Versatile Phase Transfer Method for the Efficient Surface Functionalization of Gold Nanoparticles: Towards Controlled Nanoparticle Dispersion in a Polymer Matrix

In electronic devices based on hybrid materials such as nonvolatile memory elements (NVMEs), it is essential to control precisely the dispersion of metallic nanoparticles (NPs) in an insulating polymer matrix such as polystyrene in order to control the functionality of the device. In this work the incorporation of AuNPs in polystyrene films is controlled by tuning the surface functionalization of the metallic nanoparticles via ligand exchange. Two ligands with different structures were used for functionalization: 1-decanethiol and thiol-terminated polystyrene. This paper presents a versatile method for the modification of gold nanoparticles (AuNPs) with thiol-terminated polystyrene ligands via phase transfer process. An organic colloid of AuNPs (5±1 nm diameter) is obtained by the phase transfer process (from water to toluene) that allows exchanging the ligand adsorbed on AuNPs surface (hydrophilic citrate/tannic acid to hydrophobic thiols). The stability, size distribution, and precise location of modified AuNPs in the polymer matrix are obtained from UV-Vis spectroscopy, dynamic light scattering (DLS), and electron tomography. TEM tomographic 3D imaging demonstrates that the modification of AuNPs with thiol-terminated polystyrene results in homogeneous particle distribution in the polystyrene matrix compared to 1-decanethiol modified AuNPs for which a vertical phase separation with a homogeneous layer of AuNPs located at the bottom of the polymer matrix was observed.This work was supported by FP7-NMP-2010-SMALL-4 Program (“Hybrid Organic/Inorganic Memory Elements for Integration of Electronic and Photonic Circuitry,” HYMEC), Project no. 263073. Eric Gonthier is acknowledged for technical support in the preparation of hybrid thin films. Scientific work was supported by the Polish Ministry of Science and Higher Education Funds for Science in 2011–2014 allocated for the cofunded international project

Detection Limits of DLS and UV-Vis Spectroscopy in Characterization of Polydisperse Nanoparticles Colloids

Dynamic light scattering is a method that depends on the interaction of light with particles. This method can be used for measurements of narrow particle size distributions especially in the range of 2–500 nm. Sample polydispersity can distort the results, and we could not see the real populations of particles because big particles presented in the sample can screen smaller ones. Although the theory and mathematical basics of DLS technique are already well known, little has been done to determine its limits experimentally. The size and size distribution of artificially prepared polydisperse silver nanoparticles (NPs) colloids were studied using dynamic light scattering (DLS) and ultraviolet-visible (UV-Vis) spectroscopy. Polydisperse colloids were prepared based on the mixture of chemically synthesized monodisperse colloids well characterized by atomic force microscopy (AFM), transmission electron microscopy (TEM), DLS, and UV-Vis spectroscopy. Analysis of the DLS results obtained for polydisperse colloids reveals that several percent of the volume content of bigger NPs could screen completely the presence of smaller ones. The presented results could be extremely important from nanoparticles metrology point of view and should help to understand experimental data especially for the one who works with DLS and/or UV-Vis only

Transfer międzyfazowy nanocząstek złota pozwalający na ich implementację w tuszach do wytwarzania hybrydowych organiczno/nieorganicznych układów elektronicznych

Pracę naukową zrealizowano w ramach międzynarodowego projektu badawczego 7 Programu Ramowego UE: Hybrydowe organiczno-nieorganiczne elementy pamięci wykorzystujące zintegrowane układy elektroniczne i fotoniczne (HYMEC)

Printed Nonvolatile Resistive Memories Based on a Hybrid Organic/Inorganic Functional Ink

Organic memories are increasingly being considered as promising candidates for a number of novel consumer applications, such as smart labels and smart packaging devices. Indeed, organic memories can be fabricated on highly flexible substrates at low temperatures from liquid phase, employing for instance printing techniques. In this work, a nonvolatile resistive memory element conceived for large-area processing and operation in ambient conditions is presented. In particular, a functional ink made out of an air stable organic semiconductor, namely ActivInk N1400, and gold nanoparticles (NPs) is developed and optimized for the fabrication of high performance memories through inkjet printing. The ink formulation is varied in order to explore the influence of Au NPs concentration on the switching behavior. Devices are operated in ambient conditions with reproducible memory behavior, high ON/OFF current ratios, and low programming voltages. In depth material analysis with time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy depth profiles are carried out on operated devices to shine a light on resistive switching mechanism and to determine the average gold content and its 3D distribution in stable memories

Effect of the Alkyl Chain Length of Secondary Amines on the Phase Transfer of Gold Nanoparticles from Water to Toluene

In the present paper we describe a phase transfer of aqueous synthesized gold nanoparticles (AuNPs) from water to toluene using secondary amines: dioctylamine, didodecylamine, and dioctadecylamine. The effect of the hydrocarbon chain length and amount of amines on the transfer efficiency were investigated in the case of nanoparticles (NPs) with three different sizes: 5, 9, and 13 nm. Aqueous colloids were precisely characterized before the transfer process using UV–vis spectroscopy, dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). Nanoparticles were next transferred to toluene and characterized using UV–vis and DLS techniques. It was found that dioctadecylamine provides the most effective transfer of nanoparticles. No time-dependent changes in the NP size were observed after 12 days, showing that the dioctadecylamine-stabilized nanoparticles dispersed in toluene were stable. This indicates that long hydrocarbon chains of dioctadecylamine exhibit sufficiently hydrophobic properties of nanoparticles and consequently their good dispersibility in nonpolar solvent