Journal of the American Chemical Society, Vol.125, No.49, 15250-15259, 2003
Molecular quantum cellular automata cells. Electric field driven switching of a silicon surface bound array of vertically oriented two-dot molecular quantum cellular automata
The amine functionality of the linker on the dinuclear complex [trans-Ru(dppm)(2)(CdropCFc)(NCCH2-CH2NH2)][PF6] reacts with Si-Cl bonds of a chlorinated, highly B doped Si (111) surface to yield Si-N surface-complex bonds. The surface bound complex is constrained to a near vertical orientation by the chain length of the linker as confirmed by variable angle XPS. Oxidation of the dinuclear complex with ferrocenium ion or electrochemically generates a stable, biased Fe-III-Ru-II mixed-valence complex on the surface. Characterization of the array of surface bound complexes with spectroscopic as well as electrochemical techniques confirms the presence of strongly bound, chemically robust, mixed-valence complexes. Capping the flat array of complexes with a minimally perturbing mercury electrode permits the equalization of the Fe and Ru energy wells by an applied electric field. The differential capacitance of oxidized and unoxidized bound complexes is compared as a function of voltage applied between the Hg gate and the Si. The results show that electron exchange between the Fe and Ru sites of the array of dinuclear mixed-valence complexes at energy equalization generates a fluctuating dipole that produces a maximum in the capacitance versus voltage curve for each complex-counterion combination present. Passage through the capacitance maximum corresponds to switching of the molecular quantum cellular automata (QCA) cell array by the electric field from the Fe-III-Ru-II configuration to the Fe-II-Ru-III configuration, thereby confirming that molecules possess an essential property necessary for their use as elements of a QCA device.