Molecular junctions based on ferromagnetic electrodes allow the study of electronic spin transport near the limit of spintronics miniaturization. However, these junctions reveal moderate magnetoresistance that is sensitive to the orbital structure at their ferromagnet-molecule interfaces. The key structural parameters that should be controlled in order to gain high magnetoresistance have not been established, despite their importance for efficient manipulation, of spin transport at the nanoscale. Here, we show that single-molecule junctions based on nickel electrodes and benzene molecules can yield a significant anisotropic magnetoresistance of up to similar to 200% near the conductance quantum Go. The measured magnetoresistance is mechanically tuned by changing the distance between the electrodes, revealing a nonmonotonic response to junction elongation. These findings are ascribed with the aid of first-principles calculations to variations in the metal-molecule orientation that can be adjusted to obtain highly spin-selective orbital hybridization. Our results demonstrate the important role of geometrical considerations in determining the spin transport properties of metal-molecule interfaces.
With the goal of elucidating the nature of spin-dependent electronic transport in ferromagnetic atomic contacts, we present here a combined experimental and theoretical study of the conductance and shot noise of metallic atomic contacts made of the 3d ferromagnetic materials Fe, Co, and Ni. For comparison, we also present the corresponding results for the noble metal Cu. Conductance and shot noise measurements, performed using a low-temperature break-junction setup, show that in these ferromagnetic nanowires, (i) there is no conductance quantization of any kind, (ii) transport is dominated by several partially open conduction channels, even in the case of single-atom contacts, and (iii) the Fano factor of large contacts saturates to values that clearly differ from those of monovalent (nonmagnetic) metals. We rationalize these observations with the help of a theoretical approach that combines molecular dynamics simulations to describe the junction formation with nonequilibrium Green's function techniques to compute the transport properties within the Landauer-Buttiker framework. Our theoretical approach successfully reproduces all the basic experimental results and it shows that all the observations can be traced back to the fact that the d bands of the minority-spin electrons play a fundamental role in the transport through ferromagnetic atomic-size contacts. These d bands give rise to partially open conduction channels for any contact size, which in turn lead naturally to the different observations described above. Thus, the transport picture for these nanoscale ferromagnetic wires that emerges from the ensemble of our results is clearly at variance with the well established conduction mechanism that governs the transport in macroscopic ferromagnetic wires, where the d bands are responsible for the magnetism but do not take part in the charge flow. These insights provide a fundamental framework for ferromagnetic-based spintronics at the nanoscale.
Revealing the mechanisms of electronic transport through metal-molecule interfaces is of central importance for a variety of molecule-based devices. A key method for understanding these mechanisms is based on the study of conductance versus molecule length in molecular junctions. However, previous works focused on transport governed either by coherent tunnelling or hopping, both at low conductance. Here, we study the upper limit of conductance across metal-molecule-metal interfaces. Using highly conducting single-molecule junctions based on oligoacenes with increasing length, we find that the conductance saturates at an upper limit where it is independent of molecule length. With the aid of two prototype systems, in which the molecules are contacted by either Ag or Pt electrodes, we find two different possible origins for conductance saturation. The results are explained by an intuitive model, backed by ab initio calculations. Our findings shed light on the mechanisms that constrain the conductance of metal-molecule interfaces at the high-transmission limit.
The vibration-mediated Kondo effect attracted considerable theoretical interest during the last decade. However, due to lack of extensive experimental demonstrations, the fine details of the phenomenon were not addressed. Here, we analyze the evolution of vibration-mediated Kondo effect in molecular junctions during mechanical stretching. The described analysis reveals the different contributions of Kondo and inelastic transport.
Generating highly spin-polarized currents at the nanoscale is essential for spin current manipulations and spintronic applications. We find indications for up to 100% spin-polarized currents across nickel oxide atomic junctions formed between two nickel electrodes. The degree of spin polarization is probed by analyzing the shot noise resulting from the discrete statistics of spin-polarized electron transport. We show that spin filtering can be significantly enhanced by local chemical modifications at the single-atom level. This approach paves the way for effective manipulations of spin transport at the fundamental limit of miniaturization.
The interaction of individual electrons with vibrations has been extensively studied. However, the nature of electron-vibration interaction in the presence of many-body electron correlations such as a Kondo state has not been fully investigated. Here, we present transport measurements on a Copper-phthalocyanine molecule, suspended between two silver electrodes in a break-junction setup. Our measurements reveal both zero bias and satellite conductance peaks, which are identified as Kondo resonances with a similar Kondo temperature. The relation of the satellite peaks to electron-vibration interaction is corroborated using several independent spectroscopic indications, as well as ab initio calculations. Further analysis reveals that the contribution of vibration-induced inelastic current is significant in the presence of a Kondo resonance.
We investigate periodical oscillations in the conductance of suspended Au and Pt atomic chains during elongation under mechanical stress. Analysis of conductance and shot noise measurements reveals that the oscillations are mainly related to variations in a specific conduction channel as the chain undergoes transitions between zigzag and linear atomic configurations. The calculated local electronic structure shows that the oscillations originate from varying degrees of hybridization between the atomic orbitals along the chain as a function of the zigzag angle. These variations are highly dependent on the directionally and symmetry of the relevant orbitals, in agreement with the order-of-magnitude difference between the Pt and Au oscillation amplitudes observed in experiment. Our results demonstrate that the sensitivity of conductance to structural variations can be controlled by designing atomic-scale conductors in view of the directional interactions between atomic orbitals.
Pt is known to show spontaneous formation of monatomic chains upon breaking a metallic contact. From model calculations, these chains are expected to be spin polarized. However, direct experimental evidence for or against magnetism is lacking. Here, we investigate shot noise as a potential source of information on the magnetic state of Pt atomic chains. We observe a remarkable structure in the distribution of measured shot-noise levels, where the data appear to be confined to the region of nonmagnetic states. While this suggests a nonmagnetic ground state for the Pt atomic chains, from calculations we find that the magnetism in Pt chains is due to "actor" electron channels, which contribute very little to ballistic conductance and noise. On the other hand, there are weakly polarized "spectator" channels, which carry most of the current and are only slightly modified by the magnetic state.
The effect of electron-vibration interaction in atomic-scale junctions with a single conduction channel was widely investigated both theoretically and experimentally. However, the more general case of junctions with several conduction channels has received very little attention. Here we study electron-vibration interaction in multichannel molecular junctions, formed by introduction of either benzene or carbon dioxide between platinum electrodes. By combining shot noise and differential conductance measurements, we analyze the effect of vibration activation on conductance in view of the distribution of conduction channels. Based on the shift of vibration energy while the junction is stretched, we identify vibration modes with transverse and longitudinal symmetry. The detection of different vibration modes is ascribed to efficient vibration coupling to different conduction channels according to symmetry considerations. While most of our observations can be explained in view of the theoretical models for a single conduction channel, the appearance of conductance enhancement, induced by electron-vibration interaction, at high conductance values indicates either unexpected high electron-vibration coupling or interchannel scattering.
We demonstrate a general procedure for determining the conduction channels of quantum conductors from shot noise measurements. This numerical approach allows multichannel analysis which was previously limited to superconductors. Channel analysis of Ag and Au atomic contacts reveals a remarkable behavior in which the channels fully open one by one with increasing conductance. These results allow us to unambiguously distinguish between free-electron and tight-binding descriptions for the conductance of monovalent contacts. Furthermore, the channel resolution uncovers the presence of tunneling channels in parallel to the conductance through the main contact and provides a means for distinguishing between the contact conductance and tunneling contributions. Finally, unique channel distributions were found for Al and Pt contacts reflecting their distinct valence orbital structures.
Using a break junction technique, we find a dear signature for the formation of conducting hybrid junctions composed of a single organic molecule (benzene, naphthalene, or anthracene) connected to chains of platinum atoms. The hybrid junctions exhibit metallic-like conductance (similar to 0.1-1G(0)), which is rather insensitive to further elongation by additional atoms. At low bias voltage the hybrid junctions can be elongated significantly beyond the length of the bare atomic chains. Ab initio calculations reveal that benzene based hybrid junctions have a significant binding energy and high structural flexibility that may contribute to the survival of the hybrid junction during the elongation process. The fabrication of hybrid junctions opens the way for combining the different properties of atomic chains and organic molecules to realize a new class of atomic scale interfaces.
For the study of junctions formed by single molecules shot noise offers interesting new information that cannot be easily obtained by other means. At low bias it allows, for some cases of interest, determining the transmission probability and the number of current carrying conductance channels. By this method it is possible to identify the cross-over in sign of the inelastic scattering signal in the differential conductance. This is a first step towards the study of inelastic scattering signals in shot noise, as the second moment of the current.
The simplicity of single-molecule junctions based on direct bonding of a small molecule between two metallic electrodes makes them an ideal system for the study of fundamental questions related to molecular electronics. Here we study the conductance properties of six different types of molecules by suspending individual molecules between Pt electrodes. All the molecular junctions show a typical conductance of about 1G(0) which is ascribed to the dominant role of the Pt contacts. However, despite the metalliclike conductivity, the individual molecular signature is well expressed by the effect of molecular vibrations in the inelastic contribution to the conductance.
Point contact spectroscopy on a H(2)O molecule bridging Pt electrodes reveals a clear crossover between enhancement and reduction of the conductance due to electron-vibration interaction. As single-channel models predict such a crossover at a transmission probability of tau=0.5, we used shot noise measurements to analyze the transmission and observed at least two channels across the junction where the dominant channel has a tau=0.51 +/- 0.01 transmission probability at the crossover conductance, which is consistent with the predictions for single-channel models.
We present the Kelvin probe force microscopy measurements of the Einstein relation, i.e., the relation between the diffusion coefficient of charge carriers and their mobility, in undoped and doped disordered organic thin films. The theoretical prediction of a large deviation of the Einstein relation from its classical value is verified and attributed to the energy distribution of the density of states. The results are explained in the context of degeneracy effects on the transport in disordered organic thin films, and their implications for organic-based devices are discussed.
We report on high-resolution electronic measurements of doped organic thin-film transistors using Kelvin probe force microscopy. Measurements conducted on field effect transistors made of N,N-I-diphenyl- N, N-I-bis(1-naphthyl)-1,1(I)-biphenyl-4,4(I)-diamine p-doped with tetrafluoro-tetracyanoquinodimethane have allowed us to determine the rich structure of the doping-induced density of states. In addition, the doping process changes only slightly the Fermi energy position with respect to the highest occupied molecular orbital level center. The moderate change is explained by two counter-acting effects on the Fermi energy position: the doping-induced additional charge and the broadening of the density of states.
The potential across an organic thin-film transistor is measured by Kelvin probe force microscopy and is used to determine directly the pinch-off voltage at different gate voltages. These measurements lead to the determination of a generalized threshold voltage, which corresponds to molecular level shift as a function of the gate voltage. A comparison between measured and calculated threshold voltage reveals a deviation from a simple Gaussian distribution of the transport density of states available for holes. (c) 2006 American Institute of Physics.
We investigate the density of states (DOS) for hole transport in undoped and doped amorphous organic films using high lateral resolution Kelvin probe force microscopy. Measurements are done on field effect transistors made of N,N-I-diphenyl-N, N-I-bis(1-naphthyl)-1,10-biphenyl-4,4(II)-diamine undoped or p doped with tetrafluoro-tetracyanoquinodimethane. We determine the DOS structure of the undoped material, including an anomalous peak related to interfaces between regions of different surface potential, the DOS doping-induced broadening, and doping-induced sharp peaks on the main DOS distribution.
Kelvin probe force microscopy was used for extraction of the threshold and the pinch off voltages in organic thin film transistors. The first was determined by direct detection of the charge accumulation onset and the latter by a direct observation of the pinch off region formation. In addition, an effective threshold voltage shift can be extracted from the pinch-off voltage as a function of charge concentration. The dependence of the effective threshold voltage on the gate voltage must be considered when calculating charge carrier concentrations in organic thin film transistors.
We report on high-resolution potential measurements across complete metal/organic molecular semiconductor/metal structures using Kelvin probe force microscopy in inert atmosphere. It is found that the potential distribution at the metal/organic interfaces is in agreement with an interfacial abrupt potential changes and the work function of the different metals. The potential distribution across the organic layer strongly depends on its purification. In pure Alq(3) the potential profile is flat, while in nonpurified layers there is substantial potential bending probably due to the presence of deep traps. The effect of the measuring tip is calculated and discussed. (C) 2004 American Institute of Physics.
We explore the possibility of controlling electronic properties along an inorganic nanotube (INT) through the influence of nanometer-scale features in the underlying substrate. We examined single multi-walled WS2 INTs using scanning tunneling microscopy (STM) in high vacuum. As long as the INTs He flat on MoS2 (0 0 0 1) or graphite (0 0 0 1) surfaces, they appear semimetallic. However, when the INT is suspended above the surface due to crossing steps or other nanotubes, a band gap opens up. We discuss this observation in terms of either a potential drop under the INT, or a change in its electronic properties due to its distortion when it lies flat on a surface. (C) 2001 Elsevier Science B.V. All rights reserved.