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High-resolution atomic force microscopy
of high-quality, solvent-free crystals of
[6,6]-phenyl-C
61
-butyric acid methyl ester
G.M. Lazzerini
1
, G. Patern
2
, F. Cacialli
2
, A. Yacoot
1
1
National Physical Laboratory, Hampton Road Teddington Middlesex TW11 0LW, UK
2
London Centre for Nanotechnology and Department of Physics and Astronomy,
University College London, Gower Street, London WC1E 6BT, UK
Acknowledgments
This research is supported by the European Union by funding the European
Metrology Research Programme (EMRP) project Traceable measurement of
mechanical properties of nano-objects (MechProNo)
GMP is supported by an IMPACT PhD studentship co-sponsored by UCL and
ISIS- Neutron and Muon Facility (Science and Technology Facilities Council)
Introduction
Results are presented from a study of high-quality, solvent-free single crystals of [6,6]-phenyl-C
61
-butyric acid
methyl ester (PCBM) using high-resolution traceable atomic force microscopy (AFM). The PCBM crystals were
grown by solvent casting a chlorobenzene solution on indium tin oxide pre-patterned substrates.
1
A home-made
AFM with an NPL Plane Mirror Diferential Optical interferometer was used to traceably measure the height of the
features on the surface.
2

Results showed:
the height of the single crystals takes specifc values such as 49 nm 2 nm and 105 nm 3 nm
or 72 nm 2 nm and 139 nm 3 nm.
with the low uncertainty of the AFM ( < 0.3 nm), we identifed a step on the crystal surface whose height
corresponds to one of the lattice constants of the single PCBM crystal (1.3 nm) as measured with X-ray difraction.
1

PCBM solvent-free crystals
PCBM is one of the most used electron acceptors in organic solar cells with type II heterojunction design.
Obtaining high quality PCBM solvent free crystals is crucial for:
Understanding of charge transport in PCBM;
Optimizing the performance as photovoltaic diodes, feld efect transistors and light emitting diodes.
Preparation:
drop casting of PCBM 20 mg/ml chlorobenzene solution on indium tin oxide pre-patterned substrates.
samples dried in vacuum (10
-2
mbar) overnight, at room temperature, to remove residual solvent.
X-rays difraction (XRD) measurements (I24-Microfocus MX beam-line at Diamond Light Source UK):
PCBM assembles into a monoclinic unit cell containing four PCBM molecules.
No solvent inclusion, contrary to observations made by Rispens et al.
3
The Van der Waals sphere representation
(fgure 1) indicates that there is not enough space to accommodate a solvent molecule inside the unit cell.
References
1 G. Patern, et al. J. Mater. Chem. C 1, 5619 (2013) -
Published by The Royal Society of Chemistry.
2 A. Yacoot, et al. Meas. Sci. Technol. 18, 350 (2007).
3 M.T. Rispens, et al. Chem Commun, 2116 (2003).
4 ISO 5436 (2000) Geometrical product specifcations (GPS)
Surface texture: Profle method Measurement standards
Part 1 Material measures.
Conclusions
We reported traceable, low noise AFM measurement of PCBM crystals, the election electron-acceptor in organic solar cells. The AFM measurements confrm the high quality of the surface
of these crystals, in addition to the high quality crystalline structure of the bulk material as measured via XRD. The low noise of the TS-AFM allowed measuring the roughness of the crystals
down to 0.6 nm and identifying steps in the crystal structure corresponding to the a lattice constant of the crystal.
Measurements
Multiplicity in step height
We measured the height of the crystals according
to the ISO Standard 5436
4
and interestingly we
observed:
Recurrent height values among crystals across
several samples.
Height values multiple of ~ 50 nm or ~ 70 nm
(e.g. 49 nm 2 nm and 105 nm 3 nm or
72 nm 2 nm and 139 nm 3 nm).
Crystal thickness << lateral dimensions resulting
in crystal fexibility (Figure A)
Roughness and dislocations
The roughness of the surface of the crystals can be
as low as 0.6 nm, which, together with their high
quality bulk structure make them good candidates
for studying the conduction mechanism of
the crystal both in the bulk (e.g. Hall mobility
measurements) and on its surface (e.g. feld efect
mobility measurements). (Figures D, E and F)
AFM measurements identifed steps on the crystal
surface whose height (1.3 nm) corresponds to the
a constant of the single PCBM crystal as measured
with X-ray difraction.
1
(Figures G, H and I)
Tip-sample interaction AFM
This AFM has been designed for the study of tip sample interactions and makes traceable measurements
(along the z axis) of sample morphology and of the interaction between the tip and the cantilever. It features:
A fbre interferometer (785 nm) to detect the cantilever defection (not a 4-quadrant photodiode)
A custom feedback system to work in closed loop both in contact and non-contact mode
Low noise NPL plane mirror diferential optical interferometer, fbre-fed with a frequency stabilized laser
(632.8 nm) to traceably detect the displacement along the z axis
Crystal
System
Space
Group
Unit Cell Dimension Volume Z Crystal size
Monoclinic P2(1)/n a = 13.47 a = 90
b = 15.14 = 106.90
c = 19.01 = 90
3708.70
3
4 0.04 x 0.02 x 0.01 mm
3
109 nm 0.6 nm
48.2 nm 0.9 nm
A C
E F
I
View along a-direction View along b-direction View along c-direction
D
G
B
H
~ 1.3 nm