Bilayer Molecular Electronics: All-Carbon Electronic Junctions Containing Molecular Bilayers Made with “Click” Chemistry

Abstract

Bilayer molecular junctions were fabricated by using the alkyne/azide "click" reaction on a carbon substrate, followed by deposition of a carbon top contact in a crossbar configuration. The click reaction on an alkyne layer formed by diazonium reduction permitted incorporation of a range of molecules into the resulting bilayer, including alkane, aromatic, and redox-active molecules, with high yield (>90%) and good reproducibility. Detailed characterization of the current-voltage behavior of bilayer molecular junctions indicated that charge transport is consistent with tunneling, but that the effective barrier does not strongly vary with molecular structure for the series of molecules studied.

Light‐Driven Bipolar Electrochemical Logic Gates with Electrical or Optical Outputs

“…In contrast with our last report, where the non‐SC component of the cathodic pole was connected with a wire to silicon, it was here directly deposited on the SC, which is highly beneficial for minimizing electrical connections and thus the size of the device. The carbon part was made of a band of pyrolyzed photoresist film (PPF), deposited at the edge of the p ‐SiH surface (see the Experimental Section in the Supporting Information for more details). The gate operating principle is shown in Figure a.…”

“…In contrast with our last report, where the non-SC component of the cathodic pole was connected with aw ire to silicon, [50] it was here directly deposited on the SC, which is highly beneficialf or minimizing electrical connections and thus the size of the device. The carbon part was made of ab and of pyrolyzed photoresist film (PPF), [52,53] deposited at the edgeo ft he p-SiH surface( see the Experimen-tal Sectioni nt he Supporting Information form ore details). The gate operating principle is shown in Figure 2a.I na bsence of light, that is, when In2 = 0, reduction occurs at the PPF only when E app = 10 V, that is, when In1 = 1, because the effective BE length in the dark (l = 3cmwhen p-SiH is not electrochemically active) does not allow as ufficient DV max to trigger Reactions (2) and (3) for E app = 7V .I ndeed, Equation (1) showst hat in this case DV max = 2.3 V, which is slightly lower than the threshold value neededt ot rigger Reactions (2) and (3) on carbon,a s showni nF igure S6.…”

Bottom‐Up Molecular Tunneling Junctions Formed by Self‐Assembly

“…McCreery and co-workers studied monolayers grown on carbon substrates consisting of pyrolyzed photoresists. [150,151] These monolayers were attached to the substrate through a poorly defined reaction between diazonium salts and amorphous carbon and are therefore self-organized rather than self-assembled layers. Thus, we will not discuss them further.…”

Molecular and Biological Catalysts Coimmobilization on Electrode by Combining Diazonium Electrografting and Sequential Click Chemistry

“…such as the thiol‐ene coupling reaction that has been extensively implemented in various synthetic methodologies and surface modification procedures . To date, electrode modification by combining the electrochemical reduction of diazonium salts and further derivatization via click chemistry remains limited to monofunctionalized electrode surfaces …”