Simulating photoconductive atomic-force microscopy (pc-AFM)

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.

Can acceptor aggregation be imaged with photoconductive AFM?

A range of AFM techniques are used to study the surface morphology and topography of bulk-heterojunction (BHJ) films. However, most are not able to image features below the surface. Recent articles have suggested that it is possible to detect the presence of aggregates buried within a BHJ film using Pc-AFM[1,2]. Pc-AFM uses a micrometre-size focussed laser spot to excite a film whilst a conducting AFM tip collects the resulting photocurrent. The tip size is as small as tens of nanometres, allowing photocurrent maps to be measured with better resolution than the diffraction limit of light. It is asserted, using 1D models, that the polarity of the photocurrent indicates whether an aggregate is on the surface or buried below it. Here we test this with a full 3D model.
[1] Tsoi et al., Energy & Environ. Sci. 4, 3646 (2011) [2] Reid et al., J. Appl. Phys. 108, 084320 (2010)

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.

The model explained

Simulation size 200 nm x 100 nm x 20 nm Material parameters similar to typical optimised OPV materials:
Parameter Acceptor electron mobility Donor hole mobility Recombination coefficient Built-in voltage Donor-acceptor energy gap Disorder Exciton generation rate Temperature Lattice Lattice parameter Hopping model Symbol Value ~10-7 m2V-1s-1 ~10-7 m2V-1s-1 ~10-15 m3s-1 0.25 V 1.1 eV 60 meV 10 m s
22 -2 -1

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
4

e h BR VBI Eg A, D G T
a

Charge generation and recombination

300 K homogeneous amorphous 2 nm Miller-Abrahams

 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
2

3 Energy transport Tip

Morphology and annealing

 Additional forward electron transfer rate Gij equal to exciton splitting rate across interface  Generates realistic morphology-dependent recombination rates without need for additional parameters
5

 Random donor-acceptor phase morphology generated by simulated annealing

5 Tip 3 Substrate 1 Charge transport 4 Charge generation 2 Donor-acceptor blend morphology

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