Reduced electron recombination of dye-sensitized solar cells based on TiO 2 spheres consisting of ultrathin nanosheets with [001] facet exposed

An anatase TiO 2 material with hierarchically structured spheres consisting of ultrathin nanosheets with 100% of the [001] facet exposed was employed to fabricate dye-sensitized solar cells (DSC s). Investigation of the electron transport and back reaction of the DSCs by electrochemical impedance spectroscopy showed that the spheres had a threefold lower electron recombination rate compared to the conventional TiO 2 nanoparticles. In contrast, the effective electron diffusion coefficient, D n, was not sensitive to the variation of the TiO 2 morphology. The TiO 2 spheres showed the same Dn as that of the nanoparticles. The influence of TiCl 4 post-treatment on the conduction band of the TiO 2 spheres and on the kinetics of electron transport and back reactions was also investigated. It was found that the TiCl 4 post-treatment caused a downward shift of the TiO 2 conduction band edge by 30 meV. Meanwhile, a fourfold increase of the effective electron lifetime of the DSC was also observed after TiCl4 treatment. The synergistic effect of the variation of the TiO 2 conduction band and the electron recombination determined the open-circuit voltage of the DSC. © 2012 Wang et al.

Interface control of surface photochemical reactivity in ultrathin epitaxial ferroelectric films

Asymmetrical electrical boundary conditions in (001)-oriented Pb(Zr 0.2TiO0.8)O3 (PZT) epitaxial ultrathin ferroelectric films are exploited to control surface photochemical reactivity determined by the sign of the surface polarization charge. It is shown that the preferential orientation of polarization in the as-grown PZT layer can be manipulated by choosing an appropriate type of bottom electrode material. PZT films deposited on the SrRuO3 electrodes exhibit preferential upward polarization (C) whilst the same films grown on the (La,Sr)CoO 3-electrodes are polarized downward (C-). Photochemical activity of the PZT surfaces with different surface polarization charges has been tested by studying deposition of silver nanoparticles from AgNO3 solution under UV irradiation. PZT surfaces with preferential C orientation possess a more active surface for metal reduction than their C- counterparts, evidenced by large differences in the concentration of deposited silver nanoparticles. This effect is attributed to band bending at the bottom interface which varies depending on the difference in work functions of PZT and electrode materials.

Effect of Coulomb blockade, gold resistance, and thermal expansion on the electrical resistance of ultrathin gold films

Controlling the electrical resistance of granular thin films is of great importance for many applications, yet a full understanding of electron transport in such films remains a major challenge. We have studied experimentally and by model calculations the temperature dependence of the electrical resistance of ultrathin gold films at temperatures between 2 K and 300 K. Using sputter deposition, the film morphology was varied from a discontinuous film of weakly coupled meandering islands to a continuous film of strongly coupled coalesced islands. In the weak-coupling regime, we compare the regular island array model, the cotunneling model, and the conduction percolation model with our experimental data. We show that the tunnel barriers and the Coulomb blockade energies are important at low temperatures and that the thermal expansion of the substrate and the island resistance affect the resistance at high temperatures. At low temperatures our experimental data show evidence for a transition from electron cotunneling to sequential tunneling but the data can also be interpreted in terms of conduction percolation. The resistivity and temperature coefficient of resistance of the meandering gold islands are found to resemble those of gold nanowires. We derive a simple expression for the temperature at which the resistance changes from non-metal-like behavior into metal-like behavior. In the case of strong island coupling, the total resistance is solely determined by the Ohmic island resistance.

Ultrathin hematite films deposited layer-by-layer on TiO2 underlayer for efficient water splitting under visible light

Ultrathin hematite (α-Fe2O3) film deposited on a TiO2 underlayer as a photoanode for photoelectrochemical water splitting was described. The TiO2 underlayer was coated on conductive fluorine-doped tin oxide (FTO) glass by spin coating. The hematite films were formed layer-by-layer by repeating the separated two-phase hydrolysis-solvothermal reaction of iron(III) acetylacetonate and aqueous ammonia. A photocurrent density of 0.683 mA cm−2 at +1.5 V vs. RHE (reversible hydrogen electrode) was obtained under visible light (>420 nm, 100 mW cm−2) illumination. The TiO2 underlayer plays an important role in the formation of hematite film, acting as an intermediary to alleviate the dead layer effect and as a support of large surface areas to coat greater amounts of Fe2O3. The as-prepared photoanodes are notably stable and highly efficient for photoelectrochemical water splitting under visible light. This study provides a facile synthesis process for the controlled production of highly active ultrathin hematite film and a simple route for photocurrent enhancement using several photoanodes in tandem.

Room temperature gas sensing properties of ultrathin carbon nanotubes by surfactant-free dip coating

Large-scale production of reliable carbon nanotubes (CNTs) based gas sensors involves the development of scalable and reliable processes for the fabrication of films with controlled morphology. Here, we report for the first time on highly scalable, ultrathin CNT films, to be employed as conductometric sensors for NO2 and NH3 detection at room temperature. The sensing films are produced by dip coating using dissolved CNTs in chlorosulfonic acid as a working solution. This surfactant-free approach does not require any post-treatment for the removal of dispersants or any CNTs functionalization, thus promising high quality CNTs for better sensitivity and low production costs. The effect of CNT film thickness and defect density on the gas sensing properties has been investigated. Detection limits of 1 ppm for NO2 and 7 ppm for NH3 have been achieved at room temperature. The experimental results reveal that defect density and film thickness can be controlled to optimize the sensing response. Gas desorption has been accelerated by continuous in-situ UV irradiation.

Thermoelectric power in ultrathin films, quantum wires and carbon nanotubes under classically large magnetic field: Simplified theory and relative comparison

We study the thermoelectric power under classically large magnetic field (TPM) in ultrathin films (UFs), quantum wires (QWs) of non-linear optical materials on the basis of a newly formulated electron dispersion law considering the anisotropies of the effective electron masses, the spin-orbit splitting constants and the presence of the crystal field splitting within the framework of k.p formalism. The results of quantum confined III-V compounds form the special cases of our generalized analysis. The TPM has also been studied for quantum confined II-VI, stressed materials, bismuth and carbon nanotubes (CNs) on the basis of respective dispersion relations. It is found taking quantum confined CdGeAs2, InAs, InSb, CdS, stressed n-InSb and Bi that the TPM increases with increasing film thickness and decreasing electron statistics exhibiting quantized nature for all types of quantum confinement. The TPM in CNs exhibits oscillatory dependence with increasing carrier concentration and the signature of the entirely different types of quantum systems are evident from the plots. Besides, under certain special conditions, all the results for all the materials gets simplified to the well-known expression of the TPM for non-degenerate materials having parabolic energy bands, leading to the compatibility test. (C) 2009 Elsevier B.V. All rights reserved.

Use of the liquid-liquid interface for generating ultrathin nanocrystalline films of metals, chalcogenides, and oxides

The air-water interface has traditionally been employed to prepare particle assemblies and films of metals and semiconductors. The interface between water and an organic liquid, however, has not been investigated sufficiently for possible use in preparing nanocrystals and thin films of materials. In this article, we demonstrate the use of the liquid-liquid interface as a medium for preparing ultrathin films of metals, chalcogenides and oxides. The method involves the reaction at the interface between a metal-organic compound in the organic layer and an appropriate reagent for reduction, sulfidation, etc. in the aqueous layer. Some of the materials discussed are nanocrystalline films of gold, CuS, CuSe, CuO, and Cu(OH)(2) formed at the liquid-liquid interface. The results reported in this article should demonstrate the versatility and potential of the liquid-liquid interface for preparing nanomaterials and ultrathin films and encourage further research in this area. (c) 2005 Elsevier Inc. All rights reserved.

Use of the liquid-liquid interface for generating ultrathin nanocrystalline films of metals,chalcogenides,and oxides

The air-water interface has traditionally been employed to prepare particle assemblies and films of metals and semiconductors. The interface between water and an organic liquid, however, has not been investigated sufficiently for possible use in preparing nanocrystals and thin films of materials. In this article, we demonstrate the use of the liquid-liquid interface as a medium for preparing ultrathin films of metals, chalcogenides and oxides. The method involves the reaction at the interface between a metal-organic compound in the organic layer and an appropriate reagent for reduction, sulfidation, etc. in the aqueous layer. Some of the materials discussed are nanocrystalline films of gold, CuS, CuSe, CuO, and Cu(OH)(2) formed at the liquid-liquid interface. The results reported in this article should demonstrate the versatility and potential of the liquid-liquid interface for preparing nanomaterials and ultrathin films and encourage further research in this area.

Influence of External Light Waves on the Thermoelectric Power Under Strong Magnetic Field in Ultrathin Films, Quantum Wires and Quantum Dots of Optoelectronic Materials

In this paper, an attempt is made to study the influence of external light waves on the thermoelectric power under strong magnetic field (TPSM) in ultrathin films (UFs), quantum wires (QWs) and quantum dots (QDs) of optoelectronic materials whose unperturbed dispersion relation of the conduction electrons are defined by three and two band models of Kane together with parabolic energy bands on the basis of newly formulated electron dispersion laws in each case. We have plotted the TPSM as functions of film thickness, electron concentration, light intensity and wavelength for UFs, QWs and ODs of InSb, GaAs, Hg1-xCdxTe and In1-xGaxAsyP1-y respectively. It appears from the figures that for UFs, the TPSM increases with increasing thickness in quantum steps, decreases with increasing electron degeneracy exhibiting entirely different types of oscillations and changes with both light intensity and wavelength and these two latter types of plots are the direct signature of light waves on opto-TPSM. For QWs, the opto-TPSM exhibits rectangular oscillations with increasing thickness and shows enhanced spiky oscillations with electron concentration per unit length. For QDs, the opto-TPSM increases with increasing film thickness exhibiting trapezoidal variations which occurs during quantum jumps and the length and breadth of the trapezoids are totally dependent on energy band constants. Under the condition of non-degeneracy, the results of opto-TPSM gets simplified into the well-known form of classical TPSM equation which the function of three constants only and being invariant of the signature of band structure.

Instability and dewetting of ultrathin solid viscoelastic films on homogeneous and heterogeneous substrates

Instability and dewetting engendered by the van der Waals force in soft thin (<100 nm) linear viscoelastic solid (e. g., elastomeric gel) films on uniform and patterned surfaces are explored. Linear stability analysis shows that, although the elasticity of the film controls the onset of instability and the corresponding critical wavelength, the dominant length-scale remains invariant with the elastic modulus of the film. The unstable modes are found to be long-wave, for which a nonlinear long-wave analysis and simulations are performed to uncover the dynamics and morphology of dewetting. The stored elastic energy slows down the temporal growth of instability significantly. The simulations also show that a thermodynamically stable film with zero-frequency elasticity can be made unstable in the presence of physico-chemical defects on the substrate and can follow an entirely different pathway with far fewer holes as compared to the viscous films. Further, the elastic restoring force can retard the growth of a depression adjacent to the hole-rim and thus suppress the formation of satellite holes bordering the primary holes. These findings are in contrast to the dewetting of viscoelastic liquid films where nonzero frequency elasticity accelerates the film rupture and promotes the secondary instabilities. Thus, the zero-frequency elasticity can play a major role in imposing a better-defined long-range order to the dewetted structures by arresting the secondary instabilities. (C) 2011 American Institute of Physics. doi: 10.1063/1.3554748]

Effect of granularity on the insulator-superconductor transition in ultrathin Bi films

We have studied the insulator-superconductor transition (IST) by tuning the thickness in quench-condensed Bi films. The resistive transitions of the superconducting films are smooth and can be considered to represent ''homogeneous'' films. The observation of an IST very close to the quantum resistance for pairs R-square(N) similar to h/4e(2) on several substrates supports this idea. The relevant length scales here are the localization length, and the coherence length. However, at the transition, the localization length is much higher than the superconducting coherence length, contrary to expectation for a "homogeneous" transition. This suggests the invalidity of a purely fermionic model for the transition. Furthermore, the current-voltage characteristics of the superconducting films are hysteretic, and show the films to be granular. The relevant energy scales here are the Josephson coupling energy and the charging energy. However, Josephson coupling energies (E-J) and the charging energies (E-c) at the IST, they are found to obey the relation E-j < E-c. This is again contrary to expectation, for the IST in a granular or inhomogeneous system. Hence, a purely bosonic picture of the transition is also inconsistent with our observations. We conclude that the IST observed in our experiments may be either an intermediate case between the fermioinc and bosonic mechanisms, or in a regime of charge and vortex dynamics for which a quantitative analysis has not yet been done.

Nonvolatile unipolar resistive switching in ultrathin films of graphene and carbon nanotubes

We report unipolar resistive switching in ultrathin films of chemically produced graphene (reduced graphene oxide) and multiwalled carbon nanotubes. The two-terminal devices with yield >99% are made at room temperature by forming continuous films of graphene of thickness similar to 20 nm on indium tin oxide coated glass electrode, followed by metal (Au or Al) deposition on the film. These memory devices are nonvolatile, rewritable with ON/OFF ratios up to similar to 10(5) and switching times up to 10 mu s. The devices made of MWNT films are rewritable with ON/OFF ratios up to similar to 400. The resistive switching mechanism is proposed to be nanogap formation and filamentary conduction paths. (C) 2011 Elsevier Ltd. All rights reserved.

Vortex dynamics and upper critical fields in ultrathin Bi films

Current-voltage (I-V) characteristics of quench condensed, superconducting, ultrathin Bi films in a magnetic field are reported. These I-V's show hysteresis for all films, grown both with and without thin Ge underlayers. Films on Ge underlayers, close to superconductor-insulator transition, show a peak in the critical current, indicating a structural transformation of the vortex solid. These underlayers, used to make the films more homogeneous, are found to be more effective in pinning the vortices. The upper critical fields (B-c2) of these films are determined from the resistive transitions in perpendicular magnetic field. The temperature dependence of the upper critical field is found to differ significantly from Ginzburg-Landau theory, after modifications for disorder.

Pristine, adherent ultrathin gold nanowires on substrates and between pre-defined contacts via a wet chemical route

We demonstrate a simple strategy of obtaining clean, ultrathin single crystal Au nanowires on substrates and interconnecting pre-defined contacts with an insight into the growth mechanism. The pristine nature enables electron transport measurement through such ultrathin wires and opens up possibilities of exploring its properties for a wide range of applications.