Electroforming and Ohmic contacts in Al-Al2O3-Ag diodes

Abstract

Electroforming of metal-insulator-metal (MIM) diodes is a non-destructive dielectric breakdown process that changes the diode from its initial high resistance state (HRS) to a low resistance state (LRS). After electroforming, resistance switching memories (RSMs) use voltages to switch from HRS to LRS and back. Many MIM combinations are proposed for use in RSMs. In many cases conduction in the LRS is nearly temperature independent at low temperatures; an Ohmic contact with a barrier to electron injection of ∼0 eV results from electroforming. Electroforming of Al-Al2O3-Ag diodes with amorphous anodic Al2O3 thicknesses between 12 and 41 nm has been studied. Two anodizing electrolytes have been used; 0.1 M ammonium pentaborate (bor-H2O) and a solution of 0.1 M of ammonium pentaborate per liter of ethylene glycol (bor-gly). Polarization of Al2O3 and negative charge in Al2O3 are much larger when Al2O3 is formed in bor-H2O solution than when Al is anodized in bor-gly solution. Electroforming of Al-Al2O3-Ag diodes results in an Ohmic contact at the Al-Al2O3 interface, voltage-controlled negative resistance (VCNR) in the current-voltage (I–V) characteristics, electroluminescence (EL), and electron emission into vacuum (EM) from filamentary conducting channels. Two distinct modes of electroforming occur for Al-Al2O3-Ag diodes. α-forming occurs for 2.5 V ≲ VS ≲ 5 V, where VS is the applied voltage. It is characterized by an abrupt current jump with the simultaneous appearance of EL and EM. β-forming occurs for VS ≳ 7 V. I–V curves, EL, and EM develop gradually and are smaller than for α-forming. Electroforming occurs more readily for diodes with Al2O3 formed in bor-H2O that have greater defect densities. Fully developed I-V curves have similar VCNR, EL, and EM after α-forming or β-forming. A model is proposed in which excited states of F-centers, oxygen vacancies in amorphous anodic Al2O3, form defect conduction bands. Electroforming that results in an Ohmic contact requires injection of positive charge at the Al-Al2O3 interface. α-forming is the result of ionization of F-center recombination centers with energies that are close to the Al Fermi level. Hole injection by high-field ionization of valence band states of Al2O3 causes β-forming.