SURFACE AND INTERFACE ANALYSIS

Surf. Interface Anal. 2002; 33: 75–80

Latex bead projection Nanopatterns

U. C. Fischer,∗ J. Heimel, H.-J. Maas, M. Hartig, S. Hoeppener and H. Fuchs
Physikalisches Institut, Westfaelische Wilhelms Universitaet, Wilhelm-Klemm Strasse 10, 48149 Muenster, Germany

Received 6 October 2000; Revised 23 February 2001; Accepted 30 August 2001

Monolayers of monodisperse latex beads of submicron size are used as a convenient mask for physical
vapour deposition to produce latex bead projection patterns as nanostructures that have been used often
as test structures for near-field optical applications. Variations of the fabrication technique lead to derived
nanostructures: flat surface structures are formed by embedding projection patterns consisting of one
material into the surface of a different material; complementary projection patterns are formed by using
a projection pattern as a mask for a nanoimprinting process; and submicron ring structures are formed
in a controlled way from the debris of the latex bead mask. The application of such nanostructures as
test patterns for scanning near-field optical microscopy (SNOM) is demonstrated. Copyright  2002 John
Wiley & Sons, Ltd.

KEYWORDS: scanning near-field optical microscopy; latex beads; nanostructure; nano imprinting

INTRODUCTION as test patterns for scanning near-field optical microscopy

Monolayers of monodisperse latex beads of submicron size
have been introduced as a convenient mask for physical
vapour deposition1,2 or as an etch mask3 to produce a large
variety of nanostructures for numerous applications.4 – 16
Such nanostructures have been applied often as test struc-
tures for near-field optical investigations.17 – 22 In this article
a few variations of this technique are described with an
emphasis on the application of the resulting nanostructures
as test structures for near-field optical investigations.
The basic procedure for forming latex bead projection
patterns23 as outlined in Fig. 1 consists of:
(1) Forming a monolayer of latex beads as a mask for
physical vapour deposition on a suitable substrate.
(2) Physical vapour deposition for forming the projection
pattern.
(3) Removing this mask.
The projection of a hexagonally close-packed layer of
latex beads forms the characteristic triangular protrusions
on the substrate.
It is shown here that the projection patterns may be
processed further for the fabrication of derived nanostruc-
tures. Complementary projection patterns with characteristic
triangular depressions instead of the protrusions, surface-
embedded projection patterns and ring structures serve as
examples for nanostructures that are derived from the projec-
tion patterns. An application of embedded surface structures
Ł Correspondence to: U. C. Fischer, Physikalisches Institut,
Westfaelische Wilhelms Universitaet, Wilhelm-Klemm Strasse 10,
48149 Muenster, Germany. E-mail: fischeu@nwz.uni-muenster.de
Contract/grant sponsor: German Federal Ministry of Research and
Education (BMBF).
Contract/grant sponsor: German Science Council (DFG).
(SNOM) is demonstrated.
NANOSTRUCTURE FABRICATION
Formation of the mask
A partial monolayer of hexagonally close-packed charged
latex beads is formed on a hydrophilic substrate of equal
surface charge. Here, we use negatively charged latex beads
of diameter 0.22 µm and freshly cleaved mica as a substrate.
It should be noted that the latex beads are provided by the
producers as a colloidal dispersion of the beads in water.
For stabilization, the beads bear dissociable groups at the
surface that lead to a negative or positive charging of their
surface in the dispersion, depending on the type of chemical
modification of the surface.
We start with a dispersion of 2 mg of latex beads in
1 ml of water. A 100 µl drop of this dispersion is applied
to a 10 cm2 sheet of freshly cleaved mica. After removing
superfluous liquid with tissue paper, a thin film is formed
that wets the mica surface homogeneously. The remaining
film slowly dries to form a monolayer of latex beads. In this
monolayer the latex beads may be isolated from each other or
they may form aggregates and larger patches of hexagonally
close-packed beads. The size of the hexagonally close-packed
patches increases with the concentration of latex beads in the
dispersion.
Procedures for mask formation can be varied in many
ways. Instead of just drying, the monolayer can be formed
by spin coating2 or more elaborate procedures can be used
for the drying process in order to favour the growth of two-
dimensional crystalline aggregates of the latex beads.24 When
positively charged latex beads are used a random distribu-
tion of the beads is obtained rather than hexagonal close pack-
ing. This is also the case when negatively charged latex beads
are adsorbed to a positively charged surface.2 Sometimes it

DOI: 10.1002/sia.1165 Copyright  2002 John Wiley & Sons, Ltd.

76 U. C. Fischer et al.

in combination with ultrasonic treatment. This procedure

has the problem that deposits—very often of a ring-like
form—remain due to an incomplete removal of the mask,
as shown for an SiO2 projection pattern in Fig. 2. As an
alternative, we found that the mask can be removed without
noticeable remainders and without impairing the projection
pattern by floating the mask onto a clean surface of water
if the mask and the substrate have the same surface charge
and if the projection pattern withstands this treatment as
is the case for gold and SiO2 . Details of the process of
floating the mask onto water were described by Burmeister
et al.7 An example for a projection pattern of gold formed
in this way without the ring-like remainders is shown in
Fig. 3. If the latex spheres and the substrate have opposite
surface charges, the latex beads are irreversibly bound to the
substrate and cannot be removed by this procedure.

1.00 40.0 nM

0.75 20.0 nM

0.0 nM
0.50

0.25
Figure 1. Scheme for the fabrication of projection patterns.

0
is desirable to form the latex masks on different substrates. 0 0.25 0.50 0.75 1.00
For this purpose it is possible to transfer hexagonally close- µM
packed areas of the latex bead mask onto a clean surface of
Figure 2. AFM image of an SiO2 projection pattern. The
water and subsequently transfer it to a different substrate7
triangles are very well defined due to the small grain size of
by similar techniques that usually are employed when trans-
evaporated SiO2 . In the centre of the ‘shadow’ of the latex
ferring thin films to grids with holes in the preparation of
beads, a ring-like structure is recognized. This kind of ring
specimens for transmission electron microscopy (TEM).25
structure is due to remainders of the mask when it is removed
by organic solvent. The grey scale in this image was distorted
Formation of the projection patterns
non-linearily such that the rather shallow ring structure and the
The evaporation can be varied by:
projection pattern are visible in the same image.
(1) Changing the material for physical vapour deposition.
(2) Changing the evaporation angle and using rotary 500 50.0 nM
evaporation.
This is the same as for metal shadowing techniques in the 25.0 nM
preparation of specimens for TEM.24 Apart from the inter-
est in choosing a certain material for the projection pattern
0.0 nM
due to the different physical and chemical properties, the 250
material also determines to a large extent the morphology
of the projection pattern due to the different grain size of
different materials. By adjusting the angle, an asymmetry of
the projection pattern can be induced and the use of rotary
evaporation will change the size of the characteristic triangles 0
in the projection pattern. The angle of evaporation also will 0 250 500
decide whether the characteristic triangles in the projection nM
patterns will be connected or not. Some of these influences Figure 3. The AFM image of a gold projection pattern. Here,
will be illustrated by the examples Figs 2, 3 and 8–10. the triangles are not as well defined as in the case of SiO2 due
to the larger grain size of the evaporated gold compared with
Removal of the mask SiO2 . The triangles have a pyramidal shape. No ring-like
The most frequently used procedure for removing the remainders were formed because of removal of the mask with
mask is by applying an organic solvent such as CH2 Cl2 water.

Copyright  2002 John Wiley & Sons, Ltd. Surf. Interface Anal. 2002; 33: 75–80
 Latex bead projection nanopatterns 77

FABRICATION OF DERIVED
NANOSTRUCTURES
Embedded projection patterns 4.8 nm
Flat patterns consisting of different materials embedded
into a surface are useful as test objects for SNOM in order
to distinguish optical contrast caused by the distribution
of different materials from topography-induced optical
contrast or from topography-induced artefacts.26 A flat
pattern consisting of two different materials (material 1
and material 2) is formed by evaporating material 2 onto a
projection pattern of material 1 as described previously.20,21 0.0 nm
When choosing a polymer as material 2, it can be applied
conveniently by spin-coating or dip-coating1,19 a solution of
this polymer. In our case the polymer was a polycarbonate
Figure 4. The STM image of a projection pattern of 20 nm gold
of molecular weight 20 000. After this embedding procedure,
embedded in 2 nm of Pt–C. The topography of the sample is
the mica has to be removed. For polycarbonate, the polymer
very flat; the gold triangles can be discriminated from the
film is floated onto a clean surface of water and picked up
surrounding only by the different grain sizes of gold and Pt–C.
onto a piece of glass.19,21,24 Taking two metals, the metal film
is attached by means of a polyester resin to a piece of glass.
It is possible to remove the mica from the metal film by 3.00 20.0 nM
applying gentle force between the metal film and the glass.20
Figure 4 shows a scanning tunnelling microscopy (STM) 10.0 nM
image of a 20 nm thick gold projection pattern embedded 2.00
into a 2 nm thick film of Pt–C. For this sample the procedure
0.0 nM
works very well and the gold patches exposed to the surface
can be distinguished using STM from the Pt–C sites only by
the different grain size of the different metals. An example of 1.00
an SiO2 pattern embedded into gold is shown in Fig. 5. This
combination works out less reproducibly and occasionally
the SiO2 structures are partly lifted or completely withdrawn 0
when the mica is separated from the embedded pattern. 0 1.00 2.00 3.00
µM
Table 1 gives an overview of the results obtained with
different materials. Figure 5. The AFM image of an SiO2 projection
patternembedded in gold. In this case the presence of the
Complementary projection patterns projection pattern can be inferred only from characteristic
Complementary projection patterns are formed by using holes or occasional triangular protrusions at a few places
the projection patterns as a master for a nanoimprinting where the embedded structure has been removed completely
technique, similar to that described by Terris et al.27 and by or partly lifted. The grain structure of the gold film is not
Chou et al.28 revealed in this image because of the large scan size and a
blunter AFM tip than used in the other cases.

Table 1. Summary of different materials used for the

fabrication of embedded projection patterns
Two procedures proved to be very well suited for this
nanoimprinting technique:
Material 1
(1) Nanoimprinting of an SiO2 projection pattern into polycar-
Material 2 Au Pt–C Ag Co SiO2 bonate. For this purpose a 20 nm thick SiO2 projection
pattern is formed. Then a thin film of polycarbonate
Au C C () /pC (C)
dissolved in CH2 Cl2 is applied to this pattern by spin-
Pt–C C C
coating. Afterwards, the polycarbonate film is floated
Ag (C)
onto a clean surface of water and picked up onto
Co (C)
a glass substrate such that the projection pattern is
Polymer C /pC
exposed at the sampleair interface. A complementary
SiO2  
pattern formed in polycarbonate from an SiO2 master
Material 1 is the material of the projection pattern and material 2 pattern is shown in Fig. 6. Triangular depressions are
is the embedding medium: signs C and  signify successful and formed as a complementary structure to the triangu-
unsuccessful schemes, respectively; parentheses signify partly lar protrusions in the SiO2 master. In the atomic force
successful or unsuccessful schemes; ‘p’ signifies the fabrication microscopy (AFM) image the triangular depressions of
scheme for the imprint process resulting in the complementary the polycarbonate imprint appear smaller than the cor-
patterns. responding protrusions in the SiO2 master, caused by

Copyright  2002 John Wiley & Sons, Ltd. Surf. Interface Anal. 2002; 33: 75–80
78 U. C. Fischer et al.
3.00 50.0 nM
25.0 nM
2.00
0.0 nM
1.00
0 0
0 1.00 2.00 3.00
µM
Figure 6. The AFM image of a complementary projection
pattern consisting of a nanoimprint of an SiO2 projection
pattern as shown in Fig. 2 in a thin film of spin-coated
polycarbonate. The diffuse dark areas may well be due to gas
bubbles close to the surface, which were generated in the
not-well-elaborated spin-coating process. At these sites, the
AFM imaging process seems to have failed. Nevertheless, the
characteristic imprinted structure can be recognized, including
the ring-like structures. The triangular depressions appear
smaller than the triangular protrusions of the SiO2 master,
most likely due to a convolution of the structure of the tip and
the sample in the AFM imaging process. At some places, the
triangular depressions are not formed. It seems that there the
SiO2 triangles have not been removed with the mica and thus
the triangular imprints are filled with SiO2 .
a convolution of the nanostructure with the AFM tip
shape. Because the triangles have a baseline of ¾50 nm,
we conclude that the resolution of the imprinting pro-
cess must be considerably lower than 50 nm; this is
known also from similar methods of forming such
imprints.28
(2) Nanoimprinting of a cobalt projection pattern into gold. We
attempted to form a pattern of cobalt embedded into a
surface of gold but the procedure was not successful.
When trying to separate the mica from the metal, cobalt
has remained on the mica and the gold was removed
in such a way that a complementary gold structure was
formed.
RING STRUCTURES
The ring-like remainders of the mask described above, which
at first are an undesirable artefact, may be used to form
a derived ring nanostructure of size ¾100 nm. It can be
shown definitely that the rings are due to remainders of the
mask. The latex mask has been adsorbed and subsequently
removed with CHCl2 . The resulting structure of hexagonally
arranged rings is shown in Fig. 7. As mentioned above,
these rings can be avoided by removing the mask with
water (see Fig. 3). We therefore conclude that the rings
are due to either to a water-soluble material or to a polar
substance in the dispersion of latex spheres that can be
removed with water. Our interpretation differs from that of
Winzer et al.,7 who also has observed such structures and
claimed that these consist of a metal that was deposited
Copyright  2002 John Wiley & Sons, Ltd.
10.0 nM
3.00 5.0 nM
0.0 nM
2.00
1.00
0 1.00 2.00 3.00
µM
Figure 7. The AFM image of ring-like structures. These ring
structures of diameter ¾100 nm remain on the substrate when
the mask of latex beads, which is formed by drying a
dispersion of these beads on the substrate, is removed by an
organic solvent such as dichloromethane and treatment with
ultrasound. These rings consist of a polar component of the
dispersion that can be removed with water.
a b
7.0 nm 4.101 V
0.0 nm 3.760 V
scan range: 500 nm × 500 nm
c
2.881 V
2.222 V
Figure 8. Images of a 10 nm thick latex projection pattern
embedded into a 20 nm thick film of gold as obtained in
SNOM/STM mode. (a) Topographic STM image. (b) Direct
SNOM image of the projection pattern obtained
simultaneously. The triangles are hardly visible in the SNOM
image in this case. The main features of the SNOM image
coincide with the topographic features of the STM images and
therefore cannot be distinguished from a topography-induced
optical contrast or an optical artefact caused by a cross-talk of
the STM feedback-controlled movement of the tip.26
(c) Depolarized SNOM image. The strongest contrast in this
depolarized image is associated with the triangles, which
appear 10–20% darker than the surrounding gold film.
during the evaporation process. They have noticed that
the phenomenon is influenced by the composition of the
solvent. This observation would find a simple explanation
from our result—that the rings do not consist of metal but of
remainders of the solvent. A complementary ring structure
is formed by the nanoimprinting process described above, as
Surf. Interface Anal. 2002; 33: 75–80

a b
10.0 nm 2.715 V
0.0 nm 2.517 V
scan range: 500 nm × 500 nm
3.171 V
2.516 V
Figure 9. Images obtained in the SNOM/STM mode of the
same sample as in Fig. 8 but taken with a different tip:
(a) topographic image obtained in STM mode; (b) direct SNOM
image; (c) depolarized SNOM image. In this case a contrast in
the direct SNOM image is observed for the triangles, which
appear 5–10% brighter than the surrounding gold film,
consistent with previous measurements.20 No contrast of the
triangles is observed for the triangles in the depolarized image.
The origin of the different contrast of the SNOM images of
Figs 8 and 9 is not known.
seen by the ubiquitous ring-like depressions in the embedded
projection patterns (see Figs 8–10). It is conceivable to use
these water-soluble rings as masks for further lithographic
steps to form thin films of a material with ring-like defects.
APPLICATION OF NANOSTRUCTURES AS
TEST PATTERNS FOR SNOM
All of the structures described here are of interest as test
structures for SNOM. Thus, SiO2 projection patterns on glass
were used previously as test patterns.22 For an understanding
of the contrast in SNOM images it may be of interest
to use structures of a complementary composition. It is
helpful also to use nanostructures of a different shape in
order to understand the influence of shape on the optical
contrast. In this respect the ring structures, asymmetric
projection patterns and projection patterns with connected
and unconnected triangles should be of interest.
Here, we demonstrate the use of platinum–carbon
projection patterns embedded into a film of gold that
have been used to compare SNOM images obtained with
the T-tip in SNOM/STM mode21,29 and in SNOM/AFM
mode.30 The auxiliary AFM and STM modes are used to
control the tip–sample distance and to obtain a simultaneous
topographic image of the sample.
Figures 8–10 show different results obtained on the
same sample with different tips in SNOM/STM mode.
In this case an STM image and two different SNOM
images were taken simultaneously—a direct image and a
depolarized image—by using a polarizing beam splitter and
Copyright  2002 John Wiley & Sons, Ltd.
Latex bead projection nanopatterns 79
a)
1000 nm
9.67 nm
500 nm
0.00 nm
0 nm
0 nm 500 nm 1000 nm
b)
1000 nm
3.585 V
500 nm
3.329 V
0 nm
0 nm 500 nm 1000 nm
Figure 10. Images obtained in SNOM/AFM mode of the same
structure as in Figs 8 and 9. (a) Topographic image as obtained
in AFM mode. The topographic image reveals essentially the
same features as the topographic images of Figs 8 and 9
obtained in STM mode, but the grain structure of the metal
films is not resolved. (b) The SNOM image shows a rather
pronounced contrast that seems to be correlated with the
projection pattern, but the triangles of size 50 nm are not
resolved in this case. For some reason that is not yet known,
the resolution of the SNOM images obtained in SNOM/AFM
mode is not as high as in SNOM/STM mode.
two detectors. Figure 8(a) shows the topographic STM image
of the Pt–C projection pattern embedded into gold. The Pt–C
triangles are significantly larger than the gold triangles of the
embedded structure of a complementary composition. This
difference in size is due mainly to a rotary Pt–C evaporation
at an angle of 70° , which has been used for the Pt–C triangles,
whereas a 90° angle was chosen for the gold triangles. The
ring-like depressions in the gold are quite prominent in
this case. The direct SNOM image of Fig. 8(b) shows no
strong optical contrast differing from the topography. In the
depolarized SNOM image we see, however, a rather strong
contrast that correlates with the distribution of the triangles
and that shows no strong correlation with the topographic
image. Because the triangles 120 nm apart are well separated
in the depolarized image, a resolution of the order of 100 nm
can be inferred from this SNOM image.
Figure 9 obtained with a different tip but on the same
sample, shows quite a different result. The direct SNOM
image shows quite clear contrast for the triangles, which
appear brighter by 5% than the surrounding gold, whereas
Surf. Interface Anal. 2002; 33: 75–80
80 U. C. Fischer et al.
the triangles cannot be recognized in the depolarized
image.
The origin of these differences is not clear and might be
related either to differences in the tip or to differences in the
illumination path of the light exciting the tip.
Figure 10 has resulted from imaging the same object in
SNOM/AFM mode. The overall topography of the sample is
the same as in the STM images, but the metal grains are not
resolved in the AFM image. Only the direct SNOM image
has been recorded in this case. The SNOM image shows a
rather diffuse, not well resolved contrast of the projection
pattern.
These examples demonstrate that the embedded test
samples are well suited to compare SNOM images obtained
with different tips and for different conditions and thus
will serve as a basis with which to find the conditions for
reproducible SNOM imaging.
Acknowledgements
This work was supported by the German Federal Ministry of
Research and Education (BMBF) and by the German Science Council
(DFG). Latex beads were kindly provided to us by Dr Leube from
the BASF Aktiengesellschaft.
REFERENCES
1. Fischer UC, Zingsheim HP. J. Vac. Sci. Technol. 1981; 19: 881.
2. Deckman HW, Dunsmuir JH. Appl. Phys. Lett. 1982; 41: 377.
3. Deckman HW, Dunsmuir JH. J. Vac. Sci. Technol. B 1983; 1: 1109.
4. Fischer UC. J. Opt. Soc. Am. B 1986; 3: 1239.
5. Fischer UC. J. Vac. Sci. Technol. B 1985; 3: 386.
6. Winzer M, Kleiber M, Dix N, Wiesendanger R. Appl. Phys. A
1996; 63: 199.
7. Burmeister F, Schäfle C, Matthes T, Böhmisch M, Boneberg J,
Leiderer P. Langmuir 1997; 13: 2983.
Copyright  2002 John Wiley & Sons, Ltd.
8. Deckman HW, Wronski CR, Witzke H, Yablonowitch E. Appl.
Phys. Lett. 1983; 42: 968.
9. Deckman HW, Wronski CR, Witzke H. J. Vac. Sci. Technol. A
1983; 1: 578.
10. Deckman HW, Dunsmuir JH, Abeles B. J. Vac. Sci. Technol. A
1985; 3: 950.
11. Deckman HW, Moustakas TD. J. Vac. Sci. Technol. B 1988; 6:
316.
12. Green M, Garcia-Parajo M, Khaleque F. Appl. Phys. Lett. 1993; 62:
264.
13. Roxlo CB, Deckman HW, Abeles B. Phys. Rev. Lett 1986; 57:
2462.
14. Fang H, Zeller R, Stiles PJ. Appl. Phys. Lett. 1989; 55: 1433.
15. Buncick MC, Warmack RJ, Ferrell TL. J. Opt. Soc. Am. B 1987; 4:
927.
16. Hulteen JC, Van Dyne RP. J. Vac. Sci. Technol. A 1995; 13: 1553.
17. Duerig U, Pohl DW, Rohner F. J. Appl. Phys. 1986; 59: 3318.
18. Sönnichsen C, Duch AC, Steininger G, Koch M, von Plessen G,
Feldmann J. Appl. Phys. Lett. 2000; 76: 140.
19. Kalkbrenner T, Graf R, Durkan C, Mlynek J, Sandoghdar V.
Appl. Phys. Lett. 2000; 76: 1206.
20. Ferber J, Fischer UC, Hagedorn N, Fuchs H. Appl. Phys. A 1999;
69: 58124.
21. Koglin J, Fischer UC, Fuchs H. Phys. Rev. B 1997; 55: 7977.
22. Fischer UC, Koglin J, Fuchs H. J. Micros. 1994; 176: 231.
23. Fischer UC. In Procedures in Scanning Probe Microscopies, Colton R
et al. (eds). John Wiley: Chichester, 1998; 10.
24. Michelotto R, Fukuda H, Ohtsu M. Langmuir 1995; 11: 3333.
25. Reimer L. Elektronenmikroskopische Untersuchungs und Praepara-
tionsmethoden (2nd edn). Springer Verlag: Berlin, 1967.
26. Hecht B, Bielefeldt H, Inouye Y, Pohl DW. J. Appl. Phys. 1997; 81:
2492.
27. Terris BD, Mamin HJ, Best ME, Logan JA, Rugar D. Appl. Phys.
Lett. 1996; 69: 4262.
28. Chou SY, Krauss RR, Renstrom PJ. Appl. Phys. Lett. 1995; 67:
31114.
29. Heimel J, Fischer UC, Fuchs H. J. Microsc. 2001; 202: 53
30. Naber A, Maas HJ, Razavi K, Fischer UC. Rev. Sci. Instrum. 1999;
70: 1.
Surf. Interface Anal. 2002; 33: 75–80