Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userConductance Switching of Azobenzene-Based Self-Assembled Monolayers on Cobalt Probed by UHV Conductive-AFM
51
0
0.0
(
0
)
Added by
Dominique Vuillaume
Publication date
2021
fields
Physics
and research's language is
English
Ask ChatGPT about the research
No Arabic abstract
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 Greens 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.
rate research
Read More
A new azobenzene-thiophene molecular switch is designed, synthesized and used to form self-assembled monolayers (SAM) on gold. An on/off conductance ratio up to 7x1E3 (with an average value of 1.5x1E3) is reported. The on conductance state is clearly identified to the cis isomer of the azobenzene moiety. The high on/off ratio is explained in terms of photo-induced, configuration-related, changes in the electrode-molecule interface energetics (changes in the energy position of the molecular orbitals with respect to the Fermi energy of electrodes) in addition to changes in the tunnel barrier length (length of the molecules). First principles DFT calculations demonstrate a better delocalization of the frontier orbitals, as well as a stronger electronic coupling between the azobenzene moiety and the electrode for the cis configuration over the trans one. Measured photoionization cross-sections for the molecules in the SAM are close to the known values for azobenzene derivatives in solution.
We report on the phosphonic acid route for the grafting of functional molecules, optical switch (dithienylethene diphosphonic acid, DDA), on La0.7Sr0.3MnO3 (LSMO). Compact self-assembled monolayers (SAMs) of DDA are formed on LSMO as studied by topographic atomic force microscopy (AFM), ellipsometry, water contact angle and X-ray photoemission spectroscopy (XPS). The conducting AFM measurements show that the electrical conductance of LSMO/DDA is about 3 decades below that of the bare LSMO substrate. Moreover, the presence of the DDA SAM suppresses the known conductance switching of the LSMO substrate that is induced by mechanical and/or bias constraints during C-AFM measurements. A partial light-induced conductance switching between the open and closed forms of the DDA is observed for the LSMO/DDA/C-AFM tip molecular junctions (closed/open conductance ratio of about 8). We show that, in the case of long-time exposition to UV light, this feature can be masked by a non-reversible decrease (a factor of about 15) of the conductance of the LSMO electrode.
In graphene spintronics, interaction of localized magnetic moments with the electron spins paves a new way to explore the underlying spin relaxation mechanism. A self-assembled layer of organic cobalt-porphyrin (CoPP) molecules on graphene provides a desired platform for such studies via the magnetic moments of porphyrin-bound cobalt atoms. In this work a study of spin transport properties of graphene spin-valve devices functionalized with such CoPP molecules as a function of temperature via non-local spin-valve and Hanle spin precession measurements is reported. For the functionalized (molecular) devices, we observe a slight decrease in the spin relaxation time ({tau}s), which could be an indication of enhanced spin-flip scattering of the electron spins in graphene in the presence of the molecular magnetic moments. The effect of the molecular layer is masked for low quality samples (low mobility), possibly due to dominance of Elliot-Yafet (EY) type spin relaxation mechanisms.
The next frontier in photonics will rely on the synergistic combination of disparate material systems. One unique organic molecule is azobenzene. This molecule can reversibly change conformations when optically excited in the blue (trans-to-cis) or mid-IR (cis-to-trans). Here, we demonstrate SiO2 optical resonators modified with a monolayer of azobenzene-containing 4-(4-diethylaminophenylazo)pyridine (Aazo) with quality factors over 106. Using a pair of lasers, the molecule is reversibly flipped between molecular conformations, inducing resonant wavelength shifts, and multiple switching cycles are demonstrated. The magnitude of the shift scales with the relative surface density of Aazo. The experimental data agrees with theoretical modeling.
The conductance profiles of magnetic transition metal atoms, such as Fe, Co and Mn, deposited on surfaces and probed by a scanning tunneling microscope (STM), provide detailed information on the magnetic excitations of such nano-magnets. In general the profiles are symmetric with respect to the applied bias. However a set of recent experiments has shown evidence for inherent asymmetries when either a normal or a spin-polarized STM tip is used. In order to explain such asymmetries here we expand our previously developed perturbative approach to electron-spin scattering to the spin- polarized case and to the inclusion of out of equilibrium spin populations. In the case of a magnetic STM tip we demonstrate that the asymmetries are driven by the non-equilibrium occupation of the various atomic spin-levels, an effect that reminds closely that electron spin-transfer. In contrast when the tip is not spin-polarized such non-equilibrium population cannot be build up. In this circumstance we propose that the asymmetry simply originates from the transition metal ion density of state, which is included here as a non-vanishing real component to the spin-scattering self-energy.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
