Simon Romani

Permittivity enhancement of hafnium dioxide high-κ films by cerium doping

The effect of cerium doping on the dielectric properties of hafnium dioxide is reported. Thin films of cerium-doped hafnium oxide Cex–Hf1−xO2 (x=0.10,0.17,0.34) have been grown by liquid injection atomic layer deposition. After annealing at 900 °C, all films were transformed from an amorphous state into a stabilized cubic or tetragonal phase. As-deposited films of Ce0.1–Hf0.9O2 showed low hysteresis voltages and negligible flat band voltage shifts. After annealing to form the crystalline cubic or tetragonal phase, the relative permittivity (κ) increased from 25 to 32 at 100 kHz with leakage current densities at ±1 MV cm−1 of ∼1.58×10−5 A cm−2.The effect of cerium doping on the dielectric properties of hafnium dioxide is reported. Thin films of cerium-doped hafnium oxide Cex–Hf1−xO2 (x=0.10,0.17,0.34) have been grown by liquid injection atomic layer deposition. After annealing at 900 °C, all films were transformed from an amorphous state into a stabilized cubic or tetragonal phase. As-deposited films of Ce0.1–Hf0.9O2 showed low hysteresis voltages and negligible flat band voltage shifts. After annealing to form the crystalline cubic or tetragonal phase, the relative permittivity (κ) increased from 25 to 32 at 100 kHz with leakage current densities at ±1 MV cm−1 of ∼1.58×10−5 A cm−2.

Liquid injection atomic layer deposition of silver nanoparticles

Silver nanoparticles are being developed for applications in plasmonics, catalysts and analytical methods, amongst others. Herein, we demonstrate the growth of silver nanoparticles using an atomic layer deposition (ALD) process for the first time. The silver was deposited from pulses of the organometallic precursor (hfac)Ag(1,5-COD) ((hexafluoroacetylacetonato)silver(I)(1,5-cyclooctadiene)) dissolved in a 0.1 M toluene solution. Catalytic oxidative dehydrogenation of the silver was achieved using intermittent pulses of propanol. The effect of substrate temperature on the size and distribution of nanoparticles has been investigated over the temperature range 110-150 degrees C. Transmission electron microscopy reveals that the nanoparticles consist of face centred cubic, facetted silver crystallites. The localized surface plasmon modes of the nanoparticles have been investigated using electron energy loss spectroscopy mapping. The distributions of plasmons within the ALD nanoparticles are comparable to those grown by solution methods. Both dipolar and quadrupolar resonant modes are observed, which is consistent with previous discrete dipole approximation models. Energy loss mapping of a loss feature at 8.1 eV reveals that it correlates with the bulk or volume region of the silver nanoparticles investigated here.

Computationally Assisted Identification of Functional Inorganic Materials

Modules of Desire Using computational methods to design materials with specific properties has found some limited success. Dyer et al. (p. 847, published online 11 April) have devised a method, based on extended module materials assembly, that combines chemical intuition and ab initio calculations starting from fragments or modules of structure types that show the desired functionality. The method was tested by identifying materials suitable for a solid oxide fuel cell cathode. A method using extended building blocks is developed for computationally viable predictions of stable crystal structures. The design of complex inorganic materials is a challenge because of the diversity of their potential structures. We present a method for the computational identification of materials containing multiple atom types in multiple geometries by ranking candidate structures assembled from extended modules containing chemically realistic atomic environments. Many existing functional materials can be described in this way, and their properties are often determined by the chemistry and electronic structure of their constituent modules. To demonstrate the approach, we isolated the oxide Y2.24Ba2.28Ca3.48Fe7.44Cu0.56O21, with a largest unit cell dimension of over 60 angstroms and 148 atoms in the unit cell, by using a combination of this method and experimental work and show that it has the properties necessary to function as a solid oxide fuel-cell cathode.

Atomic layer deposition of Ga-doped ZnO transparent conducting oxide substrates for CdTe-based photovoltaics

The atomic layer deposition of gallium doped zinc oxide films is investigated as a method of fabricating transparent conducting oxide substrates for cadmium telluride based photovoltaic cells. The growth parameters and properties of gallium-doped ZnO were established for a range of dopant concentrations. 1 at. % gallium-doped films exhibited the lowest electrical sheet resistances and were selected as substrates to deposit Cd1−xZnxS/CdTe photovoltaic cells. The average current density–voltage characteristics of 16 cells under AM1.5 illumination yielded a conversion efficiency of 10.8% and a fill-factor of 65%.

Synthesis of high surface area CuMn2O4 by supercritical anti-solvent precipitation for the oxidation of CO at ambient temperature

A series of high surface area nanocrystalline copper manganese oxide catalysts have been prepared by supercritical anti-solvent (SAS) precipitation using CO2 and tested for the ambient temperature oxidation of CO. The catalysts were prepared by precipitation from an ethanol/metal acetate solution and the addition of small quantities of water was found to result in a mixed acetate precursor with surface areas >200 m2 g−1, considerably higher than those prepared by conventional precipitation methods. The surface area of the final calcined mixed oxide was found to be dependent upon the initial water concentration. XRD and FT-IR analysis indicated that the addition of water promoted the formation of carbonate species in the amorphous acetate precursor, with high resolution TEM and STEM showing the material to consist of spherical agglomerations of fibrous strings of ca. 30 nm length. This is in contrast to the material prepared in the absence of water, using the same SAS methodology, which typically yields quasi-spherical particles of 100 nm size.

Interaction of hydrogen with chemical vapor deposition diamond surfaces: A thermal desorption study

The interaction of hydrogen with a chemical vapor deposition (CVD) deposited polycrystalline film on Si(100), cleaned by heating to 1500 K, has been examined. No adsorption is observed unless prior activation with a hot filament is carried out. However atomic H thereby created is found to adsorb with a high sticking probability, subsequently desorbing in the temperature range 1100–1225 K. Etching of the diamond surface, producing gaseous methane and ethane is also seen. The reactivity patterns are rather similar to those observed on C(100) and C(111) surfaces, suggesting these are suitable model substrates for the study of reaction mechanisms associated with CVD diamond growth. However, a major difference is also seen in that a mixture of hydrogen, silane, and disilane, with other minority species, is seen to evolve from the surface of the CVD diamond film at 1275 K when exposed to the reacting gas and is not detected from single‐crystal diamond surfaces. The results indicate that this arises from the sel...

The effect of metallization on the ohmic contact resistivity to heavily B-doped polycrystalline diamond films

Three metallization schemes, namely Al/Si, Ti-Au and TiWN-Au contacts on B-doped polycrystalline diamond films have been compared. After annealing at 450/spl deg/C in nitrogen Al/Si contacts show the lowest contact resistivity in the order of /spl sim/10/sup -7/ /spl Omega/ cm/sup 2/. TiWN-Au contacts were found to be the most stable contact system in view of interdiffusion and oxidation. Ti-Au contacts show a catastrophic interdiffusion at moderate annealing temperatures and strong oxidation at the very surface. High surface boron doping concentrations lead to low contact resistivities. At sufficient high doping levels current transport through the metal-diamond barrier is due to field emission. >

Morphotropic Phase Boundary in the Pb‐Free (1 − x)BiTi3/8Fe2/8Mg3/8O3–xCaTiO3 System: Tetragonal Polarization and Enhanced Electromechanical Properties

Lead-free bismuth-based perovskite oxides with polarization directed along the [001](p) primitive perovskite unit cell edge, analogous to tetragonal PbTiO3, are synthesized at ambient pressure. Enhanced piezoelectric properties, large polarizations, and high depolarization temperatures are observed in the wide morphotropic phase boundary region formed with a rhombohedral phase, with up to 92.5% Bi on the perovskite A site.

Single sublattice endotaxial phase separation driven by charge frustration in a complex oxide.

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation.

Atomic layer deposition of germanium-doped zinc oxide films with tuneable ultraviolet emission

Thin films of germanium-doped zinc oxide have been deposited by atomic layer deposition. The zinc oxide matrix was grown from cyclic pulses of diethylzinc and water vapour over the temperature range of 100–350 °C substrate temperature. Tetramethoxygermanium(IV) was employed as a novel germanium-doping source, which could be incorporated up to 17 at%. At 2.1 at% germanium doping at a deposition temperature of 250 °C, the maximum carrier concentration of 2.14 × 1020 cm−3 coincides with a carrier mobility of approximately 5 cm2 V−1 s−1. No evidence for the formation of nanometre-scale germanium clustering or segregation was observed in the X-ray diffraction patterns or high-resolution transmission electron micrographs of these films. The near band edge photoluminescence shifts to higher energy with increasing germanium incorporation either by the Burstein–Moss mechanism or by alloy formation.