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James C Blakesley, Fernando Castro, Alina Zoladek-Lemanczyk, Stephen Giblin, Alan Turnbull
National Physical Laboratory, Hampton Road, Teddington, TW11 0LW, UK
Introduction
Nanoscale optical techniques, such as photoconductive atomic-force microscopy (Pc-AFM) are a useful tool for probing nanoscale morphology and defects in organic thin films. However, the interpretation of the data can be difficult. We have developed a simulation package that can be used to aid the interpretation of data and investigate the limitations of the method.
Summary
A nanoscale 3-dimensional simulation of a Pc-AFM tip and organic thin film has been developed at NPL The simulation is used to study nanoscale photocurrent generation in the presence of an aggregate defect It is predicted that the presence of a defect can be detected by contrast in dark current and photocurrent maps The polarity of photocurrent or open-circuit voltage shift can distinguish between surface and sub-surface defects
Simulation results
A small decrease in reverse-bias photocurrent is observed above the defect. This is most pronounced when the aggregate is ~20nm below the surface. Resolution is of order 50nm.
Figure 1: Simulated photocurrent line scans of 100 nm-diameter acceptor aggregates at various depths within a BHJ film under reverse bias and ~10 Sun irradiance. Left: cross-sectional current maps for 3 aggregate depths.
Under flat-band conditions, the direction of the photocurrent is reversed by an aggregate that is in contact with the substrate. This leads to a shift in local open-circuit voltage of the order 100mV under ~104W/ m2irradiance, as observed experimentally in [2]. When the aggregate is below the surface, the reversed photocurrent occurs whenever the aggregate is illuminated, regardless of tip position; resolution is limited by laser spot size rather than tip size. Aggregates on the surface can be resolved by a halo of reversed photocurrent polarity when the tip is near, but not touching, the aggregate
Figure 3: Simulated photocurrent line scans under flat-band conditions. The insets show current-voltage curves at different positions with an acceptor aggregate on and below the surface.
The rectifying contact between the tip and the aggregate blocks dark current when the aggregate is on the surface. The surface of the aggregate can be imaged by dark current measurements with resolution limited by tip contact area. Dark currents under flatband conditions are very small; higher voltages will be needed in reality.
Figure 2: Simulated dark current line scans of 100nm-diameter acceptor aggregates at various depths within a BHJ film under flat-band dark conditions. Left: cross-sectional current maps for 3 aggregate depths.
Charge transport kij = hopping rate from i to j pi = probability of site i occupied with electron Iij = pi (1- pj) kij = mean current from i to j Solve for steady-state: j Iij =j Iji
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e h BR VBI Eg A, D G T
a
Electronic structure of acceptor LUMO and donor HOMO is simulated with Gaussian disorder Donor hole occupancy = 1- pi Recombination current governed by electron hopping from occupied acceptor to empty donor site; identical equation to charge transport
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Additional forward electron transfer rate Gij equal to exciton splitting rate across interface Generates realistic morphology-dependent recombination rates without need for additional parameters
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Photons absorbed uniformly in donor phase Monte-Carlo random walk simulates exciton transport Electron is transferred to acceptor if exciton reaches interface before decaying
Finite-element model simulates electric field between model AFM tip and conductive substrate.
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Energy transport
Tip-sample electrostatics