Investigating the thermal stability of ultra-small Ag, Au and AuAg alloy nanoparticles embedded in a silica matrix.

Thermal growth kinetics of embedded bimetallic (AuAg/SiO2) nanoparticles are explored and compared with their monometallic (Au/SiO2 and Ag/SiO2) counterparts, as their practical applicability demands stability and uniformity. The plasmonic properties of these nanoparticles (NPs) significantly improve when their size falls in the ultra-small region (diameter < 10 nm), owing to their large active surface area. Interestingly, the bimetallic NPs exhibit better optical properties and structural stability as compared to their monometallic counterparts. This calls for a thorough understanding of the nucleation and temperature-dependent growth to ensure size stability against thermal coarsening that most bimetallic NPs completely lack. Herein, the atom beam sputtered AuAg NPs are systematically analysed over a wide range of annealing temperatures (ATs), and the results are compared with those of Au and Ag NPs. The X-ray photoelectron spectroscopy spectra and other experimental results confirm the formation of AuAg alloy NPs inside the silica matrix. Furthermore, techniques like transmission electron microscopy and grazing-incidence small-/wide-angle X-ray scattering were used to explore the temperature-dependent structural and morphological stability of the NPs. Our results show that the deposited AuAg NPs retain their spherical shape and remain as an alloy for the entire range of ATs. When the AT increases from 25 °C to 800 °C, the size of the NPs also increases from 3.5 to 4.8 nm; beyond that, their size grows substantially to 13.6 nm at 900 °C. We observed that the NPs remain in the ultra-small size range (∼5 nm) until an AT of 800 °C. Beyond that Ostwald ripening is ascribed to be the major cause of particle growth, resulting in an active surface area loss. Based on the outcomes, a three-step nucleation and growth mechanism is proposed.

Multilayer Langmuir Film of Monodisperse Au Nanoclusters: Unusual Growth via Bilayers.

The assembly of nanomaterials into thin films is an important area in the nanofabrication of novel devices. The monodispersity of nanoparticles plays an essential role in the resulting quality of the assembled mono- and multilayers. Larger polydispersity leads to smaller lateral correlation lengths and smaller domains of aligned nanoparticles, thus resulting in more point and line defects. Perfectly monodisperse nanoparticles should therefore minimize the number of defects in the assembled films. Despite tremendous progress in reducing the polydispersity of nanoparticles, there has been limited research on the assembly of thin films out of perfectly monodisperse nanoclusters. Here, we show a formation of Langmuir films using perfectly monodisperse gold nanoclusters with composition Au32(nBu3P)12Cl8 exhibiting a diameter of 1.8 nm. Using both in situ and ex situ small-angle X-ray scattering, we show that the monolayer formed on a Langmuir-Blodgett trough exhibits long-range order. Moreover, after compressing the monolayer, we found that the stress accumulated prior to the monolayer collapse triggers a transition to a short-range order not previously reported. If such monolayer is compressed further, the second layer is not formed as in the case of standard nanoparticles. Instead, a growth of islands by an odd number of layers is observed, leading to a thin film with a structure consisting of two different orientations of the hexagonal lattice. Such anomalous behavior may have implications for the possibilities of thin-film formation.

A Combinatorial Study Investigating the Growth of Ultrasmall Embedded Silver Nanoparticles upon Thermal Annealing.

Ultrasmall nanoparticles (NPs) with a high active surface area are essential for optoelectronic and photovoltaic applications. However, the structural stability and sustainability of these ultrasmall NPs at higher temperatures remain a critical problem. Here, we have synthesized the nanocomposites (NCs) of Ag NPs inside the silica matrix using the atom beam co-sputtering technique. The post-deposition growth of the embedded Ag NPs is systematically investigated at a wide range of annealing temperatures (ATs). A novel, fast, and effective procedure, correlating the experimental (UV-vis absorption results) and theoretical (quantum mechanical modeling, QMM) results, is used to estimate the size of NPs. The QMM-based simulation, employed for this work, is found to be more accurate in reproducing the absorption spectra over the classical/modified Drude model, which fails to predict the expected shift in the LSPR for ultrasmall NPs. Unlike the classical Drude model, the QMM incorporates the intraband transition of the conduction band electrons to calculate the effective dielectric function of metallic NCs, which is the major contribution of LSPR shifts for ultrasmall NPs. In this framework, a direct comparison is made between experimentally and theoretically observed LSPR peak positions, and it is observed that the size of NPs grows from 3 to 18 nm as AT increases from room temperature to 900 °C. Further, in situ grazing-incidence small- & wide-angle X-ray scattering and transmission electron microscopy measurements are employed to comprehend the growth of Ag NPs and validate the UV + QMM results. We demonstrate that, unlike chemically grown NPs, the embedded Ag NPs ensure greater stability in size and remain in an ultrasmall regime up to 800 °C, and beyond this temperature, the size of NPs increases exponentially due to dominant Ostwald ripening. Finally, a three-stage mechanism is discussed to understand the process of nucleation and growth of the silica-embedded Ag NPs.

Ge/Al and Ge/Si3N4/Al Core/Shell Quantum Dot Lattices in Alumina: Boosting the Spectral Response by Tensile Strain.

We investigated the production conditions and optoelectrical properties of thin film material consisting of regularly ordered core/shell Ge/Al and Ge/Si3N4/Al quantum dots (QDs) in an alumina matrix. The materials were produced by self-assembled growth achieved by means of multilayer magnetron sputtering deposition. We demonstrated the successful fabrication of well-ordered 3D lattices of Ge/Al and Ge/Si3N4/Al core/shell quantum dots with a body-centred tetragonal arrangement within the Al2O3 matrix. The addition of shells to the Ge core enables a strong tuning of the optical and electrical properties of the material. An Al shell induces a bandgap shift toward smaller energies, and, in addition, it prevents Ge oxidation. The addition of a thin Si3N4 shell induces huge changes in the material spectral response, i.e., in the number of extracted excitons produced by a single photon. It increases both the absolute value and the width of the spectral response. For the best sample, we achieved an enhancement of over 250% of the produced number of excitons in the measured energy range. The observed changes are, as it seems, the consequence of the large tensile strain in Ge QDs which is induced by the Si3N4 shell addition and which is measured to be about 3% for the most strained QDs. The tensile strain causes activation of the direct bandgap of germanium, which has a very strong effect on the spectral response of the material.

Multiple Exciton Generation in 3D-Ordered Networks of Ge Quantum Wires in Alumina Matrix.

Thin films containing 3D-ordered semiconductor quantum wires offer a great tool to improve the properties of photosensitive devices. In the present work, we investigate the photo-generated current in thin films consisting of an interconnected 3D-ordered network of Ge quantum wires in an alumina matrix. The films are prepared using nitrogen-assisted magnetron sputtering co-deposition of Ge and Al2O3. We demonstrate a strong photocurrent generation in the films, much stronger than in similar films containing Ge quantum dots. The enhanced photocurrent generation is the consequence of the multiple exciton generation and the films' specific structure that allows for efficient carrier transport. Thin film with the largest nitrogen content showed enhanced performance compared to other thin films with 1.6 excitons created after absorption of a single photon at an energy nearly equal to the double bandgap value. The bandgap value depends on the geometrical properties of the quantum wires, and it is close to the maximum of the solar irradiance in this case. In addition, we show that the multiple exciton generation is the most pronounced at the photon energy values equal to multiple values of the thin film bandgap.

Structural, Optical and Electrical Properties of Al+MoO3 and Au+MoO3 Thin Films Prepared by Magnetron Codeposition.

Structural, optical and electrical properties of Al+MoO3 and Au+MoO3 thin films prepared by simultaneous magnetron sputtering deposition were investigated. The influence of MoO3 sputtering power on the Al and Au nanoparticle formation and spatial distribution was explored. We demonstrated the formation of spatially arranged Au nanoparticles in the MoO3 matrix, while Al incorporates in the MoO3 matrix without nanoparticle formation. The dependence of the Au nanoparticle size and arrangement on the MoO3 sputtering power was established. The Al-based films show a decrease of overall absorption with an Al content increase, while the Au-based films have the opposite trend. The transport properties of the investigated films also are completely different. The resistivity of the Al-based films increases with the Al content, while it decreases with the Au content increase. The reason is a different transport mechanism that occurs in the films due to their different structural properties. The choice of the incorporated material (Al or Au) and its volume percentage in the MoO3 matrix enables the design of materials with desirable optical and electrical characteristics for a variety of applications.

3D Networks of Ge Quantum Wires in Amorphous Alumina Matrix.

Recently demonstrated 3D networks of Ge quantum wires in an alumina matrix, produced by a simple magnetron sputtering deposition enables the realization of nanodevices with tailored conductivity and opto-electrical properties. Their growth and ordering mechanisms as well as possibilities in the design of their structure have not been explored yet. Here, we investigate a broad range of deposition conditions leading to the formation of such quantum wire networks. The resulting structures show an extraordinary tenability of the networks' geometrical properties. These properties are easily controllable by deposition temperature and Ge concentration. The network's geometry is shown to retain the same basic structure, adjusting its parameters according to Ge concentration in the material. In addition, the networks' growth and ordering mechanisms are explained. Furthermore, optical measurements demonstrate that the presented networks show strong confinement effects controllable by their geometrical parameters. Interestingly, energy shift is the largest for the longest quantum wires, and quantum wire length is the main parameter for control of confinement. Presented results demonstrate a method to produce unique materials with designable properties by a simple self-assembled growth method and reveal a self-assembling growth mechanism of novel 3D ordered Ge nanostructures with highly designable optical properties.

Deposition of Thin Alumina Films Containing 3D Ordered Network of Nanopores on Porous Substrates.

Self-supporting thin films containing nanopores are very promising materials for use for multiple applications, especially in nanofiltration. Here, we present a method for the production of nanomembranes containing a 3D ordered network of nanopores in an alumina matrix, with a diameter of about 1 nm and a body centered tetragonal structure of the network nodes. The material is produced by the magnetron sputtering deposition of a 3D ordered network of Ge nanowires in an alumina matrix, followed by a specific annealing process resulting in the evaporation of Ge. We demonstrate that the films can be easily grown on commercially available alumina substrates containing larger pores with diameters between 20 and 400 nm. We have determined the minimal film thickness needed to entirely cover the larger pores. We believe that these films have the potential for applications in the fields of filtration, separation and sensing.

Optical absorption in array of Ge/Al-shell nanoparticles in an Alumina matrix.

The absorption spectra in array of Ge, Al and Ge/Al-shell nanoparticles immersed in alumina (Al2O3) matrix is calculated in framework of ab initio macroscopic dielectric model. It is demonstrated that absorption is strongly enhanced when germanium nanospheres are encapsulated by Al-shell. Two absorption peaks, appearing in the spectra, correspond to low energy ω+ and high energy ω- plasmons which lie in visible and ultraviolet frequency range, respectively. It is demonstrated that in Ge/Al-shell composite the ω+ plasmon exists only because quantum confinement effect which provides larger Ge band gap (Δ ~ 1.5 eV) and thus prevent decay of ω+ plasmon to continuum of interband electron-hole excitation in semiconducting core. Absorption in visible frequency range enhances additional 3 times when alumina is replaced by large dielectric constant insulator, such as SiC, and additional 6 times when Ge core is replaced by wide band-gap insulator, such as Si3N4. Strong enhancement of optical absorption in visible frequency range make this composites suitable for optoelectronic application, such as solar cells or light emitting devices. The simulated plasmon peaks are brought in connection with peaks appearing in ellipsometry measurements.

Influence of Structure on Electronic Charge Transport in 3D Ge Nanowire Networks in an Alumina Matrix.

We demonstrate formation of material consisting of three-dimensional Germanium nanowire network embedded in an insulating alumina matrix. A wide range of such nanowire networks is produced using a simple magnetron sputtering deposition process. We are able to vary the network parameters including its geometry as well as the length and width of the nanowires. The charge transport in these materials is shown to be related to the nanowire surface per unit volume of the material, α. For low values of α, transport is characterized by space charge limited conduction and a drift of carriers in the extended states with intermittent trapping-detrapping in the localized states. For large values of α, charge transport occurs through hopping between localized electronic states, similar to observations in disorder-dominated arrays of quantum dots. A crossover between these two mechanisms is observed for the intermediate values of α. Our results are understood in terms of an almost linear scaling of the characteristic trap energy with changes in the nanowire network parameters.

Preparation of non-oxidized Ge quantum dot lattices in amorphous Al2O3, Si3N4 and SiC matrices.

The preparation of non-oxidized Ge quantum dot (QD) lattices embedded in Al2O3, Si3N4, SiC matrices by self-assembled growth was studied. The materials were produced by magnetron sputtering deposition, using different substrate temperatures. The deposition regimes leading to the self-assembled growth type and the formation of three-dimensionally ordered Ge QD lattices in different matrices were investigated and determined. The oxidation of the Ge QDs in different matrices was monitored and the best conditions for the production of non-oxidized Ge QDs were found. The optical properties of the Ge QD lattices in different matrices show a strong dependence on the Ge oxidation and the matrix type.