Molecule Clustering Dynamics in the Molecular Doping Process of Si(111) with Diethyl-propyl-phosphonate.

The molecular doping (MD) process is based on the deposition of dopant-containing molecules over the surface of a semiconductor substrate, followed by the thermal diffusion step. Previous studies suggest that, during the deposition, the molecules nucleate clusters, and at prolonged deposition times, they grow into self-assembled layers on the sample to be doped. Little is known about the influence of nucleation kinetics on the final properties of these layers and how they change when we modify the solution properties. In this work, we examine the nucleation rate and the molecular surface coverage kinetics of diethyl-propyl phosphonate on silicon at different solution concentrations and how these conditions influence the final electrical properties of the doped samples. We present a high-resolution morphological characterization of the as-deposited molecules together with the electrical results of the final doped samples. The experimental results show a non-obvious behavior, explained through understanding of the competition between the molecules' physisorption and chemisorption mechanisms. As a consequence, due to the deeper knowledge of the deposition phase, a finer tuning of the conductive properties of MD-doped samples is achieved.

Plasmonic and Conductive Structures of TCO Films with Embedded Cu Nanoparticles.

Cu nanoparticles were produced by using solid-state dewetting (dry) of a 1.3 nm Cu layer or laser ablation of a Cu solid target (wet) in acetone and methanol. The morphology and chemical composition of the nanoparticles were investigated as a function of the synthesis methods and their key parameters of the annealing temperature (200-500 °C) and the liquid environment during the ablation. Cu nanoparticles were then embedded in transparent conductive oxide (TCO) films as aluminum-doped zinc oxide (AZO) or zirconium-doped indium oxide (IZrO); the TCObott/Cu nanoparticle/TCOtop structures were synthesized with all combinations of AZO and IZrO as the top and bottom layers. The goal was to achieve a plasmonic and conductive structure for photovoltaic applications via a comparison of the involved methods and all fabricated structures. In particular, solid-state dewetting produced faceted or spherical (depending on the annealing temperature) nanoparticles with an average size below 150 nm while laser ablation produced spherical nanoparticles below 250 nm. Dry and wet plasmonic conductive structures as a function of the TCOs employed and the temperature of annealing could reach a sheet resistance of 86 Ω/sq. The energy band-gap Egap, absorbance, transmittance, and reflectance of the plasmonic conductive structures were investigated in the UV-vis-NIR range. They showed a dependence on the sequence of the top and bottom TCO, with best transmittances of 89.4% for the dry plasmonic conductive structure and 84.7% for the wet plasmonic conductive structure. The latter showed a higher diffused transmittance of between 10-20% in the visible range.

Fabrication of Cu(II) oxide-hydroxide nanostructures onto graphene paper by laser and thermal processes for sensitive nano-electrochemical sensing of glucose.

Glucose electrochemical sensors based on nanostructures of CuO/Cu(OH)2onto graphene paper were prepared by thermal (solid) and nanosecond pulsed laser (molten phase) dewetting of a CuO layer 6 nm thin deposited by sputtering. Dewetted systems, obtained without the use of any binder, act as array of nanoelectrodes. Solid state and molten phase dewetting produce nanostructures of copper oxide-hydroxide with different average size, shape and surface composition. Molten phase dewetting originates particles with size below 100 nm, while solid state dewetting produces particles with average size of about 200 nm. Moreover, molten phase dewetting produce drop-shaped nanostructures, conversely nanostructures derived from solid state dewetting are multifaceted. X-ray photoelectron spectroscopy (XPS) characterization revealed that the surface of nanostructures is formed by a copper(II) species CuO and Cu(OH)2. Shape of anodic branch of the cyclic voltammograms of glucose in alkali solution evidenced a convergent diffusion mechanism. Analytical performances in amperometric mode are as good as or better than other sensors based on copper oxide. Amperometric detection of glucose was done at potential as low as 0.4 V versus saturated calomel electrode by both types of electrodes. Linear range from 50µM to 10 mM, sensitivity ranging from 7 to 43µA cm-2mM-1and detection limit of 7µM was obtained. Good analytical performances were obtained by laser dewetted electrodes with a low copper content up to 1.2 by atoms percentage of the surface. Analytical performance of the proposed electrodes is compliant for the determination of glucose both in blood serum, saliva or tear.

Monte Carlo Approach to the Evaluation of Nanoparticles Size Distribution from the Analysis of UV-Vis-NIR Spectra.

How nice would it be to obtain the size distribution of a nanoparticle dispersion fast and without electron microscope measurements? UV-Vis-NIR spectrophotometry offers a very rapid solution; however, the spectra interpretation can be very challenging and needs to take into account the size distribution of the nanoparticles and agglomeration. This work suggests a Monte Carlo method for rapid fitting UV-Vis-NIR spectra using one or two size distributions starting from a dataset of precomputed spectra based on Mie theory. The proposed algorithm is tested on copper nanoparticles produced with Pulsed Laser Ablation in Liquid and on gold nanoparticles from the literature. The fitted distribution results are comparable with Transmission Electron Microscope results and, in some cases, reflect the presence of agglomeration.

Alkaline Electro-Sorption of Hydrogen Onto Nanoparticles of Pt, Pd, Pt80Pd20 and Cu(OH)2 Obtained by Pulsed Laser Ablation.

Recently, hydrogen evolution reaction (HER) in alkaline media has received a renewed interest both in the fundamental research as well as in practical applications. Pulsed Laser Ablation in Liquid (PLAL) has been demonstrated as a very useful technique for the unconventional preparation of nanomaterials with amazing electro-catalyst properties toward HER, compared to those of nanomaterials prepared by conventional methods. In this paper, we compared the electro-sorption properties of hydrogen in alkaline media by Pt, Pd, Pt80Pd20, and Cu(OH)2 nanoparticles (NPs) prepared by PLAL. The NPs were placed onto graphene paper (GP). Noble metal particles have an almost spherical shape, whereas Cu(OH)2 presents a flower-bud-like shape, formed by very thin nanowalls. XPS analyses of Cu(OH)2 are compatible with a high co-ordination of Cu(II) centers by OH and H2O. A thin layer of perfluorosulfone ionomer placed onto the surface of nanoparticles (NPs) enhances their distribution on the surface of graphene paper (GP), thereby improving their electro-catalytic properties. The proposed mechanisms for hydrogen evolution reaction (HER) on noble metals and Cu(OH)2 are in line with the adsorption energies of H, OH, and H2O on the surfaces of Pt, Pd, and oxidized copper. A significant spillover mechanism was observed for the noble metals when supported by graphene paper. Cu(OH)2 prepared by PLAL shows a competitive efficiency toward HER that is attributed to its high hydrophilicity which, in turn, is due to the high co-ordination of Cu(II) centers in very thin Cu(OH)2 layers by OH- and H2O. We propose the formation of an intermediate complex with water which can reduce the barrier energy of water adsorption and dissociation.

Model of Chronoamperometric Response towards Glucose Sensing by Arrays of Gold Nanostructures Obtained by Laser, Thermal and Wet Processes.

Non-enzymatic electrochemical glucose sensors are of great importance in biomedical applications, for the realization of portable diabetic testing kits and continuous glucose monitoring systems. Nanostructured materials show a number of advantages in the applications of analytical electrochemistry, compared to macroscopic electrodes, such as great sensitivity and little dependence on analyte diffusion close to the electrode-solution interface. Obtaining electrodes based on nanomaterials without using expensive lithographic techniques represents a great added value. In this paper, we modeled the chronoamperometric response towards glucose determination by four electrodes consisting of nanostructured gold onto graphene paper (GP). The nanostructures were obtained by electrochemical etch, thermal and laser processes of thin gold layer. We addressed experiments obtaining different size and shape of gold nanostructures. Electrodes have been characterized by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry, and chronoamperometry. We modeled the current-time response at the potential corresponding to two-electrons oxidation process of glucose by the different nanostructured gold systems. The finest nanostructures of 10-200 nm were obtained by laser dewetting of 17 nm thin and 300 °C thermal dewetting of 8 nm thin gold layers, and they show that semi-infinite linear diffusion mechanism predominates over radial diffusion. Electrochemical etching and 17 nm thin gold layer dewetted at 400 °C consist of larger gold islands up to 1 µm. In the latter case, the current-time curves can be fitted by a two-phase exponential decay function that relies on the mixed second-order formation of adsorbed glucose intermediate followed by its first-order decay to gluconolactone.

Nanoporous Ge electrode as a template for nano-sized ( <5 nm) Au aggregates.

In this paper we present the extremely peculiar electrical properties of nanoporous Ge. A full and accurate electrical characterization showed an unexpected and extremely high concentration of positive carriers. Electrochemical analyses showed that nanoporous Ge has improved charge transfer properties with respect to bulk Ge. The electrode behavior, together with the large surface-to-volume ratio, make nanoporous Ge an efficient nanostructured template for the realization of other porous materials by electrodeposition. The pores were efficiently decorated by Au nanoparticles of diameter as low as 1-5 nm, prepared by electrochemical deposition. These new results demonstrate the potential and efficient use of nanoporous Ge as a nanostructured template for nano-sized Au aggregates, opening the way for the realization of innovative sensor devices.

Electro-Sorption of Hydrogen by Platinum, Palladium and Bimetallic Pt-Pd Nanoelectrode Arrays Synthesized by Pulsed Laser Ablation.

Sustainable and renewable production of hydrogen by water electrolysers is expected to be one of the most promising methods to satisfy the ever-growing demand for renewable energy production and storage. Hydrogen evolution reaction in alkaline electrolyte is still challenging due to its slow kinetic properties. This study proposes new nanoelectrode arrays for high Faradaic efficiency of the electro-sorption reaction of hydrogen in an alkaline electrolyte. A comparative study of the nanoelectrode arrays, consisting of platinum or palladium or bimetallic nanoparticles (NPs) Pt80Pd20 (wt.%), obtained by nanosecond pulsed laser ablation in aqueous environment, casted onto graphene paper, is proposed. The effects of thin films of perfluoro-sulfonic ionomer on the material morphology, nanoparticles dispersion, and electrochemical performance have been investigated. The NPs-GP systems have been characterized by field emission scanning electron microscopy, Rutherford backscattering spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, cyclic voltammetry, and galvanostatic charge-discharge cycles. Faradaic efficiency up to 86.6% and hydrogen storage capacity up to 6 wt.% have been obtained by the Pt-ionomer and Pd/Pt80Pd20 systems, respectively.

Morphology, Electrical and Optical Properties of Cu Nanostructures Embedded in AZO: A Comparison between Dry and Wet Methods.

Herein, Cu nanostructures are obtained by solid-state dewetting of 9 nm copper layer (dry) or by ablating copper target, using a nanosecond pulsed laser at 1064 nm, in acetone and isopropyl alcohol (wet). The Cu nanostructures are embedded in aluminum-doped zinc oxide layer. Then, the electrical, optical, and morphological properties of the two kinds of systems, as a function of their synthesis parameters, are investigated. The aim is to compare the two fabrication methods and select the main conditions to achieve the best system for photovoltaic applications. The main differences, exhibited by the wet and dry processes, were in the shape and size of the Cu nanostructures. Dewetting in nitrogen produces faceted nanoparticles, with an average size below 150 nm, while laser ablation originates spherical and smaller nanoparticles, below 50 nm. Dry system underwent to thermal annealing, which improves the electrical properties, compared to the wet system, with a sheet resistance of 103 vs. 106 Ω/sq, respectively; finally, the dry system shows a maximum transmittance of 89.7% at 697 nm, compared to the wet system in acetone, 88.4% at 647 nm, as well as in isopropyl alcohol, 86.9% at 686 nm. Moreover, wet systems show higher transmittance in NUV.

Study of the Molecule Adsorption Process during the Molecular Doping.

Molecular Doping (MD) involves the deposition of molecules, containing the dopant atoms and dissolved in liquid solutions, over the surface of a semiconductor before the drive-in step. The control on the characteristics of the final doped samples resides on the in-depth study of the molecule behaviour once deposited. It is already known that the molecules form a self-assembled monolayer over the surface of the sample, but little is known about the role and behaviour of possible multiple layers that could be deposited on it after extended deposition times. In this work, we investigate the molecular surface coverage over time of diethyl-propyl phosphonate on silicon, by employing high-resolution morphological and electrical characterization, and examine the effects of the post-deposition surface treatments on it. We present these data together with density functional theory simulations of the molecules-substrate system and electrical measurements of the doped samples. The results allow us to recognise a difference in the bonding types involved in the formation of the molecular layers and how these influence the final doping profile of the samples. This will improve the control on the electrical properties of MD-based devices, allowing for a finer tuning of their performance.

Morphological and Compositional Studies on Al/Ti/TiN/Si, Al/TiN/Si, Al/W/Si, Al/WN/Si Systems to Test the Diffusion Barrier Properties of Nanoscale-Thick Layers between Al and Si.

In this work, an investigation of the properties of nanoscale-thick Ti/TiN, TiN, W, WN layers as diffusion barriers between Si and Al is carried out in view of Si-based electronic applications. Heat treatments were performed on the samples to activate interdiffusion between Si and Al. Changing annealing time and temperature, each sample was morphologically characterized by scanning electron microscopy and atomic force microscopy and compositionally characterized by Rutherford backscattering analysis. The aim is to evaluate the efficiency of the layers as diffusion barriers between Si and Al and, at the same time, to evaluate the surface morphological changes upon annealing processes.

Morphology Evolution of Nanoscale-Thick Au/Pd Bimetallic Films on Silicon Carbide Substrate.

Bimetallic Au/Pd nanoscale-thick films were sputter-deposited at room temperature on a silicon carbide (SiC) surface, and the surface-morphology evolution of the films versus thickness was studied with scanning electron microscopy. This study allowed to elucidate the Au/Pd growth mechanism by identifying characteristic growth regimes, and to quantify the characteristic parameters of the growth process. In particular, we observed that the Au/Pd film initially grew as three-dimensional clusters; then, increasing Au/Pd film thickness, film morphology evolved from isolated clusters to partially coalesced wormlike structures, followed by percolation morphology, and, finally, into a continuous rough film. The application of the interrupted coalescence model allowed us to evaluate a critical mean cluster diameter for partial coalescence, and the application of Vincent's model allowed us to quantify the critical Au/Pd coverage for percolation transition.

Disposable and Low-Cost Electrode Based on Graphene Paper-Nafion-Bi Nanostructures for Ultra-Trace Determination of Pb(II) and Cd(II).

There is a huge demand for rapid, reliable and low-cost methods for the analysis of heavy metals in drinking water, particularly in the range of sub-part per billion (ppb). In the present work, we describe the preparation, characterization and analytical performance of the disposable sensor to be employed in Square Wave Anodic Stripping Voltammetry (SWASV) for ultra-trace simultaneous determination of cadmium and lead. The electrode consists of graphene paper-perfluorosulfonic ionomer-bismuth nano-composite material. The electrode preparation implies a key step aimed to enhance the Bi3+ adsorption into nafion film, prior to the bismuth electro-deposition. Finely dispersed bismuth nanoparticles embedded in the ionomer film are obtained. The electrode was characterized by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX), Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and Electrochemical Impedance Spectroscopy (EIS). The electrode shows a linear response in the 5-100 ppb range, a time-stability tested up to almost three months, and detection limits up to 0.1 ppb for both Pb2+ and Cd2+. The electrode preparation method is simple and low in cost and the obtained analytical performance is very competitive with the state of art for the SWASV determination of Pb2+ and Cd2+ in solution.

Nanostructuration of Thin Metal Films by Pulsed Laser Irradiations: A Review.

Metal nanostructures are, nowadays, extensively used in applications such as catalysis, electronics, sensing, optoelectronics and others. These applications require the possibility to design and fabricate metal nanostructures directly on functional substrates, with specifically controlled shapes, sizes, structures and reduced costs. A promising route towards the controlled fabrication of surface-supported metal nanostructures is the processing of substrate-deposited thin metal films by fast and ultrafast pulsed lasers. In fact, the processes occurring for laser-irradiated metal films (melting, ablation, deformation) can be exploited and controlled on the nanoscale to produce metal nanostructures with the desired shape, size, and surface order. The present paper aims to overview the results concerning the use of fast and ultrafast laser-based fabrication methodologies to obtain metal nanostructures on surfaces from the processing of deposited metal films. The paper aims to focus on the correlation between the process parameter, physical parameters and the morphological/structural properties of the obtained nanostructures. We begin with a review of the basic concepts on the laser-metal films interaction to clarify the main laser, metal film, and substrate parameters governing the metal film evolution under the laser irradiation. The review then aims to provide a comprehensive schematization of some notable classes of metal nanostructures which can be fabricated and establishes general frameworks connecting the processes parameters to the characteristics of the nanostructures. To simplify the discussion, the laser types under considerations are classified into three classes on the basis of the range of the pulse duration: nanosecond-, picosecond-, femtosecond-pulsed lasers. These lasers induce different structuring mechanisms for an irradiated metal film. By discussing these mechanisms, the basic formation processes of micro- and nano-structures is illustrated and justified. A short discussion on the notable applications for the produced metal nanostructures is carried out so as to outline the strengths of the laser-based fabrication processes. Finally, the review shows the innovative contributions that can be proposed in this research field by illustrating the challenges and perspectives.

Dewetted Gold Nanostructures onto Exfoliated Graphene Paper as High Efficient Glucose Sensor.

Non-enzymatic electrochemical glucose sensing was obtained by gold nanostructures on graphene paper, produced by laser or thermal dewetting of 1.6 and 8 nm-thick Au layers, respectively. Nanosecond laser annealing produces spherical nanoparticles (AuNPs) through the molten-phase dewetting of the gold layer and simultaneous exfoliation of the graphene paper. The resulting composite electrodes were characterized by X-ray photoelectron spectroscopy, cyclic voltammetry, scanning electron microscopy, micro Raman spectroscopy and Rutherford back-scattering spectrometry. Laser dewetted electrode presents graphene nanoplatelets covered by spherical AuNPs. The sizes of AuNPs are in the range of 10-150 nm. A chemical shift in the XPS Au4f core-level of 0.25-0.3 eV suggests the occurrence of AuNPs oxidation, which are characterized by high stability under the electrochemical test. Thermal dewetting leads to electrodes characterized by faceted not oxidized gold structures. Glucose was detected in alkali media at potential of 0.15-0.17 V vs. saturated calomel electrode (SCE), in the concentration range of 2.5µM-30 mM, exploiting the peak corresponding to the oxidation of two electrons. Sensitivity of 1240 µA mM-1 cm-2, detection limit of 2.5 µM and quantifications limit of 20 µM were obtained with 8 nm gold equivalent thickness. The analytical performances are very promising and comparable to the actual state of art concerning gold based electrodes.

Sb-Doped Titanium Oxide: A Rationale for Its Photocatalytic Activity for Environmental Remediation.

The problem of water purification is one of the most urgent issues in developing countries, where large infrastructures and energy resources are limited. Among the possibilities for a cheap route to clean water, photocatalytic materials in the form of coatings or nanostructures are among the most promising. The most widely studied photocatalytic material is titanium dioxide (TiO2). Here, we investigate the photocatalytic properties of 1.5% Sb-doped TiO2 and laser-irradiated Sb-doped TiO x . Calcined Sb-doped TiO2 was found to adopt the rutile structure, but it turned amorphous after laser irradiation. Photocatalytic tests for Sb-doped TiO2 showed an activity 1 order of magnitude higher than that of an undoped TiO2 control sample under both ultraviolet and visible irradiation. A further sizeable enhancement resulted from laser irradiation. The increased photocatalytic activity is ascribed to both enhanced visible region absorption associated with Sb-induced lone pair surface electronic states and trapping of the holes at the lone pair surface sites, thus inhibiting the recombination of the electrons and holes generated in the initial photoexcitation step. This study shows the first rationalization of the photocatalytic properties of Sb-TiO2 in terms of its electronic structure.

Laser irradiation in water for the novel, scalable synthesis of black TiO x photocatalyst for environmental remediation.

Since 1970, TiO2 photocatalysis has been considered a possible alternative for sustainable water treatment. This is due to its material stability, abundance, nontoxicity and high activity. Unfortunately, its wide band gap (≈3.2 eV) in the UV portion of the spectrum makes it inefficient under solar illumination. Recently, so-called "black TiO2" has been proposed as a candidate to overcome this issue. However, typical synthesis routes require high hydrogen pressure and long annealing treatments. In this work, we present an industrially scalable synthesis of TiO2-based material based on laser irradiation. The resulting black TiO x shows a high activity and adsorbs visible radiation, overcoming the main concerns related to the use of TiO2 under solar irradiation. We employed a commercial high repetition rate green laser in order to synthesize a black TiO x layer and we demonstrate the scalability of the present methodology. The photocatalyst is composed of a nanostructured titanate film (TiO x ) synthetized on a titanium foil, directly back-contacted to a layer of Pt nanoparticles (PtNps) deposited on the rear side of the same foil. The result is a monolithic photochemical diode with a stacked, layered structure (TiO x /Ti/PtNps). The resulting high photo-efficiency is ascribed to both the scavenging of electrons by Pt nanoparticles and the presence of trap surface states for holes in an amorphous hydrogenated TiO x layer.

Complex-Morphology Metal-Based Nanostructures: Fabrication, Characterization, and Applications.

Due to their peculiar qualities, metal-based nanostructures have been extensively used in applications such as catalysis, electronics, photography, and information storage, among others. New applications for metals in areas such as photonics, sensing, imaging, and medicine are also being developed. Significantly, most of these applications require the use of metals in the form of nanostructures with specific controlled properties. The properties of nanoscale metals are determined by a set of physical parameters that include size, shape, composition, and structure. In recent years, many research fields have focused on the synthesis of nanoscale-sized metallic materials with complex shape and composition in order to optimize the optical and electrical response of devices containing metallic nanostructures. The present paper aims to overview the most recent results-in terms of fabrication methodologies, characterization of the physico-chemical properties and applications-of complex-morphology metal-based nanostructures. The paper strongly focuses on the correlation between the complex morphology and the structures' properties, showing how the morphological complexity (and its nanoscale control) can often give access to a wide range of innovative properties exploitable for innovative functional device production. We begin with an overview of the basic concepts on the correlation between structural and optical parameters of nanoscale metallic materials with complex shape and composition, and the possible solutions offered by nanotechnology in a large range of applications (catalysis, electronics, photonics, sensing). The aim is to assess the state of the art, and then show the innovative contributions that can be proposed in this research field. We subsequently report on innovative, versatile and low-cost synthesis techniques, suitable for providing a good control on the size, surface density, composition and geometry of the metallic nanostructures. The main purpose of this study is the fabrication of functional nanoscale-sized materials, whose properties can be tailored (in a wide range) simply by controlling the structural characteristics. The modulation of the structural parameters is required to tune the plasmonic properties of the nanostructures for applications such as biosensors, opto-electronic or photovoltaic devices and surface-enhanced Raman scattering (SERS) substrates. The structural characterization of the obtained nanoscale materials is employed in order to define how the synthesis parameters affect the structural characteristics of the resulting metallic nanostructures. Then, macroscopic measurements are used to probe their electrical and optical properties. Phenomenological growth models are drafted to explain the processes involved in the growth and evolution of such composite systems. After the synthesis and characterization of the metallic nanostructures, we study the effects of the incorporation of the complex morphologies on the optical and electrical responses of each specific device.

Optical Properties of Nanoporous Germanium Thin Films.

In the present article we report enhanced light absorption, tunable size-dependent blue shift, and efficient electron-hole pairs generation in Ge nanoporous films (np-Ge) grown on Si. The Ge films are grown by sputtering and molecular beam epitaxy; subsequently, the nanoporous structure is obtained by Ge+ self-implantation. We show, by surface photovoltage spectroscopy measurements, blue shift of the optical energy gap and strong signal enhancement effects in the np-Ge films. The blue shift is related to quantum confinement effects at the wall separating the pore in the structure, the signal enhancement to multiple light-scattering events, which result in enhanced absorption. All these characteristics are highly stable with time. These findings demonstrate that nanoporous Ge films can be very promising for photovoltaic applications.

Correction: Enhancing carrier generation in TiO2 by a synergistic effect between plasmon resonance in Ag nanoparticles and optical interference.

Correction for 'Enhancing carrier generation in TiO2 by a synergistic effect between plasmon resonance in Ag nanoparticles and optical interference' by Giuseppe Cacciato et al., Nanoscale, 2015, 7, 13468-13476.