Chapter 12

Nanosphere Lithography
Martin Waegner
12.1 Introduction
The development of lithography was one of the driving forces in microfabrication
technology. However, today the improvement of this technology is restrictive for
further shrinking of microelectronic and micromechanical devices, because conven-
tional lithography allows resolutions down to 100nm. So there is a need for newer
methods which allow the fabrication of structures in the sub-100nm range. There-
fore, a couple of newtechnologies were developed and are actually in use in research
and industry. Immersion lithography is an enhanced method of conventional photo-
lithography where a liquid between the lens and the wafer is used. The liquid has a
bigger refracting index then air, hence the numerical aperture NA = n sin ( half
angle of incidence) is larger and the increased resolution achieves values of a few
10nm. E-beam lithography uses a beam of electrons to reduce the diffraction limit
of photo-lithography and reaches structure sizes in the range of 20nm. Identically
to this technique, ions can be used instead of electrons which is called ion beam
lithography. All these methods have good resolution for actual needs in microelec-
tronics. But the tools have a couple of disadvantages. The throughput is quite lowand
the equipment is expensive. Thus, newer, cheaper and especially faster technologies
arouse interest in research and development.
One of these methods is nanoimprinting as it is described in Chap. 11. An
even more promising approach is the exploitation of nature-given mechanisms and
properties. These self-assembly methods are mostly cheap und fast. One example
with high potential are diblock-copolymers, composed of two different polymer
chains, are used to create self-assembled patterns. The two polymers are unable to
phase-seperate and so they form ordered structures in the macroscopic length scale.
Thereby size and shape can be controlled in manipulating the molecular weight and
M. Waegner (B)
Solid-State Electronics Laboratory, Technische Universitt Dresden,
01062 Dresden, Germany
e-mail: martin.waegner@mailbox.tu-dresden.de
G. Gerlach and K.-J. Wolter (eds.), Bio and Nano Packaging Techniques 269
for Electron Devices, DOI: 10.1007/978-3-642-28522-6_12,
Springer-Verlag Berlin Heidelberg 2012
270 M. Waegner
the composition of the two polymers. For instance, structures like spheres, cylinders
andlamellas are feasible [23] andcanbe usedas a maskfor so-calledblock-copolymer
lithography.
Fischer et al. [8] and Deckman et al. [6] were the rst in the early 1980s who
presented a nanostructuring process based on colloidal particles as a mask. Recent
advances in colloidal chemistry have enabled the production of highly monodis-
perse colloidal particles with good phase stability. Such colloidal dispersions show
a long-range ordering caused by self-assembly. Consequently, they form 2D arrays
of particles on a surface, which act in nanosphere lithography (NSL) as a mask for
etching or deposition processes. This technology has several advantages.
Colloidal dispersions are commercially available at relative low cost.
No complex equipment is required for the production of nanopatterns down to
10nm.
Layers can be easily synthesized by dip-coating and spin-coating with very eco-
nomical consumption of material.
The feature scale can be easily tuned by size and alignment of the particles.
The shape of particles and structures can be changed by etching, annealing and
tilted evaporation.
Deposition of multilayers offers the possibility to make 3D structures like hemi-
spherical metal caps, sculptured colloids [4] and nanorings [2].
NSL is suitable for biomaterials and -devices, because surface treatment of the
particles is possible [26].
The development of this promising technology is still at the beginning. The following
sections describe the capabilities of this technique. At rst, fabrication routes for
colloidal monolayers and perspective applications for deposited nanopatterns will
be introduced. Finally, particle layers as etching masks for patterning thin-layers and
surfaces with different shapes are presented.
12.2 Ordering of Nanospheres
Up-to-date research opened methods for the synthesis of monodispersed spheres
with a narrow size distribution. Accordingly a variety of materials for polymer par-
ticles like polysterene (PS) or polymethylmetacrylat (PMMA) can be fabricated by
suspension, emulsion and dispersion. The particle size can be easily controlled by
changing the reaction conditions like concentration of monomers, reaction tempera-
ture or pH-value. Inorganic particles are mostly synthesized via sol-gel routes. This
method offers only a limited inuence on the initial size of the particles, but the size
can be adapted very well through nucleation and subsequent growth [22].
Using monodispersed solutions as a mask is advantageous because the movement
of colloidal particles is inuenced by different forces [19]. Van der Waals forces,
steric repulsions and Coulombic repulsions protect the stability of the dispersion and
can be described with the Derjaguin-Landau-Verver-Overbeek (DLVO) theory [25].
12 Nanosphere Lithography 271
Fig. 12.1 Precipitation tech-
niques for close-packed
monolayers of nanospheres:
a dip-coating,
b electrophoretic deposition,
c lift-up from an interface,
and d spin-coating
(a) (b)
(c) (d)
Stability of the dispersions means that particles do not form agglomerations and,
moreover, spheres do not seperate from the dispersion. For the nal self-assembly
process the evaporation of water or organic dissolvers and the related forces play an
important role. Capillary forces inuence highly the self-ordering of the nanospheres
which leads to hexagonal closed-packages of nanospheres.
Figure 12.1 shows different routes for precipitation of monolayers. The very rst
developed method was dip-coating which is shown in Fig. 12.1a [7]. The substrate
is dipped in a solution containing the nanoshperes. While the substrate is pulled-out
a thin lm of dispersion forms and covers the surface. The controlled movement and
ordering of the nanospheres starts when the thickness of the liquid layer around the
spheres becomes smaller then the diameter of the spheres. This self-assembly process
is forced by a convective owwhich transports the particles, while the solution evap-
orates. In conclusion the formed monolayers are polycrystalline with crystallites in
the range between a few nanometers and a few microns. Nevertheless, they show
defects like grain boundaries, dislocations, vacancies and variations in layer thick-
ness. To achieve layers with less defects other, better controllable, more effective and
more qualitative methods are needed.
The electrophoretic synthesis is fast and accurate. The particles are forced in their
movement by an electrical AC- or DC-eld based on electrodynamic interactions
[18, 21]. Nevertheless, the deposition of the particles on the substrate cannot be
inuenced directly. Due to the randomdeposition process, no larger areas with close-
packed monolayers can be synthesized. As a result areas with single particles or with
agglomerations occur.
Floating on a liquid surface is one of the most promising methods for laboratory
applications (Fig. 12.1c) [20]. The nanospheres order on an liquid-gas interface of
mostly water and air. On this interface close-packed monolayers are formed by long
range repulsive forces between the spheres [1]. In particular in laboratory, the dis-
persion is droped onto a substrate with very hydrophilic properties, e.g. especially
prepared glass or silicon. Subsenquently, the solution spreads all over the substrate
at once. Therby a rst self-assembly process starts. Afterwards, the substrate with
the ne-distributed dispersion is lowered very slowly to a petri dish with ultra pure
272 M. Waegner
water. The nanospheres begin moving on the water surface and start forming an
unordered monolayer. With the addition of 2% sodium dodecyl sulfate (SDS) solu-
tion, which reduces the surface tension of water, large areas of well-ordered spheres
are formed. These monolayers can now be lifted-up by using any substrate which
again has a hydrophilic surface. Finally, the substrates have to be dried very slowly.
A medium temperature and a high value of humidity should be used, providing a
sufcient slow evaporation process to avoid destruction of the monolayers. With this
technique areas of more or less closed-packages up to several cm
2
are achievable.
Although a Langmuir-Blodgett technique is in principle usable [9], it cannot be used
for bulk production up to now. Using repeated depositions multilayers can be formed.
A better approach for large-scale production is spin-coating, which is already in
use in standard wafer processes (Fig. 12.1d). Spin-coating is a fast layer deposition
method and can be used both for small substrates and whole wafers. With regard to
the adhesion of the dispersion onto the surface, the substrates have to be hydrophilic.
Otherwise, the dispersion forms drops and does not adhere to the surface. The den-
sity of particles and similarly the number of layers can be controlled by tuning the
spin parameters (speed, acceleration, period) and the dispersion parameters (particle
concentration, addition of solvents). Using this parameter spectrum, it is possible
to fabricate either closed-packages of mono- and multilayers as well as statistically
distributed single particles with controllable density. Nevertheless, the quality of the
monolayers does not reach that one of the lift-up from an interface.
Despite its premature state recent developments showthe potential of NSLas alter-
native for expensive conventional lithography. For example, Canpean et al. demon-
strated a new method for convective coating which leads in a few of minutes to
close-packed layers over several cm
2
[3].
12.3 Modication of Nanosphere Masks
For application reasons it might be good to control the shape and the size of the
deposited nanosphere layers. Particular nanodevices need other shapes like rings and
rectangles instead of circular and triangel patterns from unmodied masks. Often
device properties do not only depend on particle size but also on their shape, for
instance in applications using local surface plasmon resonance (LSPR) [12] and
surface-enhancedRamanscattering(SERS) [24]. Toovercome the limitationinshape
variety two different process modications can be applied: (i) deposition with tilted
and rotated substrates (see Sect. 12.5) and (ii) modication of colloidal masks by
post-treatment.
Usual post-treatments are for example reactive ion etching (RIE), ion-milling
and thermal annealing. Especially RIE is a versatile tool to control pattern sizes and
shapes. As an illustration Fig. 12.2 shows a series of SEMpictures of colloidal masks
modied by RIE. The etching parameters were choosen for a maximum of isotropy
to ensure a homogenous etch rate. Zhang et al. reported an empirical equation for
the reduction of the initial diameter D of PS nanospheres in oxygen-based RIE [28].
12 Nanosphere Lithography 273
Fig. 12.2 Modication of polystyrene (PS) nanosphere masks by RIE. The SEM pictures were
made after a 4min, b 6min, c 8min, d 10min and e 12min etching time. The diameter of the sphere
could be reduced from 830nm down to 360nm (e). The white bar has a size of 2m
Fig. 12.3 Modication of
colloidal masks by RIE of a
bilayer in hcp orientation
D = D
0
cos

arcsin

k t
2D
0

(12.1)
Here t is the etching time and k a constant depending on the etching conditions
like power, pressure and gas mixture. The etching conditions should be chosen very
carefully because they have a big inuence on the etching mechanism. Increasing
power and decreasing pressure lead to higher anisotropy of particle etching. To
achieve homogeneously distributed sphere diameters, the RIE process should be
dominated by the chemical part of etching providing more isotropic conditions.
Li et al. investigated the inuence of different parameters, especially of the gas
mixture, on the etching rates of PS nanospheres [16].
An even wider diversity of mask structures can be achieved with multilayer masks.
Colloidal particles in multilayers form either face-centered cubic (fcc) or hexago-
nal close-packed (hcp) crystal structures. Depending on the orientation relative to
the crystal, the number of layers and the RIE conditions, a vast number of differ-
ent patterns like micro-channels, V-shaped grooves and pyramid pits are reachable
[27]. Figure12.3 shows a SEM picture of a bilayer colloidal mask modied by RIE.
Triangular patterns formdue to the shadowing effects of the hcp-oriented. In the case
of the fcc-orientation quadratic structures emerge.
274 M. Waegner
D
d
a
a 3 3 1
1
3
D
2
(12.2)
d
1
3
D (12.3)
F
4
3D
2
(12.4)
Fig. 12.4 Modell of a closed-hexagonal package and equations for the prediction of particle size
a, distance d between the particles and the dots density F (afer [15])
Fig. 12.5 Schematic of the angle-resolved deposition process. a Samples viewed at 0

. The inter-
stices in the nanosphere mask are equally spaced and of equal size. b Sample viewed at 30

. The
interstices in the nanosphere mask follow a pattern including two different interparticle spacing
values, and the interstitial area is smaller. c Sample viewed at 45

. The interstices are now closed

to line of sight deposition. Reprinted from [10] with permisson
12.4 Shadow Mask Technology for Deposition Processes
Nanosphere layers can be directly used as mask for the deposition of material by
evaporation or sputtering. By choosing different initial sphere diameters the size of
the resulting deposited patterns can be varied in the range from 20 to 1000nm [10].
To predict size and shape of the resulting patterns, a closed-hexagonal package of
spheres can be considered and the dimensions of the triangular-shaped material dots
on the substrate can be calculated theoretically (Fig. 12.4). Li et al. calculated the
particle size a, the distance between the particles d and the dot density F as function
of initial sphere diameter D [15]. Experimental investigations showed a sufcient
good accordance between the calculated and the measured values with a really narrow
size distribution [11].
Nevertheless, all the deposited structures will have triangular shapes if the depo-
sition of material is perpendicular to the substrate. For this purpose tilting either
the substrate or the evaporation source shows shadowing effects which lead to other
interesting structures like cups, rods and wires [14]. Figure12.5 illustrates the effect
of tilted evaporation for the resulting patterns. Furthermore, the combination of a
series of evaporation steps with different tilting angels and maybe different materials
offers the fabrication of a huge amount of different structures. Zhou et al. [29] and
Retsch et al. [17] used a conjunction of evaporating and etching steps with different
tilted angels which resulted in 3D nanostructures (Sect. 12.5).
After etching the nanospheres can be removed by sonication with a appropriate
dissolver. In the case of PS nanospheres, chloroform showed satisfying results [5].
12 Nanosphere Lithography 275
Fig. 12.6 Size-tunable colloidal lithography process using RIE and ion-milling. a Schematic of
the whole structuring process. Reprinted from [13] with permisson. b AFM pictures of a thin layer
structured by NSL
12.5 Nanosphere Masks for Conventional Etching Processes
After dissolving the nanosheres the resulting structure shapes are dened by the gaps
between the previous single spheres. This means that the nanosphere layer acted as
a negative mask.
In the next step the structure of the mask has to be transfered to the substrate.
In the case of a substrate coated with a thin-layer, the mask can be used for struc-
turing this layer with nanopatterns. Dry etching processes with high anisotropy are
usually applied. During the etching process the mask has to be stable, at least as
stable as the layer which will be structured. So the combination of mask material
and thin-layer has to be chosen very carefully. PS spheres for example show an etch-
ing rate which is approximately similar to that one of silicon. Otherwise, the mask
would be etched much faster than the thin layer or the surface. Ion-milling suites
very well the requirements for structuring metal layers, due to its anisotropy and
the resulting almost perpendicular sidewalls. The resulting pattern of the substrate
corresponds almost one-to-one to the etch mask. Figure12.6 illustrates the complete
pattern transfer process including post-treatment for mask modication and shows
an AFM picture of the resulting structures.
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