minimal processing refinement.

Quantifying Geometric Strain at the PbS QD-TiO2 Anode Interface and Its Effect on Electronic Structures

Quantum dots (QDs) show promise as the absorber in nanostructured thin film solar cells, but achieving high device efficiencies requires surface treatments to minimize interfacial recombination. In this work, lead sulfide (PbS) QDs are grown on a mesoporous TiO2 film with a crystalline TiO2 surface, versus one coated with an amorphous TiO2 layer by atomic layer deposition (ALD). These mesoporous TiO2 films sensitized with PbS QDs are characterized by X-ray and electron diffraction, as well as X-ray absorption spectroscopy (XAS) in order to link XAS features with structural distortions in the PbS QDs. The XAS features are further analyzed with quantum simulations to probe the geometric and electronic structure of the PbS QD-TiO2 interface. We show that the anatase TiO2 surface structure induces PbS bond angle distortions, which increases the energy gap of the PbS QDs at the interface.

Controlled synthesis of pure and doped ZnS nanoparticles in weak polyion assemblies: growth characteristics and fluorescence properties.

A polyelectrolyte multilayer (PEM) fabricated by the layer-by-layer (LbL) self-assembly of weak polyions of polyacrylic acid (PAA) and polyallylamine (PAH) was applied as a matrix for the in situ nucleation and growth of pure and Mn-doped ZnS nanocrystallites. The nucleation and growth is initiated by the adsorption and binding of the metal ions to the ionized carboxylic groups of the weak polyions within the matrix, followed by the subsequent precipitation of semiconductor nanocrystallites with Na(2)S. Transmission electron microscopy (TEM), atomic force microscopy (AFM) and UV-vis spectroscopy were employed to establish the growth characteristics of the spherical ZnS nanocrystallites in the polyion matrix. The conformational arrangement of polyion chains induced by variation in the assembly pH is the key parameter that affects the structural and morphological characteristics of ZnS nanocrystallites. Repeating the reaction cycle resulted in an increase in the volume density of ZnS nanoparticles and further growth of the initially formed particles by the Ostwald ripening mechanism. The surface passivation of the ZnS nanocrystallites within the polyion matrix enables the enhanced radiative emission of ZnS composite films in the UV range, whereas by doping the ZnS, nanocrystallites show emission characteristic of the manganese ions in the visible region.

Silver nanoparticles on titanate nanobelts via the self-assembly of weak polyelectrolytes: synthesis and photocatalytic properties

A weak-polyelectrolyte multilayer on a surface of titanate nanobelts (Ti-NBs) was utilized as a template for in situ Ag nanoparticle formation in the fabrication of Ag-loaded Ti-NBs nanocomposites. The polyelectrolyte multilayer (PEM) was fabricated using layer-by-layer self-assembly of poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH) on the surface of high-surface-area titanate nanobelts (Ti-NBs) synthesized using a hydrothermal procedure. The concentration of Ag nanoparticles in the PEM was controlled by repeating the ion-loading/reduction cycle. The subsequent annealing of the Ag/Ti-NBs-PEM nanocomposites yielded nanostructured crystalline Ag/Ti-NBs. Transmission electron microscopy (TEM) techniques (HRTEM, SAED) and x-ray powder diffraction (XRD) were employed to evaluate the morphological, structural and growth characteristics of the silver nanocrystallites in the Ag/Ti-NBs nanocomposites. The UV-vis photoactivity of the as-fabricated nanocomposites was monitored by the degradation of the cationic dye methylene blue (MB). An enhanced UV photo-efficiency was observed for the Ag/Ti-NBs nanocomposites compared with pure Ti-NBs. As-fabricated Ag(x)/Ti-NBs nanocomposites also exhibited visible photoactivity assisted by the near-field amplitudes of the localized surface plasmon resonance (LSPR) of the silver nanoparticles in the 1D nanocomposite.