Breakdown of Ohm's Law in Molecular Junctions with Electrodes of Single-Layer Graphene.

For sufficiently low biases, Ohm's law, the cornerstone of electricity, stating that current I and voltage V are proportional, is satisfied at low biases for all known systems ranging from macroscopic conductors to nanojunctions. In this study, we predict theoretically and demonstrate experimentally that in single-molecule junctions fabricated with single-layer graphene as electrodes the current at low V scales as the cube of V, thereby invalidating Ohm's law. The absence of the ohmic regime is a direct consequence of the unique band structure of the single-layer graphene, whose vanishing density of states at the Dirac points precludes electron transfer from and to the electrodes at low biases.

Room Temperature Crystallized Phase-Pure α-FAPbI3 Perovskite with In-Situ Grain-Boundary Passivation.

Energy loss in perovskite grain boundaries (GBs) is a primary limitation toward high-efficiency perovskite solar cells (PSCs). Two critical strategies to address this issue are high-quality crystallization and passivation of GBs. However, the established methods are generally carried out discretely due to the complicated mechanisms of grain growth and defect formation. In this study, a combined method is proposed by introducing 3,4,5-Trifluoroaniline iodide (TFAI) into the perovskite precursor. The TFAI triggers the union of nano-sized colloids into microclusters and facilitates the complete phase transition of α-FAPbI3 at room temperature. The controlled chemical reactivity and strong steric hindrance effect enable the fixed location of TFAI and suppress defects at GBs. This combination of well-crystallized perovskite grains and effectively passivated GBs leads to an improvement in the open circuit voltage (Voc ) of PSCs from 1.08 V to 1.17 V, which is one of the highest recorded Voc without interface modification. The TFAI-incorporated device achieved a champion PCE of 24.81%. The device maintained a steady power output near its maximum power output point, showing almost no decay over 280 h testing without pre-processing.

CP-AFM Molecular Tunnel Junctions with Alkyl Backbones Anchored Using Alkynyl and Thiol Groups: Microscopically Different Despite Phenomenological Similarity.

In this paper, we report results on the electronic structure and transport properties of molecular junctions fabricated via conducting probe atomic force microscopy (CP-AFM) using self-assembled monolayers (SAMs) of n-alkyl chains anchored with acetylene groups (CnA; n = 8, 9, 10, and 12) on Ag, Au, and Pt electrodes. We found that the current-voltage (I-V) characteristics of CnA CP-AFM junctions can be very accurately reproduced by the same off-resonant single-level model (orSLM) successfully utilized previously for many other junctions. We demonstrate that important insight into the energy-level alignment can be gained from experimental data of transport (processed via the orSLM) and ultraviolet photoelectron spectroscopy combined with ab initio quantum chemical information based on the many-body outer valence Green's function method. Measured conductance GAg < GAu < GPt is found to follow the same ordering as the metal work function ΦAu < ΦAu < ΦPt, a fact that points toward a transport mediated by an occupied molecular orbital (MO). Still, careful data analysis surprisingly revealed that transport is not dominated by the ubiquitous HOMO but rather by the HOMO-1. This is an important difference from other molecular tunnel junctions with p-type HOMO-mediated conduction investigated in the past, including the alkyl thiols (CnT) to which we refer in view of some similarities. Furthermore, unlike in CnT and other junctions anchored with thiol groups investigated in the past, the AFM tip causes in CnA an additional MO shift, whose independence of size (n) rules out significant image charge effects. Along with the prevalence of the HOMO-1 over the HOMO, the impact of the "second" (tip) electrode on the energy level alignment is another important finding that makes the CnA and CnT junctions different. What ultimately makes CnA unique at the microscopic level is a salient difference never reported previously, namely, that CnA's alkyne functional group gives rise to two energetically close (HOMO and HOMO-1) orbitals. This distinguishes the present CnA from the CnT, whose HOMO stemming from its thiol group is well separated energetically from the other MOs.

Boosting the Release of Leaving Group from Blebbistatin Derivative Photocages via Enhancing Intramolecular Charge Transfer and Stabilizing Cationic Intermediate.

Blebbistatin (Bleb) derivatives are a visible light photocage platform. During the photocleavage process, intramolecular charge transfer (ICT) and cationic intermediates play a decisive role. However, slow photolysis rate and low photolysis quantum yield are the main problems for Bleb's derivatives. Herein, by introducing a substituted OCH3 group at the para-position of the D ring, Bleb and Bleb derivatives with various leaving groups were synthesized and studied, and the photolysis performance was unveiled by steady-state spectra, photolysis rate experiments, photolysis quantum yield, and density functional theory calculations. Substituted OCH3 derivatives of Bleb may enhance the photolysis rate and increase the photolysis quantum yield because the electron-donating group can promote the ICT process and stabilize the cationic intermediate during the photolytic reaction. More generally, the insights gained from this structure-reactivity relationship may provide theoretical guidance and aid in the development of new highly efficient photoreactions.

Quantifying Image Charge Effects in Molecular Tunnel Junctions Based on Self-Assembled Monolayers of Substituted Oligophenylene Ethynylene Dithiols.

A number of factors contribute to orbital energy alignment with respect to the Fermi level in molecular tunnel junctions. Here, we report a combined experimental and theoretical effort to quantify the effect of metal image potentials on the highest occupied molecular orbital to Fermi level offset, εh, for molecular junctions based on self-assembled monolayers (SAMs) of oligophenylene ethynylene dithiols (OPX) on Au. Our experimental approach involves the use of both transport and photoelectron spectroscopy to extract the offsets, εhtrans and εhUPS, respectively. We take the difference in these quantities to be the image potential energy eVimage. In the theoretical approach, we use density functional theory (DFT) to calculate directly eVimage between positive charge on an OPX molecule and the negative image charge in the Au. Both approaches yield eVimage ∼ -0.1 eV per metal contact, meaning that the total image potential energy is ∼-0.2 eV for an assembled junction with two Au contacts. Thus, we find that the total image potential energy is 25-30% of the total offset εh, which means that image charge effects are significant in OPX junctions. Our methods should be generally applicable to understanding image charge effects as a function of molecular size, for example, in a variety of SAM-based junctions.

Quantitative analysis of weak current rectification in molecular tunnel junctions subject to mechanical deformation reveals two different rectification mechanisms for oligophenylene thiols versus alkane thiols.

Metal-molecule-metal junctions based on alkane thiol (CnT) and oligophenylene thiol (OPTn) self-assembled monolayers (SAMs) and Au electrodes are expected to exhibit similar electrical asymmetry, as both junctions have one chemisorbed Au-S contact and one physisorbed, van der Waals contact. Asymmetry is quantified by the current rectification ratio RR apparent in the current-voltage (I-V) characteristics. Here we show that RR < 1 for CnT and RR > 1 for OPTn junctions, in contrast to expectation, and further, that RR behaves very differently for CnT and OPTn junctions under mechanical extension using the conducting probe atomic force microscopy (CP-AFM) testbed. The analysis presented in this paper, which leverages results from the previously validated single level model and ab initio quantum chemical calculations, allows us to explain the puzzling experimental findings for CnT and OPTn in terms of different current rectification mechanisms. Specifically, in CnT-based junctions the Stark effect creates the HOMO level shifting necessary for rectification, while for OPTn junctions the level shift arises from position-dependent coupling of the HOMO wavefunction with the junction electrostatic potential profile. On the basis of these mechanisms, our quantum chemical calculations allow quantitative description of the impact of mechanical deformation on the measured current rectification. Additionally, our analysis, matched to experiment, facilitates direct estimation of the impact of intramolecular electrostatic screening on the junction potential profile. Overall, our examination of current rectification in benchmark molecular tunnel junctions illuminates key physical mechanisms at play in single step tunneling through molecules, and demonstrates the quantitative agreement that can be obtained between experiment and theory in these systems.

Strain-Work Function Relationship in Single-Crystal Tetracene.

Understanding the impact of strain on organic semiconductors is important for the development of electronic devices and sensors that are subject to environmental changes and mechanical stimuli; it is also important for understanding the fundamental mechanisms of charge trapping. Following our previous study on the strain effects in rubrene, we present here only the second example of the strain-work function relationship in an organic semiconductor; in this case, the benchmark material tetracene. Thin, platelike single crystals of tetracene with large (001) facets were laminated onto silicon and rubber substrates having significantly different coefficients of thermal expansion; mechanical strain in tetracene was subsequently induced by varying the temperature of the assembly. Tensile and compressive strains parallel to the (001) major facet were measured by grazing incidence X-ray diffraction, and the corresponding shifts in the electronic work functions were recorded via scanning Kelvin probe microscopy (SKPM). The work function of the tetracene (001) crystal surface directly correlated with the net mechanical strain and increased by ∼100 meV for in-plane tensile strains of 0.1% and decreased by approximately the same amount for in-plane compressive strains of -0.1%. This work provides evidence of the general and important impact of strain on the electrical properties of van der Waals bonded crystalline organic semiconductors and thereby supports the hypothesis that heterogeneous strains, for example in thin films, can be a major source of static electronic disorder.

Energy Level Alignment in Molecular Tunnel Junctions by Transport and Spectroscopy: Self-Consistency for the Case of Alkyl Thiols and Dithiols on Ag, Au, and Pt Electrodes.

We report here an extensive study of transport and electronic structure of molecular junctions based on alkyl thiols (CnT; n = 7, 8, 9, 10, 12) and dithiols (CnDT; n = 8, 9, 10) with various lengths contacted with different metal electrodes (Ag, Au, Pt). The dependence of the low-bias resistance (R) on contact work function indicates that transport is HOMO-assisted (p-type transport). Analysis of the current-voltage (I-V) characteristics for CnT and CnDT tunnel junctions with the analytical single-level model (SLM) provides both the HOMO-Fermi energy offset εhtrans and the average molecule-electrode coupling (Γ) as a function of molecular length (n), electrode work function (Φ), and the number of chemical contacts (one or two). The SLM analysis reveals a strong Fermi level (EF) pinning effect in all the junctions, i.e., εhtrans changes very little with n, Φ, and the number of chemical contacts, but Γ depends strongly on these variables. Significantly, independent measurements of the HOMO-Fermi level offset (εhUPS) by ultraviolet photoelectron spectroscopy (UPS) for CnT and CnDT SAMs agree remarkably well with the transport-estimated εhtrans. This result provides strong evidence for hole transport mediated by localized HOMO states at the Au-thiol interface, and not by the delocalized σ states in the C-C backbones, clarifying a long-standing issue in molecular electronics. Our results also substantiate the application of the single-level model for quantitative, unified understanding of transport in benchmark molecular junctions.

Gate-Tuned Insulator-Metal Transition in Electrolyte-Gated Transistors Based on Tellurene.

Tellurene is a recently discovered 2D material with high hole mobility and air stability, rendering it a good candidate for future applications in electronics, optoelectronics, and energy devices. However, the physical properties of tellurene remain poorly understood. In this paper, we report on the fabrication and characterization of high-performance electrolyte-gated transistors (EGTs) based on solution-grown tellurene flakes <30 nm in thickness. Both Hall measurements and resistance-temperature behavior down to 2 K are recorded at multiple gate voltages, and an electronic phase diagram is generated. The results show that it is possible to cross the insulator-metal transition in tellurene EGTs by tuning gate voltage, achieving mobility up to ∼500 cm2 V-1 s-1. In particular, a truly metallic 2D state is observed at gate-induced hole densities >1 × 1013 cm-2, as confirmed by the temperature dependence of resistance and magnetoresistance measurements. Wide-range tuning of the electronic ground state of tellurene is thus achievable in EGTs, opening up new opportunities to realize electrical control of its physical properties.

Determination of Energy-Level Alignment in Molecular Tunnel Junctions by Transport and Spectroscopy: Self-Consistency for the Case of Oligophenylene Thiols and Dithiols on Ag, Au, and Pt Electrodes.

We report detailed measurements of transport and electronic properties of molecular tunnel junctions based on self-assembled monolayers (SAMs) of oligophenylene monothiols (OPT n, n = 1-3) and dithiols (OPD n, n = 1-3) on Ag, Au, and Pt electrodes. The junctions were fabricated with the conducting probe atomic force microscope (CP-AFM) platform. Fitting of the current-voltage ( I-V) characteristics for OPT n and OPD n junctions to the analytical single-level tunneling model allows extraction of both the HOMO-to-Fermi-level offset (εh) and the average molecule-electrode coupling (Γ) as a function of molecular length ( n) and electrode work function (Φ). Significantly, direct measurements of εhUPS by ultraviolet photoelectron spectroscopy (UPS) for OPT n and OPD n SAMs on Ag, Au, and Pt agree remarkably well with the transport estimates εhtrans, providing strong support-beyond the high quality I-V simulations-for the relevance of the analytical single-level model to simple molecular tunnel junctions. Because the UPS measurements involve SAMs bonded to only one metal contact, the correspondence of εhUPS and εhtrans also indicates that the top contact has a weak effect on the HOMO energy. Corroborating ab initio calculations definitively rule out a dominant contribution of image charge effects to the magnitude of εh. Thus, the effective molecular tunnel barrier εh is determined, and essentially pinned, by the formation of a single metal-S covalent bond per OPT n or OPD n molecule.

Mechanical Deformation Distinguishes Tunneling Pathways in Molecular Junctions.

Developing a clearer understanding of electron tunneling through molecules is a central challenge in molecular electronics. Here we demonstrate the use of mechanical stretching to distinguish orbital pathways that facilitate tunneling in molecular junctions. Our experiments employ junctions based on self-assembled monolayers (SAMs) of homologous alkanethiols (C nT) and oligophenylene thiols (OPT n), which serve as prototypical examples of σ-bonded and π-bonded backbones, respectively. Surprisingly, molecular conductances ( Gmolecule) for stretched C nT SAMs have exactly the same length dependence as unstretched C nT SAMs in which molecular length is tuned by the number of CH2 repeat units, n. In contrast, OPT n SAMs exhibit a 10-fold-greater decrease in Gmolecule with molecular length for stretched versus unstretched cases. Experiment and theory show that these divergent results are explained by the dependence of the molecule-electrode electronic coupling Γ on strain and the spatial extent of the principal orbital facilitating tunneling. In particular, differences in the strain sensitivity of Γ versus the repeat-length ( n) sensitivity can be used to distinguish tunneling via delocalized orbitals versus localized orbitals. Angstrom-level tuning of interelectrode separation thus provides a strategy for examining the relationship between orbital localization or delocalization and electronic coupling in molecular junctions and therefore for distinguishing tunneling pathways.

Why one can expect large rectification in molecular junctions based on alkane monothiols and why rectification is so modest.

Many attempts to obtain high current rectification ratios (RRs) in molecular electronics are triggered by a potentiometer rule argument, which predicts that a strongly asymmetric location of the dominant molecular orbital yields large RR-values. Invoking this argument, molecular junctions based on alkane monothiols (CnT) can be expected to exhibit high RRs; the HOMO of these molecules is localized on the thiol terminal group bonded to one electrode. The extensive current-voltage (I-V) results for CP-AFM (conducting probe atomic force microscope) CnT junctions of various molecular lengths (n = 7, 8, 9, 10, and 12) and different metallic contacts (Ag, Au, and Pt) are consistent with conduction dominated by the HOMO, but the measured RR ∼ 1.5 is much smaller than that predicted by the potentiometer rule framework. Further, the linear shift in the HOMO position with applied bias, γ, which gives rise to rectification, is also smaller than expected, and critically, γ has the opposite sign from potentiometer rule predictions. Companion ab initio OVGF (outer valence Green's function) quantum chemical calculations provide important insight. Namely, a linear Stark shift γm is calculated for the HOMO of CnT molecules for electric field strengths (106-107 V cm-1) typical of molecular junctions, and the sign of γm matches the sign of the experimental γ for junctions derived from transport measurements, suggesting that the Stark effect plays an important role. However, the magnitude of the measured γ is only 10-15% of the computed value γm. We propose that this implies that the contacts are far from optimal; they substantially screen the effect of the applied bias, possibly via molecule-electrode interface states. We predict that, with optimized contacts, the rectification ratios in CnT-based junctions can reach reasonably high values (RR ≈ 500). We believe that Stark shifts and limited current rectification due to non-ideal contacts discussed here for the specific case of alkane monothiol junctions are issues of general interest for molecular electronics that deserve further consideration.

Work function and temperature dependence of electron tunneling through an N-type perylene diimide molecular junction with isocyanide surface linkers.

Conducting probe atomic force microscopy (CP-AFM) was employed to examine electron tunneling in self-assembled monolayer (SAM) junctions. A 2.3 nm long perylene tetracarboxylic acid diimide (PDI) acceptor molecule equipped with isocyanide linker groups was synthesized, adsorbed onto Ag, Au and Pt substrates, and the current-voltage (I-V) properties were measured by CP-AFM. The dependence of the low-bias resistance (R) on contact work function indicates that transport is LUMO-assisted ('n-type behavior'). A single-level tunneling model combined with transition voltage spectroscopy (TVS) was employed to analyze the experimental I-V curves and to extract the effective LUMO position εl = ELUMO - EF and the effective electronic coupling (Γ) between the PDI redox core and the contacts. This analysis revealed a strong Fermi level (EF) pinning effect in all the junctions, likely due to interface dipoles that significantly increased with increasing contact work function, as revealed by scanning Kelvin probe microscopy (SKPM). Furthermore, the temperature (T) dependence of R was found to be substantial. For Pt/Pt junctions, R varied more than two orders of magnitude in the range 248 K < T < 338 K. Importantly, the R(T) data are consistent with a single step electron tunneling mechanism and allow independent determination of εl, giving values compatible with estimates of εl based on analysis of the full I-V data. Theoretical analysis revealed a general criterion to unambiguously rule out a two-step transport mechanism: namely, if measured resistance data exhibit a pronounced Arrhenius-type temperature dependence, a two-step electron transfer scenario should be excluded in cases where the activation energy depends on contact metallurgy. Overall, our results indicate (1) the generality of the Fermi level pinning phenomenon in molecular junctions, (2) the utility of employing the single level tunneling model for determining essential electronic structure parameters (εl and Γ), and (3) the importance of changing the nature of the contacts to verify transport mechanisms.

Exceptionally Small Statistical Variations in the Transport Properties of Metal-Molecule-Metal Junctions Composed of 80 Oligophenylene Dithiol Molecules.

Strong stochastic fluctuations witnessed as very broad resistance (R) histograms with widths comparable to or even larger than the most probable values characterize many measurements in the field of molecular electronics, particularly those measurements based on single molecule junctions at room temperature. Here we show that molecular junctions containing 80 oligophenylene dithiol molecules (OPDn, 1 ≤ n ≤ 4) connected in parallel display small relative statistical deviations-δR/R ≈ 25% after only ∼200 independent measurements-and we analyze the sources of these deviations quantitatively. The junctions are made by conducting probe atomic force microscopy (CP-AFM) in which an Au-coated tip contacts a self-assembled monolayer (SAM) of OPDs on Au. Using contact mechanics and direct measurements of the molecular surface coverage, the tip radius, tip-SAM adhesion force (F), and sample elastic modulus (E), we find that the tip-SAM contact area is approximately 25 nm2, corresponding to about 80 molecules in the junction. Supplementing this information with I-V data and an analytic transport model, we are able to quantitatively describe the sources of deviations δR in R: namely, δN (deviations in the number of molecules in the junction), δε (deviations in energetic position of the dominant molecular orbital), and Î´Γ (deviations in molecule-electrode coupling). Our main results are (1) direct determination of N; (2) demonstration that δN/N for CP-AFM junctions is remarkably small (≤2%) and that the largest contributions to δR are δε and δΓ; (3) demonstration that δR/R after only ∼200 measurements is substantially smaller than most reports based on >1000 measurements for single molecule break junctions. Overall, these results highlight the excellent reproducibility of junctions composed of tens of parallel molecules, which may be important for continued efforts to build robust molecular devices.

Effect of Heteroatom Substitution on Transport in Alkanedithiol-Based Molecular Tunnel Junctions: Evidence for Universal Behavior.

The transport properties of molecular junctions based on alkanedithiols with three different methylene chain lengths were compared with junctions based on similar chains wherein every third -CH2- was replaced with O or S, that is, following the general formula HS(CH2CH2X)nCH2CH2SH, where X = CH2, O, or S and n = 1, 2, or 3. Conducting probe atomic force microscopy revealed that the low bias resistance of the chains increased upon substitution in the order CH2 < O < S. This change in resistance is ascribed to the observed identical trend in contact resistance, Rc, whereas the exponential prefactor ß (length sensitivity) was essentially the same for all chains. Using an established, analytical single-level model, we computed the effective energy offset εh (i.e., Fermi level relative to the effective HOMO level) and the electronic coupling strength Γ from the current-voltage (I-V) data. The εh values were only weakly affected by heteroatom substitution, whereas the interface coupling strength Γ varied by over an order of magnitude. Consequently, we ascribe the strong variation in Rc to the systematic change in Γ. Quantum chemical calculations reveal that the HOMO density shifts from the terminal SH groups for the alkanedithiols to the heteroatoms in the substituted chains, which provides a plausible explanation for the marked decrease in Γ for the dithiols with electron-rich heteroatoms. The results indicate that the electronic coupling and thus the resistance of alkanedithiols can be tuned by substitution of even a single atom in the middle of the molecule. Importantly, when appropriately normalized, the experimental I-V curves were accurately simulated over the full bias range (±1.5 V) using the single-level model with no adjustable parameters. The data could be collapsed to a single universal curve predicted by the model, providing clear evidence that the essential physics is captured by this analytical approach and supporting its utility for molecular electronics.

Large Magnetoresistance at Room Temperature in Organic Molecular Tunnel Junctions with Nonmagnetic Electrodes.

We report room-temperature resistance changes of up to 30% under weak magnetic fields (0.1 T) for molecular tunnel junctions composed of oligophenylene thiol molecules, 1-2 nm in length, sandwiched between gold contacts. The magnetoresistance (MR) is independent of field orientation and the length of the molecule; it appears to be an interface effect. Theoretical analysis suggests that the source of the MR is a two-carrier (two-hole) interaction at the interface, resulting in spin coupling between the tunneling hole and a localized hole at the Au/molecule contact. Such coupling leads to significantly different singlet and triplet transmission barriers at the interface. Even weak magnetic fields impede spin relaxation processes and thus modify the ratio of holes tunneling via the singlet state versus the triplet state, which leads to the large MR. Overall, the experiments and analysis suggest significant opportunities to explore large MR effects in molecular tunnel junctions based on widely available molecules.

Experimental and Theoretical Analysis of Nanotransport in Oligophenylene Dithiol Junctions as a Function of Molecular Length and Contact Work Function.

We report the results of an extensive investigation of metal-molecule-metal tunnel junctions based on oligophenylene dithiols (OPDs) bound to several types of electrodes (M1-S-(C6H4)n-S-M2, with 1 ≤ n ≤ 4 and M1,2 = Ag, Au, Pt) to examine the impact of molecular length (n) and metal work function (Φ) on junction properties. Our investigation includes (1) measurements by scanning Kelvin probe microscopy of electrode work function changes (ΔΦ = ΦSAM - Φ) caused by chemisorption of OPD self-assembled monolayers (SAMs), (2) measurements of junction current-voltage (I-V) characteristics by conducting probe atomic force microscopy in the linear and nonlinear bias ranges, and (3) direct quantitative analysis of the full I-V curves. Further, we employ transition voltage spectroscopy (TVS) to estimate the energetic alignment εh = EF - EHOMO of the dominant molecular orbital (HOMO) relative to the Fermi energy EF of the junction. Where photoelectron spectroscopy data are available, the εh values agree very well with those determined by TVS. Using a single-level model, which we justify via ab initio quantum chemical calculations at post-density functional theory level and additional UV-visible absorption measurements, we are able to quantitatively reproduce the I-V measurements in the whole bias range investigated (∼1.0-1.5 V) and to understand the behavior of εh and Γ (contact coupling strength) extracted from experiment. We find that Fermi level pinning induced by the strong dipole of the metal-S bond causes a significant shift of the HOMO energy of an adsorbed molecule, resulting in εh exhibiting a weak dependence with the work function Φ. Both of these parameters play a key role in determining the tunneling attenuation factor (ß) and junction resistance (R). Correlation among Φ, ΔΦ, R, transition voltage (Vt), and εh and accurate simulation provide a remarkably complete picture of tunneling transport in these prototypical molecular junctions.

Uncovering a law of corresponding states for electron tunneling in molecular junctions.

Laws of corresponding states known so far demonstrate that certain macroscopic systems can be described in a universal manner in terms of reduced quantities, which eliminate specific substance properties. To quantitatively describe real systems, all these laws of corresponding states contain numerical factors adjusted empirically. Here, we report a law of corresponding states deduced analytically for charge transport via tunneling in molecular junctions, which we validate against current-voltage measurements for conducting probe atomic force microscope junctions based on benchmark molecular series (oligophenylenedithiols and alkanedithiols) and electrodes (silver, gold, and platinum), as well as against transport data for scanning tunneling microscope junctions. Two salient features distinguish the present law of corresponding states from all those known previously. First, it is expressed by a universal curve free of empirical parameters. Second, it demonstrates that a universal behavior is not necessarily affected by strong stochastic fluctuations often observed in molecular electronics. An important and encouraging message of this finding is that transport behavior across different molecular platforms can be similar and extraordinarily reproducible.

Spin specific electron conduction through DNA oligomers.

Spin-based properties, applications, and devices are commonly related to magnetic effects and to magnetic materials. Most of the development in spintronics is currently based on inorganic materials. Despite the fact that the magnetoresistance effect has been observed in organic materials, until now spin selectivity of organic based spintronics devices originated from an inorganic ferromagnetic electrode and was not determined by the organic molecules themselves. Here we show that conduction through double-stranded DNA oligomers is spin selective, demonstrating a true organic spin filter. The selectivity exceeds that of any known system at room temperature. The spin dependent resistivity indicates that the effect cannot result solely from the atomic spin-orbit coupling and must relate to a special property resulting from the chirality symmetry. The results may reflect on the importance of spin in determining electron transfer rates through biological systems.

How isolated are the electronic states of the core in core/shell nanoparticles?

We investigated how isolated are the electronic states of the core in a core-shell (c/s) nanoparticles (NPs) from the surface, when the particles are self-assembled on Au substrates via a dithiol (DT) organic linker. Applying photoemission spectroscopy the electronic states of CdSe core only and CdSe/ZnS c/s NPs were compared. The results indicate that in the c/s NPs the HOMO interacts strongly with electronic states in the Au substrate and is pinned at the same energies, relative to the Fermi level, as the core only NPs. When the capping molecules of the NPs were replaced with thiolated molecules, an interaction between the thiol groups and the electronic states of the NPs was observed that depends on the properties of the NPs studied. Thiols binding to the NPs induce the formation of surface trap states. However, while for the core only CdSe NPs the LUMO states are strongly coupled to the surface traps, independent of their size, this coupling is size dependent in the case of the CdSe/ZnS c/s NPs. For a large core, the LUMO is decoupled from the surface trap states. When the core is small enough, the LUMO is delocalized and interacts with these states.