A multi-resistance wide-range calibration sample for conductive probe atomic force microscopy measurements.

In this report, we employ phase-contrast tapping mode and conductive probe atomic force microscopy (cp-AFM) as tools to investigate the nanoscale morphology and proton conductance of a 3M perfluoro-imide acid (PFIA) membrane (625 EW) over a large range of relative humidity (3-95% RH). As a point of comparison, we also investigate 3M perfluorosulfonic acid (PFSA) (825 EW) and Nafion 212. With AFM, we assess the membrane's water retention and mechanical stability at low RH and high RH, respectively. Cp-AFM allows us to spatially resolve the hydrophilic and electrochemically active domains under a similar set of conditions and observe directly the ties between membrane morphology and proton conductance. From our data, we are able to correlate the improved water retention indicated by the size of the hydrophilic domains with the proton conductance in the PFIA membrane at elevated temperature and compare the result with that observed for the PFSA and Nafion. At high RH conditions, we see evidence of a nearly continuous hydrophilic phase, which indicates a high degree of swelling.

Investigation of Laser-fired Rear-side Point Contacts of Laser-crystallized Silicon Thin-film Solar Cells by Conductive Probe Atomic Force Microscopy

The electrical conduction of self-assembled monolayers (SAMs) made from conjugated molecules was measured using conductive probe atomic force microscopy (CP-AFM), with a focus on the molecular structural effect on conduction. First, the electrical conduction of SAMs made from phenylene oligomer SAMs was measured. The resistances through the monolayers increased exponentially with an increase in molecular length and the decay constants of transconductance beta were about 0.45 to 0.61 A(-1) measured at lower bias region. We further investigated the influence of applied load on the resistances. The resistances through terphenyl SAMs increased with an increase in the applied load up to 14 nN. Second, using an insertion technique into insulating alkanethiol SAMs, the electrical conduction of single conjugated terphenyl methanethiol and oligo(para-phenylenevinylene) (OPV) molecules embedded into insulating alkanethiol SAMs were measured. Electrical currents through these single molecules of OPVs were estimated to be larger than those through single terphenyl molecules, suggesting that the OPV structure can increase the electrical conduction of single molecules. Third, apparent negative differential resistance (NDR) was observed at higher bias measurements of SAMs. The appearance of NDR might be related to roughness of SAM surface, because apparent NDR was often observed on rough surfaces. In any case, the tip-molecule contact condition strongly affected carrier transport through metal tip/SAM/metal junction.

It is widely acknowledged that Atomic force microscopy (AFM) methods such as conductive probe AFM (CAFM) and Scanning Capacitance Microscopy (SCM) are valuable tools for semiconductor failure analysis. One of the main advantages of these techniques is the ability to provide localized, die-level fault isolation over an area of several microns much faster than conventional nanoprobing methods. SCM, has advantages over CAFM in that it is not limited to bulk technologies and can be utilized for fault isolation on SOI-based technologies. Herein, we present a case-study of SCM die-level fault isolation on SOI-based FinFET technology at the 14nm node.

The low-frequency noise in a nanometer-sized virtual memristor consisting of a contact of a conductive atomic force microscope (CAFM) probe to an yttria stabilized zirconia (YSZ) thin film deposited on a conductive substrate is investigated. YSZ is a promising material for the memristor application since it is featured by high oxygen ion mobility, and the oxygen vacancy concentration in YSZ can be controlled by varying the molar fraction of the stabilizing yttrium oxide. Due to the low diameter of the CAFM probe contact to the YSZ film (∼10 nm), we are able to measure the electric current flowing through an individual filament both in the low resistive state (LRS) and in the high resistive state (HRS) of the memristor. Probability density functions (Pdfs) and spectra of the CAFM probe current in both LRS and HRS are measured. The noise in the HRS is found to be featured by nearly the same Pdf and spectrum as the inner noise of the experimental setup. In the LRS, a flicker noise 1/fγ with γ ≈ 1.3 is observed in the low-frequency band (up to 8 kHz), which is attributed to the motion (drift/diffusion) of oxygen ions via oxygen vacancies in the filament. Activation energies of oxygen ion motion determined from the flicker noise spectra are distributed in the range of [0.52; 0.68] eV at 300 K. Knowing these values is of key importance for understanding the mechanisms of the resistive switching in YSZ based memristors as well as for the numerical simulations of memristor devices.

Cruciform-like molecules with two orthogonally placed π-conjugated systems have in recent years attracted significant interest for their potential use as molecular wires in molecular electronics. Here we present synthetic protocols for a large selection of cruciform molecules based on oligo(phenyleneethynylene) (OPE) and tetrathiafulvalene (TTF) scaffolds, end-capped with acetyl-protected thiolates as electrode anchoring groups. The molecules were subjected to a comprehensive study of their conducting properties as well as their photophysical and electrochemical properties in solution. The complex nature of the molecules and their possible binding in different configurations in junctions called for different techniques of conductance measurements: (1) conducting-probe atomic force microscopy (CP-AFM) measurements on self-assembled monolayers (SAMs), (2) mechanically controlled break-junction (MCBJ) measurements, and (3) scanning tunneling microscopy break-junction (STM-BJ) measurements. The CP-AFM measurements showed structure-property relationships from SAMs of series of OPE3 and OPE5 cruciform molecules; the conductance of the SAM increased with the number of dithiafulvene (DTF) units (0, 1, 2) along the wire, and it increased when substituting two arylethynyl end groups of the OPE3 backbone with two DTF units. The MCBJ and STM-BJ studies on single molecules both showed that DTFs decreased the junction formation probability, but, in contrast, no significant influence on the single-molecule conductance was observed. We suggest that the origins of the difference between SAM and single-molecule measurements lie in the nature of the molecule-electrode interface as well as in effects arising from molecular packing in the SAMs. This comprehensive study shows that for complex molecules care should be taken when directly comparing single-molecule measurements and measurements of SAMs and solid-state devices thereof.

Molecular electronics, where nanoscale organic species are utilized as active electronic components, offers a promising approach towards ultimate miniaturization and integration of hybrid electronic materials (HEMs) with traditional silicon based complementary metal oxide semiconductors (CMOS) technology. Toward this end, fundamental research studies to understand the electronic and optical properties of these molecules are of paramount importance. In this work, conductive probe atomic force microscopy (CP-AFM) and Raman spectroscopy have been performed on ionic liquid based unique organic nanoparticles derived from a Group of Uniform Materials Based on Organic Salts (GUMBOS). Aptly named as nanoGUMBOS, the material investigated in this report is Rhodamine6G tetraphenylborate ([R6G][TPB]) as has been synthesized by a room temperature facile metathesis reaction between Rhodamine 6G chloride (R6GCl) and sodium tetraphenylborate (NaTPB) followed by an ultrasonication-assisted, additive-free, re-precipitation reaction. To the best of our knowledge, the results reported herein are first-time evidence of electrical performance exhibited by [R6G][TPB] nanoGUMBOS. In conjunction with the supportive results of Raman spectra, the current-voltage (I-V) characteristics obtained are indicative of the potential incorporation of this unique compound in hybrid electronics with respect to potential applications in optoelectronics and chemical sensing.

Halide perovskite (HaP) solar cells have an excellent voltage efficiency (>70%) and a low electron-affinity conduction band minimum, making them prospective candidates to be used as photocathodes in integrated low-cost solar fuel generators. However, halide perovskites are notoriously unstable in aqueous solutions and immediately dissolve upon exposure to liquid water. Ultrathin layers (< 10 nm) of Al2O3 deposited by atomic layer deposition are suitable encapsulants to prevent water ingression but are also electronically insulating. Embedding linear conjugated organic molecules (‘molecular relays’) that transverse the insulating layer enables selective electron transport across the insulating encapsulating layer. The electronic functionality of the embedded molecular relays is verified by conductive probe atomic force microscopy and photo-electrodeposition of metal particles (Pt and Ag) from ethanolic solutions. Lastly, the encapsulated HaP photoelectrodes were submersed in a CO2-saturated aqueous electrolyte and a photocurrent of ~100 µA/cm2 (at ~ -0.32 V vs. Ag/AgCl) was measured. This work demonstrates a way for stabilizing semiconductors in polar and protonic electrolytes as photoelectrodes for the generation of solar fuels.

The authors describe the properties of electronically active nanowires that can be assembled via DNA directed growth on a nanostructured array. DNA-modified nanoparticles are used to site-specifically address the tips of vertically aligned carbon nanotubes (CNTs) that serve as catalysts for the growth of zinc oxide (ZnO) nanorods. Using conductive probe atomic force microscopy, they measured the conductance characteristics of single ZnO-CNT structures under various force and illumination conditions and at different sites in a large array, thereby establishing that DNA directed formation of multimaterial, optically active nanostructures can yield devices that are electronically functional at the nanometer scale. The inherent ability of DNA to carry and convey encoded information provides the basis for targeted synthesis of nanostructured devices.

The charge transport mechanism between 1,8-octanedithiol (ODT, C(8)H(16)S(2)H(2)) and platinum and gold electrodes is studied by breaking bonds between single ODT molecules and atomic metal junctions using conductive probe atomic force microscopy. Histograms of conductance values show peaks that are obscured by background processes that differ from the metal-molecule-metal conduction path of interest. We introduce a new method to reduce greatly such backgrounds by dividing by a 1-octanethiol (OMT, C(8)H(17)SH) reference histogram, without data selection. The method reveals three series of conductance values for both platinum and gold contacts, which we associate with geometrically different configurations between thiol and metal atoms. The ordering of conductance values, Pt-ODT-Pt > Pt-ODT-Au> Au-ODT-Au, is consistent with a relative dependence on both the number of electron channels and the density of states.

The electrical conductivity via peptide networks was measured using conductive probe atomic force microscopy, where the tryptophan-containing peptide network (composed of Phe-Trp dipeptides) exhibited a superior (5 fold) conductivity in comparison to an all phenylalanine network (composed of Phe-Phe dipeptides). These results are in line with previous spectroscopic measurements exploring intramolecular electron transfer in proteins. Bias-scaling factors (instead of the more commonly used transition voltage spectroscopy method) were calculated for the two peptide networks. These calculations showed substantial differences between the two peptide networks, suggesting different electron transport characteristics. While the factor for the tryptophan-containing network is similar to conjugated molecules with a low electron-tunneling barrier, the one for the all phenylalanine network can be ascribed as an 'intermediate' factor between conjugated and saturated molecules.

Conductive probe atomic force microscopy (CP-AFM) has been used to investigateelectronic transport through the protein ferritin in both its holo and apo forms.The presence of the iron oxide core has a notable effect on both conductanceand the molecular response to probe-induced compression. This response canalso be contrasted with that of the much smaller metalloprotein cytochromec, across which electron transport can be simulated by a single non-resonant tunnel barriermodel. Tapping mode AFM imaging, in different compressional regimes, reveals both themineral core of holoferritin and significant collapse of the hollow protein cavity ofapoferritin. These topographic findings correlate well with CP-AFM conductance dataand facilitate a clearer description of electron transport across these molecules.

We report a new experimental method for measuring relatively small differences in electron tunneling through two distinct monolayers. We place them side by side using scanning probe nanolithography and compare the tunneling currents by conductive probe atomic force microscopy under identical force, voltage, and tip contamination conditions. We demonstrate the validity of our approach by applying it to two isomeric molecules with similar length and functional groups, with only the position of two functional groups, one aromatic and the other aliphatic, being inverted with respect to each other. The relative values of the two tunneling currents, calculated using density functional theory and the Tersoff-Hamann approach, compare very well with the experimental data, providing us with an example of theory vs experiment agreement that is rather uncommon in this field.

Halide perovskite (HaP) solar cells have an excellent voltage efficiency (>70%) and a low electron-affinity conduction band minimum, making them prospective candidates to be used as photocathodes in integrated low-cost solar fuel generators. However, halide perovskites are notoriously unstable in aqueous solutions and immediately dissolve upon exposure to water. Ultrathin layers (<10 nm) of Al2O3 deposited by atomic layer deposition are suitable encapsulants to prevent water ingression but are also electronically insulating. Embedding linear conjugated organic molecules ('molecular relays') that transverse the insulating layer enables selective electron transport across the insulating encapsulating layer. The electronic functionality of the embedded molecular relays is verified by conductive probe atomic force microscopy and photoelectrodeposition of metal particles (Pt and Ag) from ethanolic solutions. Lastly, the encapsulated HaP photoelectrodes were submersed in a CO2-saturated aqueous electrolyte and a photocurrent of ∼100 μA cm-2 (at ∼-0.32 V vs. Ag/AgCl) was measured, the highest reported for CsPbBr3 based aqueous photoelectrodes. This work demonstrates a way for stabilizing perovskite semiconductors in polar and protonic electrolytes as photoelectrodes for the generation of solar fuels.

As the field of molecular‐scale electronics matures and the prospect of devices incorporating molecular wires becomes more feasible, it is necessary to progress from the simple anchor groups used in fundamental conductance studies to more elaborate anchors designed with device stability in mind. This study presents a series of oligo(phenylene‐ethynylene) wires with one tetrapodal anchor and a phenyl or pyridyl head group. The new anchors are designed to bind strongly to gold surfaces without disrupting the conductance pathway of the wires. Conductive probe atomic force microscopy (cAFM) was used to determine the conductance of self‐assembled monolayers (SAMs) of the wires in Au–SAM–Pt and Au–SAM–graphene junctions, from which the conductance per molecule was derived. For tolane‐type wires, mean conductances per molecule of up to 10−4.37 G0 (Pt) and 10−3.78 G0 (graphene) were measured, despite limited electronic coupling to the Au electrode, demonstrating the potential of this approach. Computational studies of the surface binding geometry and transport properties rationalise and support the experimental results.