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 10(17) 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. (C) 2015 Author(s).Dutch Polymer Institute (DPI), BISTABLE [704]; Fundacao para Ciencia e Tecnologia (FCT) through the research Instituto de Telecommunicacoes (IT-Lx); project Memristor based Adaptive Neuronal Networks (MemBrAiNN) [PTDC/CTM-NAN/122868/2010]; European Community Seventh Framework Programme FP7', ONE-P [212311]; Dutch Ministry of Education, Culture and Science (Gravity Program) [024.001.035]info:eu-repo/semantics/publishedVersio

A model for exciton-polaritons in uniaxial molecular crystals describing spatial dispersion, refraction and reflection

Propagation of light through a uniaxial material is studied using field theoretical methods. The materials is modeled by cubic lattice of oriented classical Lorentz oscillators. A two-step coarse graining approach is applied. At the bulk level, excitations of the coupled light-matter system, or polaritons, are described by a Proca-type equation for massive vector bosons. On the microscopic level, multiple scattering is used to relate the sub-luminal speed of the polaritons to the polarizability of the Lorentz oscillators. For each direction of propagation of the polaritons, three independent polarizations exist, consistent with the integer spin of massive vector bosons. Reflection and refraction are calculated by imposing the requirement of a uniform gauge for the electromagnetic vector potential across the interface of the uniaxial molecular material and vacuum. Reflectance spectra near the resonance frequency are calculated. The spectra feature a characteristic minimum in middle of the reflection band, in agreement with experiment. An incident unpolarized light beam is predicted to refract into three different rays. The model supports surface bound excitations and predicts a Goos-Haenchen shift of the reflected beam upon reflection of light incident from vacuum onto the material.Comment: 55 pages, 9 figure

Charge recombination in a poly(para-phenylene vinylene)-fullerene derivative composite film studied by transient, nonresonant, hole-burning spectroscopy

Transient, nonresonant, hole-burning spectroscopy was used to study the charge recombination process in poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1-4-phenylene vinylene] (MDMO-PPV):methanofullerene (PCBM) composite films. The position and intensity of the spectral hole in the absorption band of MDMO-PPV were monitored as a function of time in the 10 ns-10 ms time range. A time-dependent red shift was obsd. The intensity of the spectral hole decayed with time according to a power law (~t-a). The exponent a ~ 0.5 is nearly independent of the excitation fluence in the range 0.05-2 mJ/cm2. The depth of the spectral hole depends sublinearly on the excitation fluence (I) and can be described by (~G-b) with b.apprx.0.5. The time-dependent red shift and the power-law type time decay can be reproduced by numerical simulations. The Monte Carlo method is used to simulate the hopping dynamics of the photoinduced charges in a lattice of energetically disordered sites before they eventually recombine at the MDMO-PPV:PCBM interface. Charge sepn. is assisted by disorder and, in the 10 ns-10 ms time range, the recombination rate is limited by the detrapping of the cationic charge carriers in MDMO-PP

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 /polyspirofluorene /Ba/Al diodes using quasistatic capacitance-voltage measurements. In the initial stage, electrons are injected into the polymer and then deeply trapped near the polyspirofluorene-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 31017 m−2

Optical modulation of nano-gap tunnelling junctions comprising self-assembled monolayers of hemicyanine dyes

Light-driven conductance switching in molecular tunnelling junctions that relies on photoisomerization is constrained by the limitations of kinetic traps and either by the sterics of rearranging atoms in a densely packed monolayer or the small absorbance of individual molecules. Here we demonstrate light-driven conductance gating; devices comprising monolayers of hemicyanine dyes trapped between two metallic nanowires exhibit higher conductance under irradiation than in the dark. The modulation of the tunnelling current occurs faster than the timescale of the measurement (∼1 min). We propose a mechanism in which a fraction of molecules enters an excited state that brings the conjugated portion of the monolayer into resonance with the electrodes. This mechanism is supported by calculations showing the delocalization of molecular orbitals near the Fermi energy in the excited and cationic states, but not the ground state and a reasonable change in conductance with respect to the effective barrier width

The role of internal structure in the anomalous switching dynamics of metal-oxide/polymer resistive random access memories

The dynamic response of a non-volatile, bistable resistive memory fabricated in the form of Al2O3/polymer diodes has been probed in both the off- and on-state using triangular and step voltage profiles. The results provide insight into the wide spread in switching times reported in the literature and explain an apparently anomalous behaviour of the on-state, namely the disappearance of the negative differential resistance region at high voltage scan rates which is commonly attributed to a “dead time” phenomenon. The off-state response follows closely the predictions based on a classical, two-layer capacitor description of the device. As voltage scan rates increase, the model predicts that the fraction of the applied voltage, Vox , appearing across the oxide decreases. Device responses to step voltages in both the off- and on-state show that switching events are characterized by a delay time. Coupling such delays to the lower values of Vox attained during fast scan rates, the anomalous observation in the on-state that, device currents decrease with increasing voltage scan rate, is readily explained. Assuming that a critical current is required to turn off a conducting channel in the oxide, a tentative model is suggested to explain the shift in the onset of negative differential resistance to lower voltages as the voltage scan rate increases. The findings also suggest that the fundamental limitations on the speed of operation of a bilayer resistive memory are the time- and voltage-dependences of the switch-on mechanism and not the switch-off process

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 10(25)/m(3). The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics. (C) 2014 Author(s)

High Circular Polarization of Electroluminescence Achieved via Self-Assembly of a Light-Emitting Chiral Conjugated Polymer into Multidomain Cholesteric Films.

We demonstrate a facile route to obtain high and broad-band circular polarization of electroluminescence in single-layer polymer OLEDs. As a light-emitting material we use a donor-acceptor polyfluorene with enantiomerically pure chiral side-chains. We show that upon thermal annealing the polymer self-assembles into a multidomain cholesteric film. By varying the thickness of the polymer emitting layer, we achieve high levels of circular polarization of electroluminescence (up to 40% excess of right-handed polarization), which are the highest reported for polymer OLEDs not using chiral dopants or alignment layers. Mueller matrix ellipsometry shows strong optical anisotropies in the film, indicating that the circular polarization of luminescence arises mainly after the photon has been generated, through selective scattering and birefringence correlated in the direction of the initial linear polarization of the photon. Our work demonstrates that chirally substituted conjugated polymers can combine photonic and semiconducting properties in advanced optoelectronic devices