Sensing the charge state of single gold nanoparticles via work function measurements.

Electrostatic interactions at the nanoscale can lead to novel properties and functionalities that bulk materials and devices do not have. Here we used Kelvin probe force microscopy (KPFM) to study the work function (WF) of gold nanoparticles (NPs) deposited on a Si wafer covered by a monolayer of alkyl chains, which provide a tunnel junction. We find that the WF of Au NPs is size-dependent and deviates strongly from that of the bulk Au. We attribute the WF change to the charging of the NPs, which is a consequence of the difference in WF between Au and the substrate. For an NP with 10 nm diameter charged with ∼ 5 electrons, the WF is found to be only ∼ 3.6 eV. A classical electrostatic model is derived that explains the observations in a quantitative way. We also demonstrate that the WF and charge state of Au NPs are influenced by chemical changes of the underlying substrate. Therefore, Au NPs could be used for chemical and biological sensing, whose environmentally sensitive charge state can be read out by work function measurements.

Gold nanoparticles on oxide-free silicon-molecule interface for single electron transport.

Two different organic monolayers were prepared on silicon Si(111) and modified for attaching gold nanoparticles. The molecules are covalently bound to silicon and form very ordered monolayers sometimes improperly called self-assembled monolayers (SAM). They are designed to be electrically insulating and to have very few electrical interface states. By positioning the tip of an STM above a nanoparticle, a double barrier tunnel junction (DBTJ) is created, and Coulomb blockade is demonstrated at 40 K. This is the first time Coulomb blockade is observed with an organic monolayer on oxide-free silicon. This work focuses on the fabrication and initial electrical characterization of this double barrier tunnel junction. The organic layers were prepared by thermal hydrosilylation of two different alkene molecules with either a long carbon chain (C11) or a shorter one (C7), and both were modified to be amine-terminated. FTIR and XPS measurements confirm that the Si(111) substrate remains unoxidized during the whole chemical process. Colloidal gold nanoparticles were prepared using two methods: either with citrate molecules (Turkevich method) or with ascorbic acid as the surfactant. In both cases AFM and STM images show a well-controlled deposition on the grafted organic monolayer. I-V curves obtained by scanning tunneling spectroscopy (STS) are presented on 8 nm diameter nanoparticles and exhibit the well-known Coulomb staircases at low temperature. The curves are discussed as a function of the organic layer thickness and silicon substrate doping.

Gold Nanoparticles on Functionalized Silicon Substrate under Coulomb Blockade Regime: An Experimental and Theoretical Investigation.

Single charge electronics offer a way for disruptive technology in nanoelectronics. Coulomb blockade is a realistic way for controlling the electric current through a device with the accuracy of one electron. In such devices the current exhibits a step-like increase upon bias which reflects the discrete nature of the fundamental charge. We have assembled a double tunnel junction on an oxide-free silicon substrate that exhibits Coulomb staircase characteristics using gold nanoparticles (AuNPs) as Coulomb islands. The first tunnel junction is an insulating layer made of a grafted organic monolayer (GOM) developed for this purpose. The GOM also serves for attaching AuNPs covalently. The second tunnel junction is made by the tip of an STM. We show that this device exhibits reproducible Coulomb blockade I-V curves at 40 K in vacuum. We also show that depending on the doping of the silicon substrate, the whole Coulomb staircase can be adjusted. We have developed a simulation approach based on the orthodox theory that was completed by calculating the bias dependent tunnel barriers and by including an accurate calculation of the band bending. This model accounts for the experimental data and the doping dependence of Coulomb oscillations. This study opens new perspectives toward designing new kind of single electron transistors (SET) based on this dependence of the Coulomb staircase with the charge carrier concentration.

Visible to near-infrared sensitization of silicon substrates via energy transfer from proximal nanocrystals: further insights for hybrid photovoltaics.

We provide a unified spectroscopic evidence of efficient energy transfer (ET) from optically excited colloidal nanocrystal quantum dots (NQDs) into Si substrates in a broad range of wavelengths: from visible (545 nm) to near-infrared (800 nm). Chemical grafting of nanocrystals on hydrogenated Si surfaces is achieved via amine-modified carboxy-alkyl chain linkers, thus ensuring complete surface passivation and accurate NQD positioning. Time-resolved photoluminescence (PL) has been measured for a set of CdSe/ZnS and CdSeTe/ZnS NQDs of various sizes and compositions grafted on Si and SiO2 substrates. The measured acceleration of the PL decays on Si substrates is in good agreement with theoretical expectations based on the frequency-dependent dielectric properties of Si and NQD-Si separation distances. A comparative analysis reveals separate contributions to ET coming from the nonradiative (NRET) and radiative (RET) channels: NRET is a dominant mechanism for proximal NQDs in the middle of the visible range and becomes comparable with RET toward near-infrared wavelengths. The broad range over which the ET efficiency is estimated to be at the level of ∼90% further supports the concept that hybrid nanocrystal/silicon thin-film photovoltaic devices could efficiently harvest solar energy across the entire spectrum of wavelengths.