Electronic properties of single Prussian Blue Analog nanocrystals determined by conductive-AFM.

We report a study of the electron transport (ET) properties at the nanoscale (conductive-AFM denoted as C-AFM hereafter) of individual Prussian Blue Analog (PBA) cubic nanocrystals (NCs) of CsCoIIIFeII, with a size between 15 and 50 nm deposited on HOPG. We demonstrate that these PBA NCs feature an almost size-independent electron injection barrier of 0.41 ± 0.02 eV and 0.27 ± 0.03 eV at the CsCoIIIFeII/HOPG and CsCoIIIFeII/C-AFM tip, respectively, and an intrinsic electron conductivity evolving from a large dispersion between ∼5 × 10-4 and 2 × 10-2 S cm-1 without a clear correlation with the nanocrystal size. The conductivity values measured on individual nanocrystals are up to fifty times higher than those reported on PBA films.

Strong and weak polarization-dependent interactions in connected and disconnected plasmonic nanostructures.

We explore numerically and experimentally the formation of hybridized modes between a bright mode displayed by a gold nanodisc and either dark or bright modes of a nanorod - both elements being either separated by a nanometer-size gap (disconnected system) or relied on a metal junction (connected system). In terms of modeling, we compare the scattering or absorption spectra and field distributions obtained under oblique-incidence plane wave illumination with quasi-normal mode computation and an analytical model based on a coupled oscillator model. Both connected and disconnected systems have very different plasmon properties in longitudinal polarization. The disconnected system can be consistently understood in terms of the nature of hybridized modes and coupling strength using either QNMs or coupled oscillator model; however the connected configuration presents intriguing peculiarities based on the strong redistribution of charges implied by the presence of the metal connection. In practice, the fabrication of disconnected or connected configurations depends on the mitigation of lithographic proximity effects inherent to top-down lithography methods, which can lead to the formation of small metal junctions, while careful lithographic dosing allows one to fabricate disconnected systems with a gap as low as 20 nm. We obtained a very good agreement between experimentally measured scattering spectra and numerical predictions. The methods and analyses presented in this work can be applied to a wide range of systems, for potential applications in light-matter interactions, biosensing or strain monitoring.

Conductance switching of azobenzene-based self-assembled monolayers on cobalt probed by UHV conductive-AFM.

We report the formation of self-assembled monolayers of a molecular photoswitch (azobenzene-bithiophene derivative, AzBT) on cobalt via a thiol covalent bond. We study the electrical properties of the molecular junctions formed with the tip of a conductive atomic force microscope under ultra-high vacuum. The statistical analysis of the current-voltage curves shows two distinct states of the molecule conductance, suggesting the coexistence of both the trans and cis azobenzene isomers on the surface. The cis isomer population (trans isomer) increases (decreases) upon UV light irradiation. The situation is reversed under blue light irradiation. The experiments are confronted to first-principle calculations performed on the molecular junctions with the Non-Equilibrium Green's Function formalism combined with Density Functional Theory (NEGF/DFT). The theoretical results consider two different molecular orientations for each isomer. Whereas the orientation does not affect the conductance of the trans isomer, it significantly modulates the conductance of the cis isomer and the resulting conductance ON/OFF ratio of the molecular junction. This helps identifying the molecular orientation at the origin of the observed current differences between the trans and cis forms. The ON state is associated to the trans isomer irrespective of its orientation in the junction, while the OFF state is identified as a cis isomer with its azobenzene moiety folded upward with respect to the bithiophene core. The experimental and calculated ON/OFF conductance ratios have a similar order of magnitude. This conductance ratio seems reasonable to make these Co-AzBT molecular junctions a good test-bed to further explore the relationship between the spin-polarized charge transport, the molecule conformation and the molecule-Co spinterface.

Precise tailoring of evaporated gold nanocones using electron beam lithography and lift-off.

The ability to fabricate nanocones with precise dimensions is essential for several emerging applications. We demonstrate here a method which can be used to fabricate arrays of gold nanocones with high dimensional precision using lithographic and lift-off means. electron beam (ebeam) writing of a spin-coated PMMA-based bilayer resist deposited onto silicon wafers is used to form a shadow mask. This mask gradually closes as the deposition of gold (using ebeam evaporation) proceeds-the result is arrays of gold nanocones on the silicon wafer surface after lift-off of the resist. Observations using scanning electron microscopy enable a statistical study of the dimensions of 360 gold nanocones-the results demonstrate the high precision of the nanocones dimensions. The fabrication process enables the creation of arrays of nanocones with a base diameter varying from 53.6 ± 2.1 nm to 94.1 ± 2.4 nm, a vertical height ranging from 71.3 ± 4.1 nm to 153.4 ± 3.4 nm, and an apex radius of curvature ranging from 8.4 ± 1.2 nm to 11.6 ± 1.5 nm. The results are compared with the predictions of a deposition model which considers the evolving shadow masking during the gold deposition to compute the nanocone profile.

Size and shape control of a variety of metallic nanostructures using tilted, rotating evaporation and lithographic lift-off techniques.

Here, we demonstrate a simple top-down method for nanotechnology whereby electron beam (ebeam) lithography can be combined with tilted, rotated thermal evaporation to control the topography and size of an assortment of metallic objects at the nanometre scale. In order to do this, the evaporation tilt angle is varied between 1 and 24°. The technique allows the 3-dimensional tailoring of a range of metallic object shapes from sharp, flat bottomed spikes to hollow cylinders and rings-all of which have rotational symmetry and whose critical dimensions are much smaller than the lithographic feature size. The lithographic feature size is varied from 400 nm down to 40 nm. The nanostructures are characterized using electron microscopy techniques-the specific shape can be predicted using topographic modelling of the deposition. Although individual nanostructures are studied here, the idea can easily be extended to fabricate arrays for e.g. photonics and metamaterials. Being a generic technique-depending on easily controlled lithographic and evaporation parameters-it can be readily incorporated into any standard planar process and could be adapted to suit other thin-film materials deposited using physical means.

Tunneling mechanism and contact mechanics of colloidal nanoparticle assemblies.

Nanoparticle assemblies with thiol-terminated alkyl chains are studied by conducting atomic force microscopy (c-AFM) regarding their use as strain gauges for touch-sensitive panels. Current-force spectroscopy is used as a characterization tool complementary to the macroscopic setup since it allows a bias to be applied to a limited number of junctions, overcoming the Coulomb blockade energy and focusing on the contact electromechanics and the transport mechanism across the ligand. First, transition voltage spectroscopy is applied with varying force to target the underlying tunneling mechanism by observing whether the transition between the ohmic and exponential current-voltage behavior is force-dependent. Secondly, current-force spectroscopy in the ohmic range below the transition voltage is performed. The current-force behavior of the AFM probe in contact with a nanoparticle multilayer is associated with the spread of force and current within the nanoparticle lattice and at the level of adjacent particles by detailed contact mechanics treatment. The result is twofold: concerning the architecture of sensors, this work is a sample case of contact electromechanics at scales ranging from the device scale down to the individual ligand molecule. Regarding transport across the molecule, the vacuum tunneling mechanism is favored over the conduction by coherent molecular states, which is a decision-making aid for the choice of ligand in applications.

High-Resolution Kelvin Probe Force Microscopy Imaging of Interface Dipoles and Photogenerated Charges in Organic Donor-Acceptor Photovoltaic Blends.

We present noncontact atomic force microscopy and Kelvin probe force microscopy studies of nanophase segregated photovoltaic blends based on an oligothiophene-fluorenone oligomer and [6,6]-phenyl C70 butyric acid methyl ester. We carried out a complete analysis of the influence of the tip-surface interaction regime on the topographic, in-dark contact potential and surface photovoltage contrasts. It is demonstrated that an optimal lateral resolution is achieved for all channels below the onset of a contrast in the damping images. With the support of electrostatic simulations, it is shown that in-dark contact potential difference contrasts above subsurface acceptor clusters are consistent with an uneven distribution of permanent charges at the donor-acceptor interfaces. A remarkable dependence of the surface photovoltage magnitude with respect to the tip-surface distance is evidenced and attributed to a local enhancement of the electromagnetic field at the tip apex.

Charge Blinking Statistics of Semiconductor Nanocrystals Revealed by Carbon Nanotube Single Charge Sensors.

We demonstrate the relation between the optical blinking of colloidal semiconductor nanocrystals (NCs) and their electrical charge blinking for which we provide the first experimental observation of power-law statistics. To show this, we harness the performance of CdSe/ZnS NCs coupled with carbon nanotube field-effect transistors (CNTFETs), which act as single charge-sensitive electrometers with submillisecond time resolution, at room temperature. A random telegraph signal (RTS) associated with the NC single-trap charging is observed and exhibits power-law temporal statistics (τ(-α), with α in the range of ∼1-3), and a Lorentzian current noise power spectrum with a well-defined 1/f(2) corner. The spectroscopic analysis of the NC-CNTFET devices is consistent with the charging of NC defect states with a charging energy of Ec ≥ 200 meV. These results pave the way for a deeper understanding of the physics and technology of nanocrystal-based optoelectronic devices.

Noise performance of frequency modulation Kelvin force microscopy.

Noise performance of a phase-locked loop (PLL) based frequency modulation Kelvin force microscope (FM-KFM) is assessed. Noise propagation is modeled step by step throughout the setup using both exact closed loop noise gains and an approximation known as "noise gain" from operational amplifier (OpAmp) design that offers the advantage of decoupling the noise performance study from considerations of stability and ideal loop response. The bandwidth can be chosen depending on how much noise is acceptable and it is shown that stability is not an issue up to a limit that will be discussed. With thermal and detector noise as the only sources, both approaches yield PLL frequency noise expressions equal to the theoretical value for self-oscillating circuits and in agreement with measurement, demonstrating that the PLL components neither modify nor contribute noise. Kelvin output noise is then investigated by modeling the surrounding bias feedback loop. A design rule is proposed that allows choosing the AC modulation frequency for optimized sharing of the PLL bandwidth between Kelvin and topography loops. A crossover criterion determines as a function of bandwidth, temperature and probe parameters whether thermal or detector noise is the dominating noise source. Probe merit factors for both cases are then established, suggesting how to tackle noise performance by probe design. Typical merit factors of common probe types are compared. This comprehensive study is an encouraging step toward a more integral performance assessment and a remedy against focusing on single aspects and optimizing around randomly chosen key values.

Imaging the operation of a carbon nanotube charge sensor at the nanoscale.

Carbon nanotube field effect transistors (CNTFETs) are of great interest for nanoelectronics applications such as nonvolatile memory elements (NVMEs) or charge sensors. In this work, we use a scanning-probe approach based on a local charge perturbation of CNTFET-based NVMEs and investigate their fundamental operation from combined transport, electrostatic scanning probe techniques and atomistic simulations. We experimentally demonstrate operating devices with threshold voltages shifts opposite to conventional gating and with almost unchanged hysteresis. The former effect is quantitatively understood as the emission of a delocalized image charge pattern in the nanotube environment, in response to local charge storage, while the latter effect points out the dominant dipolar nature of hysteresis in CNTFETs. We propose a simple model for charge sensing using CNTFETs, based on the redistribution of the nanotube image charges. This model could be extended to gas or biosensing, for example.