Benjamin F. Bory

Trapping of electrons in metal oxide-polymer memory diodes in the initial stage of electroforming

Metal oxide-polymer diodes require electroforming before they act as nonvolatile resistive switching memory diodes. Here we investigate the early stages of the electroforming process in Al/Al2O3/poly(spirofluorene)/Ba/Al diodes using quasistatic capacitance-voltage measurements. In the initial stage, electrons are injected into the polymer and then deeply trapped near the poly(spirofluorene)-Al2O3 interface. For bias voltages below 6 V, the number of trapped electrons is found to be CoxideV/q with Coxide as the geometrical capacitance of the oxide layer. This implies a density of traps for the electrons at the polymer-metal oxide interface larger than 3×1017 m−2.

Opto-electronic characterization of electron traps upon forming polymer oxide memory diodes

Metal-insulator-polymer diodes where the insulator is a thin oxide (Al2O3) layer are electroformed by applying a high bias. The initial stage is reversible and involves trapping of electrons near the oxide/polymer interface. The rate of charge trapping is limited by electron transport through the polymer. Detrapping of charge stored can be accomplished by illuminating with light under short-circuit conditions. The amount of stored charge is determined from the optically induced discharging current transient as a function of applied voltage and oxide thickness. When the charge density exceeds 8 × 1017/m2, an irreversible soft breakdown transition occurs to a non-volatile memory diode.

Lithium fluoride injection layers can form quasi-ohmic contacts for both holes and electrons

Thin LiF interlayers are typically used in organic light-emitting diodes to enhance the electron injection. Here, we show that the effective work function of a contact with a LiF interlayer can be either raised or lowered depending on the history of the applied bias. Formation of quasi-Ohmic contacts for both electrons and holes is demonstrated by electroluminescence from symmetric LiF/polymer/LiF diodes in both bias polarities. The origin of the dynamic switching is charging of electrically induced Frenkel defects. The current density–electroluminescence–voltage characteristics can qualitatively be explained. The interpretation is corroborated by unipolar memristive switching and by bias dependent reflection measurements.

Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 1025/m3. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

Unipolar resistive switching in metal oxide/organic semiconductor non-volatile memories as a critical phenomenon

Diodes incorporating a bilayer of an organic semiconductor and a wide bandgap metal oxide can show unipolar, non-volatile memory behavior after electroforming. The prolonged bias voltage stress induces defects in the metal oxide with an areal density exceeding 1017 m−2. We explain the electrical bistability by the coexistence of two thermodynamically stable phases at the interface between an organic semiconductor and metal oxide. One phase contains mainly ionized defects and has a low work function, while the other phase has mainly neutral defects and a high work function. In the diodes, domains of the phase with a low work function constitute current filaments. The phase composition and critical temperature are derived from a 2D Ising model as a function of chemical potential. The model predicts filamentary conduction exhibiting a negative differential resistance and nonvolatile memory behavior. The model is expected to be generally applicable to any bilayer system that shows unipolar resistive switching.

Electrical conduction of LiF interlayers in organic diodes

An interlayer of LiF in between a metal and an organic semiconductor is commonly used to improve the electron injection. Here, we investigate the effect of moderate bias voltages on the electrical properties of Al/LiF/poly(spirofluorene)/Ba/Al diodes by systematically varying the thickness of the LiF layer (2-50 nm). Application of forward bias V below the bandgap of LiF (V < Eg ∼ 14 V) results in reversible formation of an electrical double layer at the LiF/poly(spirofluorene) hetero-junction. Electrons are trapped on the poly(spirofluorene) side of the junction, while positively charged defects accumulate in the LiF with number densities as high as 1025/m3. Optoelectronic measurements confirm the built-up of aggregated, ionized F centres in the LiF as the positive trapped charges. The charged defects result in efficient transport of electrons from the polymer across the LiF, with current densities that are practically independent of the thickness of the LiF layer.

Charge trapping at the polymer-metal oxide interface as a first step in the electroforming of organic-inorganic memory diodes

Diodes containing a layer of aluminum oxide combined with a layer of π-conjugated polymer show nonvolatile memory effects after they have been electroformed. Electroforming is induced by application high bias voltage close to the limit for dielectric breakdown and can be performed reliably and with high yield on organic-inorganic hybrid diodes with controlled oxide thickness. Here we investigate the initial stage of the electroforming process and show through temperature dependent current-voltage characterization that electrons are trapped in deep traps at the interface between π-conjugated polyspirofluorene polymer and the aluminum oxide.