Photocatalysis on supported gold and silver nanoparticles under ultraviolet and visible light irradiation

Studies of the optical properties and catalytic capabilities of noble metal nanoparticles (NPs), such as gold (Au) and silver (Ag), have formed the basis for the very recent fast expansion of the field of green photocatalysis: photocatalysis utilizing visible and ultraviolet light, a major part of the solar spectrum. The reason for this growth is the recognition that the localised surface plasmon resonance (LSPR) effect of Au NPs and Ag NPs can couple the light flux to the conduction electrons of metal NPs, and the excited electrons and enhanced electric fields in close proximity to the NPs can contribute to converting the solar energy to chemical energy by photon-driven photocatalytic reactions. Previously the LSPR effect of noble metal NPs was utilized almost exclusively to improve the performance of semiconductor photocatalysts (for example, TiO2 and Ag halides), but recently, a conceptual breakthrough was made: studies on light driven reactions catalysed by NPs of Au or Ag on photocatalytically inactive supports (insulating solids with a very wide band gap) have demonstrated that these materials are a class of efficient photocatalysts working by mechanisms distinct from those of semiconducting photocatalysts. There are several reasons for the significant photocatalytic activity of Au and Ag NPs. (1) The conduction electrons of the particles gain the irradiation energy, resulting in high energy electrons at the NP surface which is desirable for activating molecules on the particles for chemical reactions. (2) In such a photocatalysis system, both light harvesting and the catalysing reaction take place on the nanoparticle, and so charge transfer between the NPs and support is not a prerequisite. (3) The density of the conduction electrons at the NP surface is much higher than that at the surface of any semiconductor, and these electrons can drive the reactions on the catalysts. (4) The metal NPs have much better affinity than semiconductors to many reactants, especially organic molecules. Recent progress in photocatalysis using Au and Ag NPs on insulator supports is reviewed. We focus on the mechanism differences between insulator and semiconductor-supported Au and Ag NPs when applied in photocatalytic processes, and the influence of important factors, light intensity and wavelength, in particular estimations of light irradiation contribution, by calculating the apparent activation energies of photo reactions and thermal reactions.

Different nanostructures from different plasmas : nanoflowers and nanotrees on silicon

Using the advanced radio-frequency plasma-assisted magnetron deposition system, various nanostructures such as nanoflowers of carbon nanotubes, ZnO nanobelts, and silicon nanotrees were successfully synthesized. In this paper, we present the photographs of ICP and magnetron discharges, the photograph of a complex plasma structure, and the SEM images of various nanostructures synthesized in the system with magnetron and ICP sources operating simultaneously.

The path to stoichiometric composition of III–V binary quantum dots through plasma/ion-assisted self-assembly

Semiconductor III-V quantum dots (QDs) are particularly enticing components for the integration of optically promising III-V materials with the silicon technology prevalent in the microelectronics industry. However, defects due to deviations from a stoichiometric composition [group III: group V = 1] may lead to impaired device performance. This paper investigates the initial stages of formation of InSb and GaAs QDs on Si(1 0 0) through hybrid numerical simulations. Three situations are considered: a neutral gas environment (NG), and two ionized gas environments, namely a localized ion source (LIS) and a background plasma (BP) case. It is shown that when the growth is conducted in an ionized gas environment, a stoichiometric composition may be obtained earlier in the QD as compared to a NG. Moreover, the stoichiometrization time, tst, is shorter for the BP case compared to the LIS scenario. A discussion of the effect of ion/plasma-based tools as well as a range of process conditions on the final island size distribution is also included. Our results suggest a way to obtain a deterministic level of control over nanostructure properties (in particular, elemental composition and size) during the initial stages of growth which is a crucial step towards achieving highly tailored QDs suitable for implementation in advanced technological devices.

Effect of doping with Co and/or Cu on electronic structure and optical properties of ZnO

This paper reports on ab initio numerical simulations of the effect of Co and Cu dopings on the electronic structure and optical properties of ZnO, pursued to develop diluted magnetic semiconductors vitally needed for spintronic applications. The simulations are based upon the Perdew-Burke-Enzerh generalized gradient approximation on the density functional theory. It is revealed that the electrons with energies close to the Fermi level effectively transfer only between Cu and Co ions which substitute Zn atoms, and are located in the neighbor sites connected by an O ion. The simulation results are consistent with the experimental observations that addition of Cu helps achieve stable ferromagnetism of Co-doped ZnO. It is shown that simultaneous insertion of Co and Cu atoms leads to smaller energy band gap, redshift of the optical absorption edge, as well as significant changes in the reflectivity, dielectric function, refractive index, and electron energy loss function of ZnO as compared to the doping with either Co or Cu atoms. These highly unusual optical properties are explained in terms of the computed electronic structure and are promising for the development of the next-generation room-temperature ferromagnetic semiconductors for future spintronic devices on the existing semiconductor micromanufacturing platform.

p-type doping of ZnO by means of high-density inductively coupled plasmas

A custom-designed inductively coupled plasma assisted radio-frequency magnetron sputtering deposition system has been used to fabricate N-doped p-type ZnO (ZnO:N) thin films on glass substrates from a sintered ZnO target in a reactive Ar + N2 gas mixture. X-ray diffraction and scanning electron microscopy analyses show that the ZnO:N films feature a hexagonal crystal structure with a preferential (002) crystallographic orientation and grow as vertical columnar structures. Hall effect and X-ray photoelectron spectroscopy analyses show that N-doped ZnO thin films are p-type with a hole concentration of 3.32 × 1018 cm- 3 and mobility of 1.31 cm2 V- 1 s- 1. The current-voltage measurement of the two-layer structured ZnO p-n homojunction clearly reveals the rectifying ability of the p-n junction. The achievement of p-type ZnO:N thin films is attributed to the high dissociation ability of the high-density inductively coupled plasma source and effective plasma-surface interactions during the growth process.

Electron-conduction mechanism and specific heat above transition temperature in LaFeAsO and BaFe2As2 superconductors

The ionization energy theory is used to calculate the evolution of the resistivity and specific heat curves with respect to different doping elements in the recently discovered superconducting pnictide materials. Electron-conduction mechanism in the pnictides above the structural transition temperature is explained unambiguously, which is also consistent with other strongly correlated materials, such as cuprates, manganites, titanates and magnetic semiconductors.

Reactive oxygen plasma-enabled synthesis of nanostructured CdO : tailoring nanostructures through plasma–surface interactions

Plasma-assisted synthesis of nanostructures is one of the most precise and effective approaches used in nanodevice fabrication. Here we report on the innovative approach of synthesizing nanostructured cadmium oxide films on Cd substrates using a reactive oxygen plasma-based process. Under certain conditions, the surface morphology features arrays of crystalline CdO nano/micropyramids. These nanostructures grow via unconventional plasma-assisted oxidation of a cadmium foil exposed to inductively coupled plasmas with a narrow range of process parameters. The growth of the CdO pyramidal nanostructures takes place in the solid-liquid-solid phase, with the rates determined by the interaction of plasma-produced oxygen atoms and ions with the surface. It is shown that the size of the pyramidal structures can be effectively controlled by the fluxes of oxygen atoms and ions impinging on the cadmium surface. The unique role of the reactive plasma environment in the controlled synthesis of CdO nanopyramidal structures is discussed as well.

Self-assembled low-dimensional nanomaterials via low-temperature plasma processing

Examples of successful fabrication of low-dimensional semiconducting nanomaterials in the Integrated Plasma-Aided Nanofabrication Facility are shown. Self-assembled size-uniform ZnO nanoparticles, ultra-high-aspect ratio Si nanowires, vertically aligned cadmium sulfide nanostructures, and quarternary semiconducting SiCAlN nanomaterial have been synthesized using inductively coupled plasma-assisted RF magnetron sputtering deposition. The observed increase in crystallinity and growth rates of the nanostructures are explained by using a model of plasma-enhanced adatom surface diffusion under conditions of local energy exchange between the ion flux and the growth surface. Issues related to plasma-based growth of low-dimensional semiconducting nanomaterials are discussed as well. © 2007 Elsevier B.V. All rights reserved.

Self-interaction of surface polaritons at the narrow-gap n-type semiconductor metal interface

The non-linear self-interaction of the potential surface polaritons (SP) which is due to the free carriers dispersion law where nonparabolicity is studied. The SP propagate at the interface between n-type semiconductor and a metal. The self interaction of the SP is shown to be different in semiconductors with normal and inverse zone structures. The results of the SP field envelope evolution are given. The obtained nonlinear frequency shift has been compared with shifts which are due to another self-interaction mechanisms. This comparison shows that the nonlinear self-interaction mechanism, which is due to free carriers spectrum nonparabolicity, is especially significant in narrow-gap semiconductor materials.

Third harmonic generation of the surface wave in the semiconductor-metal slowing-down structure

A nonlinear process is considered of the surface wave third harmonics generation in a slowing-down semiconductor-metal structure. The process is conditioned by non-parabolicity of the charge carrier dispersion law. It is shown that in narrow-gap semiconducting materials it is necessary to account for the process together with the surface wave second harmonics generation conditioned by nonlinearity of quasi-hydrodynamics and the Maxwell equations. The conclusion is made that the third harmonies amplitude in narrow-gap semiconductors may exceed substantially the signal amplitude at the 3w frequency in a gas plasma and be of the same order with the surface waves second harmonies amplitude.

Field-effect transistors based on self-organized molecular nanostripes

Charge transport properties in organic semiconductors depend strongly on molecular order. Here we demonstrate field-effect transistors where drain current flows through a precisely defined array of nanostripes made of crystalline and highly ordered molecules. The molecular stripes are fabricated across the channel of the transistor by a stamp-assisted deposition of the molecular semiconductors from a solution. As the solvent evaporates, the capillary forces drive the solution to form menisci under the stamp protrusions. The solute precipitates only in the regions where the solution is confined by the menisci once the critical concentration is reached and self-organizes into molecularly ordered stripes 100-200 nm wide and a few monolayers high. The charge mobility measured along the stripes is 2 orders of magnitude larger than the values measured for spin-coated thin films.

Logic-gate devices based on printed polymer semiconducting nanostripes

The applications of organic semiconductors in complex circuitry such as printed CMOS-like logic circuits demand miniaturization of the active structures to the submicrometric and nanoscale level while enhancing or at least preserving the charge transport properties upon processing. Here, we addressed this issue by using a wet lithographic technique, which exploits and enhances the molecular order in polymers by spatial confinement, to fabricate ambipolar organic field effect transistors and inverter circuits based on nanostructured single component ambipolar polymeric semiconductor. In our devices, the current flows through a precisely defined array of nanostripes made of a highly ordered diketopyrrolopyrrole-benzothiadiazole copolymer with high charge carrier mobility (1.45 cm2 V-1 s-1 for electrons and 0.70 cm2 V-1 s-1 for holes). Finally, we demonstrated the functionality of the ambipolar nanostripe transistors by assembling them into an inverter circuit that exhibits a gain (105) comparable to inverters based on single crystal semiconductors.

Charge transport study of high mobility polymer thin-film transistors based on thiophene substituted diketopyrrolopyrrole copolymers

In this paper, we report on the device physics and charge transport characteristics of high-mobility dual-gated polymer thin-film transistors with active semiconductor layers consisting of thiophene flanked DPP with thienylene-vinylene-thienylene (PDPP-TVT) alternating copolymers. Room temperature mobilities in these devices are high and can exceed 2 cm2 V-1 s-1. Steady-state and non-quasi-static measurements have been performed to extract key transport parameters and velocity distributions of charge carriers in this copolymer. Charge transport in this polymer semiconductor can be explained using a Multiple-Trap-and-Release or Monroe-type model. We also compare the activation energy vs. field-effect mobility in a few important polymer semiconductors to gain a better understanding of transport of DPP systems and make appropriate comparisons.

Characteristics of high-performance ambipolar organic field-effect transistors based on a diketopyrrolopyrrole-benzothiadiazole copolymer

In this paper, we report the device characteristics of ambipolar thin-film transistors (TFTs) based on a diketopyrrolopyrrole-benzothiadiazole copolymer. This polymer semiconductor exhibits the largest comparable electron and hole mobility values in a single organic semiconductor. The key to realizing such high mobility values, which are $0.5&cm}{2}/\hbox{V}̇\hbox{s, is molecular design, i.e., the use of suitable surface treatments of the source/drain contact electrodes and device architectures, particularly top-gate configurations. The subthreshold characteristics of the TFT devices are greatly improved by the use of dual-gate device geometry. We also report the first measurement of the velocity distribution of electron and hole velocities in an ambipolar organic semiconductor.