Guangxu Cai

Mechanism of the enhancement and quenching of ZnO photoluminescence by ZnO-Ag coupling

New nanostructural composites consisting of Ag nanoparticles (NPs)-SiO2-ZnO films were fabricated by depositing ZnO films on silica substrates which had already been implanted by Ag ions at different energies and fluences. The photoluminescence (PL) emission of ZnO films from these nanostructural composites can be enhanced or quenched comparing to that of a ZnO film directly deposited on bare silica substrate. The enhancement of the band gap emission is ascribed to the local field enhancement induced by the resonant coupling between the excitons of ZnO and the surface plasmons (SPs) of Ag NPs, while the quenching is due to the electron transfer from ZnO to Ag NPs. Our results can be used to clarify the ambiguity in controlling the light emission enhancement and quenching of a semiconductor coupled with the SPs of metal NPs, which is very important for the design and applications of semiconductor and metal coupling to highly efficient optoelectronic devices, biosensor, etc.

N Doping to ZnO Nanorods for Photoelectrochemical Water Splitting under Visible Light: Engineered Impurity Distribution and Terraced Band Structure

Solution-based ZnO nanorod arrays (NRAs) were modified with controlled N doping by an advanced ion implantation method, and were subsequently utilized as photoanodes for photoelectrochemical (PEC) water splitting under visible light irradiation. A gradient distribution of N dopants along the vertical direction of ZnO nanorods was realized. N doped ZnO NRAs displayed a markedly enhanced visible-light-driven PEC photocurrent density of ~160 μA/cm2 at 1.1 V vs. saturated calomel electrode (SCE), which was about 2 orders of magnitude higher than pristine ZnO NRAs. The gradiently distributed N dopants not only extended the optical absorption edges to visible light region, but also introduced terraced band structure. As a consequence, N gradient-doped ZnO NRAs can not only utilize the visible light irradiation but also efficiently drive photo-induced electron and hole transfer via the terraced band structure. The superior potential of ion implantation technique for creating gradient dopants distribution in host semiconductors will provide novel insights into doped photoelectrode materials for solar water splitting.

Activating ZnO nanorod photoanodes in visible light by Cu ion implantation

AbstractUtilization of visible light is of crucial importance for exploiting efficient semiconductor catalysts for solar water splitting. In this study, an advanced ion implantation method was utilized to dope Cu ions into ZnO nanorod arrays for photoelectrochemical water splitting in visible light. X-ray diffraction (XRD) and X-ray photo-electron spectroscopy (XPS) results revealed that Cu+ together with a small amount of Cu2+ were highly dispersed within the ZnO nanorod arrays. The Cu ion doped ZnO nanorod arrays displayed extended optical absorption and enhanced photoelectrochemical performance under visible light illumination (λ > 420 nm). A considerable photocurrent density of 18 μA/cm2 at 0.8 V (vs. a saturated calomel electrode) was achieved, which was about 11 times higher than that of undoped ZnO nanorod arrays. This study proposes that ion implantation could be an effective approach for developing novel visible-light-driven photocatalytic materials for water splitting.

Enhanced photocatalysis by coupling of anatase TiO2 film to triangular Ag nanoparticle island

In order to overcome the low utilization ratio of solar light and high electron-hole pair recombination rate of TiO2, the triangular Ag nanoparticle island is covered on the surface of the TiO2 thin film. Enhancement of the photocatalytic activity of the Ag/TiO2 nanocomposite system is observed. The increase of electron-hole pair generation is caused by the enhanced near-field amplitudes of localized surface plasmon of the Ag nanoparticles. The efficiently suppressed recombination of electron-hole pair caused by the metal-semiconductor contact can also enhance the photocatalytic activity of the TiO2 film.

Efficiency enhancements in Ag nanoparticles-SiO2-TiO2 sandwiched structure via plasmonic effect-enhanced light capturing

TiO2-SiO2-Ag composites are fabricated by depositing TiO2 films on silica substrates embedded with Ag nanoparticles. Enhancement of light absorption of the nanostructural composites is observed. The light absorption enhancement of the synthesized structure in comparison to TiO2 originated from the near-field enhancement caused by the plasmonic effect of Ag nanoparticles, which can be demonstrated by the optical absorption spectra, Raman scattering investigation, and the increase of the photocatalytic activity. The embedded Ag nanoparticles are formed by ion implantation, which effectively prevents Ag to be oxidized through direct contact with TiO2. The suggested incorporation of plasmonic nanostructures shows a great potential application in a highly efficient photocatalyst and ultra-thin solar cell.

Fabrication and properties of TiO2 nanofilms on different substrates by a novel and universal method of Ti-ion implantation and subsequent annealing

We report a new, novel and universal method to fabricate high-quality titanium dioxide (TiO2) nanofilms on different substrates by a solid phase growth process of ion implantation and subsequent annealing in oxygen atmosphere. Ti ions were implanted into fused silica, soda lime glass, Z-cut quartz, or (0001) α-sapphire by a metal vapor vacuum arc (MEVVA) ion source implanter to fluences of 0.75, 1.5 and 3 × 10(17) ions cm(-2) with a nominal accelerating voltage of 20 kV. To understand the influence of the annealing temperature, time, and substrate on the formation and phase transformation of the TiO2 nanofilms, the Ti-ion-implanted substrates were annealed in oxygen atmosphere from 500 to 1000 °C for 1-6 h. The formation of TiO2 nanofilms resulted from the slow out-diffusion of implanted Ti ions from the substrates which were then oxidized at the surfaces. The thickness and phase of the nanofilms can be tailored by controlling the implantation and annealing parameters. Since the TiO2 nanofilms are formed under high temperature and low growth rate, they show good crystallinity and antibacterial properties, with good film adhesion and stability, suggesting that the TiO2 nanofilms formed by this method have great potential in applications such as antibacterial and self-cleaning transparent glass.

Synergistic effect of V/N codoping by ion implantation on the electronic and optical properties of TiO2

Performance of the material depends directly on the electronic and energy band structure, to improve the photoactivity of TiO2 and decrease carrier recombination centers induced by monodoping, the TiO2 thin film has been modified with V and N codopants by ion implantation for tailing and controlling the electronic structure and energy band structure. Compared to monodopant, codopants of V and N exhibit a synergistic effect in the photoactivity enhancement of TiO2. X-ray photoelectron spectroscopy (XPS) studies demonstrate that the implanted V and N ions are introduced into the lattice of TiO2 through V and N substituting Ti and O, respectively. The electronic structure of V/N codoped TiO2 was calculated by First-principles calculations based on density-functional theory, the results show the band edges of TiO2 can be tailored by V and N codopants. UV-vis spectra consistently show the absorption edge of V/N codoped TiO2 film is widen to visible light region. More importantly, the photoactivity of TiO2 film...

Controlling the growth of ZnO quantum dots embedded in silica by Zn/F sequential ion implantation and subsequent annealing.

We report the formation of embedded ZnO quantum dots (QDs) by Zn and F ion sequential implantation and subsequent annealing. Optical absorption and photoluminescence spectrum measurements, transmission electron microscopy bright field images and selected area electron diffraction patterns indicate that ZnO QDs were formed after annealing in air or vacuum at temperatures higher than 500 °C. Atomic force microscopy images show a comparatively flat surface of the annealed samples, which indicates that only very few Zn atoms are evaporated to the surfaces. The formation of ZnO QDs during the thermal annealing can be attributed to the direct oxidization of Zn nanoparticles by the oxygen molecules in the substrate produced during the implantation of F ions. The quality of ZnO QDs increases with the increase of annealing temperature.

Origin of white light luminescence from Si+/C+ sequentially implanted and annealed silica

The white light luminescence is observed from the silica slides implanted by sequential Si+ and C+ ions or only by C+ ions followed by thermal annealing. In the photoluminescence (PL) spectra, their white emissions cover the whole visible spectral range from 350 to 800 nm. The influence of thermal annealing on the PL of the implanted samples was studied. The microstructural and optical analysis allow us to figure out the origin of the white light emission, which is mainly attributed to the emission of graphite like C clusters although the contributions from the emissions of the Si and SiC nanocrystals are also included. Compared to the white light emission of C+ implanted sample, the white light emission of Si+/C+ implanted sample has higher thermal stability.

Formation of Carbonized Polystyrene Sphere/hemisphere Shell Arrays by Ion Beam Irradiation and Subsequent Annealing or Chloroform Treatment

Heat-resistant two-dimensional (2D) sphere/hemisphere shell array is significant for the fabrication of novel nanostructures. Here large-area, well-ordered arrays of carbonized polystyrene (PS) hollow sphere/hemisphere with controlled size and morphology are prepared by combining the nanosphere self-assembly, kV Ag ion beam modification, and subsequent annealing or chloroform treatment. Potential mechanisms for the formation and evolution of the heat-resistant carbonized PS spherical shell with increasing ion fluence and energy are discussed. Combined with noble metal or semiconductor, these modified PS sphere arrays should open up new possibilities for high-performance nanoscale optical sensors or photoelectric devices.