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The quest to harvest untapped renewable infrared energy sources has led to significant research effort in design, fabrication and optimization of a self-biased rectenna that can operate without external bias voltage. At the heart of its design is the engineering of a high-frequency rectifier that can convert terahertz and infrared alternating current (AC) signals to usable direct current (DC). The Metal Insulator Metal (MIM) diode has been considered as one of the ideal candidates for the rectenna system. Its unparalleled ability to have a high response time is due to the fast, femtosecond tunneling process that governs current transport. This paper presents an overview of single, double and triple insulator MIM diodes that have been fabricated so far, in particular focusing on reviewing key figures of merit, such as zero-bias responsivity ( β 0 ), zero-bias dynamic resistance ( R 0 ) and asymmetry. The two major oxide contenders for MI n M diodes have been NiO and Al 2 O 3 , in combination with HfO 2 , Ta 2 O 5 , Nb 2 O 5 , ZnO and TiO 2 . The latter oxide has also been used in combination with Co 3 O 4 and TiO x . The most advanced rectennas based on MI 2 M diodes have shown that optimal ( β 0 and R 0 ) can be achieved by carefully tailoring fabrication processes to control oxide stoichiometry and thicknesses to sub-nanometer accuracy.

Inkjet printing offers an attractive method for the deposition of metal interconnects in electronic systems and enables a low-cost, environmentally friendly route to manufacture. However, virtually all current metal inkjet processes require post-deposition sintering treatments to achieve the optimum electrical conductivity, because the growth mechanism involves coalescence of discrete nanoparticles. A manufacturing process that reduces the number of steps by directly printing silver, removing the need to sinter the printed metal, would be highly advantageous. Here we describe a, sinter-free process that results in the direct printing of crystalline silver. This process exploits the chemistries developed for Atomic Layer Deposition (ALD), to form the basis of a new ink formulation, which we term; Reactive Organometallic inks (ROM). These ROM ink formulations are capable of depositing low temperature, high conductivity metal films, without the need for subsequent sintering treatments. To reduce the temperature for direct formation of metallic Ag, we have added an alcohol as a catalytic reducing agent to dissociate the organometallic component. Silver films printed from our novel ROM ink, on a glass substrate at 120 °C, are electrically conductive with a typical resistivity as low as 39.2% that of bulk silver, without the need for sintering.

In this research, the hafnium titanate oxide thin films, Ti x Hf 1- x O₂, with titanium contents of x = 0, 0.25, 0.9, and 1 were deposited on germanium substrates by atomic layer deposition (ALD) at 300 °C. The approximate deposition rates of 0.2 Å and 0.17 Å per cycle were obtained for titanium oxide and hafnium oxide, respectively. X-ray Photoelectron Spectroscopy (XPS) indicates the formation of GeO x and germanate at the interface. X-ray diffraction (XRD) indicates that all the thin films remain amorphous for this deposition condition. The surface roughness was analyzed using an atomic force microscope (AFM) for each sample. The electrical characterization shows very low hysteresis between ramp up and ramp down of the Capacitance-Voltage (CV) and the curves are indicative of low trap densities. A relatively large leakage current is observed and the lowest leakage current among the four samples is about 1 mA/cm² at a bias of 0.5 V for a Ti 0.9 Hf 0.1 O₂ sample. The large leakage current is partially attributed to the deterioration of the interface between Ge and Ti x Hf 1- x O₂ caused by the oxidation source from HfO₂. Consideration of the energy band diagrams for the different materials systems also provides a possible explanation for the observed leakage current behavior.

A powerful characterization technique, pulse capacitance-voltage (CV) technique, was used to investigate oxide traps before and after annealing for lanthanide zirconium oxide thin films deposited on n-type Si (111) substrates at 300 °C by liquid injection Atomic Layer Deposition (ALD). The results indicated that: (1) more traps were observed compared to the conventional capacitance-voltage characterization method in LaZrO x ; (2) the time-dependent trapping/de-trapping was influenced by the edge time, width and peak-to-peak voltage of a gate voltage pulse. Post deposition annealing was performed at 700 °C, 800 °C and 900 °C in N₂ ambient for 15 s to the samples with 200 ALD cycles. The effect of the high temperature annealing on oxide traps and leakage current were subsequently explored. It showed that more traps were generated after annealing with the trap density increasing from 1.41 × 10 12 cm -2 for as-deposited sample to 4.55 × 10 12 cm -2 for the 800 °C annealed one. In addition, the leakage current density increase from about 10 - ⁶ A/cm² at V g = +0.5 V for the as-deposited sample to 10 -3 A/cm² at V g = +0.5 V for the 900 °C annealed one.

We report here the synthesis and characterization of a family of copper(I) metal precursors based around cyclopentadienyl and isocyanide ligands. The molecular structures of several cyclopentadienylcopper(I) isocyanide complexes have been unambiguously determined by single-crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted the isopropyl isocyanide complex [(η(5)-C5H5)Cu(CN(i)Pr)] (2a) and the tert-butyl isocyanide complex [(η(5)-C5H5)Cu(CN(t)Bu)] (2b) as possible copper metal chemical vapor deposition (CVD) precursors. Further modification of the precursors with variation of the substituents on the cyclopentadienyl ligand system (varying between H, Me, Et, and (i)Pr) has allowed the affect that these changes would have on features such as stability, volatility, and decomposition to be investigated. As part of this study, the vapor pressures of the complexes 2b, [(η(5)-MeC5H4)Cu(CN(t)Bu)] (3b), [(η(5)-EtC5H4)Cu(CN(t)Bu)] (4b), and [(η(5)-(i)PrC5H4)Cu(CN(t)Bu)] (5b) over a 40-65 °C temperature range have been determined. Low-pressure chemical vapor deposition (LP-CVD) was employed using precursors 2a and 2b to synthesize thin films of metallic copper on silicon, gold, and platinum substrates under a H2 atmosphere. Analysis of the thin films deposited onto both silicon and gold substrates at substrate temperatures of 180 and 300 °C by scanning electron microscopy and atomic force microscopy reveals temperature-dependent growth features: Films grown at 300 °C are continuous and pinhole-free, whereas films grown at 180 °C consist of highly crystalline nanoparticles. In contrast, deposition onto platinum substrates at 180 °C shows a high degree of surface coverage with the formation of high-density, continuous, and pinhole-free thin films. Powder X-ray diffraction and X-ray photoelectron spectroscopy (XPS) both show the films to be high-purity metallic copper.

Oxide materials with large dielectric constants (so-called high -k dielectrics) have attracted much attention due to their potential use as gate dielectrics in Metal Oxide Semiconductor Field Effect Transistors (MOSFETs). A novel characterization (pulse capacitance-voltage) method was proposed in detail. The pulse capacitance-voltage technique was employed to characterize oxide traps of high -k dielectrics based on the Metal Oxide Semiconductor (MOS) capacitor structure. The variation of flat-band voltages of the MOS structure was observed and discussed accordingly. Some interesting trapping/detrapping results related to the lanthanide aluminum oxide traps were identified for possible application in Flash memory technology. After understanding the trapping/detrapping mechanism of the high -k oxides, a solid foundation was prepared for further exploration into charge-trapping non-volatile memory in the future.

Flash memory is the most widely used non-volatile memory device nowadays. In order to keep up with the demand for increased memory capacities, flash memory has been continuously scaled to smaller and smaller dimensions. The main benefits of down-scaling cell size and increasing integration are that they enable lower manufacturing cost as well as higher performance. Charge trapping memory is regarded as one of the most promising flash memory technologies as further down-scaling continues. In addition, more and more exploration is investigated with high -k dielectrics implemented in the charge trapping memory. The paper reviews the advanced research status concerning charge trapping memory with high -k dielectrics for the performance improvement. Application of high -k dielectric as charge trapping layer, blocking layer, and tunneling layer is comprehensively discussed accordingly.

In capacitance-voltage (C-V) measurements, frequency dispersion in high-k dielectrics is often observed. The frequency dependence of the dielectric constant (k-value), that is the intrinsic frequency dispersion, could not be assessed before suppressing the effects of extrinsic frequency dispersion, such as the effects of the lossy interfacial layer (between the high-k thin film and silicon substrate) and the parasitic effects. The effect of the lossy interfacial layer on frequency dispersion was investigated and modeled based on a dual frequency technique. The significance of parasitic effects (including series resistance and the back metal contact of the metal-oxide-semiconductor (MOS) capacitor) on frequency dispersion was also studied. The effect of surface roughness on frequency dispersion is also discussed. After taking extrinsic frequency dispersion into account, the relaxation behavior can be modeled using the Curie-von Schweidler (CS) law, the Kohlrausch-Williams-Watts (KWW) relationship and the Havriliak-Negami (HN) relationship. Dielectric relaxation mechanisms are also discussed.

La-doped zirconia films, deposited by ALD at 300°C, were found to be amorphous with dielectric constants (k-values) up to 19. A tetragonal or cubic phase was induced by post-deposition annealing (PDA) at 900°C in both nitrogen and air. Higher k-values (~32) were measured following PDA in air, but not after PDA in nitrogen. However, a significant dielectric relaxation was observed in the air-annealed film, and this is attributed to the formation of nano-crystallites. The relaxation behavior was modeled using the Curie-von Schweidler (CS) and Havriliak-Negami (HN) relationships. The k-value of the as-deposited films clearly shows a mixed CS and HN dependence on frequency. The CS dependence vanished after annealing in air, while the HN dependence disappeared after annealing in nitrogen.

Thin films of ceria (CeO(2)) have many applications, and their synthesis by liquid-injection MOCVD (metal-organic chemical vapor deposition) or ALD (atomic layer deposition) requires volatile precursor compounds. Here we report the synthesis of a series of homoleptic and heteroleptic Ce(IV) complexes with donor-functionalized alkoxide ligands mmp (1-methoxy-2-methylpropan-2-olate), dmap (1-(dimethylamino)propan-2-olate), and dmop (2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)propan-2-olate) and their potential as precursors for MOCVD and ALD of CeO(2). New complexes were synthesized by alcohol exchange reactions with [Ce(OBu(t))(4)]. [Ce(mmp)(4)] and [Ce(dmap)(4)] were both found to be excellent precursors for liquid-injection MOCVD of CeO(2), depositing high purity thin films with very low carbon contamination, and both have a large temperature window for diffusion controlled growth (350-600 °C for [Ce(mmp)(4)]; 300-600 °C for [Ce(dmap)(4)]). [Ce(mmp)(4)] is also an excellent precursor for liquid-injection ALD of CeO(2) using H(2)O as oxygen source and demonstrates self-limiting growth from 150 to 350 °C. [Ce(dmap)(4)] has lower thermal stability than [Ce(mmp)(4)] and does not show self-limiting growth in ALD. Heteroleptic complexes show a tendency to undergo ligand redistribution reactions to form mixtures in solution and are unsuitable as precursors for liquid-injection CVD.

Vertically aligned zinc oxide (ZnO) nanowires (NWs) have been grown by liquid injection Metal Organic Chemical Vapour Deposition, using oxygen donor adducts of Me2Zn. The growth and characterisation of the nanowires grown using [Me2Zn(L)] where L = monodentate ethers, tetrahydrofuran (C4H8O) (1), tetrahydropyran (C5H10O) (2), furan (C4H4O) (3) and the bidentate ethers, 1,2-dimethoxyethane (C4H12O2,) (4) 1,4-dioxane (C4H8O2) (5) and 1,4-thioxane (C4H8SO) (6) is discussed. Single crystal X-ray structures of (4), (5), (6) have been established and are included here. The ZnO NWs were deposited in the absence of a seed catalyst on Si(111) and F-doped SnO2/glass substrates over the temperature range 350-600 degrees C. X-ray diffraction (XRD) data shows that the nanowires grown from all adduct precursors were deposited in the wurtzitic phase.

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.

This article presents the design, construction, and test results of a linear ion trap, fabricated using digital light processing (DLP), which is a low-cost 3D layer-based manufacturing technique. The ion trap was incorporated into a portable mass spectrometer system and experimental mass spectrum was obtained for methamphetamine (m/z 182), cocaine (m/z 304), and rhodamine B (m/z 443), with a maximum observed resolution (FWHM) of 260. For rhodamine B, tandem MS capability is also demonstrated. The mass range (and resolution at higher m/z) of the instrument is also demonstrated by spectrum obtained from Ultramark (m/z 1621). The spectra obtained for the DLP trap occur at a considerably lower rf voltage than a rectilinear ion trap of similar size, which is a consequence of the hyperbolic electrode geometry and, hence, smaller r(0) in the DLP case. High mass range with low voltage operation is especially important with regard to 'in the field' applications requiring low power consumption for extended periods of operation., (2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.)

The optical properties of zinc oxide nanowires are critically influenced by the growth process. Herein, we describe a metal-organic chemical vapour deposition (MOCVD) process for the growth of ZnO nanowires with improved optical properties. A tetrahydrofuran adduct is used to control the reactivity of dimethylzinc to enable this. Vertically aligned zinc oxide nanowires have been grown on Si(111) substrates by liquid injection MOCVD, using a solution of [Me(2)Zn(tetrahydrofuran)] in the presence of oxygen. The ZnO morphology becomes nanowire-like in a narrow temperature range centred about 500 degrees C. Above and below this temperature range, the ZnO is deposited in the form of polycrystalline films. The ZnO nanowires grow from a polycrystalline nucleation layer, with the (0002) c-axis parallel to the Si[111] substrate orientation. High-resolution electron microscopy reveals a highly crystalline nanowire microstructure. Resonance enhanced ultraviolet Raman spectroscopy shows that the ratio of first- and second-order longitudinal optic modes is commensurate with electron-phonon coupling effects observed previously in ZnO nanostructures. Photoluminescence exhibits intense near band-edge emission with a full width at half-maximum of 110 meV at room temperature and shows negligible defect-related visible emission.

In this report, we present a prototype design of a quadrupole mass filter (QMF) with hyperbolic electrodes, fabricated at the University of Liverpool using digital light processing (DLP), a low-cost and lightweight 3D rapid prototyping (RP) technique. Experimental mass spectra are shown for H(2)(+), D(2)(+), and He(+) ions to provide proof of principle that the DLP mass filter is working as a mass analyzer in the low-mass range (1 to 10 amu). The performance of the DLP QMF has also been investigated for individual spectral peaks. Numerical simulations of the instrument were performed by coupling CPO and Liverpool QMS-2 programs to model both the ion source and mass filter, respectively, and the instrument is shown to perform as predicted by theory. DLP thus allows miniaturization of mass spectrometers at low cost, using hyperbolic (or other) geometries of mass analyzer electrodes that provide optimal ion manipulation and resolution for a given application. The potential of using RP fabrication techniques for developing miniature and microscale mass analyzers is also discussed.

Complexes of the early lanthanides with the donor-functionalized alkoxide ligand mmp (Hmmp = HOCMe(2)CH(2)OMe, 1-methoxy-2-methylpropan-2-ol) are excellent precursors for Metal Organic Chemical Vapor Deposition (MOCVD) and Atomic Layer Deposition (ALD) of lanthanide oxides; however, their coordination chemistry, which is the subject of this paper, is rather complex. Precursors for MOCVD and ALD of lanthanide oxides are prepared by the reaction of [Ln{N(SiMe(3))(2)}(3)] with 3 equiv of the alcohol Hmmp in toluene in the presence of 1 equiv of tetraglyme and are indefinitely stable in solution. Reaction of [Ln{N(SiMe(3))(2)}(3)] with 3 equiv of Hmmp in the absence of stabilizing Lewis bases gives complex condensed products with empirical formula [{Ln(mmp)(3-n)}(2)O(n)]. These condensed products show poor volatility and are unsatisfactory precursors for MOCVD or ALD of oxides. The cluster complex [La(3)(mu(3),kappa(2)-mmp)(2)(mu(2),kappa(2)-mmp)(3)(mmp)(4)] has been prepared by careful reaction of [La{N(SiMe(3))(2)}(3)] with 4 equiv of Hmmp and has been characterized by single-crystal X-ray diffraction. Salt metathesis reactions using M(mmp) (M = Li or Na) are unreliable routes to [Ln(mmp)(3)]. Crystals of the heterometallic cluster complex [NaLa(3)(mu(3)-OH)(mu(3),kappa(2)-mmp)(2)(mu(2),kappa(2)-mmp)(4)(mmp)(3)] were isolated from the reaction of [La(NO(3))(3)(tetraglyme)] with 3 equiv of Na(mmp), and crystals of [Li(kappa(2)-Hmmp)Pr(mu(2),eta(2)-mmp)(4))LiCl] were isolated from the reaction of PrCl(3) with 3 equiv of Li(mmp); both of these complexes have been characterized by single-crystal X-ray diffraction.

Femtosecond, subablation threshold photomodification of poly(methyl methacrylate) (PMMA) at 387 nm is explored to enable fabrication of optical components. Volatile fragment analysis (thermal desorption gas chromatography-mass spectrometry) and molecular weight distribution monitoring (size exclusion chromatography) suggest photochemical modification, involving direct cleavage of the polymer backbone and propagation via chain unzipping under formation of monomers, similar to the pyrolytic degradation of PMMA. Waveguides were produced in undoped, clinical-grade PMMA, showing an increased refractive index in the laser focal region (Dnmax=4x10(-3)).

It is proposed that by using the valence-band states in electron energy loss spectroscopy, high-spatial resolution maps of quantitative elemental composition may be acquired with high acquisition rates. Further, it is shown that by using the epsilon(2) spectrum instead of single scattering data, the noise in the observed transitions and associated maps is significantly reduced. The epsilon(2) spectra are derived through a Kramers-Kronig transformation from electron energy loss spectra obtained in a scanning transmission electron microscope. Using transitions that occur in the epsilon(2) absorption spectrum (<40eV), quantitative elemental maps for III-V device structures have been produced. An example is provided using the Ga 3d transition to map a GaInNAs/GaAs laser structure. Weaker transitions such as In 4d have also been used to verify the Ga elemental distribution.

Ammonolysis of reactive oxide precursors affords the vanadium(V) phase Ba(2)VO(3)N that is shown by X-ray and neutron powder diffraction and Raman spectroscopy to contain pseudotetrahedral VO(3)N(4-) anions. This is the first example of such species for the first transition series metals.

The effects of long-term exposure to aluminium on the development of Alzheimer-type neuropathological changes have been studied post-mortem in patients with chronic renal failure who did not have dialysis encephalopathy. Administration of aluminium-containing phosphate binding compounds appears to be a major factor in the accumulation of aluminium in the brain of dialysis patients. The mean serum aluminium concentrations determined during life and brain aluminium concentrations determined post-mortem correlated with both the duration and total amount of aluminium hydroxide administered to these patients. No correlation was found between the presence of bone aluminium and either the mean serum or brain aluminium concentration. Longitudinal monitoring of serum aluminium concentrations may provide a more reliable index than bone biopsy of brain aluminium concentrations in dialysis patients. Dynamic secondary ion mass spectrometry revealed focal accumulations of aluminium associated with cortical pyramidal neurones. The majority of patients also showed immunostaining in pyramidal neurones with an antibody to the N-terminal region of the beta/A4 amyloid precursor protein, while staining was absent in age-matched control cases. One-third of the patients exhibited beta/A4-positive amorphous senile plaques in the cerebral cortex. However, there was no clear correlation between either the presence and intensity of beta/A4 amyloid precursor immunostaining or the presence of senile plaques and the concentration of aluminium in the cerebral cortex. Cortical neurofibrillary tangles were not observed in any of the dialysis patients. These data suggest that it is unlikely that aluminium plays any major role in neurofibrillary tangle formation and that its putative role in senile plaque formation is likely to be only part of a complex cascade of changes.