Molecular Rectifiers

Unimolecular rectifier
Single organic molecule which functions as a rectifier i.e one way conductor of electric current. Idea proposed in 1974 by Aviram and Ratner at New York University. The proposed rectifying molecule favoured electrical conduction from electron rich subunit(e_ donor) to electron poor subunit(e_ acceptor) but disfavoured in the reverse direction.

Molecular Rectifier
Consists of a donor pi system and an acceptor pi system, separated by a sigma-bonded (methylene) tunnelling bridge.

HOMOLUMO
HOMO acronym for highest occupied molecular orbital LUMO acronym for lowest unoccupied molecular orbital. The energy difference between the HOMO and LUMO is termed the HOMO-LUMO gap. HOMO and LUMO are sometimes referred to as frontier orbitals. Roughly, the HOMO level is to organic semiconductors what the valence band maximum is to inorganic semiconductors . The same analogy exists between the LUMO level and the conduction band minimum.

ZERO BIASED CONDITION

e- donating group X tends to place more e- density on the phenyl ring. Thereby increasing the electronic repulsions thus pushes up the energy levels of the molecular orbitals on the donor side. e- acceptor group Y tends to reduce e-density on the phenyl ring and thus reduces the electronic repulsions and this in turn causes the energy level to be lowered. The aliphatic spacer group R ensures that the e- density on either side of the rectifier molecule does not equilibrate by establishing a tunnel barrier. Therefore there exists the energy barrier and no e- flow from donor to acceptor side in zero biased condition.

Forward Biasing:
Application of negative voltage on donor side and a positive voltage on acceptor side. Causes energy levels on donor side to be shifted down. Energy levels on acceptor side to be shifted up. Hence reducing the energy gaps between LUMOs of donor and acceptor to almost zero hence there is current flow by resonant etunneling through the aliphatic bridge.

Reverse Biasing
Application of positive voltage on donor side and a negative voltage on acceptor side. The acceptor side energy levels are shifted down. The donor side energy levels are shifted up. Leading to increase in energy gap between LUMOs of the donor and acceptor. This effectively blocks conduction till large voltage biases.

Why switching over to Molecular Electronics????

Due to Decrease in size. Problems facing silicon based semiconductor industry: Excessive leakage currents. Statistical variations in doping profiles in small dimensions. Density of devices envisioned for molecular electronic circuitry is ~ 1013 transistors per cm2 Molecules are small and identical so no variations in physical properties.

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