Granular Metal Films Research Articles

The effect of metal–insulator interface interactions on electrical transport in granular metals

We present an in-depth study of metal–insulator interfaces within granular metal (GM) films and correlate their interfacial interactions with structural and electrical transport properties. Nominally 100 nm thick GM films of Co and Mo dispersed within yttria-stabilized zirconia (YSZ), with volumetric metal fractions (φ) from 0.2–0.8, were grown by radio frequency co-sputtering from individual metal and YSZ targets. Scanning transmission electron microscopy and DC transport measurements find that the resulting metal islands are well-defined with 1.7–2.6 nm average diameters and percolation thresholds between φ = 0.4–0.5. The room temperature conductivities for the φ = 0.2 samples are several orders of magnitude larger than previously-reported for GMs. X-ray photoemission spectroscopy indicates both oxygen vacancy formation within the YSZ and band-bending at metal–insulator interfaces. The higher-than-predicted conductivity is largely attributed to these interface interactions. In agreement with recent theory, interactions that reduce the change in conductivity across the metal–insulator interface are seen to prevent sharp conductivity drops when the metal concentration decreases below the percolation threshold. These interface interactions help interpret the broad range of conductivities reported throughout the literature and can be used to tune the conductivities of future GMs.

Atomically Smooth Single-Crystalline Platform for Low-Loss Plasmonic Nanocavities.

Nanoparticle-on-mirror plasmonic nanocavities, capable of extreme optical confinement and enhancement, have triggered state-of-the-art progress in nanophotonics and development of applications in enhanced spectroscopies. However, the optical quality factor and thus performance of these nanoconstructs are undermined by the granular polycrystalline metal films (especially when they are optically thin) used as a mirror. Here, we report an atomically smooth single-crystalline platform for low-loss nanocavities using chemically synthesized gold microflakes as a mirror. Nanocavities constructed using gold nanorods on such microflakes exhibit a rich structure of plasmonic modes, which are highly sensitive to the thickness of optically thin (down to ∼15 nm) microflakes. The microflakes endow nanocavities with significantly improved quality factor (∼2 times) and scattering intensity (∼3 times) compared with their counterparts based on deposited films. The developed low-loss nanocavities further allow for the integration with a mature platform of fiber optics, opening opportunities for realizing nanocavity-based miniaturized photonic devices for practical applications.

Divergence of the dielectric constant in ultrathin granular metal films near the percolation threshold

We report on the electronic and optical properties of ultrathin granular films. We demonstrate that the static dielectric constant increases with thickness in the dielectric regime and diverges at the critical thickness, as predicted by classical percolation theory. However, for thicker samples, the dc conductivity does not obey scaling laws due to the presence of tunneling conduction. In this region the dielectric constant is positive, and the electronic transport is not metallic but can be described by Jonscher’s universal power law, even though there is a Drude-like response indicating the presence of free charge carriers. Only for thicker films when the dielectric constant becomes negative is there metallic conduction.

Thickness induced metal to insulator charge transport and unusual hydrogen response in granular palladium nanofilms.

This work reports a systematic study of the evolution of charge transport properties in granular ultra-thin films of palladium of thicknesses varying between 6 nm and 2 nm. While the films with thickness >4 nm exhibit metallic behaviour, that at 3 nm thickness undergoes a metal-insulator transition at 19.5 K. In contrast, the 2 nm thick film remained insulating at all temperatures, with transport following Mott's variable range hopping. At room temperature, while the thicker films exhibit resistance decrease upon H2 exposure, the insulating film showed an anomalous initial resistance increase before switching to a subsequent decrease. The nanostructure dependent transport and the ensuing H2 response is modeled on a percolation model, which also explores the relevance of film thickness as a macroscopic control parameter to engineer the desired system response in granular metal films.

Charging of highly resistive granular metal films

We have used the scanning Kelvin probe microscopy technique to monitor the charging process of highly resistive granular thin films. The sample is connected to two leads and is separated by an insulator layer from a gate electrode. When a gate voltage is applied, charges enter from the leads and rearrange across the sample. We find very slow processes with characteristic charging times exponentially distributed over a wide range of values, resulting in a logarithmic relaxation to equilibrium. After the gate voltage has been switched off, the system again relaxes logarithmically slowly to the new equilibrium. The results cannot be explained with diffusion models, but most of them can be understood with a hopping percolation model, in which the localization length is shorter than the typical site separation. The technique is very promising for the study of slow phenomena in highly resistive systems and will be able to estimate the conductance of these systems when direct macroscopic measurement techniques are not sensitive enough.

Resistivity minimum in granular composites and thin metallic films

We analyze the temperature dependence of conductivity in thick granular ferromagnetic compounds NiSiO2 and in thin weakly coupled films of Fe, Ni and Py in vicinity of metal-insulator transition. Development of resistivity minimum followed by a logarithmic variation of conductivity at lower temperatures is attributed to granular structure of compounds and thin films fabricated by conventional deposition techniques. Resistivity minimum is identified as a transition between temperature dependent intra-granular metallic conductance and thermally activated inter-granular tunneling.

Melting behavior of Sn x (SiO 2 ) 100− x granular metal films

We have prepared a series of Sn x SiO 2 ) 100− x granular metal films by RF magnetron sputtering with nominal Sn compositions from x = 30 to x = 90 at. %. X-ray diffraction and transmission electron microscopy measurements confirm that these films consist of small Sn particles, ranging from about 10 nm to 200 nm in mean diameter, embedded in an amorphous SiO 2 matrix. These measurements also indicate that the mean Sn particle size decreases and the particle size distribution becomes more narrow as the Sn concentration is reduced. A differential scanning calorimeter has been used to study the size dependence of the melting temperature of the Sn particles. The melting temperature has been found to be increasingly depressed from the bulk value as the Sn particle size decreases. No evidence of an enhancement in the melting temperature at any particle size has been found. The evolution of the melting behavior of each sample with repeated melting and solidification cycles has also been studied.

Theory of percolation and tunneling regimes in nanogranular metal films

Nanogranular metal composites, consisting of immiscible metallic and insulating phases deposited on a substrate, are characterized by two distinct electronic transport regimes depending on the relative amount of the metallic phase. At sufficiently large metallic loadings, granular metals behave as percolating systems with a well-defined critical concentration above which macroscopic clusters of physically connected conductive particles span the entire sample. Below the critical loading, granular metal films are in the dielectric regime, where current can flow throughout the composite only via hopping or tunneling processes between isolated nanosized particles or clusters. In this case transport is intrinsically non-percolative in the sense that no critical concentration can be identified for the onset of transport. It is shown here that, although being very different in nature, these two regimes can be described by treating percolation and hopping on equal footing. By considering general features of the microstructure and of the electrical connectedness, the concentration dependence of the dc conductivity of several nanogranular metal films is reproduced to high accuracy within an effective medium approach. In particular, fits to published experimental data enable us to extract the values of microscopic parameters that govern the percolation and tunneling regimes, explaining thus the transport properties observed in nanogranular metal films.

Conductance of island and granular metal films

Results of measurements of the specific surface conductance of island metal films at different temperatures are presented. The study of conduction allowed us to establish processes, which determine the transfer of charge carriers in granular and island metal structures. These processes determine the excess charge carriers concentration in film and, on the other hand, characterize the transfer speed of excess charge carriers from one island to another (i.e. mobility). Moreover, these processes occur independently from each other.

Signatures of electronic phase separation in the Hall effect of anisotropically strained La0.67Ca0.33MnO3 films

Systematic transport measurements have been performed on a series of La0.67Ca0.33MnO3 thin films with varying degrees of anisotropic strain. The strain is induced via epitaxial growth on NdGaO3(001) substrates and varied by controlling the thermal annealing time. An antiferromagnetic insulating (AFI) state, possibly associated with charge ordering, emerges upon thermal annealing. The Hall effect in these materials exhibits features that are indicative of a percolative phase transition and correlate closely with the emergence of the AFI state. In the paramagnetic phase, the Hall resistivity takes on two slopes in all samples: a decreasing negative slope with increasing temperature at low fields, which is attributed to the carrier hopping motion, and an almost temperature independent positive slope at high fields due to diffusive transport of holes. Significantly, the crossover fields of the Hall resistivity slope at different temperatures correspond to the same magnetization, which is interpreted as the critical point of a magnetic field-driven percolative phase transition. At lower temperatures near the zero-field metal–insulator transition, pronounced enhancement of the Hall coefficient with the development of the AFI state is observed. The enhancement peaks near the magnetic field-driven percolation; its magnitude correlates with the strength of the AFI state and is suppressed with the melting of the AFI state by an in-plane magnetic field. The observations resemble many features of the enhancement of the Hall coefficient in granular metal films near the composition-driven percolation.

A Bipolar Electrochemical Approach to Constructive Lithography: Metal/Monolayer Patterns via Consecutive Site-Defined Oxidation and Reduction

Experimental evidence is presented, demonstrating the feasibility of a surface-patterning strategy that allows stepwise electrochemical generation and subsequent in situ metallization of patterns of carboxylic acid functions on the outer surfaces of highly ordered OTS monolayers assembled on silicon or on a flexible polymeric substrate. The patterning process can be implemented serially with scanning probes, which is shown to allow nanoscale patterning, or in a parallel stamping configuration here demonstrated on micrometric length scales with granular metal film stamps sandwiched between two monolayer-coated substrates. The metal film, consisting of silver deposited by evaporation through a patterned contact mask on the surface of one of the organic monolayers, functions as both a cathode in the printing of the monolayer patterns and an anodic source of metal in their subsequent metallization. An ultrathin water layer adsorbed on the metal grains by capillary condensation from a humid atmosphere plays the double role of electrolyte and a source of oxidizing species in the pattern printing process. It is shown that control over both the direction of pattern printing and metal transfer to one of the two monolayer surfaces can be accomplished by simple switching of the polarity of the applied voltage bias. Thus, the patterned metal film functions as a consumable "floating" stamp capable of two-way (forward-backward) electrochemical transfer of both information and matter between the contacting monolayer surfaces involved in the process. This rather unusual electrochemical behavior, resembling the electrochemical switching in nanoionic devices based on the transport of ions in solid ionic-electronic conductors, is derived from the nanoscale thickness of the water layer acting as an electrolyte and the bipolar (cathodic-anodic) nature of the water-coated metal grains in the metal film. The floating stamp concept introduced in this report paves the way to a series of unprecedented capabilities in surface patterning, which are particularly relevant to nanofabrication by chemical means and the engineering of a new class of molecular nanoionic systems.

Magnetoconductance oscillations at a nanoparticle film–superconductor interface: a meansfor probing flux penetration depth

Interfaces between disordered normal materials and superconductors (S) can exhibit‘reflectionless tunnelling’ (RT)—a phenomenon that arises from repeated disorder-drivenelastic scattering, multiple Andreev reflections, and electron/hole interference. RT has beenused to explain zero-bias conductance peaks (ZBCPs) observed using doped semiconductorsand evaporated granular metal films as the disordered normal materials. Recently, inaddition to ZBCPs, magnetoconductance oscillations predicted by RT theory have beenobserved using a novel normal disordered material: self-assembled nanoparticle films. In thepresent study, we find that the period of these oscillations decreases as temperature(T) increases. This suggests that the magnetic flux associated with interfering pathwaysincreases accordingly. We propose that the increasing flux can be attributed to magneticfield penetration into S as . This model agrees remarkably well with knownT dependence of penetration depth predicted by Bardeen–Cooper–Schrieffer theory. Ourstudy shows that this additional region of flux is significant and must be considered inexperimental and theoretical studies of RT.

Using granular film to suppress charge leakage in a single-electron latch

A single-electron latch is a device that can be used as a building block for Quantum-dot Cellular Automata (QCA) circuits. It consists of three nanoscale metal "dots" connected in series by tunnel junctions; charging of the dots is controlled by three electrostatic gates. One very important feature of a single-electron latch is its ability to store ("latch") information represented by the location of a single electron within the three dots. To obtain latching, the undesired leakage of charge during the retention time must be suppressed. Previously, to achieve this goal, multiple tunnel junctions were used to connect the three dots. However, this method of charge leakage suppression requires an additional compensation of the background charges affecting each parasitic dot in the array of junctions. We report a single-electron latch where a granular metal film is used to fabricate the middle dot in the latch which concurrently acts as a charge leakage suppressor. This latch has no parasitic dots, therefore the background charge compensation procedure is greatly simplified. We discuss the origins of charge leakage suppression and possible applications of granular metal dots for various single-electron circuits.

Conductivity of granular metallic films

The electrical resistivity of granular metallic films with a granule size R ∼ 10–50 A decomposes into two factors. One of them depends only on the ratio (T 0(x)/T) and varies in a range of six to seven orders of magnitude. The second factor depends on the volume concentration of metallic granules x and the concentration of the solution of isolated metal atoms in their oxide and varies in a range of five to six orders of magnitude. Expressions for both factors have been obtained. The conductivity of the granular films is related to tunneling between neighboring granules. The tunneling probability depends substantially on the concentration of the solution of isolated metal atoms in the oxide.

Synthesis, Thermal Decomposition Pattern and Single Crystal X-Ray Studies of Dimeric [Cu(dmae)(OCOCH3)(H2O)]2

A dimeric precursor, <TEX>$[Cu(dmae)(OCOCH_3)(H_2O)]_2$</TEX> for the CVD of copper metal films, (dmaeH = N,N-dimethylaminoethanol) was synthesized by the reaction of copper(II) acetate monohydrate (<TEX>$Cu(OCOCH_3)_2{\cdot}H_2O$</TEX>) and dmaeH in toluene. The product was characterized by m.p. determination, elemental analysis and X-ray crystallography. Molecular structure of <TEX>$[Cu(dmae)(OCOCH_3)(H_2O)]_2$</TEX> shows that a dimeric unit <TEX>$[Cu(dmae)(OCOCH_3)(H_2O)]_2$</TEX> is linked to another through hydrogen bond and it undergoes facile decomposition at 300 C to deposit granular copper metal film under nitrogen atmosphere. The decomposition temperature, thermal behaviour, kinetic parameters, evolved gas pattern of the complex, morphology, and the composition of the film were also investigated.

Quantum Percolation in Granular Metals

Theory of quantum corrections to conductivity of granular metal films is developed for the realistic case of large randomly distributed tunnel conductances. Quantum fluctuations of intergrain voltages (at energies E much below the bare charging energy scale E(C)) suppress the mean conductance g (E) much more strongly than its standard deviation sigma(E). At sufficiently low energies E(*) any distribution becomes broad, with sigma(E(*)) approximately g (E(*)), leading to strong local fluctuations of the tunneling density of states. The percolative nature of the metal-insulator transition is established by a combination of analytic and numerical analysis of the matrix renormalization group equations.

Effect of oxidation on the electrical properties of granular copper nanostructures

The structural and electrical properties of thin granular metal films obtained by laser electrodispersion were studied. Such structures, which consist of amorphous copper grains 5 nm in size, were established to be extremely stable against oxidation. For instance, when oxidized in air, copper grains were covered by Cu2O oxide shells about 1 nm thick after a period of a few days, after which further growth of the oxide in thickness stopped. The oxidized close-packed structures conduct current through intergrain tunneling electron transitions, whereas in partially oxidized structures the conduction involves tunneling electron hopping between conducting ensembles made up of several nanoparticles. It was shown that the size of the nanoparticles and of the conducting ensembles can be found by analyzing the temperature dependence of the conductivity and, independently, from the I–V characteristics of the films.

Monte-Carlo simulation of electron transport and field effect in granular metal nanostructures

In this work we analyze the field effect in granular metal films and propose the current-switching device utilizing this effect. It is shown as a result of numerical modeling that efficient current modulation can be achieved in thin granular films if the ratio between charging energy of granules E c0 and thermal energy kT is not less than 10 and the amplitude of the random potential is low compared with the charging energy.

Two types of granular metal films––applicability for field-effect devices

In this work we report the results of numerical modeling of field-effect in granular metal films. The main requirements for this effect to be well pronounced at room temperature are formulated. The two types of real granular structures are tested by means of detailed investigations of temperature dependencies of their conductivity. The conclusion is made that ordered thin Cu granular films fabricated by laser electrodispersion technique are very attractive for the applications in field-effect devices.

Field effect in granular metal films

In this work we analyse the field effect in granular metal films and propose acurrent-switching device utilizing this effect. It is shown as a result ofnumerical modelling that efficient current modulation can be achievedin thin granular films if the ratio between charging energy of granulesEc0 andthermal energy kTis not less than 10 and the amplitude of the random potential is low compared tothe charging energy.