Atomically monodisperse nickel nanoclusters as highly active electrocatalysts for water oxidation.

Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 which initiate oxygen evolution at an amazingly low overpotential of ∼1.51 V (vs. RHE; η≈ 280 mV). The peak oxygen evolution current density (J) of ∼150 mA cm(-2) at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec(-1) is observed using Ni4(PET)8. These results are comparable to the state-of-the-art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm(-2) demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation.

Ternary chalcogenide micro-pseudocapacitors for on-chip energy storage.

We report the successful fabrication of a micro-pseudocapacitor based on ternary nickel cobalt sulfide for the first time, with performance substantially exceeding that of previously reported micro-pseudocapacitors based on binary sulfides. The CoNi2S4 micro-pseudocapacitor exhibits a maximum energy density of 18.7 mW h cm(-3) at a power density of 1163 mW cm(-3), and opens up an avenue for exploring a new family of ternary oxide/sulfide based micro-pseudocapacitors.

Low temperature processed complementary metal oxide semiconductor (CMOS) device by oxidation effect from capping layer.

In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190 °C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field.

Thin film complementary metal oxide semiconductor (CMOS) device using a single-step deposition of the channel layer.

We report, for the first time, the use of a single step deposition of semiconductor channel layer to simultaneously achieve both n- and p-type transport in transparent oxide thin film transistors (TFTs). This effect is achieved by controlling the concentration of hydroxyl groups (OH-groups) in the underlying gate dielectrics. The semiconducting tin oxide layer was deposited at room temperature, and the maximum device fabrication temperature was 350 °C. Both n and p-type TFTs showed fairly comparable performance. A functional CMOS inverter was fabricated using this novel scheme, indicating the potential use of our approach for various practical applications.

SnO2 anode surface passivation by atomic layer deposited HfO2 improves Li-ion battery performance.

For the first time, it is demonstrated that nanoscale HfO2 surface passivation layers formed by atomic layer deposition (ALD) significantly improve the performance of Li ion batteries with SnO2 -based anodes. Specifically, the measured battery capacity at a current density of 150 mAg(-1) after 100 cycles is 548 and 853 mAhg(-1) for the uncoated and HfO2 -coated anodes, respectively. Material analysis reveals that the HfO2 layers are amorphous in nature and conformably coat the SnO2 -based anodes. In addition, the analysis reveals that ALD HfO2 not only protects the SnO2 -based anodes from irreversible reactions with the electrolyte and buffers its volume change, but also chemically interacts with the SnO2 anodes to increase battery capacity, despite the fact that HfO2 is itself electrochemically inactive. The amorphous nature of HfO2 is an important factor in explaining its behavior, as it still allows sufficient Li diffusion for an efficient anode lithiation/delithiation process to occur, leading to higher battery capacity.

Enhanced rate performance of mesoporous Co(3)O(4) nanosheet supercapacitor electrodes by hydrous RuO(2) nanoparticle decoration.

Mesoporous cobalt oxide (Co3O4) nanosheet electrode arrays are directly grown over flexible carbon paper substrates using an economical and scalable two-step process for supercapacitor applications. The interconnected nanosheet arrays form a three-dimensional network with exceptional supercapacitor performance in standard two electrode configuration. Dramatic improvement in the rate capacity of the Co3O4 nanosheets is achieved by electrodeposition of nanocrystalline, hydrous RuO2 nanoparticles dispersed on the Co3O4 nanosheets. An optimum RuO2 electrodeposition time is found to result in the best supercapacitor performance, where the controlled morphology of the electrode provides a balance between good conductivity and efficient electrolyte access to the RuO2 nanoparticles. An excellent specific capacitance of 905 F/g at 1 A/g is obtained, and a nearly constant rate performance of 78% is achieved at current density ranging from 1 to 40 A/g. The sample could retain more than 96% of its maximum capacitance even after 5000 continuous charge-discharge cycles at a constant high current density of 10 A/g. Thicker RuO2 coating, while maintaining good conductivity, results in agglomeration, decreasing electrolyte access to active material and hence the capacitive performance.

P-type Cu(2)O/SnO bilayer thin film transistors processed at low temperatures.

P-type Cu2O/SnO bilayer thin film transistors (TFTs) with tunable performance were fabricated using room temperature sputtered copper and tin oxides. Using Cu2O film as capping layer on top of a SnO film to control its stoichiometry, we have optimized the performance of the resulting bilayer transistor. A transistor with 10 nm/15 nm Cu2O to SnO thickness ratio (25 nm total thickness) showed the best performance using a maximum process temperature of 170 °C. The bilayer transistor exhibited p-type behavior with field-effect mobility, on-to-off current ratio, and threshold voltage of 0.66 cm(2) V(-1) s(-1), 1.5×10(2), and -5.2 V, respectively. The advantages of the bilayer structure relative to single layer transistor are discussed.

Adsorption and electron-induced polymerization of methyl methacrylate on Ru(1010).

The adsorption and electron irradiation of methyl methacrylate (MMA) on a Ru(1010) surface have been studied using x-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD), and low energy ion scattering. TPD analysis indicates that a monolayer of MMA chemisorbs and dissociates on the Ru(1010) surface. The reaction products observed upon heating include H(2), CO, CO(2), and a small amount of MMA. Physisorbed multilayers of MMA desorb at temperatures around 170 K. Electron irradiation of physisorbed MMA at 140 K leads to a modification of the MMA film: The XPS spectra show an increase in thermal stability of the film with retention of the MMA structure, and indicate that electron irradiation induces polymerization. An increase in the electron bombardment fluence induces a degradation of the formed polymerized species and leads to the accumulation of carbon on the Ru surface. These results are relevant to the accumulation of carbon on surfaces of Ru films that serve as capping layers on MoSi multilayer mirrors used in extreme ultraviolet lithography.

Electron stimulated desorption of anionic fragments from films of pure and electron-irradiated thiophene.

The electron stimulated desorption (ESD) of anions is used to explore the effects of electron irradiation on a thiophene film and we report measurements for electron impact on multilayer thiophene condensed on a polycrystalline platinum substrate. Below 22 eV and at low electron dose, desorbed anions include H- (the dominant signal) as well as S-, CH2-, SH- and SCH2-. Yield functions show that anions are desorbed both by dissociative electron attachment (DEA) with resonances observed at 9.5, 11, and 16 eV, and for energies >13 eV, by dipolar dissociation (DD). An increase in the S- signal from electron irradiated (beam-damaged) thiophene films and the appearance of a new DEA resonance in the S- yield function at 6 eV are linked to rupture of the thiophene ring and the formation of sulfur-terminated products within the film. The threshold energy for ring rupture is 5 eV. The desorption of new anions such as C4H3S- (Thiophene-H)- is also observed from electron irradiated films and these likely arise from the decomposition of large radiation product molecules synthesized in the film. The yield functions of H-, S-, SH-, (Thiophene-H)-, and (Thiophene+H)- anions from irradiated thiophene films that have been annealed to 300 K, each exhibit a single resonant feature centered around 5.1 eV, suggesting that all signals derive from DEA to the same molecular radiation product. In contrast, only H- and S- are observed to desorb from films of 2-2-bithiophene and no resonance is seen below approximately 10 eV in the anion yield functions. These data suggest that electron irradiation causes formation of ring-opened oligomers, and that closed-ring or 'classical" oligomers, (similar to bithiophene) if formed, contribute little to the ESD of anions.

Adsorption and reaction of SO2 with a polycrystalline UO2 film: promotion of S-O bond cleavage by creation of O-defects and Na or Ca coadsorption.

To characterize UO(2) for its possible use in desulfurization applications, the interactions of molecular sulfur dioxide (SO(2)) with a polycrystalline uranium dioxide film have been studied by means of X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD), and low-energy ion scattering (LEIS). The stoichiometric, oxygen-deficient, calcium-precovered and sodium-precovered UO(2) surfaces have been characterized. The changes in oxide reactivity upon creation of oxygen vacancies and coadsorption of sodium and calcium have been studied. After creation of a reduced UO(2-x) surface (x approximately 0.44) via Ar(+) sputtering, the U 4f XPS spectrum shows conspicuous differences that are good indicators of the surface stoichiometry. Molecular SO(x) formation (x = 2-4) is observed after SO(2) deposition onto stoichiometric UO(2) and onto UO(2) precovered with small amounts (<1 ML) of Na or Ca; complete dissociation of SO(2) is not observed. Heating leads to desorption of the SO(x) species and to transformation of SO(2) to SO(3) and SO(3) to SO(4). On oxygen-deficient UO(2) and on UO(2) precovered with large Na or Ca coverages (> or =4 ML), both the formation of SO(x)= species and complete dissociation of SO(2) are observed. A higher thermal stability of the sulfur components is observed on these surfaces. In all cases for which dissociation occurs, the XPS peak of atomic sulfur shows similar structure: three different binding states are observed. The reactivity of oxygen-deficient UO(2) and sodium- and calcium-precovered UO(2) (coverages > or = 4 ML) is attributed to charge transfer into the antibonding LUMO of the adsorbed molecule.