Microstructures Prepared Via Inkjet Printing and Embossing Techniques

Microstructures prepared via inkjet printing and
embossing techniques
Perelaer, J.
DOI:
10.6100/IR640389
Published: 01/01/2009
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Perelaer, J. (2009). Microstructures prepared via inkjet printing and embossing techniques Eindhoven:
Technische Universiteit Eindhoven DOI: 10.6100/IR640389
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Microstructures Prepared via Inkjet Printing
and Embossing Techniques
PROEFSCHRIFT
ter verkrijging van de graad van doctor aan de Technische Universiteit Eindhoven,
op gezag van de Rector Magnificus, prof.dr.ir. C.J. van Duijn, voor een commissie
aangewezen door het College voor Promoties in het openbaar te verdedigen op
donderdag 5 maart 2009 om 16.00 uur
door
Jolke Perelaer
geboren te Neerijnen
Dit proefschrift is goedgekeurd door de promotor:
prof.dr. U.S. Schubert
Copromotor:
dr. P.J. Smith
Microstructures Prepared via Inkjet Printing and Embossing Techniques / by Jolke Perelaer
The research described in this thesis forms part of the research programme of the Dutch Polymer
Institute (DPI, P.O.Box 902, 5600 MB, Eindhoven), Technology Area High Throughput
Experimentation, DPI project #546
Technische Universiteit Eindhoven, 2009

A catalogue record is available from the Eindhoven University of Technology Library
Proefschrift, ISBN: 978-90-386-1529-5
Cover design by Jolke Perelaer and Felice Kroworsch
Printed at PrintPartners Ipskamp, Enschede, The Netherlands
An electronic copy of this thesis is available at the site of the Library of Eindhoven University of Technology
Microstructures Prepared via Inkjet Printing
and Embossing Techniques
Kerncomissie:
Prof. Dr. U. S. Schubert (Eindhoven University of Technology)
Dr. P. J. Smith (University of Freiburg)
Prof. Dr. R. R. Baumann (Chemnitz University of Technology)
Prof. Dr. S. Magdassi (Hebrew University of Jerusalem)
Prof. Dr. D. J. Broer (Eindhoven University of Technology)
Overige commissieleden:
Prof. Dr. V. Subramanian (University of California, Berkeley)
Dr. A. W. M. de Laat (Philips Applied Technologies)
... omdat er brood ligt soms bij de Gedchtniskirche, soms op het Alexanderplein
Klein Orkest, Over de Muur (1984)
Met diploma's en een yuppie pak, heb je misschien meer kans,

maar een b(r)oer op klompen blijft ook in balans
Normaal, Kwestie van Balans (1991)

Table of contents
Table of contents
Chapter 1
Inkjet printing: from graphical arts to a state-of-the art research technique ................... 1
1.1 A historical overview .............................................................................................................. 2
1.2 Working principle of piezoelectric printheads ........................................................................ 7
1.3 Fluid dynamics...................................................................................................................... 10
1.4 Aim and outline of the thesis ................................................................................................ 12
1.5 References............................................................................................................................. 13
Chapter 2
Ink behaviour in-flight and at the substrate........................................................................ 17
2.1 Introduction........................................................................................................................... 18
2.2 Influence of the printing height............................................................................................. 21
2.2.1 Introduction..................................................................................................................... 21
2.2.2 Experimental ................................................................................................................... 22
2.2.3 Results and discussion .................................................................................................... 23
2.3 The behaviour of inkjet printed droplets of polymer solutions on a dry solid substrate ....... 29
2.3.1 Introduction..................................................................................................................... 29
2.3.2 Experimental ................................................................................................................... 29
2.3.3.1 Molar mass influence on droplet spreading............................................................. 30
2.3.3.2 Comparison of the maximum spreading diameters ................................................. 31
2.3.3.3 Printing height influence on droplet spreading under constant vapour pressure ..... 37
2.4 Preferential deposition and size-selective segregation at the boundary of inkjet printed
features .................................................................................................................................. 40
2.4.1 Introduction..................................................................................................................... 40
2.4.2 Experimental ................................................................................................................... 40
2.4.3.1 Contact angle dependency of a drying droplet ........................................................ 42
2.4.3.2 Coffee drop effect with monomodal PMMA latex suspensions.............................. 44
2.4.3.3 Coffee drop effect with monomodal silica particles ................................................ 47
2.4.3.4 Particle size dependency in the coffee drop effect of inkjet printed suspensions.... 48
2.4.3.5 The effect of contact angle on the position of suspended silica particles ................ 54
2.5 Conclusions........................................................................................................................... 58
2.6 References............................................................................................................................. 59
Table of contents
Chapter 3
Inkjet printing of functional materials ................................................................................. 65
3.1 Introduction............................................................................................................................66
3.2 Inkjet printing of three-dimensional polyurethane structures ................................................69
3.2.1 Introduction .....................................................................................................................69
3.2.2 Experimental....................................................................................................................70
3.2.3 Results and discussions ...................................................................................................71
3.2.3.1 Inkjet printing of droplets of a polyurethane dispersion...........................................71
3.2.3.2 Inkjet printing of 3D polyurethane structures...........................................................71
3.2.3.3 Inkjet printing of colour gradients............................................................................73
3.3 Geometric control of inkjet printed features using a gelating polymer .................................74
3.3.1 Introduction .....................................................................................................................74
3.3.2 Experimental....................................................................................................................76
3.3.3.1 Thermal flocculation ................................................................................................77
3.3.3.2 Inkjet printing of droplets of a TiO2 dispersion........................................................78
3.3.3.3 Inkjet printing of lines of a TiO2 dispersion .............................................................80
3.3.3.4 Formation of lines on hydrophobic surfaces ............................................................82
3.4 Improved resolution of direct inkjet printed conductive silver tracks on untreated polymer
substrates................................................................................................................................85
3.4.1 Introduction .....................................................................................................................85
3.4.2 Experimental....................................................................................................................86
3.5 Conclusions............................................................................................................................89
3.6 References and notes .............................................................................................................90
Chapter 4
Methods for sintering nanoparticle inks .............................................................................. 93
4.1 Introduction............................................................................................................................94
4.2 Thermal sintering of silver nanoparticles ..............................................................................98
4.2.1 Introduction .....................................................................................................................98
4.2.2 Experimental....................................................................................................................99
4.2.3 Results and discussions .................................................................................................100
4.2.3.1 Conductivity development of inkjet printed silver lines ........................................100
4.2.3.2 Thermal-stability of inkjet printed silver tracks .....................................................106
4.3 Sintering of silver nanoparticles by microwave radiation ...................................................109
4.3.1 Introduction ...................................................................................................................109
Table of contents
4.3.2 Experimental ................................................................................................................. 114

4.3.3 Results and discussions................................................................................................. 115
4.3.3.1 Microwave sintering of conductive silver tracks ................................................... 115
4.3.3.2 Microwave flash sintering of conductive silver tracks .......................................... 117
4.4 Sintering of silver nanoparticles by plasma exposure......................................................... 122
4.4.1 Introduction................................................................................................................... 122
4.4.2 Experimental ................................................................................................................. 124
4.4.3.1 Sintering with argon plasma .................................................................................. 125
4.4.3.2 Skin layer formation analysis ................................................................................ 127
4.5 Conclusions......................................................................................................................... 131
4.6 References........................................................................................................................... 132
Chapter 5
Microstructures prepared by photo-embossing ................................................................ 137
5.1 Introduction......................................................................................................................... 138
5.2 Photo-embossed structures with an increased aspect ratio by addition of hydroquinones . 139
5.2.1 Introduction................................................................................................................... 139
5.2.2 Experimental ................................................................................................................. 140
5.3 Photo-embossed surface relief structures with an increased aspect ratio by addition of
reversible addition-fragmentation chain transfer (RAFT) agent......................................... 146
5.3.1 Introduction................................................................................................................... 146
5.3.2 Experimental ................................................................................................................. 147
5.3.3.1 High-throughput experimentation for identifying the best RAFT agent ............... 149
5.3.3.2 Influence of oxygen on the RAFT agent in photo-embossed structures................ 151
5.4 Conclusions......................................................................................................................... 154
5.5 References........................................................................................................................... 154
Chapter 6
Inkjet printing of conductive features onto embossed structures ................................... 157
6.1 Introduction......................................................................................................................... 158
6.2 Experimental ....................................................................................................................... 160
6.3 Results and discussions....................................................................................................... 162
6.3.1 Inkjet printing onto photo-embossed structures............................................................ 162
6.3.2 Inkjet printing onto hot-embossed structures................................................................ 163
Table of contents
6.3.2.1 Hot-embossing masters ..........................................................................................163

6.3.2.2 Conductive silver tracks in hot-embossed channels ...............................................164
6.3.2.3 Conductivity measurements ...................................................................................167
6.3.2.4 Line structures with improved resolution in polycarbonate ...................................168
6.4 Conclusions..........................................................................................................................170
6.5 References............................................................................................................................171
Colour figures ....................................................................................................................... 173
Summary ............................................................................................................................... 178
Samenvatting......................................................................................................................... 180
Nomenclature ........................................................................................................................ 182
Curriculum vitae .................................................................................................................. 187
List of publications ............................................................................................................... 188
Acknowledgements ............................................................................................................... 192
The She-wolf Suckling Romulus and Remus (National Gallery of Art, Washington D.C., USA)
Manneke Pis (Brussels, Belgium)

1
Inkjet printing: from graphical arts to a state-
of-the art research technique
Abstract
Inkjet printing is a nascent technology that is developing from only printing text and graphics into a
major topic of scientific research and R&D, where it can be used as a highly reproducible non-contact
patterning technique to print at high speeds either small or large areas with high quality features.
Inkjet printing is an additive technique, which requires only small amounts of functional materials,
which can vary from a simple polymer solution to advanced nanoparticle dispersions. The latter form
of ink has been investigated more and more during the last few years, in order to produce conductive
features that require a reduced amount of processing steps. The present chapter provides a literature
survey that describes the history and recent achievements in the inkjet printing field, as an
introduction to the main research topic of this thesis.
Parts of this chapter will be published: J. Perelaer, U.S. Schubert, manuscript in preparation.
Chapter 1
1.1 A historical overview

The origin of inkjet printing goes back to the eighteenth century when Abb Nollet
published his experiments on the effect of static electricity on a stream of droplets in 1749.[1]
Almost a century later, in 1833, Felix Savart discovered the basics for the technique used in
modern inkjet printers: an acoustic energy can break up a laminar flow-jet into a train of
droplets.[2] It was, however, only in 1858 that the first practical inkjet device was invented by
William Thomson, later known as Lord Kelvin.[3] This machine was called the Siphon
recorder, shown in Figure 1.1a, and was used for automatic recordings of telegraph
messages.[4]
(a) (b)
Figure 1.1 The Siphon recorder (a) was the worlds first practical inkjet device and was invented by William
Thomson (b) in 1858. Reprinted from ref. [4].
The Belgian physicist Joseph Plateau and the English physicist Lord Rayleigh studied the
break-up of liquid streams and are, therefore, seen as the founders of modern inkjet printing
technology. The break-up of a liquid jet takes place because the surface energy of a liquid
sphere is smaller than that of a cylinder, while having the same volume see Figure 1.2.[5]
Figure 1.2 Break-up of a laminar flow-jet into a train of droplets, because of Rayleigh-Plateau instability.
Reprinted from ref. [5].
2
Inkjet printing: from graphical arts to a state-of-the art research technique
When applying an acoustic energy, the frequency of the mechanical vibrations is

approximately equal to the spontaneous drop-formation rate. Subsequently, the drop-
formation process is synchronised by the forced mechanical vibration and therefore produces
ink drops of uniform mass. Lord Rayleigh published several papers on the instability and
varicosity of jets,[6-9] where he calculated a characteristic wavelength for a fluid stream and
jet orifice diameter d given by:
= 4.443d (1.1)
The numerical value was later slightly corrected to 4.508.[10,11] Plateau derived a
relationship between jet diameter and droplet size.[12] However, it took another 50 years
before the first design of a continuous inkjet printer, based on Rayleighs findings, was filed
as a patent by Rune Elmqvist.[13] He developed the first inkjet electrocardiogram printer that
was marketed under the name Mingograf by Elema-Schnander in Sweden and Oscillomink
by Siemens in Germany.[14]
In the beginning of the 1960s, two continuous inkjet (CIJ) systems were developed
simultaneously, with a difference only in function of the electrical driving signals.[15,16] The
first system was developed by Richard Sweet at Stanford University. He made a high
frequency oscillograph, where droplets were formed at a rate of 100 kHz and controlled with
respect to their direction by the electrical signal.[17-19] Later, in 1968, the A. B. Dick Company
elaborated upon Sweets invention to produce a device that was used for character printing
and named it the Videojet 9600: this was the first commercial continuous inkjet printer. In
parallel at the Lund Institute of Technology in Sweden, Hertz et al. had developed a similar
system where an electrical signal was used to disperse the droplets into a mist, which enables
frequencies up to 500 kHz.[20,21] However, since their technique used a narrower nozzle
diameter, 10 m versus 50 m, the chance of nozzle clogging was greater.[22]
Instead of firing droplets in a continuous method, it is also possible to produce droplets
when required, hence an impulse jet, or better known as drop-on-demand (DoD). In the late
1940s, Clarence Hansell invented the DoD device, at the Radio Corporation of America
(RCA).[23] Figure 1.3 shows the schematics of his invention, which was never developed into
a commercial product at that time. It took until 1971 when Casio Company released the model
500 Typuter, which was an electrostatic pull DoD device.
3
Chapter 1
Figure 1.3 Schematic drawing of the first drop-on-demand piezoelectric device, patented in 1950 by Hansell.
Reprinted from ref [23].
Despite the fact that the basis of thermal inkjet (TIJ) DoD devices in the form of the
sudden stream printer had already been developed in 1965 at the Sperry Rand Company,[24]
this idea was picked up much later by the Canon company when in 1979 they filed the patent
for the first thermal inkjet printhead.[25-28] Simultaneously, Hewlett-Packard independently
developed a similar technology that was first filed in 1981.[29] Thermal inkjet printers are
actuated by a water vapour bubble, hence their name bubble jet. The bubble is created by a
thermal transducer that heats the ink above its boiling point and, thereby, causes a local
expansion of the ink, resulting in droplet formation. The location of the thermal transducer
can be either at the top of the reservoir as used by HP or at its side, which is the technique
Canon uses.
At the beginning of the 1970s the piezoelectric inkjet (PIJ) DoD system was developed.[30]
At the Philips laboratories in Hamburg printers operating on the DoD principle were the
subject of investigation for several years.[31,32] In 1981 the P2131 printhead was developed for
the Philips P2000T microcomputer, which had a Z80 microprocessor running at 2.5 MHz.
Later the inkjet activities of Philips in Hamburg were continued under the spin-off company
Microdrop Technologies.[33] The first piezoelectric DoD printer on the market was the serial
character printer Siemens PT80 in 1977.
Four different modes for droplet generation by means of a piezoelectric device were
developed in the 1970s, which are summarised in Figure 1.4, and further explained below.[34]
4
(a) Squeeze mode (b) Bend mode (c) Push mode (d) Shear mode
Figure 1.4 Different piezoelectric drop-on-demand technologies. Reprinted from ref. [34].
Firstly, the squeeze method, invented by Steven Zoltan,[35] uses a hollow tube of
piezoelectric material, that squeezes the ink chamber upon an applied voltage (Figure 1.4a).
The squeeze method is nowadays also used in Microdrop printing devices.[36] Secondly, the
bend-mode (Figure 1.4b) uses the bending of a wall of the ink chamber as method for droplet
ejection and was discovered simultaneously by Stemme[37,38] of the Chalmers University in
Sweden and Kyser et al. of the Silonics company in the USA.[39,40] This technique is used for
example in Tektronix and Epson printers. The third mode is the pushing method by Howkins
(Figure 1.4c),[41] where a piezoelectric element pushes against an ink chamber wall to expel
droplets, and is nowadays used in Trident, Brother and Epson printers. Finally, Fishbeck et al.
proposed the shear-mode (Figure 1.4d),[42] where the electric field is designed to be
perpendicular to the polarization of the piezo-ceramics. Typical pioneers in shear mode
printheads are Xaar and Spectra.[34]
Besides the continuous and drop-on-demand inkjet technique, a third type of inkjet
printing is known, which is based on the electrostatic generation of ink droplets.[43,44] The
system is weakly pressurised, causing the formation of a convex meniscus of a conductive
ink. An electrostatic force, which exceeds the meniscus surface tension, is applied between
the ink hemisphere and the flat electrode by setting a voltage. Depending on the nature of the
electrical potential the system can either be a continuous or drop-on-demand inkjet: the pulse
duration determines whether the ejected ink is a continuous stream or a stream of droplets. As
a summary of the different inkjet printing technologies, Figure 1.5 schematically represents a
classification thereof.
5
Chapter 1
Inkjet technology
Continuous Drop-on-Demand
Undeflected Deflected Unvibrated Acoustic Piezo Electrostatic Thermal
Binary Multiple Top shooter Side shooter
Bend Shear Push Squeeze
Figure 1.5 Classification of inkjet printing technologies, adapted from [45].
Although inkjet printing offers a simple and direct method of electronic controlled writing
with many advantages, including high speed production, silent, non-impact and fully
electronic operation, inkjet printers failed to be commercially successful in their beginning:
print quality as well as reliability and costs were hard to combine in a single printing
technique. Whereas CIJ provides high throughput, it also requires high costs to gain good
quality. Nowadays this technique is used in lower quality and high speed graphical
applications such as textile printing and labelling. On the other hand, PIJ usually provides
good quality but lacks high printing velocities: although this can be compensated for by using
multi nozzle systems, but this increases the production costs as well. TIJ changed the image of
inkjet printing dramatically. Not only could thermal transducers be manufactured in much
smaller sizes, since they require a simple resistor instead of a piezoelectric element, but also at
lower costs. Therefore, thermal inkjet printers dominate the colour printing market
nowadays.[45,46]
In scientific research piezoelectric DoD inkjet systems are mainly used, because of their
ability to dispense a wide variety of solvents, whereas thermal DoD printers are more
compatible with aqueous solutions.[47,48] Furthermore, the rapid and localised heating of the
ink within TIJ induces thermal stress on the ink. Nevertheless, research has been conducted
using TIJ printers, for example to form conductive patterns, either by printing the water
soluble conjugated polymer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate)
(PEDOT:PSS),[49,50] or by printing aqueous solutions of conductive multi-walled carbon
nanotubes.[51] Furthermore, TIJ has been used to prepare small unilamellar vesicles with good
precision.[52]
6
1.2 Working principle of piezoelectric printheads

Within a piezoelectric DoD printer a piezo-ceramic plate alters its thickness if an
electrical field is applied between its opposite surfaces. Subsequently, a pressure wave is
induced into the fluid that causes a droplet to be emitted from the nozzle.[53,54] Fluid is
normally retained at the orifice due to surface tension at the fluid/air interface, hence the
action of the pressure wave is to overcome this surface tension and to expel a stream of liquid
from the orifice. In order to minimise internal energies in the liquid, again due to the surface
tension of the liquid, droplets will be formed and droplets are ejected from the nozzle. Typical
repetition rates, i.e. print frequencies, of DoD printers are in the range of 0.1 to 30 kHz.
(a) I - Piezo move outwards
(b) II - Negative waves travel outwards
(c) III - Waves reflect and one reverses
(d) IV - Waves arrive at centre

when piezo contracts
(e) V - Wave is magnified and

drop ejected
Figure 1.6 Schematic representation of the acoustic wave propagation through a glass capillary used in
piezoelectric drop-on-demand devices. A colour version is available on page 173.
Upon setting a voltage the piezoelectric element, which is usually made from lead
zirconate titanate, expands (Figure 1.6a) and a pressure wave travels in two directions (Figure
1.6b). When it arrives at the nozzle orifice the pressure wave is conserved, since it is
considered as a closed end due to its small diameter compared to the tube diameter, while
inversion takes places when arriving at the reservoir, which acts as an open end (Figure
1.6c).[53] The moment that both pressure waves arrive at the centre of the nozzle the actuator
will close (Figure 1.6d), which generates a compressive pulse that propagates in phase and
reinforces the reflected compression wave and cancels the returning dilation wave. Due to an
7
Chapter 1
enhanced compression wave a droplet can be ejected from the nozzle orifice (Figure 1.6e).
The propagation and reflection of acoustic pressure waves depend on the printhead design,
nozzle orifice diameter, and materials properties. Hence, the desired superposition is typically
achieved via adjustments of the electrical signals driving the piezoelectric actuator.
A typical waveform is the so called trapezoidal driving waveform, shown in Figure 1.7,[55]
which is composed of voltage rising time tr, dwell time td and voltage falling time tf. It is
important for successful droplet ejection to find a balance between the applied voltage over
the piezoelectric element and the duration of the pulse. The latter one is defined as the sum of
tr and td. Due to this balance multiple combinations can be found with good droplet formation.
Voltage (V)
tr td tf
Pulse width (s)

Figure 1.7 Typical waveform with voltage and pulse width settings. Reprinted from ref. [55].
The individual settings of voltage and pulse width, however, have a large effect on the
droplet. A minimum of voltage is necessary for droplet ejection. Above this threshold value
the voltage has a linear influence on the droplet volume, as can be seen in Figure 1.8. The
piezoelectric displacement correlates with the applied electric field; a larger voltage amplitude
results in larger volume changes of the piezoelectric element in the same amount of time,
hence a larger pressure wave is induced, which results in a larger ejected droplet volume due
to stronger fluid accelerations.
8
Volume (pL)
2
140 Linear fit (R = 0.94)
120
100
80
60
40
90 100 110 120 130

Voltage (V)
Figure 1.8 Influence of the amplitude of the piezoelectric actuator driving signal on the ejected droplet volume.
Data for ethylene glycol, dispensed from a 70 m nozzle, at a frequency of 100 Hz and a pulse duration of 42 s.
The pulse width shows an oscillating and more complex behaviour on the droplet volume,
as was revealed by Reis et al.[56] The frequency is the rate at which the waveform, depicted in
Figure 1.7, is repeated and has a strong influence on the ejected droplet velocity.[57] The
frequency affects the acoustic wave speed and thus also depends on the fluid properties, in
particular its viscous properties.[58] Obviously, if the frequency is increased more pressure
waves propagate through the liquid medium and may cause disturbances, which can have an
influence on the droplet formation as well.
A typical droplet formation of ethylene glycol is shown as a sequence of images in Figure
1.9. First, a liquid column of ink is ejected from the nozzle, which will immediately adapt to a
spherical shape due to the surface tension of the liquid. The liquid remains attached to the
nozzle by a fluid filament, which can form a secondary filament, shown in the third image
from the left. Disintegration of the fluid filament starts with the formation of a pinch point
behind the primary droplet, followed by the formation of secondary droplets, also known as
satellite droplets. Laplace pressure driven fluid drainage from the filament into the droplets
finally leads to filament rupture.[59] The as-formed satellite droplet has a lower mass than the
main droplet and, consequently, has a larger velocity. Therefore, the satellite can merge with
the main droplet, as shown in the image in the middle of Figure 1.9. After merging of the two
droplets, the total droplet oscillates and balances into a stable spherical shaped droplet, as
depicted in the last image on the right-hand side of Figure 1.9.
9
Chapter 1
Figure 1.9 Stroboscopic photographs of a typical droplet formation of ethylene glycol from a 70 m nozzle. The
time interval between two images was 50 s. The applied voltage and pulse width were 120 V and 42 s,
respectively. The scale bar is 100 m.
1.3 Fluid dynamics

After a droplet has been successfully formed from an inkjet printers nozzle, its journey
towards the substrate starts. The time necessary to reach the substrate lies in the order of
micro- to milliseconds, depending on the distance between the nozzle and the substrate as
well as the droplet velocity.
The main advantage of inkjet printing is its ability to precisely produce droplets with a
consistent volume,[56,60] which enables systematic and statistical studies, since many droplets
can be printed in sequence that are equally sized.[61] However, the application of inkjet
printing of solutions, particularly polymer containing inks, is strongly dependent on ink
formulation,[62] the choice of print head and substrate,[63,64] and the rate of solvent evaporation
versus marangoni-flow.[65,66]
A primary consideration for inkjet printing is that liquids must fit the physical and
rheological requirements of fluid flow in the printhead, in particular viscosity, in order to be
successfully ejected. If the ink is too viscous then a large pressure pulse is needed to generate
a droplet. Whereas if the surface tension is too low the printhead will generate attendant
satellites as well as the desired droplet, which reduces the resolution of the final as-printed
feature. The two main parameters that were varied in this study were the voltage applied
across the piezoelectric actuator and the pulse width, the time taken for the voltage to return
back to its starting value.
In order to quantify and compare liquid properties, both in-flight and upon impacting the
substrate, the dimensionless Reynolds and Weber numbers are important. The Reynolds
number is a dimensionless ratio of the inertial forces versus the viscous stress within a
droplet:
10
dv
Re = (1.2)

where is the density, d the orifice diameter, v the velocity and the viscosity of the in-
flight droplet. The Weber number is a dimensionless ratio of inertia forces versus the
interfacial stress:
dv 2
We = (1.3)

where is the surface tension of the liquid. Both dimensionless numbers have a large
influence on the droplet impact and spreading, as shown by Fukai et al.[67] Typically for inkjet
print experiments, both the Reynolds and Weber number are relatively low and in the order of
1 100, since the velocity and the size of the droplets are relatively small, which usually
prevents splashing of the droplets upon impacting the surface.
Fromms dimensionless Z-number, which is the inverse of the Ohnesorge number (Oh),
has been used to analyze droplet formation[56,68] and can be written as a function of both
dimensionless Re and We number:
d Re
Z = Oh 1 = = (1.4)
We
Fromm predicted that drop formation in DoD systems was only possible for Z greater than
2 and that the droplet volume increases as the value of Z increases. However, Derby et al.
refined this prediction to 1 < Z < 10, but seems to be valid only for concentrated wax or
paraffin suspensions.[56] In practice, however, the lower limit is determined by the viscosity
that dissipates the pressure pulse, whereas the upper limit represents the formation of satellite
droplets.[57] Furthermore, systems where the Z-number is much larger than 10 are printable as
long as the formed satellites merge with the main droplet. It has been demonstrated that
common solvents with a Z-number up to 91 could be successfully inkjet printed.[59]} The main
factor that appeared to affect printability was their vapour pressure, with unstable droplets and
no droplets being produced for solvents with vapour pressures higher than approximately
13 kPa.
11
Chapter 1
1.4 Aim and outline of the thesis

Inkjet printing, and in particular drop-on-demand inkjet printing, has developed from only
printing text and graphics into a major research topic, which has, for example, been used for
manufacturing microelectronic devices. Inkjet printing can compete with lithography
techniques, since it places material on demand and in a direct way, which reduces the number
of processing steps and the amount of material required. Furthermore, inkjet printing can also
be combined with roll-to-roll production. Typical applications can be seen in the field of
plastic electronic devices, which are prepared on flexible polymer substrates, including radio
frequency identification tags or electrodes for thin-film transistor circuits.
This dissertation is divided into two sections. The first part (Chapters 1 to 4) describes a
procedure using inkjet printing to fabricate microstructures onto polymer substrates. The first
chapter provides an overview of the history of inkjet printing and discusses the operation of
the various types of printers. In the next chapter, the inks behaviour in-flight, upon impact
with the substrate, and upon drying on the substrate is discussed since these basics must be
understood for successful inkjet printing. The third chapter describes the inkjet printing of
functional materials, including silver nanoparticle dispersions, with a resolution down to 40
m. For this purpose, slightly heated substrates in combination with relatively low surface
energy substrates were utilised. Nanoparticles smaller than 10 nm have their melting
temperature reduced to below 300 C, as a result of their large surface curvature. After
depositing these inks a thermal sintering step is required in order to render the particles
conductive, which will be discussed in Chapter 4. Alternative methods for the conversion of
nanoparticles into conductive features and the mechanisms involved are also discussed.
Polymer substrates can usually not withstand high temperatures and, therefore, require a low
temperature during the sintering process. Two new and selective sintering techniques are
discussed: exposure to microwave radiation and argon plasma. Both techniques sinter the
nanoparticles in a selective way, so that the polymer substrate is not affected. The
conductivity after sintering is similar compared to samples that were sintered thermally.
The second part of this thesis (Chapters 5 and 6) describes a new technique called photo-
embossing for the creation of surface relief structures. These structures can be created without
any etching steps, but usually have an aspect ratio smaller than 0.05. Chapter 5 describes the
improvement of the aspect ratio of photo-embossed structures by a factor of 10. Finally,
12
surface relief structures prepared by hot-embossing are used to further improve the printing
resolution down to a few micrometers. Hot-embossing is then applied for the engineering of
micro-channels in a polymer substrate and, subsequently, an inkjet printer is used for filling
the micro-channels by means of capillary forces with a silver nanoparticle dispersion.
It is concluded that inkjet printing represents a highly suitable technique for the
preparation of high-resolution conductive features on or into polymer substrates by tuning the
polymer substrate properties as well as the inks. Moreover, new and alternative techniques
can be used to improve the sintering time and circumstances. Together with a combination of
different embossing techniques this could lead to more continuous overall processing of
flexible electronic devices in the future.
1.5 References
1 J. A. Nollet, W. Watson, Philos. Trans. 1749, 46, 368.

2 F. Savart, Ann. Chim. Phys. 1833, 53, 337.
3 W. Thomson, UK Patent 2,147, 1867.
4 http://en.wikipedia.org/wiki/Lord_Kelvin (last accessed: 5th January 2009).
5 E. F. Goedde, M. C. Yuen, J. Fluid Mech. 1970, 40, 495.
6 Lord Rayleigh, Proc. London Math. Soc. 1878, 10, 4.
7 Lord Rayleigh, Proc. London Math. Soc. 1879, 29, 71.
8 Lord Rayleigh, Nature 1891, 44, 249.
9 Lord Rayleigh, Philos. Mag. 1892, 34, 145.
10 H. C. Lee, IBM J. Res. Develop. 1974, 18, 364.
11 D. B. Bogy, Ann. Rev. Fluid. Mech. 1979, 11, 207.
12 J. A. F. Plateau. Philos. Mag. 1856, 12, 286.
13 R. Elmqvist, US Patent 2,566,443, 1951.
14 F. J. Kamphoefner, IEEE T. Electron. Dev. 1972, 19, 584.
15 M. R. Keeling, Phys. Technol. 1981, 12, 196.
16 J. M. Schneider, C. D. Hendricks, Rev. Sci. Instrum. 1964, 35, 1349.
17 R. G. Sweet, R. C. Cumming, US Patent 3,373,437, 1968.
18 R. G. Sweet, Rev. Sci. Instr. 1965, 36, 131.
19 R. G. Sweet, US Patent 3,596,275, 1971.
20 C. H. Hertz, S.-I. Simonsson, US Patent 3,416,153, 1968.
21 C. H. Hertz, S.-I. Simonsson, Med. & Biol. Eng. 1969, 7, 337.
22 J. Heinzl, C. H. Hertz, Adv. Electron. Electron Phys. 1985, 65, 91.
23 C. W. Hansell, US Patent 2,512,743, 1950.
13
Chapter 1
24 M. Naiman, US Patent 3,179,042, 1965.

25 H. Kobayashi, N. Koumara, S. Ohno, US Patent 4,243,994, 1981.
26 I. Endo, Y. Sato, S. Saito, T. Nakagiri, S. Ohno, GB Patent 2,007,162, 1979.
27 I. Endo, Y. Sato, S. Saito, T. Nakagiri, S. Ohno, US Patent 4,723,129, 1988.
28 I. Endo, Y. Sato, S. Saito, T. Nakagiri, S. Ohno, US Patent 4,740,796, 1988.
29 J. L. Vaught, F. L. Cloutier, D. K. Donald, J. D. Meyer, C. A. Tacklind, H. H. Taub,
US Patent 4,490,728, 1984.
30 R. D. Carnahan, S. L. Hou, IEEE Trans. Ind. Appl. 1977, IA-13, 95.
31 M. Dring, Philips Tech. Rev. 1982, 40, 192.
32 J. van Randeraat, R. E. Setterington, Piezoelectric Ceramics, Philips Application-Book, 2nd
Edition, Mullard Ltd., London, 1974.
33 http://www.microdrop.de (last accessed: 5th January 2009).
34 J. Brnahl, A. M. Grishin, Sens. Actuators A 2002, 101, 371.
35 S. I. Zoltan, US Patent 3,683,212/ 1972.
36 http://www.microdrop.de/wDeutsch/technology/microdrop.shtml?navid=28
(last accessed: 5th January 2009).
37 N. G. E. Stemme, US Patent 3,747,120, 1972.
38 E. Stemme, S.-G. Larsson, IEEE Trans. Electron. Dev. 1973, 20, 14.
39 E. L. Kyser, S. B. Sears, US Patent 3,946,398, 1976.
40 E. L. Kyser, L. F. Collins, N. Herbert, J. App. Photographic Engineering 1981, 7, 73.
41 S. D. Howkins, US Patent 4,459,601, 1984.
42 K. H. Fishbeck, A. T. Wright, US Patent 4,584,590, 1986.
43 C. R. Winston, US Patent 3,060,429, 1962.
44 C. R. Winston, US Patent 3,432,844, 1969.
45 H. P. Le, J. Imag. Sci Technol. 1998, 42, 49.
46 H. Kipphan, Handbook of print media: Technologies and manufacturing processes, Springer,
2001.
47 B.-J. de Gans, P. C. Duineveld, U. S. Schubert, Adv. Mater. 2004, 16, 203.
48 P. Calvert, Chem. Mater. 2001, 13, 3299.
49 Y. Yoshioka, G. E. Jabbour, Synth. Met. 2006, 156, 779.
50 B. Ballarin, A. Fraleoni-Morgera, D. Frascaro, S. Marazzita, C. Piana, L. Setti, Synth. Met.
2004, 146, 201.
51 K. Kords, T. Mustonen, G. Tth, H. Jantunen, M. Lajunen, C. Soldano, S. Talapatra, S. Kar,
R. Vajtai, P. M. Ajayan, Small 2006, 2, 1021.
52 S. Hauschild, U. Lipprandt, A. Rumplecker, U. Borchert, A. Rank, R. Schubert, S. Frster,
Small 2005, 1, 1177.
53 D. B. Bogy, F. E. Talke, IBM J. Res. Develop. 1984, 28, 314.
54 J. F. Dijksman, J. Fluid Mech. 1984, 139, 173.
55 D.-Y. Shin, P. J. Smith, J. Appl. Phys. 2008, 103, 114905.
56 N. Reis, C. Ainsley, B. Derby, J. Appl. Phys. 2005, 97, 094903.
14
57 K. A. M. Seerden, N. Reis, J. R. G. Evans, P. S. Grant, J. W. Halloran, B. Derby, J. Am.

Ceram. Soc. 2001, 84, 2514.
58 C. Ainsley, N. Reis, B. Derby, J. Mater. Sci. 2002, 37, 3155.
59 B.-J. de Gans, E. Kazancioglu, W. Meyer, U. S. Schubert, Macromol. Rapid Commun. 2004,
25, 292.
60 H. Dong, W. Carr, J. F. Morris, Phys. Fluids 2006, 18, 072102.
61 J. Perelaer, P. J. Smith, C. E. Hendriks, A. M. J. van den Berg, U. S. Schubert, Soft Matter
2008, 4, 1072.
62 A. M. J. van den Berg, A. W. M. de Laat, P. J. Smith, J. Perelaer, U. S. Schubert, J. Mater.
Chem. 2007, 17, 677.
63 J. F. Dijksman, P. C. Duineveld, M. J. J. Hack, A. Pierik, J. Rensen, J.-E. Rubingh, I. Schram,
M. M. Vernhout, J. Mater. Chem. 2007, 17, 511.
64 B.-J. de Gans, U. S. Schubert, Macromol. Rapid Commun. 2003, 24, 659.
65 H. Hu, R. G. Larson, Langmuir 2005, 21, 3963.
66 H. Hu, R. G. Larson, J. Phys. Chem. B 2006, 110, 7090.
67 J. Fukai, Z. Zhao, D. Poulikakos, C. M. Megaridis, O. Miyatake, Phys. Fluids A 1993, 5,
2588.
68 E. Tekin, P. J. Smith, U. S. Schubert, Soft Matter 2008, 4, 703.
15
2
Ink behaviour in-flight and at the substrate
Abstract
This chapter describes the behaviour of an ink droplet both in-flight as well as upon impinging the
substrate. Firstly, an experimental study into the in-flight evaporation and impact of equally-sized
inkjet printed droplets that consist of a systematically varied polystyrene concentration in either
toluene or butyl acetate is presented. At low polymer concentrations, a linear relationship, which
decreased, was observed between the dried droplet diameter and the printing height. Whereas,
increased concentrations revealed an initial exponential decay in the dried droplet diameter, which
stabilised at greater heights. At higher concentrations and heights, the polymer forms a skin on the
surface of the inkjet printed droplet, which causes inhibition of the in-flight evaporation of the solvent.
Secondly, the spreading of inkjet printed droplets on solid dry surfaces of a polystyrene/toluene
solution with a varied molar mass of the polymer has been studied. The polymers molar mass was
varied between 1.5 and 545 kDa, which caused a variation in the viscosity from 0.6 to 1.7 mPa s. The
results were compared with theoretical models for droplet spreading and were found to fit with an
error between 2 and 20% with the predictions.
Finally, the size-selective segregation of silica based particle populations in drying droplets was
studied. It was found that, after drying, smaller particles were located close to the periphery of a
droplet, whereas larger particles settle nearer to the centre. It was observed that monodisperse
micron-sized particles sediment as close as possible towards the periphery; the actual distance
between the location of segregated particles and the contact line increases with increasing particle
size.
Parts of this chapter have been and will be published: (1) J. Perelaer, P. J. Smith, M. M. P. Wijnen, E. van den
Bosch, R. Eckardt, P. H. J. M. Ketelaars, U. S. Schubert, Macromol. Chem. Phys. 2009, in press; (2) J. Perelaer,
P. J. Smith, E. van den Bosch, S. S. C. van Grootel, P. H. J. M. Ketelaars, U. S. Schubert, Macromol. Chem.
Phys. 2009, in press; (3) J. Perelaer, P. J. Smith, C. E. Hendriks, A. M. J. van den Berg, U. S. Schubert, Soft
Matter 2008, 4, 1072.
Chapter 2
2.1 Introduction
Inkjet printing has become a major topic in scientific research and has been conducted for
various areas of research.[1,2] In particular, inkjet printing has matured as a technique for
depositing small amounts of functional materials in a precise and selective way onto a wide
range of substrates.[3] For example, inkjet printing is used to produce microelectronic devices,
such as conductive antennas for radio frequency identification (RFID) tags,[4-6] organic light-
emitting displays (OLED),[7-9] and field-effect transistors (OFET).[10,11] The amount of waste
that is generated during processing is drastically reduced due to the selective deposition of
materials, which lowers the production costs and favours the environment significantly.
An important topic in understanding the fundamentals of inkjet printing is the impact and
spreading behaviour of droplets, which continues to be investigated and has been the topic of
studies for over a century.[12,13] The control of droplet deposition is essential in other industrial
applications besides inkjet printing, for example spray painting, spray coating and rapid spray
cooling of hot surfaces. The type of impact made by an impinging droplet on a surface
depends on the surface morphology as well as the liquid properties of the droplet.[14] Upon
impact of a droplet on a solid surface four different events can take place: normal deposition,
(partial) splashing, receding break-up, or a (partial) rebound.[15,16] The impact has been
studied both theoretically, as well as experimentally.[17-21] Due to these studies various impact
scenarios of a droplet on a surface are now under control. For example, the rebound of
droplets[22] can be suppressed by adding small amounts of flexible polymers, whose
elongation viscosity damps the droplet retraction.[23] Furthermore, it has been found that the
splash during the impact of a droplet on a solid surface can be controlled by reducing the
surrounding atmosphere pressure.[24,25] When the impact takes place on a liquid surface, for
example water, the splashing effect can be minimised either by a hydrophobic layer around
the impinging droplet[26] or by perfectly smooth spheres.[27]
The impact and spreading of droplets have been visualised by researchers using high-
speed photography or flash techniques. The difference between the two techniques is that the
former records a high number of frames of a single experiment, whereas the latter one is a
stroboscopic method whereby a sequence of identical droplets are recorded and reconstructed
by merging the frames of several identical events.[18,28] Flash photography techniques require
that identical droplets, in terms of velocity, shape and volume, are generated. Inkjet printed
droplets have been proven to fulfil these requirements.[29,30] However, inkjet printers have
18
scarcely been used in impact and spreading studies,[31,32] and relatively large droplets in the
order of millimetres have mainly been used.[15,33-35]
Another important topic is the behaviour of liquid droplets on a solid substrate, which is
generally well-understood for pure liquids,[36-37] but the behaviour of either a solution or a
suspension on a substrate continues to stimulate debate.[38-42] An often seen phenomenon is
that droplets of solutions and suspensions dry in such a fashion that the dried material forms a
ring. Deegan et al. gave three conditions for ring formation:[39] the solvent meets the substrate
at a non-zero contact angle, the solvent evaporates, and the contact line is pinned to its
original position. A fourth condition was suggested by Hu and Larson who reported that
suppression of the Marangoni flow that results from the latent heat of evaporation is also
required.[38] However, Sommer and Rozlosnik have recently provided experimental evidence
which they say shows that pinning of the contact line is not necessary for ring formation.[42]
The coffee drop effect is named after the commonly observed dark coloured rings of dried
coffee droplets, as shown in Figure 2.1a. Deegan explained the appearance of these and other
rings as being caused by a replenishing flow which originates in a drying droplets interior
and travels towards the substrate-air-liquid interface, i.e. the contact line.[40]
(a) (b)
Figure 2.1 Photograph of a single dried droplet (a) and a cluster of three droplets (b) of fresh morning coffee
with its typical appearance of ring formation.
Deegan explains the replenishing flow as being a consequence of the evaporation rate
being higher at the contact line and the line being pinned. Therefore, as solvent evaporates
from the droplet, liquid is carried towards the droplets boundary since the contact line is
unable to retreat. The higher evaporation rate causes a non-uniform evaporative flux over the
surface of the droplet, which Deegan explains is due to the fact that a random walk of an
evaporating solvent molecule initiated at the centre of a droplet has a higher chance of re-
absorption than the same random walk initiated from the edge, as depicted in Figure 2.2.[40]
19
Chapter 2
As a consequence of the replenishing flow, liquid and any solute or suspended particles are
transported towards the edge of a droplet. Furthermore, when droplets are close to each other,
their evaporation behaviour is affected, as can be seen in Figure 2.1b: the outer rim of each
droplet is darker coloured than the inner rim, indicating a larger amount of material settled
from the liquid. A locally higher vapour pressure at the region where the three droplets meet
reduces the evaporation rate and thereby the deposition of solid material, i.e. coffee in this
example.
Figure 2.2 The probability of escape of an evaporating molecule is affected by its point of departure. A random
walk initiated at the centre of the drop results in the molecule being reabsorbed so that the final step is not
completed (indicated by the dashed line). However, the same random walk initiated from the edge allows the
evaporating molecule to escape. Reprinted from ref. [40].
The strength of the replenishing flow was demonstrated by Magdassi et al. who found that
a metallic ring, which had formed at room temperature via the evaporation of an aqueous
droplet containing silver nanoparticles, exhibited high electrical conductivity (up to 15% of
bulk silver).[43] Similarly, colloidal systems consisting of monodisperse microspheres have
been investigated for their self-assembly properties upon evaporation of the solvent,[44,45] bio-
mimicry patterning,[46] and as photonic bandgap materials.[47] Furthermore, it was reported
that in a drying droplet containing a bi-modal particle population of 60 nm and 200 nm sized
polystyrene nanoparticles, the larger particles aggregated at the border of the ring, whereas the
smaller particles were found as an inner ring nearer to the centre of the dried droplet.[48] This
observation is fascinating, but counterintuitive, because it contradicts the classical laws of
movement: smaller particles are easier to move than larger particles due to their smaller mass.
However, these results suggest that this method could be used as a size separation technique,
since particles are segregated according to their size.
20
This chapter discusses three fundamental parameters that affect the application of inkjet
printing. Firstly, the printing height, which is the distance between the printhead and the
substrate, is systematically varied to study the effect on the impression that polymer solutions
leave on a substrate. Then, the effect of the molar mass of the dissolved polymer is altered and
studied. Finally, suspended micron-sized particles are inkjet printed in order to study their
preferred positioning towards the droplets contact line. The purpose of these studies allows an
increased interpretation to be made of the results that are obtained by inkjet printing.
2.2 Influence of the printing height
2.2.1 Introduction
The impact of inkjet printed and other dispensed droplets strongly depends on their
dimensionless Reynolds and Weber numbers.[15,31] Similarly, printing height also influences
droplet impact and spreading. This particular factor, however, has not been investigated so
far. As long as the accuracy of droplet positioning is not affected, an increase in height may
be a simple way to decrease droplet radius since the droplet, which is primarily composed of a
volatile solvent, spends more time in flight and, therefore, has more time to evaporate. This
could lead to finer resolution features being produced by inkjet printing. Such an increase in
height may even be coupled with the use of a heated substrate, which could further increase
the rate of evaporation for certain systems.
Here, the observations of the in-flight evaporation and impact on solid dry substrates of
uniformly-sized inkjet printed droplets with various concentrations of polystyrene is
described. To reveal information of in-flight evaporation the height between printhead and
underlying substrate was systematically increased. After impact on the substrate the droplets
evaporate and leave a coffee stained ring of dried polymer behind (as will be discussed in
further detail in Section 2.3). The ring diameter, measured by means of optical profilometry,
was investigated as function of printing height and polymer concentration. An inkjet printer
was used to produce a series of equal-sized small droplets dispensed into a 10 10 matrix
with a droplet interspacing of 1 mm. Using an inkjet printer reduced the error per droplet and
significantly increased experimental reproducibility. From these 100 printed droplets, odd
shaped droplets were excluded (7%) and from 10 droplets the horizontal and vertical
diameters were measured and averaged.
21
Chapter 2
2.2.2 Experimental
Materials
Butyl acetate was purchased from Fluka and toluene was purchased from Biosolve. All
solvents were used as delivered. Polystyrene was purchased from Shell (Styron 648) and its
number averaged molar mass was measured to be 90.2 kDa (Mw = 112 kDa, PDI 1.24) by gel
permeation chromatography. Prior to inkjet printing all solutions were ultra-sonicated and
filtered with a 5 m filter (Rezist 30, Whatman GmbH, Dassel, Germany) to prevent nozzle
clogging. The contact angle and surface tension were measured using a Dataphysics OCA 30
(Filderstadt, Germany). Typical errors in the surface tension were smaller than 0.2 mN m-1.
Substrates
Commercially available glass substrates of 3 1 inch (Marienfeld, Lauda-Knigshofen,
Germany) were thoroughly cleaned by washing subsequently with soap, water, acetone and
isopropanol.[49] After a second rinsing step with isopropanol the glass slides were dried under
a flow of air.
Inkjet printing
Inkjet printing was performed using a piezoelectric Autodrop system (Microdrop
Technologies, Norderstedt, Germany). This system was fitted with a 70 m printhead, which
can be moved in the z-direction. Droplets were generated using a frequency of 200 Hz. The
glass samples were placed onto a heatable platen that can move in x- and y-direction. The
Autodrop system has a positioning accuracy of 1 m and a stroboscopic video camera to
investigate and optimise droplet formation. Typical printing settings used a voltage between
150 and 160 V and a pulse width between 100 and 115 s, which gave an initial in-flight
droplet radius of 55 m for the 1 wt% polystyrene/solvent solutions. All samples were printed
at room temperature.
Characterisation
Gel permeation chromatography was measured on a Shimadzu system equipped with a SCK-
10A system controller, a LC-10AD pump, a RID-10A refractive index detector and a PL gel
5 m Mixed-D column at 50 C utilising a chloroform : triethylamine : isopropanol (94:4:2)
mixture as eluent at a flow rate of 1 mL min-1. The molar masses were calculated against
polystyrene standards. Profiles of the printed tracks were measured by confocal microscopy
22
(Surf, Nanofocus, Germany) using a 20 objective. The droplet profiles were measured
using Scanning Probe Image Processor, SPIP software, version 4.1.
Dynamic and kinetic viscosities were measured on an Anton Paar AVMn automated micro-
viscometer which is based on the approved and acknowledged rolling/falling ball principle
according to DIN 53015 and ISO 12058. The system allows a variable inclination angle of the
measurement capillary. Using a 0.900 mm capillary and a gold coated ball with a diameter of
0.794 mm at 20.00 C, times were determined as the average of 4 determinations per varied
angle (30, 50 and 70, respectively). Dynamic viscosities were directly calculated by the
instruments software.
2.2.3 Results and discussion

To observe the in-flight evaporation, various concentrations of polystyrene in toluene
were inkjet printed from different heights. The first experiment was performed from a
nominal height of 0 mm, which means a position as close as possible to the substrate. To
prevent damage to the nozzle during printing and to prevent smearing out of the printed
droplets by the nozzle tip, the printhead was set to a minimal height of approximately 150 m
above the substrate at the starting height. Immediately after ejection from the nozzle, the
droplet has to reach equilibrium size and velocity.[50] Therefore, the distance travelled by the
droplet over periods of 25 s was captured and measured using stroboscopic images taken
during droplet formation. Figure 2.3a shows an oscillating behaviour of the velocity over time
and reveals that the droplet reached equilibrium after 150 s, with a final velocity of
approximately 1 m s-1. In the first 150 microseconds, i.e. when the distance between printhead
and substrate is smaller than 0.5 mm, the velocity is between 2.5 and 3.5 m s-1. When a
droplets impact velocity is larger the spreading of the droplet is also larger due to a
corresponding increase of the Re and We numbers, thus leaving a large diameter droplet on
the substrate.[17]
Figure 2.3b shows the typical droplet formation for a 2 wt% PS solution in butyl acetate
(left) and a 2 wt% PS solution in toluene (right) in stroboscopic images, where the time
between each droplet is 100 s. It can be seen that after approximately four droplets in time
the droplet has reached a steady shape, thus equilibrium. Hence, printing should be performed
at least from a height where the final equilibrium velocity has been reached. In the
experiments the first data point that was recorded with the minimal printing height was,
therefore, neglected.
23
Chapter 2
It can be seen that a filament is formed during the start of the formation of the
toluene/polystyrene droplet. This behaviour has been observed by other researchers for
polymer solutions and is explained as being due to the stretching of the polymer and the non-
Newtonian behaviour of the ink.[51-53]
Droplet velocity (m s ) 4.0

-1
Butyl acetate
3.5 Toluene (a)
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0 100 200 300 400 500 600 700 800
Time (s)
(b)
100 m
Figure 2.3 Velocity as function of time (a) for droplet of a 2 wt% solution of polystyrene in butyl acetate and
toluene from a dispenser nozzle. Photographic images of the droplet formation (b) of 2 wt% PS in butyl acetate
(left) and 2 wt% PS in toluene (right). Subsequently, seven images form a multi-layered image, each with a time
interval of 100 s.
The printing height was increased up to 25 mm above the substrate in steps of 1 mm. It
should be mentioned that the positioning of the droplets into a matrix at heights above 15 mm
is less accurate due to small disturbances in the atmosphere caused by the movement of the
platen, whereon the substrate was placed. It was noticed that the matrix becomes less
symmetric and at heights above 25 mm several droplets are overlapping. Therefore, printing
from these heights is not applicable in practice. However, it was found that jetting at heights
of up to 15 mm did not affect droplet placement accuracy for this series of experiments. One
24
suggestion to improve the symmetry of the printed matrix is to print at a greater velocity,
which makes the droplets less sensitive to air disturbances.[15]
Figure 2.4 shows the measured droplet diameter as a function of printing height with
toluene as solvent and representative three-dimensional images of dried droplets that were
dispensed from 2, 8 and 18 mm, respectively. All droplets show a rim of polymer material,
formed by a replenishing flow during solvent evaporation (the coffee drop effect). The data
points in Figure 2.4a were fitted with a linear regression (dotted line) or a first order
exponential decay (solid line). The first data point has been excluded from the regression
fitting, as explained above. As can be seen, the dried droplet diameter decreases for all
concentrations of polymer. The 1 wt% solution shows a linear downwards trend (R2 = 0.97).
This trend can be explained by the partial evaporation of the solvent during the descent of the
droplet. During the flight of the droplet, the velocity of the droplet is constant, due to a
balance between drag and internal forces.[54] Therefore, when a droplet travels for a longer
distance there is more time for evaporation. Upon evaporation the droplets in-flight diameter
decreases as well, thus leaving a smaller dried droplet on the surface.
Droplet diameter (m)
220
1 wt% PS/toluene
210
200
2 wt% PS/toluene
Linear fit
(a)
190 Exponentional fit
180
170
160
150
140
130
120
110
100
90
80
0 2 4 6 8 10 12 14 16 18 20 22 24 26
Height (mm)
(b)
Figure 2.4 Dried droplet diameter as a function of nozzle height for solutions of different concentrations of
narrow polydispersity polystyrene in toluene (a). Three-dimensional picture of the dried droplet from a 2 wt%
polystyrene/toluene solution (b): from left to right, droplets are shown that were printed from 2, 8 and 18 mm,
respectively.
25
Chapter 2
In contrast, when a 2 wt% solution of polystyrene in toluene was printed the dried droplet
diameter does not show a linear downwards trend but an exponential behaviour (R2 = 0.97).
This suggests that the evaporation of the toluene is halted at a certain height. The main factors
that could decrease the diameter of the dried droplet on the substrate are the in-flight droplet
diameter and the overall viscosity of the solution.[17] The in-flight diameter can only be
decreased by solvent evaporation, which is significant during the droplets free-fall. The
viscosity increases upon solvent evaporation, which is similar to the 1 wt% solution, and
limits the spreading of the droplet on the surface. Unlike the 1 wt% solution, a higher solute
concentration has a greater effect on the viscosity of the solution upon solvent evaporation. It
is believed that the polymer forms a skin on the outside of the droplet and evaporation of the
solvent is inhibited.[55,56] Furthermore, it was observed that for long hydrocarbon chains there
is a stronger retarding effect on the evaporation of the solvent.[57]
It is important to note that both polymer/toluene solutions were inkjet printed with the
same settings, in order to obtain a comparable droplet diameter and velocity. Therefore, it is
expected that the dried droplet diameters at the start, i.e. the range 1 2 mm, would be similar
for the two concentrations. However, at a height of 2 mm the droplet diameter for the 2 wt%
solution is noticeably smaller than for the droplets produced from the 1 wt% solution (180 m
and 130 m, respectively). This difference can be explained as being due to a difference in the
viscosities (see Table 2.1) of the two solutions; this, in turn, affects the Z-number, which
influences the droplet size.[29] The increased viscosity also limits the ability of a droplet to
spread on the substrate.[17]
Table 2.1 Typical ink properties for various concentrations (C) of polystyrene in butyl acetate or toluene: surface
tension (), viscosity (), Reynold (Re), Weber (We), Z-number, and contact angle () on the substrate.
Solvent C Re We Z
-1
(wt%) (mN m ) (mPa s) (-) (-) (-) ()
Toluene 0 24.7 0.599 0.006 97.6 2.37 63.4 <5

Toluene 1 24.3 1.071 0.002 54.6 2.40 35.2 <5
Toluene 2 24.7 2.048 0.001 28.6 2.37 18.6 <5
Butyl acetate 0 27.0 0.729 0.004 84.6 2.28 56.0 <5
Butyl acetate 1 27.1 1.227 0.014 50.3 2.28 33.3 <5
Butyl acetate 2 27.5 1.729 0.003 35.7 2.24 23.9 <5
Butyl acetate 5 27.3 5.169 0.018 11.9 2.26 7.92 <5
A further investigation into the trend of decreased dried droplet diameters was performed
using another solvent that has a lower vapour pressure than toluene. In order to keep the
26
experiment comparable, a solvent with similar Reynolds and Weber number was chosen.
Butyl acetate was identified as an appropriate candidate. In order to have comparable print
results, the print parameters were set in such a way that the droplet velocity and in-flight
diameter (55 m) were equal to the previous experiment for 1 wt % polystyrene.
Using butyl acetate as the solvent, an experiment identical to that with toluene was
performed. Figure 2.5 shows the results for a varied concentration of polystyrene in butyl
acetate. Again, all droplets reveal a strong coffee drop effect, similar to the
polystyrene/toluene experiments. It can be seen in Figure 2.5a that both the 1 wt% and 2 wt%
show a linear decrease in the droplet diameter as height increase (R2 = 0.76 and 0.91,
respectively), which is similar to the 1 wt% polystyrene/toluene mixture. However, at a
concentration of 5 wt% a similar saturating trend as with the 2 wt% polystyrene/toluene is
seen (R2 = 0.94). Since the same polymer is used for both experiments, the effect seen at
5 wt% is thought to be due to the solvent properties. The vapour pressure of toluene is
3.79 kPa, whereas butyl acetate has a value of 1.66 kPa. Therefore, since butyl acetate has a
lower vapour pressure, less evaporation of the solvent takes place in flight and more time is
taken to reach a critical viscosity than with toluene. Therefore, a higher concentration of
polymer is required to see the saturation trend.
340
1 wt% PS/BuAc
320
300
2 wt% PS/BuAc (a)
5 wt% PS/BuAc
280
Linear fit
260 Exponential fit
240
220
200
180
160
140
120
100
80
0 2 4 6 8 10 12 14 16 18 20 22 24 26
Height (mm)
(b)
Figure 2.5 Dried droplet diameter as a function of nozzle height for solutions of different concentrations of
narrow polydispersity polystyrene in butyl acetate (a). Three-dimensional picture of the dried droplet from a
2 wt% polystyrene/butyl acetate solution (b): from left to right, droplets are shown that were printed from 2, 8
and 18 mm, respectively.
27
Chapter 2
The dried droplet diameters in the 1 to 2 mm range for the three concentrations of butyl
acetate solutions deviate from each other, in the same way as for toluene. Again a difference
in viscosity can explain the different spreading behaviour: an increased viscosity limits the
droplet spreading on the substrate and also affects the Z-number. Section 2.3 describes further
research on the influence of the viscosity on inkjet printed droplets and their impact.
Further observations can be drawn from Figures 2.4 and 2.5. First of all, the droplet
diameter at large heights (10 20 mm) for both the 2 wt% PS/toluene and the 5 wt%
PS/BuAc solutions is comparable. This indicates that the condition of the formation of a skin
of precipitated polymer on the surface of the droplet may have been reached, which inhibits
further evaporation of the solvent. Secondly, the linear regression of the data for the 1 wt% PS
solutions with toluene and butyl acetate revealed that the slope for toluene is one and a half
times larger than for butyl acetate. This difference can be attributed to the larger vapour
pressure for toluene. This trend can also be seen in Figures 2.4b and 2.5b, where a larger
decrease in droplet diameter is seen in the three-dimensional images of the droplet. Finally,
the error bars for butyl acetate are larger than for toluene. It was noticed during droplet
diameter measurements that the shapes of the droplets formed from the toluene solution were
more circular than those formed from butyl acetate, as shown in Figures 2.4b and 2.5b. This
may be explained by the small difference in viscosity between toluene (0.560 mPa s) and
butyl acetate (0.685 mPa s).[58]
In summary, it was demonstrated that for inkjet printed droplets of a varied concentration
of polystyrene, dissolved either in butyl acetate or toluene, the in-flight evaporation of the
solvent can be increased by increasing the printing height. This has the advantage of reducing
the size of the deposited droplet and thereby increasing the printing resolution. With low
polymer concentrations, a linear decrease between dried droplet diameter and printing height
was observed; whereas increased concentrations revealed an initial exponential decay in the
dried droplet diameter before stabilising at greater heights. An explanation of this observation
is that at higher concentration, the polymer forms a skin on the surface of the inkjet printed
droplet, which inhibits the in-flight evaporation of the solvent. The influence of this skin on
solvent evaporation may be worth bearing in mind when considering the more practical
application of printing onto heated substrates regardless of whether one increases the
printhead height.
28
2.3 The behaviour of inkjet printed droplets of polymer solutions on a dry

solid substrate
2.3.1 Introduction
In this section the observations on the impact and spreading of inkjet printed droplets of a
polymer solution is described. The first experiments are conducted with a solution that
contains a systematically varied molar mass of linear polystyrene in toluene while
maintaining a constant concentration of 1 wt% for each solution. The obtained results are
compared with recently described models for spreading of droplets in the open literature. A
second set of experiments was done to reveal the effect of the printing height on the droplet
spreading, while maintaining a constant vapour pressure for all solutions. According to
Raoults Law, the vapour pressure decreases with increased solute concentration. Therefore,
various concentrations with a varied molar mass of polystyrene in toluene were prepared and
inkjet printed from a systematically increased height onto a glass substrate.
An inkjet printer was used in order to produce a series of equal-sized droplets, which
allowed the error in the measurements to be reduced and significantly increased experimental
reproducibility.
2.3.2 Experimental
Materials
Toluene was purchased from Biosolve and used as delivered. Linear polystyrene standards
were purchased from PSS (Polymer Standards Service GmbH, Mainz, Germany). Prior to
inkjet printing all solutions were filtered with a 5 m filter (Rezist 30, Whatman GmbH,
Dassel, Germany) to prevent nozzle clogging by dust particles. The contact angle and surface
tension were measured using a Dataphysics OCA 30 (Filderstadt, Germany).
Substrates
Commercially available glass substrates of 3 1 inch (Marienfeld, Lauda-Knigshofen,
Germany) were thoroughly cleaned by washing subsequently with soap, water, acetone and
isopropanol, respectively. After a second rinsing step with isopropanol the glass slides were
dried under a flow of air.
29
Chapter 2
Inkjet printing
Inkjet printing was performed by using a piezoelectric Autodrop system (Microdrop
Technologies, Norderstedt, Germany). This system was fitted with a 70 m printhead, which
can be moved in the z-direction. Droplets were generated using a frequency of 200 Hz. The
glass samples were placed onto a heatable platen that can move in x- and y-direction. The
Autodrop system has a positioning accuracy of 1 m and a stroboscopic video camera to
investigate and optimise droplet formation. Typical printing settings used a voltage between
75 and 80 V and a pulse width between 23 and 25 s. All samples were printed at room
temperature.
Characterisation
Droplet diameter and velocity were calculated from the stroboscopic images that were
captured during droplet formation with the inkjet printer. Droplet profiles were characterised
using an optical profilometer (Fogale Zoomsurf, France, white light, magnification 5).
2.3.3.1 Molar mass influence on droplet spreading

The influence of the molar mass of polystyrene on the final dried droplet diameter on a
glass substrate is here discussed. Glass was chosen since it is wetted very well by toluene,
with a contact angle smaller than 5. This provides a higher contrast between different
spreading behaviours.[59] Toluene was chosen, because of its good solubility properties with
polystyrene. Polystyrene with a low polydispersity index (PDI < 1.07) has been used and all
solutions were made with 1 wt% of polymer. Since standard viscosity measurements require a
relatively large amount of materials, we have calculated the dynamic viscosity of each
polymer solution using the Staudinger equation for the intrinsic viscosity:
[ ] = KM a (2.1)
where a and K are the parameters tabulated for a variety of polymer-solvent systems.[60,61]
Here a value of 0.69 and 0.017 cm3 g-1 were taken for a and K, respectively. The solution
properties are summarised in Table 2.2.
30
Table 2.2 Properties for the prepared 1 wt% polymer solutions with varied number averaged molar mass (Mn)
and low polydispersity indices (PDI). Viscosity () is calculated using the Staudinger equation, whereas surface
tension (), density () and contact angle () are measured. The droplets velocity (v) and in-flight diameter (d0)
are calculated from the stroboscopic images. From these values the Reynolds (Re), Weber (We) and Z-numbers
were calculated.
Mn PDI Re We Z v d0
-1 -3 -1
(kDa) (-) (mPa s) (mN m ) (kg m ) () (-) (-) (-) (m s ) (m)
1.50 0.06 1.04 0.60 24.31 0.05 836 <5 110.8 2.75 66.8 1.04 80.1
16.8 0.70 1.04 0.66 24.48 0.06 844 <5 107.9 3.10 61.3 1.06 80.1
60.6 1.82 1.03 0.78 23.86 0.05 828 <5 83.27 2.70 50.7 0.99 79.1
124 8.68 1.07 0.92 24.27 0.07 837 <10 79.15 3.32 43.4 1.11 78.1
236 11.8 1.05 1.14 24.13 0.05 835 ~10 52.01 2.24 34.8 0.92 77.2
545 16.4 1.03 1.71 24.21 0.05 836 ~13 39.07 2.77 23.5 1.02 80.2
The viscosity has a significant effect on the spreading of a droplet after impact.[17]
Therefore, the spreading factor (), defined as the ratio of the final diameter of the droplet on
the substrate (D) and the in-flight (d0) droplet diameter, has been measured as function of
molar mass of the dissolved polymer.
An inkjet printer was used to dispense multiple droplets onto the substrate into a 10 10
matrix from a fixed height of 1 mm. From these 100 drops, 10 droplets were chosen and
characterised by measuring their diameters in both the x- and y-directions; with the averaged
diameter per droplet being used for further calculations.
2.3.3.2 Comparison of the maximum spreading diameters

During the last few decades, many theoretical models have been described for the normal
impact and spreading of droplets on various surfaces, including extensive reviews.[22,34,62]
Although there are many different models, all take the following energy balance into account:
Ek = Ev + E s (2.2)
which states that all of the kinetic energy (Ek) of the impinging droplet is converted into
viscous energy (Ev) and surface tension energy (Es). From hereon, assumptions have to be
made in order to be able to solve the equations numerically, for example by applying finite
elemental methods.[17] Five models were selected to compare with the experimental results.
31
Chapter 2
Firstly, a simple model that neglects the viscous dissipation and assumes that the droplet
spreads into a cylindrical disk is based on the finding of Collings et al.[63]
We + 12
max = (2.3)
3(1 cos )
where max is the maximum dimensionless spreading factor and the contact angle that the
liquid droplet forms with the substrate.
The second model, that of Pasandideh-Fard et al.,[35] describes the deduction of a model
that includes viscous dissipation, resulting in an extra factor depending on the Reynolds and
Weber number. Typically, this model is valid when the Reynolds number is larger than 4:
We + 12
max =
We (2.4)
3(1 cos ) + 4
Re
Although, the models from Collings and Pasandideh-Fard are similar, the difference is
that Collings equation is valid for Reynolds numbers much larger than the Weber number,
We
which makes the factor negligibly small. This is the case when viscosity effects are
Re
neglected.
Thirdly, Ukiwe et al. suggested considering the surface energy term at maximum
spread,[33] resulting in the following expression:
8
We + 12
max
max = (2.5)
We
3(1 cos ) + 4
Re
The fourth model by Bennet et al.,[34] adapted from the model of Madesjki,[64] was used,
which is valid only for Reynolds numbers larger than 100:
[
3 (1 cos ) max
2
4 ]
+
1 max

5
=1 (2.6)
We Re 1.2941
32
The last model, that of Park et al.,[65] discards the assumption that a droplet forms a
cylindrical disk, because this is not reasonable for low impact velocities, particularly for high
contact angles where the surface area of the cylindrical disk is much higher than the actual
surface area. Therefore, they assume the droplet will be a truncated sphere after impact with a
constant volume. Their original equation is
We 1 1 1 cos 2 We E
0.33 cos + max 1 + 2 SP = 0 (2.7)
Re 4 2 sin 2 12 d LV
Rewriting Equation 2.7 into an expression similar as Equations 2.3 2.5, results in
We + 12 Q
max =
We (2.8)
3( f s cos ) + 4
Re
where Q represents the ratio of the increase in surface and interfacial energies for spontaneous
spreading (ESP) and the squared in-flight droplet diameter multiplied by the surface energy
of the liquid-vapour:
E SP
Q = 12 (2.9)
d 2 LV
with
cos 1 1 cos
E SP = d 2 LV g ( ) (2.10)
4 2 sin 2
2
4 sin 3 3
g ( ) = (2.11)
(
2 3 cos + cos
3
)
2(1 cos )
fs = (2.12)
sin 2
33
Chapter 2
where fs is the ratio of the fluid-vapour surface and the fluid-solid surface, which can be
deduced directly from Tadmors Langmuir paper.[66] Herein, he derives two equations for the
surface of a spherical cap with volume V and equilibrium contact angle :
2
2

(
ASL = V 2 3 cos + cos3
3 ) 3
sin 2 (2.13)
3
2
2
ALV

(
= V 2 3 cos + cos3
3 ) 3
(1 cos ) (2.14)
3
The ratio of the fluid-vapour surface (ALV) and the fluid-solid surface (ASL), defined as fs,
becomes then
2
2
A

( 3
2V 2 3 cos + cos3 (1 cos )
3 ) 2(1 cos )
f s = LV = 3 = (2.12)
ASL 2
2
sin 2

( 3
V 3 2 3 cos + cos sin
3 2
)
3
When substituting Equations 2.10, 2.11 and 2.12 into Equation 2.9 the term Q becomes,
2
cos 1 1 cos 4 sin 3 3
Q = 12 g ( ) = 3( f s cos ) (2.15)
4 2 sin 2 ( )
2 3 cos + cos
3
Finally, the maximum spreading factor (max) for low viscous liquids can be written as:
2
4 sin 3 3
We + 12 + 3( f s cos )
max =
( 3
2 3 cos + cos ) (2.16)
We
3( f s cos ) + 4
Re
where the extra term in the numerator compensates the cap shaped drying droplet on the
surface. The extra term in the numerator is a result of the assumption of the truncated sphere
and is for all contact angles (0 < < 180) greater than zero.
34
The spreading factors for the selected models were calculated using Equations 2.3 2.6
and 2.16 and compared with the experimental results. Figure 2.6 and Table 2.3 show the
maximum spreading factor as a function of number averaged molar mass (Mn) for the various
models and the experimental data. The horizontal error bars with the experimental data
represent the polydispersity of used polymers, whereas the vertical error bars show the
measurement errors in the diameter. The experimental data was fitted to an exponential decay
function and revealed a good correlation (R2 = 0.92).
5.0
Spreading factor max (-)
Pasandideh-Fard (2.4)
Ukiwe (2.5)
4.5 Bennett (2.6)
Park (2.16)
Experimental
4.0 Exponential fit
3.5
3.0
2.5
2.0
0 100 200 300 400 500 600
Number averaged molar mass (kDa)
Figure 2.6 Droplet diameter after impact on the surface for different number averaged molar masses of
polystyrene/toluene solutions. The closed symbols represent the experimental data, while the errors bar in x-
direction show the molar mass distribution. The dashed line is a first order exponential decay fit (R2 = 0.92). The
open symbols show the calculated diameters for various models.
Table 2.3 Maximum spreading factor (max) for various models from literature and experimental values for
1 wt% polymer solutions with a varied number averaged molar mass (Mn).
Spreading factor max
[63] [33] [35] [34] [65]
Mn Experimental Collings Ukiwe Pasandideh-Fard Bennet Park
(kDa) (-) (-) (-) (-) (-) (-)
1.50 0.06 4.49 0.04 89.84 3.44 3.75 4.64 3.76

16.8 0.70 4.28 0.12 90.91 3.25 3.55 4.53 3.56
60.6 1.82 3.69 0.08 89.67 3.21 3.52 4.4 3.53
124 8.68 2.92 0.02 36.63 2.90 3.19 4.21 3.21
236 11.8 2.92 0.03 16.99 2.95 3.32 4.05 3.37
545 16.4 2.73 0.07 13.75 2.49 2.83 3.70 2.89
35
Chapter 2
When observing Table 2.3, it can be seen that the predictions according to the Collings
model are off by a large margin when compared with the experimental data. This is expected,
since this model does not take viscous dissipation into account. When looking at Figure 2.6,
the model of Bennet overestimates the spreading factor for all Mn values by 20 to 40%
compared to the experiments. Only in the regime where the Weber number is above 100, i.e.
with the lowest Mn values, the predictions come close to the experimental values. In general,
Ukiwes model underestimates the spreading factor, but only overlaps with Mn values above
100 kDa, where the error is 1 to 9%. The predictions of the models of Pasandideh-Fard and
Park show a relatively large deviation of 14 to 17% with low molar masses, whereas the
experimental observations for a Mn value above 100 kDa fit with both models, where the
deviation is only between 2 and 6%. This could be explained by the fact that the model of
Park assumes that the droplet has the form of a truncated sphere rather than a cylindrical disk,
i.e. a droplet on a substrate with a certain (small) contact angle. Only for a Mn value of
236 kDa did the calculated maximum spreading factor deviate strongly from the
experimental results.
Of interest is the observation that the maximum spreading factor for the experimental data
of low molar mass polymers is larger than the predictions of most of the models, whereas for
high molar mass polymers this trend is inverted: all but one of the models overestimate (albeit
slightly in the case of two of them) the maximum spreading ratio. This could be caused by a
partial dissipation of the kinetic energy during inertial oscillation when high molar mass
polymers are used, due to their greater elongation viscosity, which lowers the amount of
energy available for spreading.[23] However, in general none of the models describe the
experimental results over the whole molar mass region. This suggests that the models should
be improved.
Figure 2.7 displays images of the dried droplets taken with a white light interferometer.
The impressions, i.e. their ring effect, left at the substrate strongly depend on the Mn value of
the dissolved polystyrene. It can be seen that a higher molar mass polymer leaves a more
distinct coffee ring than a low molar mass polymer. This may be due to the higher molar mass
polymer droplets containing less solute molecules, which may contribute to an increased
evaporation rate at the edge. Furthermore, polymer solutions containing a low molar mass
polymer form rings with a greater diameter than when containing a high molar mass polymer,
which is due to their lower viscosity, as can be seen in Table 2.2.
36
Mn = 1.5 kDa Mn = 124 kDa
Mn = 16.8 kDa Mn = 236 kDa
Mn = 60.6 kDa Mn = 545 kDa
Figure 2.7 Three-dimensional images of dried droplets on a substrate from a polystyrene/toluene solution with a
varied polymers Mn value. Shown are from top to bottom and left to right, polystyrene with a Mn value varied
between 1.5 and 545 kDa. A colour version is available on page 173.
2.3.3.3 Printing height influence on droplet spreading under constant vapour pressure
In the previous section the maximum spreading factor was investigated as a function of
the polymers molar mass in the solution. The influence of the printing height on the
spreading factor was also investigated. However, in-flight evaporation depends also on the
dissolved materials and its concentration. In fact, the law of Raoult[67] says that the vapour
pressure of the solvent in a solution is directly proportional to its solute mole fraction, which
can be written for dilute solutions as:
PA = X A PA0 (2.17)
where PA is the vapour pressure of component A in solution, XA the mole fraction of A and PA0
the vapour pressure of pure component A. For polymer solutions Equation (2.17) can be
converted into the following:
37
Chapter 2
PA0
Mn = C (2.18)
PA0 PA
where Mn and C are the number averaged molar mass and the concentration of the polymer,
respectively.[68] Equation 2.18 states that in order to maintain a constant vapour pressure the
Mn values is reciprocally related to its concentration.
A set of experiments was performed, where the vapour pressure was kept constant for
polymers with various molar masses. Therefore, three polymer solutions were prepared with a
varied concentration from 0.256 to 1 wt% depending on the Mn value of the polymer, with the
smallest concentration for the lowest molar masses, as shown in Table 2.4. In this way all
solutions have an equal number of solute molecules and thus a similar vapour pressure of
approximately 2.914 kPa.
Table 2.4 Properties for three prepared polymer (Mn) solution having a constant vapour pressure, but varied
concentration (C). The viscosity (), Reynolds (Re), Weber (We) and Z-numbers are calculated. The droplets
velocity (v) and in-flight diameter (d0) are calculated from the stroboscopic images.
Mn C Re We Z v d0
-1 -3 -1
(kDa) (mPa s) (mN m ) (kg m ) (wt%) (-) (-) (-) (m s ) (m)
60.6 0.64 25.1 0.2 858 0.26 98.7 2.42 63.4 0.96 76.7
124 0.75 25.1 0.2 839 0.53 89.5 2.89 52.6 1.08 74.1
236 1.14 24.13 0.05 835 1.0 52.0 2.24 34.8 0.92 77.2
These solutions were inkjet printed from a systematically varied height and the results are
shown in Figure 2.8. It can be seen that all three solutions show a linear downward trend (R2
between 0.54 and 0.68), although the data for the 0.256 wt% solution with polystyrene
60.6 kDa shows a little scatter, which could explain the converging trend of the slopes of the
linear fits. The data in Figure 2.8 shows that the vapour pressure is not the only important
parameter that determines in-flight evaporation of the free-falling droplet, because the data
points are not overlapping. The (entanglement) viscosity of the droplet differs per solution,
since a longer polymer has a stronger effect on the viscosity than small polymer chains.
38
380
PS 60.6 kDa / 0.256 wt%

360 PS 124 kDa / 0.525 wt%
PS 236 kDa / 1.00 wt%
340
Linear fit
320
300
280
260
240
220
200
180
0 5 10 15 20 25
Height (mm)
Figure 2.8. Dried droplet diameter after impact on the surface for polystyrene/toluene solutions having a
constant vapour pressure as a function of the printing height. The dashed lines are linear fits with the data points.
It is important to note that all of the polymer solutions were inkjet printed with the same
settings, in order to obtain a comparable droplet diameter and velocity. Therefore, it was
expected that the dried droplet diameters at the start, i.e. the range from 1 to 2 mm, would be
similar for all concentrations. However, at a height of 2 mm the dried droplet diameter for the
solution of the 236 kDa / 1 wt% solution is noticeably smaller than for the droplets produced
from the 124 kDa / 0.525 wt% solution and the 60.6 kDa / 0.256 wt% (220 m, 266 m and
293 m, respectively). This difference can be explained as being due to a difference in the
viscosities (see Table 2.4) of the three solutions; this, in turn, affects the Z-number, which
influences the dried droplet size at the substrate.[29] An increased polymer concentration also
increases the viscosity, which limits the ability for a droplet to spread on the substrate.[17]
Therefore, the in-flight evaporation depends not only on the vapour pressure, but also on the
viscosity of the solution.
In summary, it has been demonstrated that for inkjet printed droplets of a polystyrene
solution the spreading on the substrate after impact strongly depends on the polymers molar
mass due to its influence on viscosity. The polymers molar mass was varied between 1.5 and
545 kDa and the results were compared with theoretical models for droplet spreading. The
relative errors between experimental data and the models were between 2% and 20%, which
suggests further improvement of the theoretical models. In a second set of experiments, the
in-flight evaporation was investigated while maintaining a constant vapour pressure by having
a constant number of polymers in solution, depending on its Mn value and in agreement to
39
Chapter 2
Raoults law. This revealed that the in-flight evaporation of the solvent is not only depending
on the vapour pressure, but also on the viscosity of the solution, since a solution with a higher
viscosity left a smaller dried droplet at the substrate.
2.4 Preferential deposition and size-selective segregation at the boundary

of inkjet printed features
2.4.1 Introduction
The coffee drop effect is a frequently observed phenomenon and can be seen in any
application that deposits bodies of solution or suspensions onto a relative smooth surface;
such as drop-casting, spin-coating, and inkjet printing. As a consequence of depositing liquid
onto a substrate, the coffee drop effect has often been observed in inkjet printed features.[69-71]
The effect can be minimised by either using a solvent mixture system,[72] which reduces the
higher evaporation rate at a liquid features edge, or by making surface-energy patterns, which
direct the ink to predefined areas on the substrate.[73-74] Conversely, the coffee drop effect has
also been exploited as an advanced etching technique to create polymer-relief microstructures
by inkjet etching.[75,76]
Here the observations of the behaviour of aqueous droplets of colloidal micron-sized
particle systems on glass slides that have different surface energies, as a result of different
surface treatments, are presented. Single-sized silica micro-spheres with sizes ranging from
330 nm up to 5 m were used; these monodisperse particles negate the effect of gravitational
force on particle deposition.[48] An inkjet printer was used to produce a series of equal-sized
droplets, which allowed us to reduce the error in the measurements and to significantly
increase experimental reproducibility. Also reported are the observations of droplets of
aqueous suspensions of PMMA latex spheres (with an average diameter of 300 nm) that were
produced by drop-casting.
2.4.2 Experimental
Materials
Four batches of monodisperse silica microspheres with a polydispersity less than 3% were
obtained from Bangs Laboratories Inc. (Fishers, IN, USA). The silica particles had hydroxyl
40
or silanol (Si-OH) surface groups and diameters of 0.33, 0.97, 3.01 and 4.74 m, respectively.
All colloidal suspensions were diluted to 1 wt% prior to usage.
The PMMA latex particle suspension (3 wt%) was prepared according to literature.[77]
Substrates
The substrates were commercially available microscope slides (3 1 inch slides from
Marienfeld, Lauda-Knigshofen, Germany) and were thoroughly cleaned by first washing
with sodium dodecyl sulfate solution, then rinsed with de-ionised water, then washed with
acetone and finally with isopropanol before being dried under a flow of air. These substrate
had a contact angle of 20 (A = 30, R = 10). Hydrophobic substrates were prepared by
coating glass slides with octadecyl trichlorosilane (OTS), which decreases the surface energy;
the contact angle was 103 (A = 110, R = 95).[78] Hydrophilic substrates were prepared by
ashing the glass slides, which were cleaned as described before, with O2 plasma in a plasma
asher (K1050X, Emitech, Kent, UK), which increases the surface energy of the glass; the
contact angle was 5. The glass slides for the second printing experiments were cleaned by
rinsing subsequently with acetone and ethanol, followed by drying with an air gun; this
resulted in a contact angle of 25 (A = 34, R = 15). The advancing, receding and
equilibrium contact angles were measured using a Dataphysics OCA 30 (Filderstadt,
Germany).
Inkjet printing
Inkjet printing was performed using an Autodrop system (Microdrop Technologies,
Norderstedt, Germany). This system was fitted with a 70 m printhead, which can be moved
in the z-direction. Droplets were generated using a frequency of 200 Hz. The glass slides were
placed onto a platen that can move in the x- and y-direction. The Autodrop system has a
positioning accuracy of 1 m and a stroboscopic video camera setup to investigate and
optimise droplet formation. For the first setup of printing experiments, an MD-K-140 head
was used with a voltage of 85 V and a pulse width of 30 s. The second printing series was
performed using an MD-K-130 head with a voltage of 47 V and a pulse width of 57 s. All
samples were printed at room temperature.
41
Chapter 2
Characterisation
Optical and scanning electron microscopy (SEM) images were taken using optical microscopy
(Axioplan Imaging 2, Zeiss, Germany) and a FEG E-SEM XL30 (Philips, Eindhoven, The
Netherlands).
2.4.3.1 Contact angle dependency of a drying droplet

Deegan identified the cause of the replenishing flow, which moves material from the
centre of a drying droplet towards the edge, as being due to the difference in evaporation rate
at the centre compared to the edge. He explains this difference by saying that solvent
molecules with a random walk initiated at the periphery of the droplet have a higher chance of
escaping than solvent molecules at the centre.[40] However, the dimensions of solvent
molecules are much smaller than those of droplets Angstroms compared to millimetres so
the majority of a droplets surface appears flat to an evaporating molecule. Only at the very
edge of the droplet, i.e. at the contact line, will the surface appear differently to the
evaporating molecule; with the contact angle of the droplet possibly influencing the escape
probability of solvent molecules.
Shanahan suggests that a sessile droplet in an atmosphere saturated with its vapour is not
in equilibrium.[79] Although some claim that a sessile droplet is in equilibrium,[80] current
opinion supports Shanahans theory.[81] For most droplets it is safe to assume that the local
atmosphere is under-saturated, which suggests that once a solvent molecule has left the
droplet from any point on its surface it is not likely to be reabsorbed. Subsequently, the
chances of re-absorption for a solvent molecule at the edge of a drying droplet are similar to
those at the centre.
In order to study the evaporation of sessile droplets on a substrate with a varied surface
energy, water droplets of equal volume (1.5 L) were placed onto cleaned glass slides and
OTS-treated glass slides,[82] as shown in Figure 2.9. The initial equilibrium contact angle
formed by water on the OTS-treated glass slide was 103 (A = 110, R = 95), whereas the
contact angle for water on the cleaned glass slide was 20 (A = 34, R = 15). It was
observed that it took 20 minutes for a droplet of water on OTS-treated glass to evaporate,
whereas a water droplet of the same volume on cleaned glass took only 8 minutes.
42
Figure 2.9 shows that the contact angle changes for both droplets during drying. The
contact angle of a drying water droplet on the OTS-coated surface changes from 103 to 30
over a period of 20 minutes (Figure 2.9a.i a.iii) and the angle on the cleaned glass substrate
decreases from 20 to 4 over 5 minutes (Figure 2.9b.i b.ii). According to the measured
receding contact angles for both substrates, the droplets do not retract until the receding angle
has been reached, which is 95 and 15 for OTS-coated and cleaned glass, respectively. This
appears to contradict the explanation of Ko et al.,[45] who report that an aqueous droplet on a
OTS-self-assembled monolayer film retracts and retains its hemispherical shape upon drying.
(a) (b)
i) ii) iii) i) ii)
Figure 2.9 Photograph of a drying water droplet an OTS-coated glass slide (a) and on an acetone/isopropanol
cleaned glass slide (b). The droplet on OTS-treated glass (a) shows three superimposed pictures, which were
taken after 0, 10 and 20 minutes (i-iii), respectively. The two superimposed photos of the drying droplet on
cleaned glass (b) were captured with a time interval of only 5 minutes (i-ii). The arrows are drawn to guide the
eye in following the shrinkage of the droplet during drying. The scale bar corresponds to 1 mm.
Rather a decrease in contact angle was observed as evaporation proceeded that agreed
with the findings of Bourgs-Monnier and Shanahan, who found that the evaporation rate
increases as the solid/liquid interface radius increases.[83] Contact angles remain constant
when the surrounding atmosphere is saturated in the vapour of the liquid. Furthermore, they
describe that there are three regimes that a solvent droplet on a smooth substrate undergoes
during evaporation. In the first regime, the diameter of the droplet remains constant, i.e. the
droplet-substrate area is unaffected. As the droplet loses mass through evaporation, the
contact angle and the droplets height decrease until the receding angle is reached. Thereupon,
the second regime starts, in which the droplets diameter begins to shrink. The contact angle
remains constant while the droplet-substrate area diminishes. Finally, both the droplets
diameter and contact angle shrink until evaporation is complete. As a general rule, droplets
with smaller initial contact angles have higher evaporation rates and mass loss is linear. The
evaporation of a droplet on a rough surface behaved similarly as on smooth substrates except
43
Chapter 2
that the second regime was not entered; the diameter remained constant due to the pinning of
the droplets contact line by the rough surface. However, it is worth mentioning that one
static, metastable contact angle is not the most precise way to characterise a surface since it
falls somewhere between the advancing and receding contact angles.[84]
2.4.3.2 Coffee drop effect with monomodal PMMA latex suspensions

In order to observe the coffee drop effect better, the initial experiments involved drop-
casting an aqueous suspension of PMMA latex particles with an average particle size of
300 nm onto cleaned glass slides. The drying was monitored using an optical microscope;
Figure 2.10 shows several images taken from this observation.
(a) (b)
(c) (d)
44
(e) (f)
(g) (h)
Figure 2.10 Bright field microscopy images of a drying droplet of an aqueous suspension of PMMA latex
particles ( 300 nm), with (a) the droplet just after placing it onto the glass substrate; (b) the same droplet after
90 seconds of drying, subsequently after 120 seconds (c), 180 seconds (d), after 300 seconds (e) and after
complete evaporation, 380 seconds (f). Image of the left edge of a similar droplet after 180 seconds of
evaporation (g) and after complete evaporation of the solvent, after 300 seconds (h). The black arrows (g)
indicate the bulges appearing the inside of the rim. The white arrow in (g) and (h) shows a defect, caused by dust
particles since the experiment was performed under ambient conditions. The scale bar in (a-f) is 500 m, 200 m
in (g) and 100 m in (h), respectively.
The initial droplet in Figure 2.10a-f has a diameter of roughly 3 mm. The image in Figure
2.10a shows a darker area in the centre of the droplet, whereas the outer region is lighter,
which indicates that at the start of the drying the material is more or less homogeneously
spread throughout the droplet.[85] As evaporation at the edge occurs, material within the
droplet moves towards the edge and deposits onto the substrate, forming a rim at the edge of
the droplet. The deposited material prevents movement of the contact line and, therefore, the
droplet contact diameter does not change with drying. Therefore, the contact line is anchored
by the deposited material and not the other way around, which was suggested by Deegan.[39,40]
45
Chapter 2
The rim is formed from the outside towards the centre of the droplet as was expected.
Furthermore, the droplet defines the space that particles can move in and thus no material
goes beyond the contact line.
When looking at Figure 2.10b, which was taken after 90 seconds had elapsed, it can be
seen that dark spots and ripples have appeared. These are thought to be caused by a locally
higher concentration of particles; Figure 2.10g shows these streams in greater detail. The
formation of these high particle density streams is essentially stochastic and is thought to
occur due to differences in temperature between the top and the edge of the drying droplet,
which are caused by evaporative cooling at the edge. It has been described in literature from
flow visualization studies and surface profiling that evaporative cooling produces Bernard-
Marangoni convection patterns which accrete the solute along two key boundaries of the flow,
namely the three phase contact line and the outer edge of a stagnant region about the ribbon
apex.[70,86] The appearance of these ripples becomes more pronounced over time Figure
2.10c-d and they continue to carry nanoparticles towards the droplets boundary, which in
turn thickens.
When a ripple contacts the rim, a bulge is formed as indicated by the black arrows in
Figure 2.10g which strongly suggest that these ripples are composed of a higher
concentration of material. The points at which the ripples contact the rim are random, leading
to an overall smoothness of the inside of the rim Figure 2.10d-e. The black white arrow in
Figure 2.10g and h shows a defect, caused by dust particles since the experiment was
performed under ambient conditions.
After all of the solvent has evaporated Figure 2.10f and h cracks form in the rim,[87]
which are probably due to localised contraction. It can be seen that not all of the material has
been transported towards the periphery; the interior of the dried droplet also shows deposited
material. This can be explained as follows: there is a higher evaporation rate of the solvent at
the end of the drying process than at the beginning due to increased surface-to-volume ratio
i.e. the droplet dome flattens. Although more material is transported, not all material can be
moved, because of the decreasing amount of solvent. Furthermore, a particle can only move in
the space delineated by the liquid. The high liquid dome at the start of drying allows a particle
the scope to move upwards as well as parallel to the substrate. As evaporation nears
completion, and the liquid dome decreases in height, a free particles movement becomes
increasingly restricted to the x- and y- directions.
46
2.4.3.3 Coffee drop effect with monomodal silica particles

A series of experimentation was performed to observe how particles behave at the contact
line, using drop-cast monodisperse suspensions of silica particles. Figure 2.11 shows optical
microscopy images of the edge of a drying droplet of an aqueous suspension of 5 m silica
particles on a cleaned glass substrate. The behaviours of the thirteen particles enclosed in the
red boxes are of interest. In the left image, the thirteen particles can be seen to form three
groups. These particles combine into a larger cluster over time (six seconds), as illustrated by
the images moving from left to right. It can be seen that the particles are not positioned at the
contact line and although they are unable to move back into the bulk of the droplet, due to the
replenishing flow, they are able to move parallel to the contact line.
Figure 2.11 Bright field optical microscopy images of a drying droplet of an aqueous suspension of 5 m sized
silica particles. The white arrow indicates the water contact line, whereas the black arrow points out the place
where particles sediment. The time between each image is 2 seconds and the scale bar represents 50 m.
47
Chapter 2
Figure 2.12 illustrates the dependence of the particles sedimentation to the contact angle
formed by the solvent with the substrate. Particles with a larger diameter end up further from
the contact line, i.e. nearer the droplets centre, than smaller sized particles. This theory was
tested experimentally and is discussed in the next section.
Figure 2.12 Schematic representation of the situation at the contact line where microsphere particles segregate at
different positions. Particle sizes are not drawn to scale, and indicates the contact angle the liquid forms with
the substrate.
2.4.3.4 Particle size dependency in the coffee drop effect of inkjet printed suspensions
In contrast to earlier studies on the coffee drop effect whereby only single droplets were
investigated,[39-43] the behaviour of differently sized particles at the periphery of a drying
droplet were performed using inkjet printing, which produces droplets of equal volumes.[29]
This allowed the creation of a matrix consisting of 10 10 droplets of equal volumes. From
these 100 drops, 7% were identified as imperfect droplets on account of having an elliptical
shape, which may have formed due to chemical or physical imperfections on the substrate,
and were discounted. For each sample, 10 droplets were characterised by measuring their
diameters in both the x- and y-directions; with the averaged diameter per droplet being used
for further calculations.
Four monomodal particle suspensions, with particle diameters (their radii are given in
parentheses) of 0.33 (0.165), 0.97 (0.485), 3.01 (1.505) and 4.97 (2.485) m, were inkjet
48
printed onto cleaned glass slides. All of the suspensions were deposited at room temperature,
using the same printer settings to ensure that the droplet diameter (65.3 m) and, therefore,
the volume (147 pL) of each droplet was the same. It was expected that only particles with
sizes below 3.5 m would be printable, since the printheads nozzle diameter was 70 m. As a
general rule, particles that are greater than 5% of the orifice diameter will cause at least some
instability in the drop generation behaviour and may lead to nozzle clogging.[88] However, no
problems with clogging were observed when printing the larger 5 m particles. To the casual
reader the fact that a 5 m particle passes through a 70 m nozzle may not seem remarkable.
However, the piezoelectric drop-on-demand inkjet nozzles, which were used in this study,
generate droplets by means of pressure waves. Particles abrade the inside of the nozzle, which
will in time change the acoustics inside the nozzle, leading to the end of droplet generation at
worse. At best, new printing parameters need to be determined, which in this experiment,
where comparison between dispensing-runs is important, may well have led to droplets with
different volumes. Two explanations are offered for the successful printing of the larger
particles. Firstly, the concentration of the suspension is very low, only 1 wt%. Therefore, the
chance of particles clustering to form agglomerates is reduced. The second explanation is that
the silica microspheres are not functionalised and the surface groups are hydroxyl or silanol
(Si-OH), which show a low tendency for agglomeration.
Figure 2.13 shows selected dried droplets that were obtained from the four printed
suspensions. It can be seen that droplets of suspensions containing smaller sized particles
leave a larger dried droplet on the surface after drying. These sizes can be explained in terms
of the contact angle that the solvent formed and the ability of a particle to approach the
contact line. The shape of a solvent droplets edge on a substrate can be thought of as a
triangular wedge, as shown in Figure 2.12. The contact angle of the droplet on a substrate
limits the place of sedimentation of the particles within the droplet. The larger the particles
are, the greater the distance will be between these particles and the initial contact line.
Therefore, the diameter of a dried droplet decreases with increased particle size since larger
particles cannot travel as near to the contact line as smaller particles.
49
Chapter 2
(a) (b)
(c) (d)
Figure 2.13 Bright field microscopy images of inkjet printed droplets of aqueous suspensions containing 0.33
m (a), 1 m (b), 3 m (c) and 5 m (d) sized silica particles. The photograph that shows the 3 m particle (c)
has the focus point on the contact line rather than on the particles.
The same jetting parameters were used for the inkjet printed droplets of all four silica
microsphere 1 wt% suspensions; therefore it is assumed that volumes of the droplets are
equal. If the edge of the droplet is simplified to the triangle shown in the inset of Figure 2.14,
the distance from a deposited particle to the contact line can be calculated by using a simple
tangent equation:
r
x= (2.19)
tan( / 2)
where x represents the distance between the contact line and the centre of the particle, which
is sitting on the surface; r is particle radius and the contact angle that the solvent forms with
the substrate.
50
r
2
D
a x
Figure 2.14 Phase contrast microscopy images of inkjet printed droplets of an aqueous suspension containing
3 m sized silica particles. The white arrow shows the contact line of the liquid, whereas the black arrow
indicates the position where the particles sediment. The inset shows a schematic representation of the edge of the
droplet, where r is the radius of the particle, x the distance from the particle to the contact line, and the contact
angle that the droplet forms with the substrate.
Extrand recently presented a relationship between the contact angle, the cross-sectional
area and the volume of a sessile liquid droplet.[89] Firstly, the two equations for the maximum
cross-sectional area A were taken:
2
3V 3
A = ( cos sin ) (2.20)
(1 cos ) (2 + cos )
2
D 2 ( cos sin )
A= (2.21)
4 sin 2
where V is the droplet volume, and the contact angle with the substrate and D the contact
diameter of the droplet with the substrate. When substituting Equation 2.20 into 2.21:
D 2
3V 3
= (2.22)
4 sin (1 cos ) (2 + cos )
2 2
51
Chapter 2
2
3V 3
D 2 = 4 sin 2 (2.23)
(1 cos ) (2 + cos )
2
with
1 3
V= d (2.24)
6
where d is the in-flight droplet diameter before surface impact. The equation can be
recombined and simplified:
1
d 3 3
D = 2 sin (2.25)
(1 cos ) (2 + cos )
2
Finally, this can be written:
4
D( , d ) = d sin 3 (2.26)
(1 cos ) (2 + cos )
2
Equation 2.26 describes the contact diameter (D) of the deposited droplet sitting on the
surface as a function of the in-flight droplet diameter (d) and the contact angle (). From
Figure 2.14, a relationship can now be derived, where the dried droplet diameter a, can be
written as a function of contact diameter and contact angle:
2r
a = D 2 x = D (2.27)
tan( / 2)
Table 2.5 shows the measured and calculated values of a for all four particle radii. The
droplet in-flight diameter was 65.3 m and its calculated volume 147 pL. The values for the
measured contact droplet diameters deviate within 7% from the calculated values. The error in
the dried droplet diameter increases with larger particle sizes. It is expected that these values
vary with particle size, since the distance from the actual position of the particle and the edge
52
of the droplet increases with increasing particle size. The assumption is also made that all of
the droplets produced by the inkjet printer are uniform.[29] However, it is possible that slight
variations occurred, e.g. small fluctuation in the holding pressure, which produced variably
sized droplets.
Table 2.5 Particle size dependency of the dried droplet features; where r is the particle radius, is the contact
angle of the liquid with the substrate, D is the contact diameter as calculated from Equation 2.26, x the distance
from the placement of the particles to the original contact line of the droplet that is calculated from Equation
2.19, acalculated the calculated droplet diameter from Equation 2.27, and ameasured the measured droplet diameter
from the inkjet printed droplets.
r D x acalculated ameasured
(m) () (m) (m) (m) (m)
0.165 20 160.6 0.9 158.8 171 4

0.485 20 160.6 2.7 155.2 160 4
1.505 20 160.6 8.3 144.0 134 3
2.485 20 160.6 13.7 133.2 128 11
The experiments mentioned before were all performed on cleaned glass slides. Therefore
the contact angle had a constant value of 20, with an advancing contact angle (A) of 34 and
a receding contact angle (R) of 15. The contact diameter in Equation 2.26 shows
approximately an exponential decay with the contact angle, as shown in Figure 2.15, which
has been observed in literature previously.[71] The contact diameter will be large for small
contact angles and vice versa. Therefore, it is interesting to also investigate the effect of
varying the contact angle on the dried droplet diameter, which is discussed in the following
section.
10
Spreading factor max (-)
2
9 Exponential fit (R = 0.98)
0
0 20 40 60 80 100 120
Contact angle ()
Figure 2.15 Maximum spreading factor max, defined as the contact diameter D divided by the in-flight droplet
diameter d, as function of the contact angle that the liquid forms with the substrate.
53
Chapter 2
2.4.3.5 The effect of contact angle on the position of suspended silica particles
In order to investigate the effect of varying the contact angle on the placement of the
particles on the substrate, suspensions of silica particles with different particle sizes were
inkjet printed onto glass substrates, whose surface energy had been modified.
Firstly, droplets were inkjet printed onto glass slides that were cleaned following a slightly
altered procedure: rinsing with acetone, rinsing with ethanol and subsequently drying with an
air gun. Using ethanol rather than isopropanol and by skipping the washing step, with sodium
dodecyl sulfate solution, slightly decreases the wettability of the glass slides. The contact
angle was found to be 25 (A = 34, R = 15). Secondly, glass slides cleaned as described
above were coated with an OTS monolayer, which renders the substrate hydrophobic.[78,82]
The contact angle was measured to be 103 (A = 110, R 95). As a third substrate, the
cleaned glass slides were ashed with O2 plasma, which increased the hydrophilicity of glass.
The contact angle of the substrate was approximately 5. Here, the advancing and receding
contact angles were too low to measure.
Three silica particle suspensions were printed using the same printer settings. The in-flight
droplet size and volume were 73.2 m and 205.4 pL, respectively. The difference between
droplet volumes produced in this set of experiments and those reported earlier is due to a
different printhead (MD-K-130) being used. Again matrices of 10 10 were printed, of which
less than 10 droplets were rejected due to having non-circular geometries. From 10 droplets,
the diameter both horizontally as well as vertically was measured and averaged.
In Figure 2.16 and Table 2.6 the results of inkjet printed droplets on substrates with
different contact angles are shown. In the previous section, it was shown that when the
particle size was decreased the dried droplet features have a larger diameter see Figure
2.16b. This trend can be also observed for particles on a substrate with a high surface energy,
i.e. low contact angle , as depicted in Figure 2.16a. However, when the contact angle is
increased to 90 or higher the discrimination of particle sizes vanishes and all particle sizes
show a similar dried droplet diameter on a substrate with a low surface energy see Figure
2.16c.
(a)
54
(b)
(c)
Figure 2.16 Phase contrast microscopy images of inkjet printed droplets of aqueous suspensions of silica
particles onto high surface energy substrate (a), cleaned glass slide (b), and low energy substrate (c). Each row
shows, from left to right, a particle size of 0.33 m, 1 m and 3 m, respectively.
Table 2.6 Contact angle and particle dependency of the dried inkjet printed droplet features. In the top columns
different contact angles are shown: OTS is a glass substrate coated with an OTS monolayer, cleaned glass is
simply cleaned glass, and plasma treated glass is rendered hydrophilic by using plasma ashing. In the first
column, r represents the particle radius, D is the contact diameter as calculated from Equation 2.26, x is the
distance from the placement of the particles to the original contact line of the droplet calculated from Equation
2.19, acalculated the calculated dried droplet diameter from Equation 2.27, and ameasured is the measured dried
droplet diameter from the inkjet printed droplets. All values are displayed in micrometer.
OTS ( = 103) Cleaned glass ( = 25) Plasma treated glass ( = 5)
r D x acalculated ameasured D x acalculated ameasured D x acalculated ameasured
0.165 81.7 0.2 81.3 28.7 2 168.4 0.8 166.8 172.3 3 310.4 4.7 301.0 307.1 5
0.485 81.7 0.7 80.3 31.4 2 168.4 2.2 164.0 143.8 4 310.4 13.9 282.6 299.9 5
1.505 81.7 2.1 77.5 40.9 3 168.4 6.9 154.6 123.4 4 310.4 43.1 224.2 232.4 3
Scanning electron microscopy (SEM) was used to look closer at the printed three-
dimensional features on OTS coated glass substrates. Figure 2.17 shows a polycrystalline
formation of the particles, even for small grain sizes. Furthermore, it was observed that with
increasing particle size the dried droplet feature increases as well. Since each particle
suspension was printed with equal weight percentages of solid material, and all silica particles
have equal density, an increase of dried droplet diameter is observed due to the fact that larger
sphere shaped particles leave more unoccupied volume i.e. holes in their close-packed
structure. The stapling is not ideal and therefore, it can not be assigned to be either hexagonal
55
Chapter 2
close-packed or cubic close-packed. Nevertheless, equally sized spheres with radius r packed
into a three-dimensional structure create holes that have an unoccupied volume for spheres
not larger than 0.414r (for an octahedral hole) or 0.225r (for a tetrahedral hole).[90]
(a)
(b)
(c)
Figure 2.17 Scanning electron microscopy (SEM) images of silica particles with a particle diameter of 0.33 m
(a), 1 m (b) and 3 m (c) on OTS coated glass slides.
Furthermore, when calculating the total volume of the inkjet printed particles and
comparing that value to the volume of the hemisphere formed after drying (calculated by the
56
measured dried droplet diameter) the deviation for large particles between measured and
observed volume is larger than for small particles, as shown in Table 2.7 (last column;
packing factor). This was expected, and observed previously in the literature,[45] since the
packing of large particles is less efficient then the packing of small particles, when the initial
droplet volume remained the same.
Despite the high packing factors that indicate a good particle stapling, a value above 0.68
(body-centred cubic) or 0.74 (face-centred cubic) is not possible.[90] Moreover, the SEM
images in Figure 2.17 show defects in the three-dimensional structures. Two explanations for
the overestimated packing factors in Table 2.7 can be given; the first is that the inkjet printed
droplet volume, which scales to the power third with the measured in-flight droplet diameter,
was measured too large. A larger droplet contains more particles and consequently increases
the packing factor. Secondly, the assumption that the particles form a hemispheric structure
may not be correct. It can be seen in Figure 2.17c that the top of the 3D structure is somewhat
flattened.
Table 2.7 Packing efficiency for silica microspheres with different particle radius r. The second column shows
the amount of particles per mL, obtained from the supplier of the particles. The number of particles on the
surface shows the amount of particles within one inkjet printed droplet, and subsequently the total particle
volume is the number of particles multiplied by their own volume. The droplet volume shows the volume of the
hemisphere formed at the surface, calculated from the measured feature diameter on the substrate. Finally, the
packing factor is the ratio of the total particle volume and the droplet volume.
r Particles per mL Number of particles printed Total particle volume Droplet volume Packing factor
(m) (-) (-) (pL) (pL) (%)
12
0.165 2.797 10 569749 10.7 12.3 87
11
0.485 1.101 10 22427 10.7 16.1 66
9
1.505 3.608 10 733 10.5 17.9 59
In summary, investigations to further understanding the coffee drop effect were made. It
was published earlier by Deegan that solute does not influence the observed final features,
which has led to the popular explanation that material always sediments at the contact line.
However, it was shown here that suspended media plays a part in the final feature size by
depositing as close as possible to the contact line. The findings also suggest that it is the
sedimentation of material at the contact line that pins a droplet.
An inkjet printer was used to produce an array of uniformly sized droplets, which were
composed of monodisperse silica micro-spheres suspended in water and observed an
influence on final dried droplet diameter as a consequence of particle size. It was found that
57
Chapter 2
for larger particles there was a greater difference between the initial droplet diameter and the
dried droplet diameter. The distance between the contact line and the deposited particles,
which make up the dried droplet, depends on the contact angle that the solvent forms with the
substrate and the size of the suspended particles. This preferential deposition of particles is
caused by the wedge-shaped dome of the drying droplet, which physically limits the ability of
the larger particles to move nearer to the periphery. If the contact angle is 90 or higher, this
discrimination of particle size no longer occurs.
2.5 Conclusions
It has been described how an ink droplet behaves after being ejected from the printhead,
both in-flight as well as upon impinging the substrate. An experimental study into the in-flight
evaporation and impact of equally-sized inkjet printed droplets that consist of a systematically
varied polystyrene concentration in either toluene or butyl acetate was performed. Hereby, the
influence of the printing height on the impression that the droplet left at the substrate was
studied. At low polymer concentrations, a linear relationship that decreased was observed
between the dried droplet diameter and the printing height. Whereas, increased concentrations
revealed an initial exponential decay in the dried droplet diameter, which stabilised at greater
heights. It is thought that at higher concentration and height the polymer forms a skin on the
surface of the inkjet printed droplet, which causes inhibition of the in-flight evaporation of the
solvent. Therefore, the in-flight evaporation of the solvent can be influenced by altering the
printing height: an increased printing height results in smaller droplets at the substrate and
thereby increasing the printing resolution.
Furthermore, the spreading of inkjet printed droplets on solid dry surfaces of a
polystyrene/toluene solution with a varied molar mass has been studied. The polymers molar
mass was varied between 1.5 and 545 kDa, which also caused a variation in the viscosity from
0.6 to 1.7 mPa s. The results were compared with theoretical models for droplet spreading and
were found to fit with an error between 2 and 20% with the predictions. The in-flight
evaporation was investigated while maintaining a constant vapour pressure by having a
constant number of polymers in solution, depending on its Mn value and in agreement to
Raoults law. This revealed that the in-flight evaporation of the solvent is not only depending
on the vapour pressure, but also on the viscosity of the solution, since a solution with a higher
viscosity left a smaller dried droplet at the substrate.
58
Finally, the size-selective segregation of silica based particle populations in drying

droplets was studied. It was observed that monodisperse micron-sized particles sediment as
close as possible towards the periphery; the actual distance between the location of segregated
particles and the contact line increases with increasing particle size. Moreover, the distance
between the contact line and the deposited particles, which make up the dried droplet, also
depends on the contact angle that the solvent forms with the substrate. This preferential
deposition of particles is caused by the wedge-shaped dome of the drying droplet, which
physically limits the ability of the larger particles to move nearer to the periphery. If the
contact angle is 90 or higher, this discrimination of particle size no longer occurs.
These findings are in contrast to the work that was published earlier by Deegan, where it
was written that the solute does not influence the observed final features, which has led to the
popular explanation that material always sediments at the contact line. Here, it was shown that
suspended media plays an important part in the final feature size by depositing as close as
possible to the contact line. Furthermore, it can be concluded that the deposited material
prevents movement of the contact line and that the droplet contact diameter does not change
with drying. Therefore, the contact line is anchored by the deposited material and not the
other way around.
In contrast to earlier studies whereby only single droplets were investigated, all
experiments described here were performed using an inkjet printer, which produces droplets
of equal volumes. This allowed the creation of a matrix consisting of droplets with equal
volumes. From these 100 droplets, only 7% were identified as imperfect droplets. Therefore,
the technique of inkjet printing can be used for systematic and statistical studies.
2.6 References

2 B.-J. de Gans, P. C. Duineveld, U. S. Schubert, Adv. Mater. 2004, 16, 203.
3 Inkjet Printing of Functional Materials, MRS Bulletin 2003, 28, 11.
4 T. H. J. van Osch, J. Perelaer, A. W. M. de Laat, U. S. Schubert, Adv. Mater. 2008, 20, 343.
5 D. C. Huang, F. Liao, S. Molesa, D. Redinger, V. Subramanian, J. Electrochem. Soc. 2003,
150, G412.
6 D. Redinger, S. Molesa, S. Yin, R. Farschi, V. Subramanian, IEEE Trans. Electron. Devices
2004, 51, 1978.
7 J. F. Dijksman, P. C. Duineveld, M. J. J. Hack, A. Pierik, J. Rensen, J.-E. Rubingh, I. Schram,
M. M. Vernhout, J. Mater. Chem. 2007, 17, 511.
59
Chapter 2

9 D. B. van Dam, J. G. M. Kuerten, Langmuir 2008, 24, 582.
10 H. Sirringhaus, T. Kawase, R. H. Friend, T. Shimoda, M. Inbasekaran, W. Wu, E. P. Woo,
Science 2000, 290, 2123.
11 J. Z. Wang, J. Gu, F. Zehnhausern, H. Sirringhaus, Appl. Phys. Lett. 2006, 88, 133502.
12 Lord Rayleigh, Nature 1891, 44, 249.
13 A. M. Worthington, A Study of Splashes, Longmans, London, 1908, 129.
14 M. Rein, Fluid Dynam. Res. 1993, 12, 61.
15 R. Rioboo, M. Marengo, C. Tropea, Exp. Fluids 2002, 33, 112.
16 R. Rioboo, C. Tropea, M. Marengo, At. Sprays 2001, 11, 155.
17 J. Fukai, Z. Zhao, D. Poulikakos, C. M. Megaridis, O. Miyatake, Phys. Fluids A 1993, 5,
2588.
18 D. Attinger, Z. Zhao, D. Poulikakos, J. Heat Transfer 2000, 122, 544.
19 J. Fukai, Y. Shiiba, T. Yamamoto, O. Miyatake, D. Poulikakos, C. M. Megaridis, Z. Zhao,
Phys. Fluids 1995, 7, 236.
20 A. L. Yarin, Annu. Rev. Fluid. Mech. 2006, 38, 159.
21 M. Francois, W. Shyy, Prog. Aero. Sci. 2002, 38, 275.
22 T. Mao, D. C. S. Kuhn, H. Tran, AIChE J. 1997, 43, 2169.
23 V. Bergeron, D. Bonn, J. Y. Martin, L. Vovelle, Nature 2000, 405, 772.
24 L. Xu, W. W. Zhang, S. R. Nagel, Phys. Rev. Lett. 2005, 94, 184505.
25 D. Qur, Nature 2005, 435, 1168.
26 C. Duez, C. Ybert, C. Clanet, L. Bocquet, Nat. Phys. 2007, 3, 180.
27 J. Eggers, Nat. Phys. 2007, 3, 145.
28 S. T. Thoroddsen, T. G. Etoh, K. Takehara, Annu. Rev. Fluid Mech. 2008, 40, 257.
30 H. Dong, W. Carr, J. F. Morris, Phys. Fluids 2006, 18, 072102.
31 D. B. van Dam, C. Le Clerc, Phys. Fluids 2004, 16, 3403.
32 Y. Son, C. Kim, D. H. Yang, D. J. Ahn, Langmuir 2008, 24, 2900.
33 C. Ukiwe, A. Mansouri, D. Y. Kwok, J. Colloid Interface Sci. 2005, 285, 760.
34 T. Bennett, D. Poulikakos, J. Mater. Sci. 1993, 28, 963.
35 M. Pasandideh-Fard, Y. M. Qiao, S. Chandra, J. Mostaghimi, Phys. Fluids 1996, 8, 650.
36 T. Young, Trans. R. Soc. London 1805, 95, 65.
37 P. G. de Gennes, Rev. Mod. Phys. 1985, 57, 827.
38 H. Hu, R. G. Larson, J. Phys. Chem. B 2006, 110, 7090.
39 R. D. Deegan, O. Bakajin, T. F. Dupont, G. Huber, S. R. Nagel, T. A. Witten, Nature 1997,
389, 827.
40 R. D. Deegan, O. Bakajin, T. F. Dupont, G. Huber, S. R. Nagel, T. A. Witten, Phys. Rev. E
2000, 62, 756.
41 R. D. Deegan, Phys. Rev. E 2000, 61, 475.
42 A. P. Sommer, N. Rozlosnik, Crystal Growth Des. 2005, 5, 551.
60
43 S. Magdassi, M. Grouchko, D. Toker, A. Kamynshny, I. Balberg, O. Millo, Langmuir 2005,

21, 10264.
44 J. Park, J. Moon, Langmuir 2006, 22, 3506.
45 H.-Y. Ko, J. Park, H. Shin, J. Moon, Chem. Mater. 2004, 16, 4212.
46 A. P. Sommer, R.-P. Franke, Nano Lett. 2003, 3, 573.
47 C. Lpez, Adv. Mater. 2003, 15, 1679.
48 A. P. Sommer, M. Ben-Moshe, S. Magdassi, J. Phys. Chem. B 2004, 108, 8.
Chem. 2007, 17, 677.
50 D. B. Bogy, F. E. Talke, IBM J. Res. Develop. 1984, 28, 314.
25, 292.
52 Y. Christanti, L. M. Walker, J. Non-Newtonian Fluid Mech. 2001, 100, 9.
53 J. J. Cooper-White, J. E. Fagan, V. Tirtaatmadja, D. R. Lester, D. V. Boger, J. Non-Newtonian
Fluid Mech. 2002, 106, 29.
54 J. Kukkonen, R. Vesala, M. Kulmala, J. Aerosol Sci. 1989, 20, 749.
55 J. J. Spillman, Aeronaut. J. 1984, 88, 181.
56 S. Akbar, PhD Thesis, University of Aston, Birmingham, England, 1988.
57 W. D. Garrett, J. Atmos. Sci. 1971, 28, 816.
58 D. R. Lide, Handbook of Chemistry and Physics 2008, CRC Press, Boca Raton.
59 J. Perelaer, P. J. Smith, C. E. Hendriks, A. M. J. van den Berg, U. S. Schubert, Soft Matter
2008, 4, 1072.
60 G. M. Pavlov, A. S. Gubarev, I. I. Zaitseva, M. A. Sibileva, Russ. J. Appl. Chem. 2006, 79,
1407.
61 J. Brandrup, E. H. Immergut, E. A. Grulke, Edt., Polymer Handbook, 4th Edition, Wiley-
Interscience Publication, New York 1999, VII-23.
62 W. M. Healy, J. G. Hartley, S. I. Abdel-Khalik, Int. J. Heat Mass Transfer 1996, 39, 3079.
63 E. W. Collings, A. J. Markworth, J. K. McCoy, J. H. Saunders, J. Mater. Sci. 1990, 25, 3677.
64 J. Madejski, Int. J. Heat Mass Transfer 1975, 19, 1009.
65 H. Park, W. W. Carr, J. Zhu, J. F. Morris, AlChE J. 2003, 49, 2461.
66 R. Tadmor, Langmuir 2004, 20, 7659.
67 F.-M. Raoult, Compt. Rend. Acad. Sci. (Paris) 1887, 104, 1430.
68 I. Tinoco Jr., K. Sauer, J. C. Wang, Physical Chemistry: Principles and Application in
Biological Sciences, 3rd Edition, Prentice-Hall, New Jersey, 1995, 227-233.
69 J. Perelaer, B.-J. de Gans, U. S. Schubert, Adv. Mater. 2006, 18, 2101.
70 T. Cuk, S. M. Troian, C. Min Hong, S. Wagner, Appl. Phys. Lett. 2000, 77, 2063.
71 P. J. Smith, D.-Y. Shin, J. E. Stringer, B. Derby, N. Reis, J. Mater. Sci. 2006, 41, 4153.
72 E. Tekin, B.-J. de Gans, U. S. Schubert, J. Mater. Chem. 2004, 14, 2627.
73 J. Z. Wang, Z. H. Zheng, H. W. Li, W. T. S. Huck, H. Sirringhaus, Nature Mater. 2004, 3,
171.
74 B.-J. de Gans, U. S. Schubert, Langmuir 2004, 20, 7789.
61
Chapter 2
75 B.-J. de Gans, S. Hoeppener, U. S. Schubert, Adv. Mater. 2006, 18, 910.

76 G. Li, K. Graf, E. Bonaccurso, D. S. Golovko, A. Best, H.-J. Butt, Macromol. Chem. Phys.
2007, 208, 2134.
77 M. Egen, R. Zentel, Macromol. Chem. Phys. 2004, 205, 1479.
78 D. Wouters, U. S. Schubert, Langmuir 2003, 19, 9033.
79 M. E. R. Shanahan, Langmuir 2002, 18, 7763.
80 J. Meunier, D. Bonn, Langmuir 2003, 19, 5553.
81 C. Della Volpe, S. Siboni, Langmuir 2006, 22, 5963.
82 J. Sagiv, J. Am. Chem. Soc. 1980, 102, 92.
83 C. Bourgs-Monnier, M. E. R. Shanahan, Langmuir, 1995, 11, 2820.
84 L. Gao, T. J. McCarthy, Langmuir 2006, 22, 6234.
85 T. Kajiya, D. Kaneko, M. Doi, Langmuir 2008, 24, 12369.
86 R. F. Probstein, Physicochemical Hydrodynamics, 2nd Edition Wiley, New York, 1994,
Chapter 10 and references therein.
87 E. R. Dufresne, D. J. Stark, N. A. Greenblatt, J. X. Cheng, J. W. Hutchinson, L. Mahadevan,
D. A. Weitz, Langmuir 2006, 22, 7144.
88 http://www.microfab.com/equipment/technotes/technote99-02.pdf
89 C. W. Extrand, Langmuir 2006, 22, 8431.
90 D. F. Shriver, P. W. Atkins, C. H. Langford, Inorganic Chemistry, 2nd Edition, Oford
University Press, 1998, 146-151.
62
63
Thomas Jefferson Memorial (Washington D.C., USA)
3
Inkjet printing of functional materials
Abstract
Basic principles for inkjet printing dots, lines and films are explained in terms of dot spacing,
resolution and droplet spreading on the substrate. After this, the inkjet printing of various functional
materials is described.
Firstly, the inkjet printing of an aqueous 40 wt% dispersion of polyurethane is discussed. Simple
layered structures, as well as dots, were fabricated. A single layer was found to have a structure
height of 10 m; a value that suggests that this polyurethane dispersion may be suitable for use in
rapid prototyping since tall structures can be rapidly produced using only a few printing passes. Also
via the simple addition of a water-soluble dye, colour gradients were produced using inkjet printing.
Secondly, in order to control the geometry of inkjet printed features on a substrate, an aqueous
TiO2 nanoparticle ink was printed that gels above a certain temperature, due to the limited solubility
of the buoyant block, which is part of the stabilising polymer around the nanoparticles. Droplets and
lines with improved morphological control and resolution were achieved using this thermal gelation
effect. Moreover, defect-free straight lines could be printed on hydrophobic surfaces, which is
impossible with regular inks due to the dewetting nature of these substrates.
Finally, the resolution of directly inkjet printed lines, which are formed from silver nanoparticles,
on an untreated polyarylate substrate was improved by using an inkjet printer that is able to produce
droplets with a volume of 1 pL. The transparent polyarylate foils have a lower surface energy than
PET or polyimide. This resulted in the printing of lines with a diameter of 40 m.
A basic understanding of inkjet printing various functional materials is crucial in order to
improve important processing parameters, such as resolution and line/film morphology. By
decreasing the droplet size as well as its spreading on a substrate, and by using inks with a thermal
gelation effect, narrow and continuous lines with good morphological properties were obtained.
Parts of this chapter have been published: (1) A. M. J. van den Berg, P. J. Smith, J. Perelaer, W. Schrof, S.
Koltzenburg, U. S. Schubert, Soft Matter 2007, 3, 238; (2) A. M. J. van den Berg, A. W. M. de Laat, P. J. Smith,
J. Perelaer, U. S. Schubert, J. Mater. Chem. 2007, 17, 677; (3) T. H. J. van Osch, J. Perelaer, A. W. M. de Laat,
U. S. Schubert, Adv. Mater. 2008, 20, 343.
Chapter 3
3.1 Introduction
In the previous chapter, inkjet printing was used as a high-throughput experimenting tool,
since it produces multiple equally sized droplets that can be systematically studied. This
introduced the possibility of using an inkjet printer for statistical studies.
The behaviour of droplets on a substrate, and the subsequent lines and films that can be
formed by over-lapping droplets, is a critical consideration in inkjet printing since this
strongly influences the usefulness of the end product, and thereby its application. In contrast
to its original application in graphics where separate dots are placed, defect-free continuous
structures are often required with functional materials.
An important parameter, therefore, is the dot spacing, which is the centre to centre
distance between two adjacent droplets. Obviously, when a chosen dot spacing is larger than
the droplets diameter after impact at a surface, the droplets will not merge and thereby not
form a continuous feature in either x- nor y-direction. When the dot spacing in one of the two
dimensions is smaller or equal to the droplet diameter at the substrate horizontal or
vertical lines will be formed. Subsequently, the dot spacing in two dimensions equal to or
smaller than the droplet diameter will result in films. Figure 3.1 illustrates the concept of
varied dot spacing.
(a) (b) (c) (d)
Figure 3.1 Schematic representation of variations in dot spacing: (a) single droplets when dot spacing in x- and
y-direction is larger than the droplet diameter on the substrate, (b) horizontal lines when the dot spacing in x-
direction is reduced and (c) vertical lines for a reduced dot spacing in y-direction. Continuous films (d) are
formed when in both x- and y-directions the dot spacings are smaller than the droplet diameter on the substrate.
It was found that there is a linear relation between the dot spacing and the line width and
line height.[1] Figure 3.2a shows the line width and height of inkjet printed lines (silver
nanoparticles in ethanol/ethylene glycol) as a function of dot spacing on glass substrates,
including their three-dimensional representations (Figure 3.2b-d). It can be seen in Figure 3.2a
66
that with an increase of 1.5 of the dot spacing a line width and height reduction of
approximately 37% and 50% was obtained, respectively.
500 10
Line width (m)
Line height (m)

Line height
450 (a) 2
Linear fit (R =0.988)
8
400
6
350
300 4
250
2
200
0
150 Line width
2
100 -2
70 80 90 100 110 120 130 140 150
Dot spacing (m)
(b) (c) (d)
Figure 3.2 Line width and height as function of dot spacing for inkjet printed Cabot silver nanoparticles at room
temperature onto glass substrates (a). Three-dimensional white light interferometry images of the lines inkjet
printed with a dot spacing of 80, 100 and 120 m, respectively (b,c,d). A colour version is available on page 174.
Depending on the dot spacing that is used differences in line morphology can occur, as
was demonstrated by Subramanian and co-workers,[2] who showed structures ranging from
separate droplets to lines that were either scalloped or uniform or exhibited bulges or
resembled stacked coins, as depicted in Figure 3.3a-e, respectively. They found that the dot
spacing and the delay time between each printed droplet as well as the volatility of the solvent
resulted in the different line morphologies. If the chosen dot spacing is too large, separate
droplets will form on the substrate and lead to discontinuous features (Figure 3.3a) whereas a
too small dot spacing results in too much material per unit of length, which will lead to line
bulging and bleeding (Figure 3.3d). Therefore, the preferred situation is to print uniform lines,
where the lines have a constant and defined line width as well as height (Figure 3.3c and e).
67
Chapter 3
Much research has been conducted into the successful inkjet printing of polymer films.
Typically, films that were printed using a solvent always suffered from coffee staining.[3-5]
This drawback could be overcome by the use of two appropriate solvents with different
boiling temperatures. One of the solvents has a low boiling point, while the other has a
significantly higher boiling point. The effects of solvent mass ratio, print head velocity, dot
spacing and printing method were also investigated and optimised to reproducibly obtain
homogeneous polymer films. These obtained results represent an important step towards the
application of inkjet printing for the controlled deposition of polymer dots and libraries.[3]
Figure 3.3 Examples of principal printed line behaviours: (a) individual drops, (b) scalloped, (c) uniform, (d)
bulging, and (e) stacked coins. The inset shows the stacked coins in more detail. Dot spacing decreases from left
to right. Reprinted from ref. [2].
The behaviour, or stability of inkjet printed lines composed of a liquid, which formed a
zero receding contact angle with a homogeneous substrate, was investigated by Duineveld.[6]
He found that these lines became unstable when the equilibrium contact angle of the liquid
was larger than the advancing contact angle. This instability then causes sequences of
regularly occurring bulges (Figure 3.3d).
In this chapter, it will be demonstrated that various functional materials can be inkjet
printed to form simple micron-scale structures, such as dots, lines and three-dimensional
features. The first part will describe the inkjet printing of three-dimensional polyurethane
structures by directly printing a dispersion of polyurethane nanoparticles.
Subsequently, two methods for improving the printing resolution are described. The first
technique is to control the geometry of the inkjet printed feature by using a thermal gelation
68
effect. An aqueous TiO2 nanoparticle ink was hereto printed that gels above a certain
temperature, due to the limited solubility of the buoyant block, which is part of the stabilising
polymer around the nanoparticles. The second technique is a direct printing technique
whereby a polymer foil is chosen as substrate with its surface energy lower than common
polymer foils, like PET or polyimide. A combination of printing 1 pL droplets of a silver
nanoparticle ink onto said substrate resulted in conductive silver lines with a diameter
of 40m.
3.2 Inkjet printing of three-dimensional polyurethane structures
3.2.1 Introduction
Inkjet printing has found considerable use in the field of rapid prototyping, in which a
two-dimensional layer is printed repeatedly to produce three-dimensional (3D) structures.
Rapid prototyping, or layered manufacturing as it is sometimes called, has become useful to
industry since it allows swift visualization of concept models. It was first employed by Sachs
et al. who prepared ceramic components by printing a binder phase into a bed of powder.[7]
After a number of layers was printed the free powder was removed, leaving the 3D object.
This approach, however, has limitations since the use of a powder bed limits the range of
accessible composition variations. Evans and co-workers developed a direct inkjet deposition
method, whereby they used dilute particle dispersion and a modified desktop printer to build
up ceramic structures.[8] The main disadvantage of this approach was the very dilute nature of
the ceramic inks, which caused an increase in processing time since a greater number of
layers had to be deposited in order to obtain a specified thickness. A quicker way to build
structures makes use of a phase change ink, which either solidifies upon impact with the
substrate such as molten wax,[9] or undergoes a gel transition via a photo-induced cross-
linking step.[10]
Here, an initial investigation into printing layered, 3D structures using a polyurethane
(PU) dispersion is described. Simple structures were printed such as five-layer pyramids and
step structures. Subsequently, these structures were examined to determine height and
resolution. Finally, a water-soluble dye was added to the PU dispersion, and step structures
were printed to obtain colour gradients.
Besides inkjet printing a dispersion, PU can also be created at the substrate, by using a
technique called reactive inkjet printing.[11] Hereby, the PU is synthesised in-situ at the
69
Chapter 3
substrate by inkjet printing droplets of two reactive compounds from separate print nozzles on
top of each other. One ink contains isophorone diisocyanate, while the other ink is a solution
of poly(propylene glycol), a catalyst and a cross-linking agent. At the substrate, droplets of
both inks merge and a fast polymerisation occurs, resulting in solid PU structures within five
minutes.
3.2.2 Experimental
Materials
An aqueous polyurethane dispersion (LR 9005, particles size 100 to 200 nm, Mn = 1.6 kDa,
BASF-AG, Ludwigshafen, Germany) was used with an approximate solid content of 40 wt%,
which had a viscosity of 20 mPa s at 23 C. Disperse Red (Aldrich) was used to make the
colour gradients.
Substrates
acetone and finally with isopropanol before being dried under a flow of air.
Inkjet printing
Inkjet printing was carried out with a piezoelectric Autodrop printer from Microdrop
Technologies GmbH equipped with a 100 m nozzle diameter MDH-712-PH dispenser. The
polyurethane ink was typically printed at 96 V and a 28 s pulse width, while using a
frequency of 200 Hz. Inkjet printing was performed at room temperature.
Characterisation
The contact angle that the aqueous polyurethane dispersion made with the cleaned glass slide
was measured (Dataphysics OCA 30, Filderstadt, Germany) and found to be 45.
The profiles of the inkjet printed tracks were measured by confocal laser scanning microscopy
(Surf, Nanofocus, Germany) using a 20 objective. The profiles were measured using
Scanning Probe Image Processor, SPIP software, version 4.1.
70
3.2.3 Results and discussions
3.2.3.1 Inkjet printing of droplets of a polyurethane dispersion

In order to print structures with appreciable heights one can either use an ink with a high-
solids content,[9] since this requires a smaller number of passes or one can perform a larger
number of passes using a more dilute ink.[12] Here, the approach of using the high-solids ink
was adopted, since the as-received dispersion was 40 wt% and the used printing system is
capable of dealing with inks viscosities up to 20 mPa s.[13]
A series of dots of the polyurethane dispersion was printed in order to observe individual
droplet behaviour. A typical sequence is illustrated in Figure 3.4. The average height of each
individual deposit was measured as being approximately 3 m, which suggests that it may be
suitable for rapid prototyping, where the ability to form thick layers quickly is desirable. This
value of height was attributed to the high contact angle (45 ) that the dispersion formed with
the cleaned substrates. A lower contact angle would have lead to a decrease in droplet height
and a broader base.
Z (m)
0
0 1 2
X (mm)
Figure 3.4 Three-dimensional interferometry image of a sequence of single dots of a 40 wt% polyurethane
dispersion. The inset shows their associated cross-sectional profiles.
3.2.3.2 Inkjet printing of 3D polyurethane structures

In order to produce functional structures, the individual polyurethane droplets were
printed with a dot spacing such that partial overlap occurs as to produce linear features. Well-
defined lines with a width of 224 12 m were obtained using a dot spacing of 100 m. By
printing a sequence of lines whose inter-line spacing corresponded to the dot spacing,
71
Chapter 3
homogeneous films with an average height of 12.5 0.2 m were obtained. When the dot
spacing is decreased, the height of the printed structure increases.[14]
Ten layers were printed on top of each other, which resulted in a film thickness value of
approximately 60 m. However, these ten-layered films were not homogeneous since
successive layers were deposited on top of earlier layers that had not thoroughly dried.
Therefore, a drying step of 5 minutes was introduced before printing the next layer. It is worth
commenting that all printing was performed at room temperature and the time of this drying
step could be reduced, or removed, by heating the substrate holder of the printer. The obtained
thickness gradient resembled a step structure, i.e. the base layer was the largest in terms of
area and each subsequent step had a reduced area, which is shown in Figure 3.5. An initial
6 6 mm square base was printed and allowed to dry, which resulted in a layer thickness of
12.5 m. Subsequently, a second 4.5 6 mm rectangular layer was printed, which had a
height of 13.0 m. Two more step-like layers of 3 6 mm and 1.5 6 mm, respectively, were
printed to produce a thickness gradient. These two layers had a height of 8.5 and 6.0 m,
respectively.
The decrease in layer thickness can be explained by the fact that the previous layer is
partially dissolved by the layer printed on top of it. For the first layer this effect does not
count since this one is printed directly on the glass substrate. It can also be seen that the
highest step displays the greatest variation in thickness and, as can be seen from Figure 3.5, it
has a pronounced slope towards the back of the step structure. This slope may be a
consequence of the combined settling of the three underlying layers.
0 1 2 3 4 5 6 7 mm
0
m Length = 7.51 mm Pt = 46 m Scale = 100 m
0.5
100 1
1.5
80
mm
60
40
20
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 mm
Figure 3.5 Cross-sectional interferometry profile of a thickness gradient produced by printing a structure
composed of well-defined steps of a 40 wt% polyurethane dispersion. The inset shows the view of the structure
from the top.
72
Using this step-building method, a square-based, pyramid-like structure was subsequently

obtained by printing five layers on top of each other; again each layer was produced using a
single pass of the printhead and allowed 5 minutes to dry (Figure 3.6). The base was 10 10
mm and the area of each subsequent step decreased by 2 mm per side; with the uppermost
layer being 2 2 mm. The pyramids height was found to be 70.7 m, with each step having
the following thicknesses: layer 1 = 14.5 m, layer 2 = 17.5 m, layer 3 = 9.5 m, layer 4 =
13.7 m and layer 5 = 15.5 m.
(a) (b)
Figure 3.6 Three-dimensional interferometry image (a) and top-view (b) of a pyramid-like structure of 40 wt%
polyurethane dispersion obtained from printing successively smaller layers.
3.2.3.3 Inkjet printing of colour gradients

The final part of the investigations involved the fabrication of colour gradients, which
were obtained by adding 0.5 wt% Disperse Red to the polyurethane dispersion. Thickness
gradients, similar to those shown in Figure 3.5 but composed of five layers, were printed.
Figure 3.7a illustrates two of the colour gradients that were prepared. The most intense red
colour was seen in the area that was composed of five layers. It is suggested that these colour-
gradients could be used as colour filters[15,16] for creating two-dimensional gradients on a
substrate that has been coated with a photo-curable material.[17] The UV-VIS spectra of the
films are shown in Figure 3.7b. It can be seen that polyurethane and glass exhibit a similar
absorbance behaviour in the visible spectrum to that of glass, with the only difference that the
PU layer shows a strong absorption in the UV part. The trace for glass/polyurethane/Disperse
Red displays a clear absorbance in the blue-green part of the visible spectrum, leaving a red
colour.
73
Chapter 3
0.8
Absorbance (-)
(a) 0.7 (b) glass + polyurethane + disperse red
glass + polyurethane
glass
0.6
0.5
0.4
0.3
0.2
0.1
10 mm
0.0
350 400 450 500 550 600 650 700 750 800
Wavelenght (nm)
Figure 3.7 A photograph of the inkjet printed colour gradients by addition of 0.5 wt% Disperse Red to the
40 wt% polyurethane dispersion (a). UV-VIS spectra of inkjet printed 40 wt% polyurethane films with and
without the addition of 0.5% wt Disperse Red onto cleaned glass slides (b). A colour version is available on page
174.
In summary, an aqueous 40 wt% dispersion of polyurethane has been successfully printed

at room temperature using a piezoelectric inkjet printer. Simple layered structures such as
pyramids and step-structures, as well as dots, were printed. The height of the individual dots
were found to be 3 m, which suggests that this polyurethane dispersion may be suitable for
use in rapid prototyping since tall structures can be rapidly produced using only a few printing
passes. A possible drawback in using this dispersion could be the 5 minute drying time that
was used for each printed step. However, this could be reduced or even removed if the
dispersion was printed at elevated temperatures.
Finally, via the simple addition of a water-soluble dye, colour gradients were produced
using this multi-layer inkjet printing technique.
3.3 Geometric control of inkjet printed features using a gelating polymer
3.3.1 Introduction
One way of controlling the inks behaviour is by modifying the surface energy of a
substrate, such as Sirringhaus et al. employed.[18] They obtained line widths of 5 micrometers
by patterning the surface in such a way that the flow of water-based polymer droplets, which
had been inkjet printed onto the substrate, were directed to designated regions. A variation on
this approach removed the need for lithography. Instead, after the first conductive pattern was
printed, its surface energy was either modified by a plasma treatment or by the initial addition
74
of a suitable surfactant to the ink that formed the first feature.[19] This influenced the as-
printed geometry taken by the second ink.
An alternative to modifying the surface energy of a substrate, which also reduces the
number of production steps, is to limit the mobility of the ink once it makes contact with the
substrate. This can be readily achieved by using phase-change inks, such as alumina-filled
wax suspensions.[9,20] Here, the ink is kept at 100 C before jetting, which ensures its liquid
status. When droplets land on the much cooler substrate they rapidly solidify, thus controlling
spreading and feature geometry. There are, however, two problems associated with using
wax-based inks. The first is that since the carrier fluid solidifies upon contact with the
substrate it remains and an additional processing step is required to remove it, which can
cause shrinkage-related anisotropy in the final product.[21] The second is that if the ink is used
in the fabrication of three-dimensional structures, successive layers will melt the underlying
deposits at the moment of impact, causing a loss in feature resolution.
The approach that has been used here is related to the phase-change ink approach.
However, instead of changing the phase of the carrier the inks viscosity is controlled by
changing the colloidal stability of the particles in the ink. The colloidal stability of particles
can be controlled by the adsorption of polymers onto their surfaces in sufficiently thick layers
to realise steric repulsion.[22] Although homopolymers and random copolymers can be used for
steric stabilisation, block copolymers are far more effective, because the properties needed for
adsorption to the nanoparticle surface can be separated from those required to make a stable
colloidal diserpersion. Previously, a poly(vinylmethylether)-block-poly(vinyloxy-4-butyric
acid) (PVME-b-PVOBA) diblock copolymer was designed to control colloidal stability using
the temperature-dependent solubility of the buoyant PVME block in water.[23] Figure 3.8
shows the chemical structure of the diblock copolymer.
612 38
O O
-
O
+
NH4
O
Figure 3.8 Chemical structure of diblock copolymer PVME-b-PVOBA, which is short for
poly(vinylmethylether)-block-poly(vinyloxy-4-butyric acid).
75
Chapter 3
The thickness of the buoyant block determines the colloidal stability. The lower critical
solution temperature (LCST) of PVME in water is close to 33 C. Above the LCST, PVME
becomes insoluble and the adsorbed layer collapses on the particles surface causing the
colloidal stability to be lost. For example, aqueous Fe2O3 dispersions stabilised with PVME-
b-PVOBA diblock copolymers have low viscosities at room temperature.[24] Upon heating,
rapid flocculation occurs and the dispersion gels at the so-called critical flocculation
temperature (CFT). A good correlation between the CFT and the LCST of PVME in water
was found. This effect is now being explored as a potentially useful strategy to control the
printed geometries of inkjet printed materials on substrates. TiO2 has been chosen as a model
functional material to study the usefulness of this concept.
3.3.2 Experimental
Ink formulation
The TiO2 dispersion was prepared by mixing 46.140 g TiO2 powder with an average particle
size of 160 nm (Kronos 2300, Kronos, Leverkusen, Germany) with 9.548 g of a 10 wt%
poly(vinylmethylether)-block-poly(vinyloxy-4-butyric acid) aqueous solution at pH = 10. The
block copolymer will be abbreviated to PVME612-b-PVOBA38, where the numbers indicate
the block lengths (degree of polymerisation). A high degree of dispersion was achieved by
milling with 0.8 mm ZrO2-Y beads for 24 h on a roller bench. The resulting dispersion was
diluted with water to make up the ink and dipropylene glycol (DPG) was added, which serves
as a humectant to prevent nozzle clogging. The ink was passed over a Millipore SLAP filter to
remove any dust or remaining large particles. The ink that was used contained 20 wt% TiO2
and 5%wt DPG.
Substrates
acetone and finally with isopropanol before being dried under a flow of air. Hydrophobic
substrates were prepared by coating glass slides with octadecyl trichlorosilane (OTS), which
decreases the surface energy.[25,26] Hydrophilic substrates were prepared by ashing the glass
slides, which were cleaned as described before, with oxygen plasma in a plasma asher
(K1050X, Emitech, Kent, UK), which increases the surface energy of the glass.
76
Inkjet printing
Technologies GmbH equipped with a 100 m nozzle diameter MD-K-140 dispenser. The
TiO2 ink was typically printed at 119 V, 35 s pulse width, while using a frequency of 200
Hz.
Characterisation
The profiles of the inkjet printed tracks were measured by confocal laser scanning microscopy
(Surf, Nanofocus, Germany) using a 20 objective. Optical images of the printed features
were taken using optical microscopy (Axioplan Imaging 2, Zeiss, Germany). The profiles
were measured using Scanning Probe Image Processor, SPIP software, version 4.1. The
temperatures of the substrates were measured with an IR-Non Contact Thermometer (Extech
Instruments, Massachusetts, USA). The temperature-dependent viscosity of the ink was
measured using a MCR300 rheometer (Paar Physica, Graz, Austria) equipped with spindle
CP50-1, using a shear rate of 10 s-1. The measurements were taken over a temperature range
that started at 20 C and increased up to 45 C at a rate of 0.2 C s-1.
The contact angles formed by water, ethylene glycol, diiodomethane and the TiO2 ink on the
three types of substrates were measured (Dataphysics OCA 30, Filderstadt, Germany).
3.3.3.1 Thermal flocculation

The TiO2 inks viscosity dependency on the temperature was measured between 20 C
and 45 C, as shown in Figure 3.9. At temperatures below 35 C, low values of viscosity of
approximately 20 mPa s were seen, as was expected for a stable colloidal dispersion. At
36.8 C, the viscosity began to change and increased rapidly as the temperature continued to
rise, which indicated that gelation of the dispersion had occurred. Although the desired
gelating effect is clearly present in this ink, the actual CFT is slightly higher than the LCST of
PVME in water. It is thought that this is due to the DPG addition to the ink; DPG enhances
the solubility of PVME in water, which shifts the LCST to a slightly higher value.[27]
77
Chapter 3
1.6
Viscosity (Pa.s)
1.2
0.8
0.4
0.0
20 25 30 35 40 45
Temperature (C)
Figure 3.9 Influence of temperature on the viscosity of the TiO2 ink.
3.3.3.2 Inkjet printing of droplets of a TiO2 dispersion

Initial experiments were performed to verify the influence of the substrate temperature on
the printed TiO2 dispersions behaviour. Single TiO2 dots were printed onto cleaned glass
slides at different temperatures: room temperature, 33 C, 41 C, and 60 C. For each thermal
value, the dots were left to dry for about 5 minutes.
Figure 3.10 shows a temperature-related increase in the height of the dried droplet and a
corresponding decrease in droplet width for the TiO2 ink. An initial explanation for the
observed change in droplet height and width, as substrate temperature is increased, is that the
solvent evaporates faster at higher temperatures and, therefore, the spreading of the ink is
minimised. This reduction in spreading for the same volume of printed material is an obvious
cause for higher as-deposited droplets. When the profiles of these droplets are examined, as
shown in Figure 3.10b, a significant morphological difference is observed for the samples
printed at room temperature and 33 C compared to the other four. The two lowest
temperature samples show a significant dip in their centres, whereas the others show a
uniform domed shape. The dipped profiles are suggestive of the coffee drop effect, which
has been discussed in Chapter 2. When higher temperatures are employed the evaporation rate
over the entire feature is increased, which reduces the total amount of time for evaporation to
occur, and therefore reduces the severity of the effect.
78
Droplet width (m)

320 16
Droplet height (m)

300 (a) Droplet height
Droplet width 14
280
12
260
10
240
8
220
6
200
4
180
160 2
140 0
20 30 40 50 60 70 80
Substrate temperatue (C)
Droplet height (m)
12
(b) 74 C
60 C
(c)
10 52 C
41 C
33 C
8 25 C
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Droplet width (m)
Figure 3.10 Dried droplet width and height as function of the substrate temperature (a). The influence of
substrate temperature on droplet profile formation of two droplets (b). Three-dimensional images (c) of a single
droplet printed at 33 C (lower) and 60 C (upper). All droplets were printed on cleaned glass slides. A colour
version is available on page 174.
However, in this case, it is proposed that the main influence on morphology, i.e. the
absence of the coffee stain effect, for the droplets printed at 41 C and above is the gel
network set up by the flocculated TiO2 particles. Obviously, material can only be transported
to the edge of a feature if there is sufficient mobility. The thermal gelation blocks this liquid
transport and allows the deposited droplet to assume a more homogenous material distribution
after drying. The continuing change in droplet height and width, above the CFT of the ink,
can be explained as being due to the faster solvent evaporation upon impact of the droplet on
the substrate, which limits the droplet spreading.
79
Chapter 3
3.3.3.3 Inkjet printing of lines of a TiO2 dispersion

The effect of the three surface treatments of the glass substrate was measured by printing
lines of the TiO2 ink using a dot spacing of 100 m, and a substrate temperature of 42 C. The
averaged profiles of the TiO2 lines, on each of the three surfaces, are shown in Figure 3.11.
The effect of the three different surface energies (their corresponding contact angles and line
widths are shown in Table 3.1) can clearly be seen: the more hydrophobic, OTS treated
substrate give the highest and narrowest profile, while the TiO2 lines on plasma treated glass
slides were the widest lines.
Table 3.1 Variously treated glass substrates with their corresponding contact angles.
Contact angle ()
Line width (m)
Water Ethylene glycol Diiodomethane TiO2 ink
Cleaned glass 26.6 17.8 49.8 42.5 196

Plasma treated glass <5 <5 45.0 23.4 238
OTS treated glass 98.3 75.5 89.5 84.9 107
18
Line height (m)
OTS treated glass

16 Cleaned glass
Plasma treated glass
14
12
10
0
150 200 250 300 350 400 450 500 550
Line width (m)
Figure 3.11 Influence of surface treatment on the spreading of the TiO2 ink, whereby the substrate temperature
was 42 C.
A more involved examination of the TiO2 ink and the three different types of substrates
was then undertaken using different dot spacings, namely 50, 80, 100 and 120 m and various
substrate temperatures. Two temperatures were chosen well below and above the CFT, being
25 and 60 C, respectively. The third temperature was chosen just above the CFT (42 C).
80
Figure 3.12 shows the measured widths of the final as-printed lines against the substrate
temperature, for each of the four dot spacings used. Each data point is an average of nine
measurements. Data for lines on OTS treated glass at 25 C are not given as significant bulges
were observed. Finally, continuous lines could not be obtained on the OTS treated glass when
a dot spacing of 120 m was used, which is reflected in Figure 3.12d.
400 400
Line width (m)
Line width (m)

Plasma treated glass Plasma treated glass
360 Cleaned glass (a) 360 Cleaned glass (b)
OTS treated glass OTS treated glass
320 320
280 280
240 240
200 200
160 160
120 120
80 80
20 30 40 50 60 70 20 30 40 50 60 70
o o
Substrate temperature ( C) Substrate temperature ( C)
400 400
Line width (m)
Line width (m)
Plasma treated glass Plasma treated glass

360 Cleaned glass (c) 360 Cleaned glass (d)
OTS treated glass
320 320
280 280
240 240
200 200
160 160
120 120
80 80
20 30 40 50 60 70 20 30 40 50 60 70
o o
Substrate temperature ( C) Substrate temperature ( C)
Figure 3.12 Printed TiO2 line width compared to substrate temperature on three different surface treated glass
slides. The dot spacings used were 50 m (a), 80 m (b), 100 m (c) and 120 m (d). The four plots show the
influence of the PVME-PVOBA block copolymer on the ink spreading.
The influence of substrate temperature on the printed lines can be clearly seen for the
oxygen plasma treated slides; the widths of the lines printed at 25 C for all of the dot
spacings are much larger than the lines printed at 42 C, which are slightly larger than the
lines which were printed at 60 C. A similar influence is seen for the ink printed on cleaned
glass slides. All of the lines printed at 25 C are significantly wider then those lines printed at
higher temperatures. In Figure 3.12a and b, the decrease in line width between 42 C and
60 C is much less than that observed between 25 C and 42 C. The smaller decrease in line
81
Chapter 3
width at 60 C, compared to 42 C, may be due to the increased evaporation rate of water at

this higher temperature, thus contributing to a lower degree of spreading. A faster gelation
may occur due to a faster heating to the gel temperature with a warmer substrate. However,
this explanation does not account for the slight increase seen when wider dot spacings were
used (Figure 3.12c and d).
Figure 3.13 displays profiles of a TiO2 line printed at 25 C and 60 C using a dot spacing
of 50 m. The line at 25 C is broader and displays a dip in its centre, while the line at 60 C
shows a more controlled, narrower shape. Both the reduced line width and improved
morphology of the line are a consequence of the thermal gelation of the ink when the
substrates temperature is above the inks CFT. Once the CFT is exceeded, the colloidal
stability of the dispersion is lost, which causes a rapid increase in viscosity and reduces
spreading of the TiO2 ink.
14
Line height (m)
60 C
12 25 C
10
0
100 200 300 400 500 600
Line width (m)
Figure 3.13 Cross-sectional profiles of printed lines of TiO2 on oxygen plasma treated glass at elevated
temperatures.
3.3.3.4 Formation of lines on hydrophobic surfaces

The formation of continuous lines with consistent morphologies on hydrophobic surfaces
is difficult to achieve because of the strong dewetting caused by the substrate. Either lines
with large bulges result after printing or the line breaks up into separate droplets.[6] Therefore,
printing on hydrophobic substrates, using the thermal gelation effect to block liquid flow
before dewetting occurs, was investigated.
A series of regularly spaced bulges appeared in the printed lines when printing was
performed at 25 C, shown in Figure 3.14, similar to what has been reported by Duineveld.[6]
82
He explained that these bulges are generated by surface tension and grow by having liquid
pumped through the connecting ridge to the bulge by the advancing feature-front, i.e. as
successive droplets land to form the feature they increase the pressure at the feature-front. It is
this pressure that causes material to be pumped back into the bulge. It was also found that the
number of bulges linearly correlates to the dot spacing that was used to print the line, as
depicted in Figure 3.14e.
(a) (b)
(c) (d)
14
Bulges (cm )
Bulges per cm
-1
12
(e) 2
10
4
30 40 50 60 70 80 90 100 110
Dot spacing (m)
Figure 3.14 Optical microscopy images of lines formed after printing the TiO2 ink at 25 C on OTS treated glass
with a dot spacing of 50 m (a), 80 m (b), 100 m (c) and 120 m (d), respectively. Correlation between dot
spacing and the number of bulges per cm appearing in the printed line (e).
83
Chapter 3
The TiO2 lines printed on OTS treated glass at 42 C and 60 C did not exhibit these
bulges and result in well-defined straight lines as depicted in Figure 3.15. At these
temperatures the thermal gelation effect is activated and the formation of the bulges is
prevented due to the reduced mobility of the ink.
(a) (b)
Figure 3.15 Optical microscopy images of lines formed after printing the TiO2 ink at 42 C (a) and 60 C (b) on
OTS treated glass with a dot spacing of 100 m.
In summary, the PVME-b-PVOBA diblock copolymer has been shown to act as powerful
colloidal stabiliser for TiO2 particles in an aqueous ink. Above the LCST of PVME in the
continuous medium of the ink, which is approximately 37 C, the buoyant PVME blocks
become insoluble and reduce the colloidal stability. At this so called critical flocculation
temperature (CFT) the particles flocculate causing the gelation of the ink. This property was
exploited to limit material transport during drying and to achieve improved control over the
dried morphologies.
Printing on substrates, whose surface energy was varied between being hydrophobic and
hydrophilic, above the CFT resulted in lines and droplets with improved morphologies after
drying, i.e. with a reduced or absent coffee drop effect in the feature. The spreading on the
substrate was limited, which resulted in reduced widths of lines and droplets. Well-defined
straight lines without bulges were printed on hydrophobic surfaces using this gelation effect.
84
3.4 Improved resolution of direct inkjet printed conductive silver tracks

on untreated polymer substrates
3.4.1 Introduction
Typical dimensions of inkjet printed features depend on the nozzle diameter and are
usually not below 100 m.[28,29] The most obvious way to minimise the feature size, i.e. line
width, is by reducing the nozzle diameter.[30,31] However, this introduces a narrow window
with respect to surface tension and viscosity of the inks, and thereby, the inks that can be
printed.[13,32] Furthermore, when printing dispersions the particles should be sufficiently
smaller than the nozzle diameter; otherwise nozzle clogging occurs. When using piezo-
electric based DoD inkjet printers, smaller droplets can also be produced by modifying the
waveform.[33]
Other techniques to minimise feature sizes include an increased substrates temperature,
which will stimulate solvent evaporation and leave smaller droplets on the substrate due to a
limited spreading,[28] and fluid-assisted dewetting effects.[34] The latter and relatively new
method was described by Poulikakos and co-workers: a line of gold nanoparticle dispersion in
toluene was deposited on a glass substrate, after which a water droplet was dispensed over the
line. Subsequently, the pattern shrank due to a transport of the toluene from the gold
dispersion into the water region, triggered by controlled heat addition from the substrate,
whose temperature was set to 95 C. Toluene and water are practically immiscible at room
temperature, but at this temperature toluene mixes very well with water. During the dewetting
phase, the three-phase-contact line is pulled by the uncompensated Youngs force.
Furthermore, they explain the dewetting dynamics by the action of thermocapillarity
enhanced by the convection microflow generated in the water layer.
Much research has been done on predefined surface energy patterns on a substrate that
forces material to remain in a preferred area on the surface.[35-37] These techniques rely on the
use of expensive masks and conventional photolithography, which subsequently increases
production costs. Here, a method to produce narrow conductive silver tracks without pre-
patterning or modifying the surface energy of the substrate is presented.
85
Chapter 3
3.4.2 Experimental
Materials
A silver nanoparticle dispersion in an ethylene glycol/ethanol mixture was purchased from
Cabot (Cabot Printing Electronics and Displays, Albuquerque, USA). The silver ink contains
20 wt% of silver nanoparticles, with the particle diameter ranging from 30 to 50 nm. The
viscosity and surface tension of the ink were 14.4 mPa s and 31 mN m-1, respectively.
Substrates
Transparent and colourless polyarylate (Arylite A200HC, Ferrania, Italy, 200 m thickness)
foils with a glass transition temperature of 330 C were used as substrate material. The silver
ink had a contact angle of 31.8 2.1 with the polyarylate foils. Furthermore, teflon foil
(Teflon A and LP, DuPont de Nemours, Mechelen, Belgium), polyimide and PET (Kapton
and Melinex, Dr. D. Mller GmbH, Ahlhorn, Germany) were obtained commercially.
Inkjet printing
Inkjet printing was performed using a piezoelectric Dimatix DMP 2800 (Dimatix-Fujifilm
Inc., Santa Clara, USA), equipped with a 1 pL cartridge (DMCLCP-11601). The printhead
contains 16 squared (8.6 8.6 m) nozzles with a diameter of 12.1 m. The dispersion was
typically printed at 16.0 V, a frequency of 5.0 kHz and a customised waveform. The substrate
holder was set to a temperature of 60 C.
Characterisation
Surface topography, thickness and cross-sectional areas of printed silver tracks were
measured with an optical profilometer (Fogale Zoomsurf, white light, magnification 5).
Scanning electron microscopy (SEM) images were taken using a FEG E-SEM XL30 (Philips,
Eindhoven, The Netherlands). An OCA30 optical contact angle measuring instrument from
Dataphysics was used to determine the contact angles of both diiodomethane and ethylene
glycol as apolar and polar test liquids, respectively. Surface energies were calculated from the
obtained contact angles using the Neumann equation of state.[38]
86

Preferably, the substrates surface energy should not be too low, because printing on such
foils introduces bulges into the printed features,[6,27] for example with polytetrafluorethylene
(PTFE) foils, as can be seen on the left-hand side in Figure 3.16. Commonly used polymer
substrates, like polyethylene terephthalate (PET) or polyimide (PI), have a relatively high
surface energy, shown on the right-hand side in Figure 3.16. Although printing on these
substrates leads to continuous and straight lines, broad lines are obtained over the whole
printed feature, due to the relatively good wetting of the solvent with the substrate. Clearly, an
optimum between surface energy and solvent is necessary. Polyarylate polymer foils fulfil this
need, since they have a surface energy between the value of PTFE and PI.
45
-1
Surface energy mN.m
40
35
30
25
20
15
Teflon A Teflon LP Polyarylate PET Kapton
Polymer substrate
Figure 3.16 Surface energy of five commercially available polymer substrates and an impression of the printed
lines on these surfaces.
In order to print conductive nanoparticles, a commercially available ink from Cabot that
requires a typical sintering temperature of 200 C was used; the process of sintering
nanoparticles will be further explained in the next chapter. Although the Cabot silver
nanoparticles show conductivity at temperatures of 150 C, the resistivity reaches a value of
5 to 6 times the value of bulk silver only when sintering temperatures of 200 C or higher
are used. Due to this preferred sintering temperature, the polymer foils need a relatively high
glass transition temperature. The silver ink was inkjet printed using a cartridge able to
dispense droplets with a volume as small as 1 pL.
Besides a decrease in nozzle size, and thus a higher print resolution, further decrease in
line diameter was realised by heating the sample holder of the printer to its maximum
87
Chapter 3
temperature (60 C), which stimulates the evaporation of the solvent and prevents broadening
of the lines.[27,28] Figure 3.17a shows the dependency of line width on dot spacing; a decrease
in line width is observed when the dot spacing is increased. Obviously, with increased dot
spacing less material is deposited per unit length, resulting in smaller structures. Partially
continuous lines were formed, when a dot spacing larger than 25 m was used and further
increase led to individual droplets. Therefore, using a dot spacing of 25 m resulted in the
smallest line width of 40 m, which is approximately 600 dots per inch.[39]
In the same way, the resistance will increase when the dot spacing is increased, as
depicted in Figure 3.17b. However, the number of layers printed on top of each other strongly
influences the dependency. The resistance of lines consisting of 3 layers strongly increases
with dot spacing, whereas the resistance shows a much more gradual increase with dot
spacing when 5 layers are printed on top. This can be explained by the formation of more
parallel percolating pathways when more material is deposited per unit length.[40]
100 1000
Line width (m)
Resistance ( cm )
-1
(a) 3 layers printed at 60 C (b) 3 layers printed at 60 C

90 5 layers printed at 60 C 5 layers printed at 60 C
800
80
600
70
400
60
200
50
40 0
5 10 15 20 25 5 10 15 20 25
Dotspacing (m) Dotspacing (m)
Figure 3.17 Line width (a) and resistance (b) as function of dot spacing for three and five layers subsequently
printed on top of each other.
Typical dimensions of printed silver tracks onto polyarylate films are shown in Figure
3.18. Narrow features on polyarylate foil with a line width of 40 m and without any defects
such as bulges or coffee drop effects were obtained using a dot spacing of 25 m. The silver
lines were sintered after drying in an oven at 200 C for 1 hour. Subsequently, the resistance
was measured by using the 4-point method. The electrical resistivity of an inkjet printed line
was then calculated from resistance R, length l , and cross sectional area A of the line, using
= R A / l and subsequently compared to the value of bulk silver (1.59 10-8 m).[28] The
cross-sectional area was determined by numerical integration of a measured profile. The
88
conductivity (1/) was 23% of the bulk silver value for tracks printed with a dot spacing of
5 m and 13% when using a dot spacing of 25 m.
(a) (b)
Figure 3.18 Cross-sectional image and 3D image of inkjet printed silver tracks on polyarylate films using a dot
spacing of 5 m (a) and 25 m (b). The substrate was heated to 60 C and five layers were printed on top of each
other. A colour version is available on page 175.
In summary, two methods for the preparation of narrow conductive tracks on a flexible
polymer substrate without the need of predefined (surface energy) patterns were combined.
Firstly, the polyarylate substrate has a surface energy low enough to limit the wetting of the
silver nanoparticle dispersion but high enough to prevent line bulging. Secondly, inkjet
printing of 1 pL droplets resulted in the direct inkjet printing of lines with a diameter of 40
m. The silver tracks were sintered at 200 C for one hour, which resulted in a conductivity of
13 to 23% compared to bulk silver. The inkjet printed narrow silver tracks can be used for
instance in (plastic) electronic applications, such as radio frequency identification (RFID) tags
or electrodes for thin-film transistor (TFT) circuits.
3.5 Conclusions
In this chapter the inkjet printing of functional materials has been described, such as
polyurethane, and a TiO2 and silver nanoparticle dispersion. An aqueous 40 wt% dispersion of
polyurethane was inkjet printed into simple layered structures, like lines and pyramids. A
single layer was found to have a structure height of 10 m, which suggests that this
polyurethane dispersion may be suitable for use in rapid prototyping since tall structures can
be rapidly produced using only a few printing passes. By the addition of a water-soluble dye,
colour gradients were also produced using this printing technique.
89
Chapter 3
In order to control the geometry of inkjet printed features on a substrate, an aqueous TiO2
nanoparticle ink was printed that gels above a certain temperature, due to the limited
solubility of the buoyant block, which is part of the stabilising polymer around the
nanoparticles. Droplets and lines with improved morphological control and resolution were
achieved using this thermal gelation effect. Moreover, defect-free straight lines could be
printed on hydrophobic surfaces, which is impossible with regular inks due to the dewetting
nature of these substrates.
Finally, the resolution of direct inkjet printed lines comprising silver nanoparticles onto an
untreated polymer substrate could significantly be improved. Hereto, an inkjet printer able to
produce droplets with a volume of 1 pL was used in combination with transparent polyarylate
foils that have a lower surface energy than PET or polyimide. This combination made it
possible to print lines with a diameter of 40 m.
Fundamental understanding of inkjet printing functional materials is crucial in order to
improve processing parameters, such as resolution and line/film morphology. By decreasing
the droplet size as well as its spreading on a substrate, and by using inks with a thermal
gelation effect, narrow and continuous lines with good morphological properties were
obtained.
3.6 References and notes
1 J. Perelaer, C. E. Hendriks, I. Reinhold, R. Eckardt, T. H. J. van Osch, U. S. Schubert, in

Proceedings of the 24th International Conference on Digital Printing Technology and Digital
Fabrication 2008, 697 (Pittsburgh, USA).
2 D. Soltman, V. Subramanian, Langmuir 2008, 24, 2224.
3 E. Tekin, B.-J. de Gans, U. S. Schubert, J. Mater. Chem. 2004, 14, 2627.
25, 292.
5 E. Tekin, H. Wijlaars, E. Holder, D. A. M. Egbe, U. S. Schubert, J. Mater. Chem. 2006, 16,
4294.
6 P. C. Duineveld, J. Fluid Mech. 2003, 477, 175.
7 E. M. Sachs, M. Cima, P. Williams, D. Bracazio, J. Cornie, J. Eng. Ind. (Trans ASME), 1992,
114, 481.
8 J. H. Song, M. J. Edirisinghe, J. R. G. Evans, J. Am. Ceram. Soc. 1999, 82, 3374.
9 K. A. M. Seerden, N. Reis, J. R. G. Evans, P. S. Grant, J. W. Holloran, B. Derby, J. Am.
Ceram. Soc. 2001, 84, 2514.
10 J. Stampfl, R. Liska, Macromol. Chem. Phys. 2005, 206, 1253.
11 P. Krber, J. T. Delaney, J. Perelaer, U. S. Schubert, submitted.
90
12 M. Mott, J.-H. Song, J. R. Evans, J. Am. Ceram. Soc. 1999, 82, 1653.
13 http://www.microdrop.com/wDeutsch/products/MD_Heads_e_0707.pdf
14 E. Tekin, E. Holder, V. Marin, B.-J. de Gans, U. S. Schubert, Macromol. Rapid Commun.
2005, 26, 293.
15 C.-J. Chang, S.-J. Chang, K.-C. Shih, F.-L. Pan, J. Polym. Sci. Part B: Polym Phys. 2005, 43,
3337.
16 H.-S. Koo, P.-C. Pan, T. Kawai, M. Chen, F.-M. Wu, Y.-T. Liu and S.-J. Chang, Appl. Phys.
Lett. 2006, 88, 11908.
17 J. C. Meredith, A. P. Smith, A. Karim, E. J. Amis, Macromolecules 2000, 33, 9747.
Science 2000, 290, 2123.
19 C. W. Sele, T. von Werne, R. H. Friend, H. Sirringhaus, Adv. Mater. 2005, 17, 997.
21 P. J. Smith, B. Derby, N. Reis, A. Wallwork, C. Ainsley, Key Eng. Mater. 2004, 693, 264.
22 D. H. Napper, Polymeric Stabilization of Colloidal Dispersions, Academic Press, London,
1983.
23 A. W. M. de Laat, H. F. M. Schoo, Colloid. Polym. Sci. 1998, 276, 176.
24 A. W. M. de Laat, H. F. M. Schoo, J. Colloid. Interface Sci. 1998, 200, 228.
25 J. Sagiv, J. Am. Chem. Soc. 1980, 102, 92.
26 D. Wouters, U. S. Schubert, Langmuir 2003, 19, 9033.
Chem. 2007, 17, 677.
29 D. Kim, S. Jeong, J. Moon, K. Kang, Mol. Cryst. Liq. Cryst. 2006, 459, 45.
30 H. P. Le, J. Imaging Sci. Technol. 1998, 42, 49.
31 C.-Y. Kung, M. D. Barnes, N. Lermer, W. B. Whitten, J. M. Ramsey, Appl. Optics 1999, 38,
1481.
32 http://www.dimatix.com/files/Dimatix-Materials-Printer-Jettable-Fluid-Formulation-
Guidelines.pdf (last accessed: 5th January 2009).
33 A. U. Chen, O. A. Basarana, Phys. Fluids 2002, 14, L1.
34 C. P. R. Dockendorf, T.-Y. Choi, D. Poulikakos, A. Stemmer, Appl. Phys. Lett. 2006, 88,
131903.
35 J. Z. Wang, J. Gu, F. Zenhausern, H. Sirringhaus, Appl. Phys. Lett. 2006, 88, 133502.
36 E. Menard, M. A. Meitl, Y. Sun, J.-U. Park, D. Jay-Lee Shir, Y.-S. Nam, S. Jeon, J. A.
Rogers, Chem. Rev. 2007, 107, 1117.
37 C. Bae, H. Shin, J. Moon, Chem. Mater. 2007, 19, 1531.
38 S. Wijnans, B.-J. de Gans, F. Wiesbrock, R. Hoogenboom, U. S. Schubert, Macromol. Rapid
Commun. 2004, 25, 1958.
39 600 dots per inch (DPI) correspond to a single dot diameter of 2.54/600 cm = 42.3 m.
40 P. J. Smith, D.-Y. Shin, J. E. Stringer, N. Reis, B. Derby, J. Mater. Sci. 2006, 41, 4153.
91
Romanesco Cauliflower
4
Methods for sintering nanoparticle inks
Abstract
This chapter describes three methods for the sintering of silver nanopatricles after being inkjet
printed onto polymer substrates. First, the thermal curing behaviour and conductivity development of
several commercially available silver inks is discussed. In addition, the preparation and
characterisation of a silver particle ink that shows a curing temperature of 80 C is described.
Conductivity values of 5 to 56% of bulk silver have been reached by using a small amount of organic
additives without strong adsorbing groups. Secondly, the temperature stability of silver tracks,
comprising different colloidal silver dispersions, was investigated. Hereto, the resistance was
measured on-line during heating the silver tracks, from room temperature to 650 C.
Besides the conventional thermal sintering, two alternative methods have been developed by using
microwave radiation or plasma exposure. By using microwave radiation, the sintering time was
shortened by a factor of 20 and three minutes were sufficient for sintering. The conductive silver
nanoparticles absorb the microwaves and sinter. Furthermore, the presence of conductive antennae
promotes sintering in pre-cured ink lines to an extent that depends on the total area of the antennae.
For cured nanoparticle inks that are connected to antennae sintering times of 1 second are sufficient
to obtain pronounced nanoparticle sintering. After microwave sintering conductivity values of 5 to
34% of the bulk silver value were obtained.
A second alternative sintering technique, by argon plasma exposure, yielded resistivity values of
2.5 to 3 the bulk silver value. The process shows a clear evolution starting from a sintered top layer
into bulk material, which determines the resistivity of the sintered material.
The curing temperature of 80 C together with the alternative and selective sintering methods
open new routes to produce conductive features on common polymer foils that have a relatively low
glass transition temperature (Tg), like PET or polycarbonate. Together with the technique of inkjet
printing, materials can be saved, since it is only dispensed on demand.
Parts of this chapter have been and will be published: (1) J. Perelaer, B.-J. de Gans, U. S. Schubert,
PCT/EP2006/009437, Dutch Polymer Institute; (2) J. Perelaer, B.-J. de Gans, U. S. Schubert, Adv. Mater. 2006,
18, 2101; (3) T. H. J. van Osch, J. Perelaer, A. W. M. de Laat, U. S. Schubert, Adv. Mater. 2008, 20, 343; (4) J.
Perelaer, A. W. M. de Laat, C. E. Hendriks, U. S. Schubert, J. Mater. Chem. 2008, 18, 3209; (5) J. Perelaer, M.
Klokkenburg, U. S. Schubert, PCT/EP2008/08021042.0, Dutch Polymer Institute and TNO; (6) J. Perelaer, M.
Klokkenburg, C. E. Hendriks, U. S. Schubert, submitted; (7) I. Reinhold, C. E. Hendriks, R. Eckardt, J. M.
Kranenburg, J. Perelaer, R. R. Baumann, U. S. Schubert, submitted.
Chapter 4
4.1 Introduction
During the last few decades, inkjet printing has grown into a mature non-contact
patterning method since it can produce large-area patterns with high-resolution at relatively
high speeds, while using only small amounts of functional materials.[1,2] With direct inkjet
printing, functional features can be fabricated on demand and with less processing steps,
thereby reducing time, space and waste consumption within production. Moreover, this
technique introduces the possibility for the production of flexible electronics using a roll-to-
roll (R2R) process.[3]
Similarly, over the few last years, there has been a growing interest in the inkjet printing
of conductive materials. One of the compound types that has been frequently used is the
conductive polymer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate)
(PEDOT:PSS), due to its relatively low costs. However, it does not have a high
conductivity.[4] Besides conductive polymers, inks that contain metals have been used to
create microstructures on polymer substrates.[5-7] It has been shown that inkjet printing of
conductive materials is a relatively cheap alternative for the fabrication of electronic devices
when compared to other micro- and nanopatterning techniques,[8-10] such as photo-
lithography[11] or laser patterning.[12,13]
Although metals like copper[14,15] and gold[16,17] have been used for inkjet printing
applications, direct inkjet printing of conductive silver tracks onto flexible substrates has
gained interest due to silver having the lowest resistivity value of 1.59 10-8 m and the
relatively simple synthesis of silver nanoparticles.[18] Therefore, it has been used for many
applications, such as interconnections for a circuitry on a printed circuit board,[19] disposable
displays and radio frequency identification (RFID) tags,[20-23] organic thin-film
transistors,[6,7,24] and electrochromic devices.[25,26] Furthermore, printing large area displays
belong to the possibilities.[27]
Conductive materials that are suitable for inkjet printing can be either solution-based or
particle based. The former one is usually based on a metallo-organic decomposition (MOD)
ink, in particular silver neodecanoate dissolved in an aromatic solvent.[5,28] These MOD inks
have been used for inkjet printing since the late 1980s.[29,30] In order to obtain metal features,
a conversion of organometallic silver inks is required, which usually takes place at relatively
low temperatures below 200 C,[31] although temperatures as low as 150 C have been
reported as well.[5,32] The typical metal loading of organometallic inks is 10 to 20 wt%.
94
In contrast to metal containing inks based on complexes, inks consisting of a dispersion of

nanoparticles have been investigated as well, with the ability to have a silver loading >20 wt%
being one of the reasons. Such a dispersion contains metallic nanoparticles with a diameter
between 1 and 100 nm. It was found by Buffat & Borel in 1976 that gold nanoparticles with a
diameter below 100 nm reveal a significant reduction in their melting temperature, as depicted
in Figure 4.1a,[33] from their bulk melting temperature of 1064 C to well below 300 C when
the diameter is below 5 nm. Allen et al. showed later that this reduction of the melting
temperature is also valid for other metals, including tin, lead and bismuth.[34] In a graph
(Figure 4.1b) of the melting temperature against the reciprocal of the particle radius the data
exhibit near-linear relationships. It was also found that plates instead of spheres do not show a
reduced melting temperature. This suggests that the size dependence of melting in particles is
related to the internal hydrostatic pressure caused by the surface stress and by the large
surface curvature of the particles, but not by the planar surfaces of platelets.
(a) (b)
Diameter () Inverse radius (nm-1)
Figure 4.1 Influence of the gold (a) and lead, bismuth, tin and indium (b) particle diameter on their melting
temperature. Reprinted from ref. [33] and [34].
Given the reduced melting temperature of nanoparticles, these particles are the ideal
candidates for dispersion in a liquid medium and, subsequently, for inkjet printing. However,
when two or more particles are in contact, merging of nanoparticles into larger clusters can
take place due to the large surface curvature of the individual nanoparticles. This process is
called sintering and with small particles takes place within the medium and at room
temperature. Therefore, the nanoparticles have to be protected by a shell to prevent
agglomeration in solution and to obtain a stable colloidal dispersion, as schematically
depicted in Figure 4.2.[35]
95
Chapter 4
Figure 4.2 Schematic illustration of a silver nanoparticle with carboxylic acid as capping agent. A colour version
is available on page 175.
In non-polar solvents usually long alkyl chains with a polar head, like thiols, amines or
carboxylic acids, are used to stabilise the nanoparticles.[36] Steric stabilisation of these
particles in non-polar solvents substantially screens van der Waals attractions and introduces
steep steric repulsion between the particles at contact, which avoids agglomeration.[37] In
addition, organic binders are often added to the ink to assure not only mechanical integrity
and adhesion to the substrate, but also to promote the printability of the ink.[36]
After silver containing inks have been inkjet printed, and solvent evaporation has
occurred, another processing step is necessary to form conductive features since the organic
shell inhibits close contact of the nanoparticles. Although evaporation of the solvent forces
the particles close together, conductivity only arises when metallic contact between the
particles is present and a continuous percolating network is formed throughout the printed
feature. An organic layer between the silver particles as thin as a few nanometers is enough to
prevent electrons moving from one particle to the other.[38-40] The adsorbed dispersant stays
on the surface of the particles and, typically, is removed by an increase in temperature.
Mostly, particulate features have been rendered conductive by applying heat. This thermal
sintering method usually requires temperatures above 200 C.[41, 42] Other techniques that have
been used to for conductive features include LASER sintering,[43] exposure to UV
radiation,[44] high temperature plasma sintering[45] and pulse electric current sintering.[46]
However, most of these techniques are not suitable for polymer substrate materials due to the
large overall thermal energy impact. In particular, when using common polymer substrates,
like polycarbonate (PC) and polyethylene terephthalate (PET), that have their glass transition
96
temperature (Tg) well below the temperature required for sintering. In fact, only the expensive
high-performance polymers, like polytetrafluoroethylene, polyetheretherketone and polyimide
(PI) can be used at high temperatures, which represents a drawback for implementation in a
large area production of plastic electronics and not favourable in terms of costs.
In the field of sintering two properties are very important; firstly, the lowest temperature
at which printed features become conductive, which is mainly determined by the organic
additives in the ink.[47] Secondly, obtaining the lowest possible resistance of the printed
features at the lowest possible temperature. To achieve a low resistance, sintering of the
particles is required to transform the initially very small contact areas to thicker necks and,
eventually, to a dense layer. High conductivities, hence low resistance, can then be obtained
through the formation of large necks, which decrease constriction resistance and eventually
form a metallic crystal structure with a low number of grain boundaries.
In the low temperature regime, the driving forces for sintering are mainly surface energy
reduction due to the particles large surface-to-volume ratio, a process known as Ostwald
ripening.[48,49] This process triggers surface and grain boundary diffusion rather than bulk
diffusion within the coalesced particles, as schematically depicted in Figure 4.3. Grain
boundary diffusion allows for neck formation and neck radii increase, which is diminished by
the energy required for grain boundary creation.[50,51] Therefore, the process will stall
eventually, leaving a porous structure behind, which leads to lower conductivity values when
compared to the bulk material.
1 1. Lattice diffusion (no densification)
4 2. Surface diffusion (no densification)

2
3. Through-lattice diffusion (densification)
3
4. Grain boundary diffusion (densification)
Figure 4.3 A schematic representation of various atomic diffusion paths between two contacting particles. Paths
1 and 2 do not produce any shrinkage whilst paths 3 and 4 enable the sphere centres to approach one another,
resulting in densification. Reprinted from ref. [51].
At high temperatures, however, lattice diffusion leads to closure of pores and

densification. However, long sintering times are necessary for creating dense conductive
97
Chapter 4
features in a thermal process and obstruct the feasibility for an efficient industrial production
processes.
In order to reduce production costs, alternative techniques that sinter silver nanoparticles
in a selective manner without harming the underlying polymer substrate need to be found. In
this chapter, two techniques that use either plasma exposure or microwave radiation will be
described as possible candidates for selective sintering. Before finding new methods,
however, one should understand the basics of sintering and, therefore, the first part of this
chapter will discuss thermal sintering.
4.2 Thermal sintering of silver nanoparticles
4.2.1 Introduction
A major concern with printed electronics involves not only the control of the morphology
of the tracks,[5,20,41,52] but also the stability and adhesion of the obtained conductive tracks,
although this has scarcely been investigated.[53] However, the main focus in plastic electronics
lies in the low curing temperature of the conductive ink. For particle-based inks, the curing
temperature is defined as the temperature where particles loose their organic shell and start
showing conductance by direct physical contact. Whereas sintering (which is often mistakenly
used instead of curing temperature) takes place at a higher temperature when all the organic
material has been burnt off and necks begin to form between particles. The lowest
temperature at which printed features become conductive is mainly determined by the organic
additives in the ink.[47] Often high temperatures typically up to 300 C are required to burn
off the organic additives and stimulate the sintering process to realise a more densely packed
silver layer and a lower resistivity.[4,5,8,9] Lee et al. describe an aqueous silver colloid
dispersion which is prepared mainly with environmentally friendly chemicals, like water and
diethylene glycol.[10] Although short times of only 10 minutes are necessary, high
temperatures (200-300 C) are required to obtain good conducting lines. It is therefore of
utmost importance if further progress is to be made to identify an optimum between time,
temperature and the obtained conductivity.
However, in applications, such as the manufacturing of plasma display panels[54] the
conductivity also needs to be maintained at temperatures as high as 600 C. At this
temperature, the separately produced back and front panels are joined together. So far no
studies have been published in the open literature which investigate the thermal-stability of
98
printed nanoparticle features at temperatures higher than 350 C. Only a study on the pressure
stability of silver nanoparticles has been reported.[55]
In view of these important applications, the first part of this section reports on the curing
properties and conductivity development of several commercially available inks and on
formulating an ink with a low curing temperature. The second part describes the effect of
higher temperatures on the conductivity and the stability of printed conductive features. The
electrical resistance behaviour of four different types of silver-based inks were investigated
during heating up to 650 C.
4.2.2 Experimental
Ink formulation
Four types of silver inks were used. Two inks were obtained commercially: aqueous Nippon
SVW102 silver (Nippon Paint Co. Ltd., Osaka, Japan), with a particle size of 10.8 6.7 nm
(subsequently called Nippon ink), and an ethylene glycol/ethanol based silver ink from Cabot
(Cabot Printing Electronics and Displays, Albuquerque, USA), with a particle size of
52.4 11.0 nm (Cabot ink). The two other inks were prepared in house. The ink with Mitsui
particles was prepared in the following way: 13 g of Ag powder (SPQ03S, Mitsui-Kinzoku,
Japan) was dispersed in 13 grams of an aqueous medium containing 0.85 wt% polyvinyl
alcohol with a number average molar mass (Mn) of 108 kD (Gohsenol, Nippon Gohsei, Japan)
and 5 wt% dipropylene glycol. Full dispersion is realised by milling on a rollerbench for
24 hours with the aid of 0.8 mm glass beads. After milling, the beads are separated and the ink
is passed over a 10 m sieve to remove any large particles. A second ink with Merck
nanoparticles with a particle diameter of 8.9 4.5 nm, and therefore referred to as Merck ink,
was prepared in the following way: 4 g of Ag powder (Merck, Germany) are mixed in
9.6 grams of an aqueous solution having 2 wt% polyethylene oxide (Mn = 20 kD) and 5 wt%
dipropylene glycol. Milling is not needed as this powder disperses spontaneously. The ink is
passed over a filter (Slap, Millipore) to remove any large residue. Both inks are degassed by
passing through He gas for one minute or by treatment in an ultrasonic bath just before use.
Inkjet printing
Technologies GmbH equipped with a 68 m nozzle diameter MD-K-140 dispenser. The
following printing parameters for voltage and pulse width were used: Cabot, 172 V, 120 s;
99
Chapter 4
Nippon, 134 V, 82 s; Merck, 174 V, 40 s and Mitsui, 140 V, 45 s, respectively. All inks
were printed at room temperature and typically into a pattern of five parallel lines, each with a
length of 1 cm.
Boron-silicate glass substrates were cleaned by first washing with acetone, followed by
rinsing with isopropanol before being dried under a flow of air.
Characterisation
Conductivity measurements were performed using a custom built steel sample holder,
wherein the substrate was placed in a fixed position. Via small holes in the steel device, high
temperature stable wires were guided from the multimeter (Voltcraft Digital Multimeter VC-
960, Conrad Electronics GmbH, Germany) to the substrate and thereon attached to the ends of
a single silver line with a length of 1 cm using Leitsilber L100 conductive silver paste (Kemo-
electronic, Germany), which has a resistance of 0.02 to 0.1 cm-2. A thermocouple equipped
with a K-type sensor (Voltcraft Data-Logger Thermometer 306, Conrad Electronics GmbH,
Germany) was used to measure the exact temperature. Multimeter and thermocouple were
connected to a computer that recorded the resistance and the temperature every two seconds.
The samples were heated in an oven at a rate of 10 C min-1.
Thermogravimetric analyses (TGA) were performed with a TG 209 F1 Iris by Netzsch under
ambient atmosphere in the range from 25 to 650 C with a heating rate of 10 C min-1.
Samples of 5 to 10 mg were analyzed and prior to measuring all samples were heated to 50 C
for 20 minutes to evaporate volatile solvents. Scanning electron microscopy (SEM) images
were taken using a FEG E-SEM XL30 (Philips, The Netherlands). Surface topography,
thickness and cross-sectional areas of the printed silver tracks were measured with an optical
profilometer (Fogale Zoomsurf, France, white light, magnification 5). Transmission electron
microscopy (TEM) images were recorded on a Technai G2 Sphera (FEI) electron microscope
using an acceleration voltage of 200 kV.
4.2.3.1 Conductivity development of inkjet printed silver lines

The investigations into the critical curing temperatures of several silver inks, either made
in the laboratory or obtained commercially, are described here. The critical curing
temperature is defined in this case as the temperature at which the sample becomes
100
conductive, i.e. having a resistance lower than 40 M which is the upper measuring limit of
the used multi-meter.
Single lines with a length of 1 cm of the specific ink were inkjet printed onto boron-
silicate glass and subsequently heated to 650 C in an oven at a heating rate of 10 C min-1.
During heating the resistance was measured online in a semi-continuous way, by measuring
every 2 seconds. Using this dynamic scan approach, differences between the various inks can
be determined. Table 4.1 summarises the composition of each ink that has been investigated.
Table 4.1 Detailed information on the composition of the used silver inks. Each column shows the silver
content, the amount of binding material per gram silver and the solvent content of the inks, respectively.
Ink Ag content Ratio binding agent to silver Solvent
(wt%) (g/g) (wt%)
Cabot 20 0.50 ~70

Nippon 30 0.25 ~60
Merck 30 0.12 66.5
Mitsui 50 0.0085 49.6
Typical resistance results for the Cabot and Nippon inks are shown in Figure 4.4a and
Figure 4.5a, respectively. The resistance of the lines for both inks decreases rapidly when
heated above the critical curing temperature. The critical curing temperature for the Cabot
silver ink is 194 C, which is lower than the Nippon ink, 269 C. According to the particle
size measurements, 52.4 11.0 nm for the Cabot ink and 10.8 6.7 nm for the Nippon ink
(see Figures 4.4b and 4.5b), it was expected that the smaller particles would sinter at the lower
temperature because of their higher sintering activity.[33,34,56] This indicates that the organic
additives in the ink strongly affect the critical curing temperature. Unfortunately, the nature of
the organic additives in these commercially available inks is not disclosed.
To elaborate on this the mass decrease upon heating by means of thermogravimetric
analysis (TGA) was also investigated. It should be mentioned that all inks have been dried
prior to measuring by heating to 50 C for 20 minutes, which removed volatile solvents. The
TGA curve for Cabot silver ink shows a decrease of 72 wt%, which is not only the organic
binder that is around each nanoparticle but also the non-volatile solvent ethylene glycol which
is present in the ink (Figure 4.4a). The critical curing temperature corresponds to a
temperature at which the initial sharp weight loss slows down. The first step in the removal of
the organic materials has ended at this temperature. The steep decrease in resistance relates to
the temperature range in which the last part of the organics is burnt off. Apparently, all
101
Chapter 4
organics have to be removed before the sintering of the Ag particles can proceed in a fast
way. This is indicative of an additive that is strongly adsorbed on the surface of the silver
particles.
9
10 35
% particles
(b)
Resistance ()
Mass (%)
100 30
(a) 8
10 25
90 20
7
10
15
80
6
10 10
70 5
5
10
0
10 20 30 40 50 60 70 80 90
60 4 Particle size (nm)
10
50 3
10
40 2
10
30 1
10
0
20 10
0 100 200 300 400 500 600 700
Temperature (C) 50 nm
(c)
500 nm
20 m
Figure 4.4 Resistance over a single inkjet printed line with a length of 1 cm as function of temperature and
thermogravimetric analysis (TGA) of Cabot silver ink (a). Transmission electron microscopy (TEM) image and
particle size distribution of Cabot silver nanoparticles (b). Scanning electron microscopy (SEM) image of
sintered Cabot silver nanoparticles at a temperature of 650 C (c).
The lines printed with the Nippon ink reveal a critical curing temperature and a fast
decrease in resistance when only about 15% of the organic additives are removed (Figure
4.5a). Obviously, these particles can make metallic contact long before all the organics are
gone. In addition, sintering proceeds very fast due to the small particle size. At the
temperature where the organics have been completely burnt off, only a small additional
decrease in resistance occurs. In this ink, only a minor part of the organic additives interferes
with the sintering process but it does shift the critical curing temperature to a high value. For
both inks, however, the resistance value levels off at a certain temperature. At this
temperature all organics are burnt off and, apparently, the sintering process has ended and a
silver layer with a final density and morphology has formed.
102
Figure 4.4c shows a scanning electron microscopy (SEM) image of a Cabot silver track
that has been heated to 650 C. As can be seen the particles have sintered to a dense
continuous line. The electrical resistivity of the inkjet printed lines was calculated after
heating to 650 C, using
= R A/l (4.1)
with the lines resistance R, its length l , and its cross sectional area A, and compared to the
value of bulk silver (1.59 10-8 m).[57] The resistivity was calculated to be 3.10 10-8 m
(51%) and 3.06 10-8 m (52%) for Cabot and Nippon, respectively. The values in brackets
indicate the percentage of conductivity (1/) of bulk silver.
12
9
10
% particles (b)
Resistance ()
Mass (%)
100 10
(a) 8
10
8
90
7
10 6
80 4
6
10
2
70 5
10 0
0 5 10 15 20 25 30
60 4 Particle size (nm)
10
50 3
10
40 2
10
30 1
10
0
20 10
0 100 200 300 400 500 600 700
thermogravimetric analysis (TGA) of Nippon silver ink (a). Transmission electron microscopy (TEM) image and
particle size distribution of Nippon silver nanoparticles (b).
After these experiments, the two in-house silver inks were tested. Thermogravimetric
analysis of the Merck silver shows a complex behaviour, as shown in Figure 4.6a. Clearly, the
ink consists of many components, indicated by the multiple steps in the mass decrease. Figure
4.6b shows the particle size distribution and the calculated average particle size which was
8.9 4.5 nm. The total organic content is about 30 wt%. Furthermore, Figure 4.6a displays
the resistance as a function of temperature for five printed lines on top of each other (the
results of single layer inkjet printed lines show a different sintering behaviour and will be
discussed in the next paragraph). The loss of mass does not immediately cause the silver
nanoparticles to make contact and render the lines conductive. The behaviour around the
critical curing temperature of 275 C is, however, the same as for the commercial inks. At this
103
Chapter 4
temperature approximately half of the organic material is burnt off. The sharp decrease in
resistance indicates a fast sintering process. This is due to the small particle size and that the
temperature is already at a high value at the moment when initial contact occurs. Both the
weight loss and the resistance show a gradual decrease above 400 C.
9
10 15
(b)
Resistance ()
% particles
Mass (%)
100
(a) 8
10
10
90
7
10
80
6
10 5
70 5
10
0
0 5 10 15 20 25 30
60 4
10 Particle size (nm)
50 3
10
40 2
10
30 1
10
0
20 10
0 100 200 300 400 500 600 700
Figure 4.6 Resistance over a five layers inkjet printed line with a length of 1 cm as function of temperature for a
five layers inkjet printed line and thermogravimetric analysis (TGA) of Merck silver ink (a). Transmission
electron microscopy (TEM) image and particle size distribution of Merck silver ink (b).
To investigate the possibilities for obtaining a material with a low critical curing
temperature an ink was formulated with a very low amount of organic additives that did not
have any strong adsorbing groups, such as amines, amides or mercapto groups. Instead,
materials that only weakly bond towards the silver particles, like poly(ethylene oxide) or
poly(vinyl alcohol), have been used. The silver ink was prepared using the unmodified silver
powder from Mitsui, which has a broad range of particle sizes and shapes.
After heating the inkjet printed lines to a temperature of 650 C, while measuring the
resistance over the lines, the obtained results were compared to those of the commercial inks;
the results are shown in Figure 4.7. The low content of organic additives is reflected in the
TGA curve. It can be seen that this ink reveals a much lower critical curing temperature than
the other silver inks: a temperature as low as 80 C, as depicted in Figure 4.7a. Apparently,
the particles make metallic contact after removal of only a small part of the organic material,
most probably the dipropylene glycol (DPG). Initially, the resistance decreases slowly with
increasing temperature, but above 140 C, where most organics are removed, the decrease is
faster and reaches a minimum value of 5 cm-1 at a temperature slightly above 300 C. This
is calculated to be 56% of the conductivity of bulk silver. The relatively slow decrease of the
104
resistance with increasing temperature above 160 C, as compared to the other inks, is
expected to be due to the low sinter activity of the larger silver particles.
Figure 4.7b shows scanning electron microscopy (SEM) images of the Mitsui particles.
The largest particles are almost 2 m in diameter. Generally, particles that are greater than 5%
of the orifice diameter will cause at least some instability in the droplet generation
behaviour.[58] Since the printheads nozzle used for these experiments had a diameter of
70 m, particles with sizes below 3.5 m would be printable (for more details see Chapter 2,
Section 2.4.3.4). No problems with clogging were observed when printing this specific
aqueous ink.
Figure 4.7c displays a single printed line of Mitsui particles that was heated to 650 C and
it can be seen that some voids are present in the line, which causes the conductivity to be
lower than that of bulk silver.
(b)
9
10
Resistance ()
Mass (%)
100 (a) 8
10
90 7
10
2 m
80 6
10
70 5
10 50 m
60 4
10
50 3
10 (c)
2
40 10
1
30 10
0
20 10
0 100 200 300 400 500 600 700
Temperature (C)
10 m
20 m
thermogravimetric analysis (TGA) of Mitsui silver ink (a). Scanning electron microscopy (SEM) image of inkjet
printed Mitsui silver particles at room temperature (b) and after heating to 650 C (c).
In addition to the dynamic heating, some experiments were done at a constant

temperature. A typical result is shown in Figure 4.8a. Heating to a temperature of 140 C
results in a resistance of 50 to 60 cm-1, which decreases only slightly when heating for a
longer period of time at this temperature. However, increasing the temperature to 160 C
105
Chapter 4
lowers the resistance down to 25 cm-1. At this temperature all organics are removed from
the particles and the sintering process is further stimulated by the higher temperature.
Evidently, the final resistance value after a longer time at 160 C is much lower than the value
recorded in the dynamic experiment (Figure 4.7a). To study the effect of longer curing times
on the resistance decrease, different silver lines, again 1 cm in length, were heated
isothermally at various temperatures for 60 minutes. Figure 4.8b shows that at a temperature
of 80 C a relatively low resistance of 102 to 103 cm-1 were obtained. Even at these low
temperatures conductivities of approximately 5% compared to bulk silver were observed.
These findings were also observed by Greer et al. and were attributed to an initiated polymer
flow after solvent evaporation, causing metallic contacts at temperatures as low as 100 C.[51]
It is, therefore, of less importance for a low sintering temperature what the exact size of
the particles is, but more important which and how much additives have been used as binding
materials to stabilise the particles in solution. The organic material needs to be burnt off
before the particle can overlap and form a conductive path through the inkjet printed line.
9 9
10 10
Resistance ()
Temperature (C)
200
180
(a) 10
8
10
8
(b)
7 7
10 10
160
6 6
10 10
140
5 5
10 10
120
4 4
10 10
100
3 3
80 10 10
2 2
60 10 10
1 1
40 10 10
0 0
20 10 10
0 20 40 60 80 100 120 140 160 180 0 100 200 300 400 500 600 700
Time (min) Temperature (C)
Figure 4.8 Isothermal conductivity development of Mitsui silver ink, for a temperatures of 140 C and 160 C
(a), respectively. Resistance over a single inkjet printed line with a length of 1 cm as function of temperature for
different Mitsui silver lines; each point represents a single line that has been heated for 60 minutes at one
temperature (b).
4.2.3.2 Thermal-stability of inkjet printed silver tracks

High temperature stability is essential in certain applications such as plasma display
panels.[54,59-60] Therefore, the samples resistance during heating was measured until 650 C.
The printed lines of most of the inks discussed in the previous section are stable in terms of
resistance at high temperatures, independent of their line thickness. In contrast to this, we
106
have observed with the Merck silver nanoparticles ink, that the inkjet printed lines do not
show a stable and low value for the resistance at high temperature. When a single line with a
height of 1.5 m is heated to 650 C the resistance decreases at a temperature of 275 C and
reaches a minimum of 160 cm-1 at 325 C, as shown in Figure 4.9a. When heating further,
the resistance suddenly increases at 350 C and the conductivity of the lines is lost within a
temperature increase of 20 C. With further heating the lines do not become conducting
anymore. These results are in contrast to the findings described in the previous section: when
lines with greater line thickness were sintered, no loss of conductivity was observed (Figure
4.6b). Three-dimensional images of the printed lines are shown in Figure 4.9b. Typically, the
layer thickness for a single line is 1.5 m and for 5 layers printed on top of each other the
layer thickness is approximately 6 m.
(b)
9
10
Resistance ()
Mass (%)
100
(a) 8
10
90
7
10
80
6
10 1 layer
70 5
10
60 4
10
(c)
50 3
10
40 2
10
30 1
10
0
20 10
0 100 200 300 400 500 600 700
Temperature (C)
5 layers
thermogravimetric analysis (TGA) for a single layer line of inkjet printed Merck silver ink (a). Three-
dimensional images of inkjet printed silver tracks consisting of Merck silver nanoparticles: topography of a
single layer silver line (b) and five layers printed on top of each (c) other are shown.
The reason for the sharp increase of the resistance when sintering lines with a height of
1.5 m is most probably due to the formation of cracks in the printed tracks. Since the silver
ink contains 30 wt% of organic material, the shrinkage of the lines upon heating is significant.
This shrinkage creates voids in the lines which results in a smaller amount of percolating
pathways for the electrons, thus a higher resistance. The evaporation of the solvent and
transport mechanism of the solute is expected to play an important role in this process.[61]
107
Chapter 4
Besides the shrinkage, the formation of numerous large silver agglomerates also plays a role
in the breaking up of the conductive path, as was described before for very thin spin coated
films (< 100 nm) of silver nanoparticles by Chou et al.[42] When thicker lines are sintered, no
cracks are formed at elevated temperature in contrast to the single layer lines. It is believed
that despite the formation of cracks, there is enough material to compensate the vertical
shrinkage and fill the formed cracks. This leaves a sufficient high amount of percolating
pathways within the line, and thus a low resistance.
Furthermore, in Figure 4.10 a second and very small line around the printed silver line can
be seen that follows the same scalloped pattern of the printed line, indicated by the black
arrow. The line shows the original line width of the printed tracks before heating (106 m).
This indicates that during heating to 650 C not only the height of the line but also its width
reduces significantly, since before heating no such line around the track was visible, as
depicted in the inset of Figure 4.10. The width of the sintered track is 72 m.
50 m
10 m
Figure 4.10 Optical microscopy image of a single layer line of inkjet printed Merck silver ink onto a glass
substrate after being heated to 650 C, showing crack formation: the arrow indicates the line width before
heating to 650 C. The inset shows the unsintered air-dried line.
In summary, a silver nanoparticle ink was prepared that has a critical curing temperature
of 80 C. Conductivity values of 10 to 56% of bulk silver have been reached by using a very
small amount of organic additives which do not have any strong adsorbing groups such as
amines, amides or mercapto groups. This low temperature opens the possibility to produce
electronic devices on polymer foils that have a low glass transition temperature, for example
PET. In order to reveal first structure-property relationships and to develop the new ink, the
sintering behaviour of other inkjet printed silver tracks based on commercial or home-made
108
inks was studied in detail. Furthermore, the temperature stability of inkjet printed silver tracks
was studied in detail. Three of the four silver inks that were tested revealed a low and stable
resistance up to a temperature of 650 C. A fourth ink showed a loss of the conductance at
temperatures above 350 C when the tracks had a thickness of 1.5 m. When increasing the
layer thickness of the silver tracks, i.e. by using multiple inkjet printed layers, this loss of
conductance disappeared and again a low and stable resistance was measured up to a
temperature of 650 C. This effect can be explained by the large amount of organic material
(30 wt%) present in the silver ink. High temperature stable inkjet printed silver tracks can be
used for applications, where high processing temperatures are necessary, for example in
plasma display production.
4.3 Sintering of silver nanoparticles by microwave radiation
4.3.1 Introduction
In the past, two different techniques were used to sinter printed nanoparticle structures,
conventional radiation-conduction-convection heating being the most common method.
Sintering temperatures are typically above 200 C, as was described in Chapter 4.2. Therefore,
many potentially interesting substrate materials, such as common polymer foils or paper,
cannot be used. Moreover, the long sintering time of 60 minutes or more that is generally
required according to the ink supplier to create conductive features, also obstruct industrial
implementation. One selective technique for nanoparticle sintering that has been described in
literature is based on an Argon ion LASER beam that follows the as-printed feature and
selectively sinters the central region.[43] Features with a line width smaller than 10 m have
been created with this technique.[62] However, the large overall thermal energy impact
together with the low writing speed of 0.2 mm s-1 of the translational stage are limiting
factors.[63] In fact, with this particularly technique low writing speeds are required for good
electrical behaviour since resistance increases for faster write speeds.[5] Thus, other techniques
have to be used in order to facilitate fast and selective heating of the printed structures only.
Microwave heating fulfils these requirements.[64]
Microwave heating is widely used for sintering of dielectric materials,[65] conductive
materials,[66,67] and in synthetic chemistry.[68,69] It offers the advantage of uniform, fast and
volumetric heating.[70] The interaction of electromagnetic waves with dielectric materials can
be described using Maxwells equations, which are
109
Chapter 4
D
B = J + (4.2)
t
B
E = (4.3)
t
B = 0 (4.4)
D = (4.5)
where B denotes the magnetic field vector, J the current density vector, D is the electric
displacement vector, E the electric field vector, is the charge density and t is the time.
The magnetic flux density is related to the magnetic field strength as
B = 0 r H (4.6)
and the electrical displacement results from
D = 0 r E (4.7)
Here and are the permeability and permittivity, respectively. The indices r and 0 relate to
the relative and free space value, respectively, and H the magnetic field.
The dielectric response to a field is given by the complex permittivity

r = '+i " = '+i (4.8)
0
where ' accounts for energy storage, " for energy loss of the incident electromagnetic wave
or so-called dissipation, i the imaginary unit ( i = 1 ), the conductivity and the angular
frequency. The ratio of the imaginary to the real part of the permittivity defines the capability
of the material to dissipate power compared to energy storage and is generally know as the
loss tangent.
"
tan = (4.9)
'
There are three basic types of energy dissipation. Firstly, conduction loss occurs due to the
movement of free charges in a conductive medium. As can be seen in Equation 4.8, this
110
directly translates to the increasing loss with higher conductivity.[71] Secondly, dielectric
resonance is the dissipation through atoms and molecules, e.g. bond vibrations, but is only
effective at frequencies much higher than the ones contemplated here. Thirdly, a loss due to
dielectric relaxation relies on the property of materials to polarise under the influence of an
externally applied field, characterised by a finite displacement of charge or a rotation of the
dipoles. Upon removal of the field force, dipoles relax under interaction with their
surrounding and thereby dissipate power.[65,72] For a spherical molecule, for instance, the
relaxation time may be calculated using
4r 3
= (4.10)
kT
emphasising the importance of the volume of the molecule and the viscosity of the
surrounding medium.[71]
Depending on their loss characteristic, and thus their conductivity, materials can be
opaque, transparent or an absorber, as shown in Figure 4.11. For bulk metals, being good
electronic conductors, no internal electrical field is generated and the induced electrical
charge remains at the surface of the sample.[73] Consequently, metals reflect microwaves;
while bulk metals do not absorb until they have been heated to about 500 C, powders with
particle sizes within the micrometer-region are rather good absorbers.[74] It is believed that the
conductive particle interaction with microwave radiation, i.e. inductive coupling, is mainly
based on Maxwell-Wagner polarisation, which results from the accumulation of charge at the
materials interfaces, electric conduction, and eddy currents. However, the main reasons for
successful heating of metallic particles through microwave radiation are not yet fully
understood.
Transparent
Power absorbed
per unit volume
(arbitrary units)
Receptive
region Metals
Insulators
10-1 0.2 100 101 14 102

Effective conductivity (S.m-1) at 2.45 GHz
Figure 4.11 Microwave energy absorption as a function of electrical conductivity. Reprinted from ref. [74].
111
Chapter 4
The penetration depth d is defined as the distance into the material at which the incident
power is reduced to 1/e (36.8%) of the surface value and is given by
c 0 1
d= = (4.11)
2f " f
with c being the speed of light, f the frequency of the microwave radiation. Typically, highly
conductive materials (e.g. metals) have a very small penetration depth. For example, the
penetration depth of microwaves with a frequency of 2.45 GHz for metal powders of silver
and copper is 1.3 and 1.6 m, respectively.[75] In contrast to the relatively strong microwave
absorption by the conductive particles, the polarisation of dipoles in thermoplastic polymers
below the Tg is limited, which makes the polymer foils skin depth almost infinite, hence
transparent, to microwave radiation.
The absorbed microwave radiation power per unit volume P is given by
2 2
P = E " E (4.12)
with E the electromagnetic field amplitude.
The different modes in a multimode cavity result in multiple hotspots. Higher uniformity
in heating can be achieved by scaling up of the cavity, which increases the frequency on the
expense of a loss in penetration depth, motion of the sample or the utilisation of mode stirrers.
According to the patent literature TE31 is one of the most probable modes inside a resonant
microwave cavity.[76] The field distributions within a single mode cavity were recently
analytically solved by Reinhold using finite element methods and finite difference time
domain simulations.[70]
Figure 4.12 visualises the absolute values of the complex-valued electric and magnet
fields vectors (quantities are normalised to their respective maximum). It can be seen that the
model is capable of giving a qualitative field distribution for a standard circular sectoral
cavity applicator. A defined maximum of the electrical field is present at the half-height of the
cavity, providing more field intensity than at other placement in the z-direction, and therefore
increases heat generation. The field intensity in the centre region, where the reaction vial is
placed, exhibits relatively low electric fields. In organic or polymer synthesis the vial usually
contains a liquid and the small difference in the electric field is homogenised by a magnetic
112
stirrer in the vial.[69] However, when the vial is loaded with a solid sample, small differences
in the electric field cannot be compensated for by stirring, which makes placement of the vial
more critical.
(a) (b)
X Y
E field H field
(c)
Z
X
Figure 4.12 Electrical (a) and magnetic field (b) distributions in a sectoral circular resonator (normalised values,
vector length and colour proportional to magnitude, solid line represents the boundary of the cavity). Magnitude
of the electrical field in a cross-section at half-height of the contemplated cavity geometry (c) (logarithmic
depiction). Reprinted from ref. [70]. A colour version is available on page 175 and 176.
Microwave sintering can only be successful if the dimension of the object perpendicular to
the plane of incidence is of the order of the penetration depth. Inkjet printed conductive
nanoparticle tracks fulfil this requirement. In the next sections it is described how inkjet
printed lines consisting of silver nanoparticles on polymer foils can be sintered in a fast and
efficient way by exposure to microwave radiation for 3 to 4 minutes. Furthermore, it will be
presented that when these inkjet printed silver lines are connected to conductive antenna
structures the conductivity build-up occurs even faster; exposure to microwaves for only
1 second is sufficient to obtain pronounced nanoparticle sintering and reveal a relatively good
conductivity.
113
Chapter 4
4.3.2 Experimental
Materials
Two batches of silver ink dispersions were purchased: the first ink contains 57.8 wt% of silver
nanoparticles with a diameter of 5 to 10 nm dissolved in tetradecane (Nanopaste NPS-J,
Harima Chemicals, Japan). The second ink contains 20 wt% of silver nanoparticles with a
diameter of 30 to 50 nm in an ethylene glycol/ethanol mixture (Cabot Printing Electronics and
Displays, USA). Polyimide (Kapton HN500, 100 m thickness, Tg = 385 C) and
polyethylene naphthalate (PEN, DuPont Teijin, The Netherlands, 125 m thickness,
Tg = 120 C) were used as substrate materials. Plasma treatment of the PEN substrates was
performed using a Branson IPC S2100/11220 apparatus with a 2000 TI controller, operating
at a frequency of 13.56 MHz. The power and time were set to 600 W and 1 minute,
respectively, and nitrogen was used as carrier gas (500 mL min-1).
Inkjet printing
The Harima ink was inkjet printed using a piezoelectric Autodrop printer from Microdrop
Technologies GmbH that was equipped with a 100 m nozzle diameter MD-K-140 dispenser.
The dispersion was typically printed at 115 V, 64 s pulse width, while using a frequency of
200 Hz. The Cabot ink was inkjet printed using a piezoelectric Dimatix DMP 2800 (Dimatix-
Fujifilm Inc., USA), equipped with a 10 pL cartridge (DMC-11610). The printhead contains
16 squared nozzles with a diameter of 30 m. The dispersion was typically printed at a
voltage of 28 V, using a frequency of 20 kHz and a customised waveform. The printing height
was set to 0.5 mm, while using a dot spacing of 20 m.
Sintering and characterisation

The as-printed structures were sintered in capped reaction vials using either the Emrys
Liberator (300 W) or the Biotage Initiator monomodal microwave system, both operating at
frequency of 2.45 GHz. The power was set to its minimum of 1 W. Surface topography,
thickness and cross-sectional areas of printed silver tracks were measured with an optical
profilometer (Fogale Zoomsurf, France, white light, magnification 5). Scanning electron
microscopy (SEM) images were taken using a FEG E-SEM XL30 (Philips, The Netherlands).
114
4.3.3.1 Microwave sintering of conductive silver tracks

The Harima ink was inkjet printed onto polyimide (PI) foils. To prevent line instabilities
and bleeding of the ink, the temperature of the substrate was raised to 150 C. Good quality
lines were obtained within a narrow interval of dot spacings around 100 m. The average
height of a single inkjet printed track of silver nanoparticles was measured to be 4.1 m. The
calculated penetration depth of the microwave irradiation into silver at a frequency of
2.45 GHz using Equation 4.11 is only 1.3 m. Therefore, it is to be expected that microwave
heating will not be uniform throughout the complete line. However, since silver is a good
thermal conductor in comparison to the polymer substrate, the silver tracks will be heated
uniformly by thermal conductance.
Unsintered non-conductive silver lines were treated in a microwave reactor operating in
constant power mode (300 W). Sintering times are dramatically shortened in the microwave,
from 60 minutes or more down to 240 seconds, as shown in Figure 4.13a. Within the reactor
vessel the temperature reaches 200 C, which is near the sintering temperature of 220 C for
conventional thermal sintering.[8] Longer sintering times did not increase the conductivity, but
sometimes resulted in deformation or decomposition of the substrate at the edges of the silver
lines and the substrate.
Conductance ( )
0.30
-1
0.25 (a) (b)

0.20
0.15
0.10
0.05
0.00
0 100 200 300 400 500
Time (s)
Figure 4.13 Conductance as function of time for the microwave sintering of silver tracks (a) printed onto a
polyimide substrate (b). A colour version is available on page 176.
Figure 4.14 shows SEM pictures of an inkjet printed silver track on polyimide before (a)
and after (b) sintering in the microwave. The structure of the unsintered silver tracks is
homogeneous at all length scales. The sintered lines, however, consist of clusters of silver
115
Chapter 4
(nano)particles with a diameter of about 500 nm. Since the original size of the nanoparticles is
5 to 10 nm, the clusters in the tracks after microwave exposure must have been formed by
sintering after decomposition of the organic binder around the nanoparticles.
(a) (b)
Figure 4.14 Scanning electron microscopy (SEM) images of inkjet printed silver tracks on polyimide before and
after sintering in the microwave. The images on the left (a) show unsintered silver tracks, whereas the images on
the right (b) show the sintered silver tracks.
The resistance of the conducting silver tracks was measured by the 4-point method. The
electrical resistivity of an inkjet printed line was calculated from Equation 4.1. The cross-
sectional area was determined by numerical integration of a measured profile. A typical
resistivity value is 3.0 10-7 m, which is approximately 20 the bulk silver value. With
thermal sintering in an oven (220 C, 60 minutes) similar values are obtained, which are also
in close correspondence to what is reported by other authors.[8]
116
In summary, a new method for the preparation of conducting silver tracks on a polyimide
polymer substrate was developed by using microwave radiation to sinter the silver
nanoparticles. Since the polymer substrate is virtually transparent to microwave radiation, a
negligible amount of energy is absorbed by the substrate, whereas the conductive silver
nanoparticles with a high dielectric loss-factor absorb the microwaves strongly. The obtained
resistivity is 20 the value of bulk silver, which is comparable to values that are produced
with conventional thermal sintering. Moreover, this method shortens the necessary sintering
time by a factor of 20.
4.3.3.2 Microwave flash sintering of conductive silver tracks

As discussed in the previous section, it is possible to make printed features conductive
with microwave radiation within 3 minutes. However, the obtained conductivity is only
approximately 5% of the value of bulk silver. It was subsequently discovered that conductive
antenna structures are more susceptible for absorption of microwaves than the printed feature
by itself. Therefore, conductive antenna structures have been applied onto the polymer foil
and were found to improve the sintering process, and thereby the obtained conductivity,
significantly. Figure 4.15 shows the template in a schematic representation.
Inkjet printed line
5 mm
2 mm
Electrodes / antennae
Figure 4.15 Schematic representation of the printed template onto a PEN substrate (a), with four silver antennae
in gray and a single silver line inkjet printed on top of the antennae in black. The total length of the line is
1.6 cm.
The antenna structures were fabricated by inkjet printing of a colloidal dispersion of silver
nanoparticles onto a flexible polyethylene naphthalate (PEN) foil. The template consists of
four metal areas, each having a surface area of 11 mm2. Subsequently, curing of the antenna
template was performed at 110 C for 60 minutes. These antennae were used both to measure
the resistance of the single ink line and to capture electromagnetic waves, which was possible
117
Chapter 4
since the electrodes were composed of particles that are able to absorb microwaves. After this,
a single silver ink line was printed over the metallic probes (black line in Figure 4.15a) and
shortly cured in an oven for 1 to 5 minutes at a temperature of 110 C. This relatively short
time was chosen to stimulate solvent evaporation, but to minimise thermal curing. After this
treatment, the single line had a relatively high resistance in the order of 102 to 104 . The
sample was subsequently exposed to microwave radiation for at least 1 second, while
applying the lowest possible set-power of 1 W. This resulted in a pronounced decrease of the
resistance of which the exact outcome depends on the initial resistance.
The antenna effect, which reflects the capability of absorbing microwaves into the
material, was studied systematically by altering the surface area of the electrodes of the
template. When increasing the size of the electrodes a rapid decrease of the resistance after
microwave exposure was revealed, as is shown in Figure 4.16 for pre-dried samples. This may
be explained by the improved absorption of the microwaves due to an increased surface area
of the electrodes.
5
10
5
10
Resistance ()
Resistance ()
(a) (b) A = 0 mm
2
A = 0 mm
2
4 A = 20 mm
2
4 A = 20 mm
10 10 2
A = 31 mm
2
A = 31 mm
2
A = 44 mm
2
A = 44 mm
3 3
10 10
2 2
10 10
1 1
10 10
0 0
10 10
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (s) Time (s)
Figure 4.16 Influence of the total surface of the four electrodes on the template for an initial line resistance of
100 (b) and 1 k (c) on microwave flash exposure for 1 to 60 seconds.
The antenna effect, however, is larger when the initial line resistance is small (Figure
4.16a), which is likely due to enhanced heat conduction from the electrodes to the ink line.
For ink lines with an initially large resistance (Figure 4.16b), the energy transfer is still very
effective, although the total antenna area has less impact on the final resistance. The data
obtained in the absence of antennae (A = 0 mm2) clearly demonstrate that the energy
absorption by the printed line is negligibly small at these short times.
118
The absorption of microwave radiation may be improved by the presence of antennae due
to a subsequently smaller impedance mismatch between air and sample. According to
Zuckerman et al. the intrinsic impedance Z of a circuit relative to free space is given by
Z = Z0 * (4.13)
where Z0 is the impedance of free space (Z0 = 377 ) and * is the complex permittivity of the
circuit relative to free space. The complex permittivity is related to the dielectric constant and
loss factor, according to Equation 4.8, where the real part is the ability of the material to
store energy and where the imaginary part accounts for the losses via energy dissipation.
The reflection, i.e. impedance mismatch Z/Z0, scales with the square root of the complex
permittivity * and thus, in our experiments, with the resistance of the electrodes, which
depends on their total surface area.[77]
Figure 4.17 depicts the effect of the initial resistance of the printed line on the final
resistance after microwave exposure for different times. When the flashing time is equal to
1 second, the resistance can be decreased to a few Ohm per line, only if the initial resistance is
within a range of 102 to 104 . Above a threshold of 105 , the microwave coupling and
transfer at the antenna-line interface is insufficient to accomplish pronounced sintering of the
nanoparticles and to form a good percolating network through the line. Therefore, longer
sintering times are necessary for lowering the resistance. An exposure of 60 seconds increases
the initial threshold resistance from 105 up to 107 . Obviously, higher power settings
and/or longer exposure times would even further increase this threshold value.
9
10
Rafter ()
8
1s
10 60 s
7
10
6
10
5
10
4
10
3
10
2
10
1
10
0
10
1 2 3 4 5 6 7 8 9
10 10 10 10 10 10 10 10 10
Rbefore ()
Figure 4.17 Effect of the initial line resistance (Rbefore) on the resistance after microwave flash exposure (Rafter)
for 1 or 60 seconds.
119
Chapter 4
To highlight the effect of the surface area of the ink line on the final resistance, lines were
inkjet printed onto the foil with modified surface wetting properties, while using equal print
settings to dispense the same volume of material. On the one hand, the surface wetting was
decreased by increasing the platen temperature to 60 C, which stimulates solvent evaporation
and, therefore, results in a different line geometry.[2,78] On the other hand, a plasma surface
treatment was applied to increase the surface energy, which improves the wetting behaviour
of the ink, and consequently gives broader lines. The line width was measured to be 172 m
and 161 m for lines printed at room temperature and 60 C, respectively, while after plasma
treatment the lines were 353 m in width. Figure 4.18 shows the effect of the line width on
the resistance after microwave flash exposure. It can be inferred that a narrow line shows a
three times higher resistance than a broad line for sintering times shorter than 10 seconds.
This suggests that there is a positive correlation between surface area of the line, which is
directly linked to the linewidth, and the amount of energy absorbed. However, this surface
effect diminishes after 30 seconds of microwave exposure, which indicates that the surface
area of the electrodes mainly determines the effective sintering time.
4
10
Resistance ()
Line width 161 3 m

Line width 172 8 m
Line width 353 27 m
3
10
2
10
1
10
0
10
0 10 20 30 40 50 60
Time (s)
Figure 4.18 The effect of the line width on the resistance per line after 1 to 60 seconds microwave flash
exposure.
The electrical resistivity of an inkjet printed line was subsequently calculated from
Equation 4.1. The conductivity (1/) for the maximum surface area (44 mm2) of the antennae
was found to be 34% when compared to the bulk silver value. A conductivity of 10% was
revealed for the antennae with a surface area of 20 mm2. This value, however, is significantly
larger than the 5% that was reported in the previous section.
120
Scanning electron microscopy (SEM) images of the printed silver tracks in Figure 4.19
show the morphology and particle packing within the line before and after printing. In Figure
4.19a, a close-up of the unsintered but pre-cured track is depicted, where the silver
nanoparticles with a typical diameter of 30 to 50 nm can still be distinguished individually.
Upon drying, the particles probably have lost a part of their organic protecting shell, which
causes the particles to form a percolating pathway for the electrons in an early stage.[36] After
microwave flash sintering most of the organic material was expected to be removed from the
particles, which resulted in the melting of the particles into larger agglomerates as shown by
the cross-section in Figure 4.19b; the bottom part represents the polymer foil and the top layer
is the as-printed silver line, which is depicted in more detail in the inset. It can also be seen
that the agglomerates form a relatively dense packed layer of silver, which increases the
amount of percolating pathways for the electrons through the line. This also explains the
relatively high conductivity values of 34%.
(a) (b)
200 nm
100 nm 1 m
Figure 4.19 Scanning electron microscopy (SEM) image of an inkjet printed silver track on polymer substrate
before (a) and after sintering (b). The unsintered track (a) shows a detailed view of the silver nanoparticles with a
typical diameter between 30 and 50 nm. A sintered track (b) after flash exposure to microwaves with a total
electrode area of 20 mm2. The inset shows a more detailed view into the track.
In summary, it was demonstrated that the presence of conductive antennae unambiguously

promotes nanoparticle sintering in pre-cured ink lines to an extent that depends on the total
area of the antennae. Furthermore, flash microwave sintering of inkjet printed colloidal
dispersions strongly depends the pre-curing time and the geometry of the line. After sintering
the tracks revealed conductivity values of 10 to 34%, when compared to the bulk silver value.
These values are significantly higher than conventional thermal sintering, where values of 5%
were obtained.
121
Chapter 4
This process of improved sintering in the presence of conductive antenna structures may
be implemented in a roll-to-roll (R2R) production for sintering of inkjet printed silver tracks.
The antennae do not need to make contact with the unsintered features, which makes
recycling of the antennae possible; it was found that sintering took place even with a gap up to
0.5 cm between the antennae and the printed line. Increasing the distance reduces, however,
the final conductivity. Thus, the antenna structures need to be close enough to the unsintered
features, since the relay of electromagnetic waves is limited.
4.4 Sintering of silver nanoparticles by plasma exposure
4.4.1 Introduction
As discussed in the previous section, microwave radiation was successfully used as an
alternative method for sintering silver nanopatricles. Another technique that has been shown
to densify particulate materials is by exposure to plasma sources, such as argon or oxygen.
Typically, this technique demands high temperatures, but can also process thermally
vulnerable materials in etching and sintering.[45]
Plasmas represent a collection of charged bodies that are on average electrically neutral.
The interaction of high energy plasma species with metallic surfaces and enhanced grain
boundary diffusion has been reported,[79] making it feasible for the fabrication of highly
conductive features. Low temperature plasma sintering of capped nanoparticle systems has
only been mentioned recently in the patent literature,[80] where various process gases and
mixtures have been used, including nitrogen, oxygen, hydrogen and argon, which are
examples of inert, oxidative and reductive gases, respectively. In this process the plasma
enables chain scission until the steric stabilising molecules are small enough to evaporate.
Renn et al. further claim that full densification can only be reached with applying further
energy through thermal treatment using classical thermal, LASER or spark plasma
sintering.[80] The electromagnetic energy within the processing chamber may also be used to
generate currents within conductive features and further sinter through Joule heating.
In an inert gas the degree of ionisation increases with increasing power.[81] The energy of
the ions is highly dependent on the pressure within the chamber, as the amount of collisions
increases with the increasing number of molecules available. Higher gas pressures also
increase the temperature, which may be transferred to the structure.
122
The ions arrive at the substrate with an energy that equals the difference between the
plasma potential and the floating potential of the dielectric material.[82] The floating potential
over the substrate may be approximated by
0.5
2kTe m i
V float = ln
(4.14)
2e 2m e
where Te is the electron temperature, k is the Boltzmann constant (1.381 10-23 J K-1), e is the
elementary charge (1.602 10-19 C), mi is the mass of the ion and me is the mass of an
electron (9.109 10-31 kg).[83] Due to the charging of the substrate a sheath develops and
enables acceleration of ions towards the substrate, while electrons are pushed back into the
plasma. In an argon plasma, ions arriving at the sheath edge will have an increased energy of
approximately 10 their initial energy.[70,83]
While electronic loss is characteristic for highly energetic ions,[84] nuclear collision is
most important at low ion energies.[85] The ion penetrates the surface of a solid to a certain
distance and transfers kinetic energy to the lattice. The depth of penetration is dependent on
the kinetic energy, the mass and the angle of the incident ion as well as the mass and
arrangement of the atoms in the lattice.[86] The inward energy flux from the kinetic energy of
ions may be expressed as
kTe 0.5e (V pl V float )

J k = ne e (4.15)
mi
where ne denotes the number of electrons and Vpl the potential of the plasma.[87]
The work functions for both silver and polymers are relatively similar, which prevents
selectivity in absorbance, but the thermal conductivity of the polymers is three orders of
magnitude lower than that of silver. Therefore, the heat will be more easily transferred into a
metal lattice than into the polymer film.[70]
As plasmas are extensively employed in todays manufacturing, e.g. for surface energy
manipulation, their application for sintering may open a new route to an efficient sintering
technology. Therefore, this section describes the low-pressure plasma sintering as a single
step method for the low temperature conversion of inkjet printed silver nanoparticles into
conductive features.
123
Chapter 4
4.4.2 Experimental
Materials
A silver nanoparticle dispersion in tetradecane was purchased from Harima Chemical Inc.,
containing 57.4 wt% of silver, with a particle diameter of 5 to 10 nm.
Armorphous polycarbonate (PC) foil (Makrofol, Bayer MaterialScience GmbH, Tg = 148 C)
and semi-crystalline polyethylene terephthalate (PET) foil (Bi-axially oriented, Tenolan OAN,
Tg = 98 C) were used as substrates and cleaned with isopropanol prior to printing.
Comparative studies to conventional sintering were carried out on microscopy slides, which
were cleaned following standard procedures.[88]
Inkjet printing
Inkjet printing was performed using an Autodrop printer (Microdrop Technologies GmbH,
Germany) equipped with a 70 m piezoelectrically actuated nozzle. Droplet volume was
calculated to be 127 pL. The substrate temperature during printing was maintained at 120 C
to stimulate solvent evaporation. Dot spacings were 75 m on polymer foils and 85 m on
glass. Multilayer tracks were printed with a time delay of 60 seconds between successive print
runs to inhibit lateral broadening of the tracks by wet-on-wet processing.
Sintering and characterisation

Plasma post treatment was carried out using a commercial plasma asher (K1050X, Emitech
Ltd., UK). Supplied radio frequency power could be controlled with 5 to 100 W at 13.56 MHz
with most stable plasma condition between 40 and 80 W. After pumpdown to 0.6 mbar, pure
Argon was lead into the chamber at 2.76 bar for 250 s yielding a working pressure of 1 mbar.
To verify general applicability of low pressure argon plasmas, a kHz excited, capacitively
coupled plasma setup was used (Nano, Diener electronic GmbH & Co. KG, Germany).
Comparative samples on glass were thermally sintered at 220 C in a convection oven.
An optical profilometer (Fogale Zoomsurf, France, white light, magnification 5) was used to
measure surface topography, thickness, width and cross-sectional areas of printed silver
tracks. Scanning electron microscopy (SEM) images were taken using a FEG E-SEM XL30
(Philips, The Netherlands).
124
X-ray diffraction (XRD) data was recorded using a Rigaku D/Max-gB diffractometer with
Bragg-Brentano geometry (flat graphite monochromator, scintillation counter) using CuK
radiation operating at 40 kV, 30 mA at room temperature. Step scans were conducted from
2 to 90 with a step size of 0.02, a dwell time of 1.2 s and a scan speed of 1 min-1. Samples
for XRD were inkjet printed on glass with an area of 5 5 mm2 and a dot spacing of 75 m.
4.4.3.1 Sintering with argon plasma

Line patterns were inkjet printed onto polycarbonate (PC), polyethylene terephthalate
(PET) and glass substrates, while the substrate temperature was set to 120 C. This
temperature is sufficient for stimulation of solvent evaporation, but still too low for significant
sintering of the nanoparticles in the ink. The dried as-printed samples were placed centrically
onto an isolated sample holder located in the middle of a barrel plasma chamber. Radio
frequency power was chosen to be within 40 and 80 W to ensure homogeneous and stable
argon plasma conditions and to adjust the degree of ionisation in the reactor. Argon was
chosen as feeding gas for plasma generation, since inert gasses did not result in the
deformation of the polymer substrates, in contrast to oxidative gasses, like oxygen.[89]
Figure 4.20a demonstrates the establishment of resistivity, calculated using Equation 4.1,
on glass substrates as a function of time, yielding resistivities of 2.5 to 3 the bulk silver value
for thermal sintering at 220 C and argon plasma at 80 W, respectively, after 60 minutes. The
results for polymer film substrates (Figure 4.20b) show a clear exponential decay of the
resistivity with increasing energy applied. This is attributed to the increased ionisation of the
plasma gas and, as a consequence, the generated high energy plasma species arriving at the
metal surface and subsequent recombination through atomic diffusion (Ostwald ripening) of
silver particles into larger clusters.[90] The energetic ions as well as UV radiation from the
plasma are expected to decrease the chain length of the organic coating around the
nanoparticles.[80] The low pressure in the barrel reactor favours evaporation of these fragments
and allows the partially uncoated particles to get into direct contact and sinter.
125
Chapter 4
-5
1x10 -3
10
Resistivity ( m)
Resistivity ( m)
Plasma PC
(a) Thermal
Bulk Ag -4
(b) PET
Glass
1x10 2
Linear fit (R = 0.93)
-6
10
-5
1x10
-6
10
-7
10
-7
10
-8 -8
10 10
2 3 4 5 6 7
0 20 40 60 80 100 120 10 10 10 10 10 10
Time (min) E (J)
Figure 4.20 Resistivity as function of time (a) and applied energy (b) for plasma processed nanoparticle ink
tracks on polycarbonate, polyethylene terephthalate and glass samples. The dashed line in (a) shows the bulk
silver resistivity, while the dashed lines in (b) show linear fits to the data points.
Figure 1b shows the effective resistivity for lines sintered by plasma exposure on glass,
PC and PET. The small difference in resistivity of the lines on the polymer foils can be
explained by the different wetting properties of the substrates:[91] the line width for the lines
on PC and PET were measured to be 169 m and 218 m, respectively. Since broader lines
were obtained on PET substrates, the effective surface area for the absorption of the plasma is
also larger, which results in a higher degree of sintered material, hence a lower resistivity.
In order to assess the effect of surface area and penetration depth to the resistivity,
multiple layers were printed and sintered as multilayer sample. Post-processing was
conducted in an argon plasma at 80 W for 20 minutes to ensure partial sintering only.
Assuming a constant ejected volume, length and resistivity, the resistance of a multilayer line
obeys the characteristic resistance given by
l R0
R ( n) = = (4.16)
n A n
where is the electric resistivity, l the length of the track, A the cross-sectional area, n the
number of deposited layers and R0 the resistance of the single layer. Figure 4.21 depicts the
experimental data, showing approximately constant resistances for all multiple layer samples,
whereas the theory predicts a decay. The results imply that an equivalent amount of material
is sintered in the top layer independent of the thickness of the underlying structure.
Furthermore, this implies that plasma processing results in the formation of a conductive skin
layer whose thickness grows with increasing plasma exposure time. Another indication for the
126
skin layer can be deduced from the difference in visual appearance of the material between a
single or multiple layers sample when looking from the bottom side through the transparent
substrate: after plasma sintering a single layer sample, the deposit exhibits a metallic
appearance, signifying through-sintering, while after plasma sintering multiple layers the
characteristic bluish appearance of unsintered nanoparticles prevails.[92]
R ( cm ) 20
-1
18
16
14
12
10
0
0 1 2 3 4 5 6 7
Number of layers
Figure 4.21 Comparison of measured (data points) and calculated behaviour (continuous line) of resistance over
multiple numbers of layers printed on PC. The dashed line shows the average resistance of the data points.
4.4.3.2 Skin layer formation analysis

To verify skin layer formation, adhesive tape was applied to multilayer samples on glass
that were sintered for 60 minutes at 80 W in an argon plasma. These multilayer samples also
had a bluish appearance when looking from the bottom side through the substrate.
Subsequently, the tape was removed warily in order to only detach the conductive top layer,
while leaving the unsintered part of the material behind. Removing the upper layer revealed
the characteristic bluish appearance of nanoparticles and showed no conductivity of the
remainder on the substrate. The crust that was transferred to the adhesive tape, however, was
conductive and showed similar resistance compared to the complete track before. Subsequent
plasma processing of the same sample after removing the crust yielded again a low resistance
for all lines. This implies that the non-conductivity in the previous step originated from
unsintered material rather than conduction path discontinuities. On the left-hand side of
Figure 4.22, scanning electron microscopy (SEM) images of the transitions between the
different regions are depicted. These regions are a result from a twofold application of the
adhesive tape to a multilayer sample with repeated plasma sintering. The structural change in
127
Chapter 4
the ink is obvious in the lower picture (Figure 4.22 II), where sintered and unsintered material
meet. The SEM pictures on the right-hand side show that the unsintered material looks
smooth (Figure 4.22 V), while obvious grain growth has taken place during sintering (Figure
4.22 III and IV). The comparison of the microstructure of the samples that were plasma
processed once and twice for one hour shows no noticeable difference.
Figure 4.22 Skin layer removal and microstructures after repetitive sintering.
Furthermore, results from SEM evaluations from single layer tracks can be seen in Figure
4.23. The SEM images I-III show the time dependent evolution of the skin layer for single
layer experiments for 7.5, 30 and 60 minutes, respectively. For (I) and (II) two distinct regions
can be identified: the bottom layer represents the unsintered nanoparticles, whereas the top
layer shows the sintered and conductive material. At 60 minutes (Figure 4.23 III) the
conductive skin layer has grown to its full extent and the layer thickness decreased due to
densification. This observation is supported by the disappearance of the bluish colour from
unsintered nanoparticles when looking through the substrate. Therefore, all the material
contributes to electric conductivity.
Figure 4.23 Temporal evolution of the sintering process on glass, cross sections of the deposited material after
plasma sintering at 80 W for 7.5, 30 and 60 minutes, respectively I-III.
128
For studies of densification, the cross-sectional area A was chosen to be the characteristic
feature. This also determines the resistivity of the produced structure. The cross-sectional line
profile was measured by interferometry at three different positions on glass samples.
Furthermore, anisotropy of the densification process was found by measuring height and
width within the obtained profiles. Area loss compared to the initial area, as depicted in
Figure 4.24, shows comparable behaviour for plasma and thermal sintering. In case of thermal
processing it exhibits an abrupt increase in densification of approximately 20% in the early
stages of the sintering process (about 10 minutes), followed by stagnation at a saturating value
after approximately 60 minutes. In the case of plasma processing the changes proceed slower,
but also show after 60 minutes of plasma exposure a saturation of approximately 50%. This is
in agreement with the results shown in Figure 4.20a. Moreover, the densification studies show
that the integral area loss is merely attributed to a change in the height of the track rather than
their width.
0.0
Area (thermal)
Normalised cross-sectional area and
-0.1 Height (thermal)

Area (plasma)
-0.2 Height (plasma)
height change (-)
-0.3
-0.4
-0.5
-0.6
-0.7
0 20 40 60 80 100 120
Time (min)
Figure 4.24 The change in cross-sectional area and height during processing on glass for both thermal and
plasma sintering.
Even though the temperature in the plasma reactor could not be measured directly,
thermal stability of the polymer foil provides an indirect measure of the maximum
temperature during processing to be below 98 C, being the Tg of PET. The relatively low
temperature makes surface and grain boundary diffusion the leading mechanisms during
plasma treatment, yielding in increased neck and pore formation with increased time.
The conductivity is attributed to a good electrical contact between adjacent silver
particles. The crystallinity of plasma and thermally processed ink deposits on glass was
129
Chapter 4
measured using X-ray diffraction (XRD) crystallography. The results are depicted in Figure
4.25, showing a face-centred cubic crystal structure of bulk silver with good agreement to
theoretical lattice parameters, calculated from Braggs law, for plasma sintering at 80 W and
thermal sintering at 220 C for 60 minutes, respectively. While XRD data for nanoparticles
with diameters of 20 to 30 nm are reported in the literature,[93] the size of the unprocessed
nanoparticle material used here is small (5 to 10 nm) and the number of atoms in the
nanoparticles is too small to introduce adequate constructive and destructive interference,
resulting in a significant broadening of the peak.[94] This broadening can be also seen in the
bottom of the (111) peak for plasma sintered samples and are an indication of presence of
residual unsintered nanoparticle material, mentioned above.
Figure 4.25 X-ray diffraction pattern of unprocessed, plasma and thermally processed nanoparticle ink on glass.
In summary, an alternative and selective low pressure sintering method was evaluated for
inkjet printed colloidal silver inks on common polymer substrates, without affecting the
substrate. The process yields comparable conductivities to conventional heating methods.
Effective resistivities of less than one order of magnitude higher than the bulk silver value
were achieved on polymer foils, like polycarbonate and polyethylene terephthalate, while
three times the bulk silver resistivity was obtained when using glass as a substrate. The
plasma sintering process shows a clear evolution starting from a sintered top layer into bulk
material, which determines the effective resistivity of the sintered material. Through-sintering
does not occur with greater thicknesses than the penetration depth of the plasma species.
Additional experiments with a kHz excited capacitively coupled argon plasma, instead of
MHz, also showed conductivity achievement and may improve the process due to higher
kinetic energies of the ions, which results in a larger penetration depth.
130
4.5 Conclusions
Various methods for sintering silver nanoparticles after being inkjet printed onto polymer
substrates have been described in this chapter. The standard method for sintering is by
applying heat, typically above 200 C, which is not compatible with the common polymer
foils that are being considered as substrates for plastic electronics applications.
In order to develop better and alternative sintering methods, a basic understanding of
thermal sintering and how particles sinter has been described. Hereto, the conductivity
development of several commercially available silver inks has been discussed. In addition, the
preparation and characterisation of a silver particle ink that shows a curing temperature as low
as 80 C is described. Good to excellent conductivity values of 5 to 56% of bulk silver have
been reached by using a very small amount of organic additives without any strong adsorbing
groups. Furthermore, the temperature stability of silver tracks, prepared by inkjet printing
different colloidal silver dispersions, was investigated. Hereto, the resistance was measured
on-line during the heating of the silver tracks from room temperature to 650 C.
As well as conventional thermal sintering, two alternative methods have been developed
using microwave radiation or plasma exposure. By using microwave radiation, the sintering
time of silver nanoparticles was shortened by a factor of 20, i.e. instead of 60 minutes three
minutes were sufficient for sintering. The polymer substrate is virtually transparent to
microwave radiation, whereas the conductive silver nanoparticles absorb the microwaves
strongly and sinter.
Furthermore, the presence of conductive antennae promotes nanoparticle sintering in pre-
cured ink lines to an extent that depends on the total area of the antennae. For cured
nanoparticle inks that are connected to antennae, sintering times of 1 second are sufficient to
obtain pronounced nanoparticle sintering. The antenna effect is more pronounced if the ink
line already exhibits conductivity. It is believed that this is due to the decreased mismatch
between the impedance of air and sample. Using metal antennae, it was revealed that 1 second
is sufficient to obtain pronounced sintering by microwave heating. The degree of sintering for
these short exposure periods, however, strongly depends on the initial resistance of the pre-
cured ink lines. Furthermore, increasing the width of the lines enhances the initial
conductivity rise due to improved energy absorption as a result of the increased surface area.
After microwave flash sintering, the tracks revealed conductivity values of 10 to 34%
compared to the bulk silver value, which is significantly higher compared to conventional
heating methods. The procedure of printing and subsequently microwave flash sintering can
131
Chapter 4
be used, for example, in roll-to-roll (R2R) production applications, such as large area
fabrication of RFID tags or solar cells. Its major advantage pertains to both the high process
speed and the low processing temperature, which reduce processing costs, as common
polymer foils like polyethylene naphthalate (PEN) can be used.
A second alternative sintering technique, namely low pressure argon plasma exposure,
was used and yielded comparable conductivities to conventional heating methods. Typical
resistivity values of 2.5 to 3 the bulk silver value were achieved. The process shows a clear
evolution starting from a sintered top layer into bulk material, which determines the resistivity
of the sintered material. Through-sintering does not occur with greater thicknesses than the
penetration depth of the plasma species. Plasma processing causes substantial cross-sectional
area and height loss, indicating that densification and sintering takes place.
The silver ink that has a low curing temperature of 80 C together with the alternative and
selective sintering methods open new routes to produce conductive features on common
polymer foils that have a relatively low glass transition temperature (Tg), like PET or PC.
Together with the technique of inkjet printing, materials can be saved, since it is only
dispensed on demand. This combination may be then employed in R2R printed plastic
electronics.
4.6 References

3 S. R. Forrest, Nature 2004, 428, 911.
6 D.-Y. Shin, P. J. Smith, J. Appl. Phys. 2008, 103, 114905.
7 D. Kim, S. Jeong, S. Lee, B. Kyun Park, J. Moon, Thin Solid Films 2007, 515, 7692.
8 K. Cheng, M.-H. Yang, W. W. W. Chiu, C.-Y Huang, J. Chang, T.-F. Ying, Y. Yang,
Macromol. Rapid Commun. 2005, 26, 247.
9 Y. Yoshioka, P. D. Calvert, G. E. Jabbour, Macromol. Rapid Commun. 2005, 26, 238.
10 H.-H. Lee, K.-S. Chou, K.-C. Huang, Nanotechnology 2005, 16, 2436.
11 E. Menard, M. A. Meit, Y. Sun, J.-U. Park, D. Jay-Lee Shir, Y.-S. Nam, S. Jeon, J. A. Rogers,
Chem. Rev. 2007, 107, 1117.
12 J. G. Liu, C. H. Chen, J. S. Zheng, J. Y. Huang, Appl. Surf. Sci. 2005, 245, 155.
13 C. N. LaFratta, D. Lim, K. O'Malley, T. Baldacchini, J. T. Fourkas, Chem. Mater. 2006, 18,
2038.
132
14 T. Cuk, S. M. Troian, C. M. Hong, S. Wagner, Appl. Phys. Lett. 2000, 77, 2063.
15 C. Min Hong, S. Wagner, IEEE Electron Device Letters 2000, 21, 384.
16 S. Molesa, D. R. Redinger, D. C. Huang, V. Subramanian, Mat. Res. Soc. Symp. Proc. 2003,
769, H8.3.1.
17 H. M. Nur, J. H. Song, J. R. G. Evans, M. J. Edirisinghe, J. Mater. Sci. 2002, 13, 213.
18 G. Schmid, Nanoparticles: From Theory to Applications, Wiley, Weinheim, 2004, 185-238.
19 J. B. Szczech, C. M. Megaridis, D. R. Gamota, J. Zhang, IEEE Trans. On Electronics
Packaging Manuf. 2002, 25, 26.
20 D. Huang, F. Liao, S. Molesa, D. Redinger, V. Subramanian, J. Electrochem. Soc. 2003, 150,
412.
21 S. Zampolli, I. Elmi, E. Cozzani, G. C. Cardinali, A. Scorzoni, M. Cicioni, S. Marco, F.
Palacio, J. M. Gmez-Cama, I. Sayhan, T. Becker, Microsyst. Technol. 2008, 14, 581.
22 T. Sutter, Circuit World 2005, 3, 4.
23 D. Huang, F. Liao, S. Molesa, D. Redinger, V. Subramanian, IEEE Trans. Electron. Devices
2004, 51, 1978.
24 S. Gamerith, A. Klug, H. Schreiber, U. Scherf, E. Moderegger, E. J. W. List, Adv. Funct.
Mater. 2007, 17, 3111.
25 A. A. Argun, P.-H. Aubert, B. C. Thompson, I. Schwendeman, C. L. Gaupp, J. Hwang, N. J.
Pinto, D. B. Tanner, A. G. MacDiarmid, J. R. Reynolds, Chem. Mater. 2004, 16, 4401.
26 G. H. Shim, M. G. Han, J. C. Sharp-Norton, S. E. Creager, S. H. Foulger, J. Mater. Chem.
2008, 18, 594.
27 P. Calvert, Chem. Mater. 2001, 13, 3299.
28 A. L. Dearden, P. J. Smith, D.-Y. Shin, N. Reis, B. Derby, P. OBrien, Macromol. Rapid
Commun. 2005, 26, 315.
29 R. W. Vest, E. P. Tweedell, R. C. Buchanan, Intl. J. Hybrid Microelectron 1983, 6, 261.
30 K. F. Teng, R. W. Vest, IEEE Trans. Compon. Hybrids, Manuf. Technol. 1987, 12, 545.
31 Y. Wu, Y. Li, B. S. Ong, J. Am. Chem. Soc. 2007, 129, 1862.
32 C.-A. Lu, P. Lin, H.-C. Lin, S.-F. Wang, Jpn. J. Appl. Phys. 2007, 46, 251.
33 P. Buffat, J.-P. Borel, Phys. Rev. A 1976, 13, 2287.
34 G. L. Allen, R. A. Bayles, W. W. Gile, W. A. Jesser, Thin Solid Films 1986, 144, 297.
35 K. J. Lee, B. H. Jun, T. H. Kim, J. Joung, Nanotechnology 2006, 17, 2424.
36 J. Perelaer, A. W. M. de Laat, C. E. Hendriks, U. S. Schubert, J. Mater. Chem. 2008, 18, 3209.
37 H. Bnnemann, R. M. Richards, Eur. J. Inorg. Chem. 2001, 2455.
38 N. Yang, K. Aoki, Electrochim. Acta 2005, 50, 4868.
39 A. J. Lovinger, J. Adhesion 1979, 10, 1.
40 L. Maissel, R. Glang, Handbook of Thin Film Technology, McGraw Hill, 1970.
41 J.-W. Park, S.-G. Baek, Scripta Mater. 2006, 55, 1139.
42 K.-S. Chou, K.-C. Huang, H.-H. Lee, Nanotechnology 2005, 16, 779.
43 S. H. Ko, H. Pan, C. P. Grigoropoulos, C. K. Luscombe, J. M. J. Frchet, D. Poulikakos, Appl.
Phys. Lett. 2007, 90, 141103.
133
Chapter 4
44 Z. Radivojevic, K. Andersson, K. Hashizume, M. Heino, M. Mantysalo, P. Mansikkamaki, Y.

Matsuba, N. Terada, in: Proc. 12th Intl. Workshop on Thermal investigations of ICs 2006.
45 J. R. Groza, S. H. Risbud, K. Yamazaki, J. Mater. Res. 1992, 7, 2643.
46 G. Xie, O. Ohashi, N. Yamaguchi, A. Wang, Metall. Mater. Trans. A 2003, 34A, 2655.
47 L. H. Liang, C. M. Shen, S. X. Du, W. M. Liu, X. C. Xie, H. J. Gao, Phys. Rev B. 2004, 70,
205419.
48 W. Ostwald, Lehrbruck der Allgemeinen Chemie, Vol. 2, Part 1, Leipzig, Germany, 1896.
49 W. Ostwald, Z. Phys. Chem. 1901, 37, 385.
50 K. Hajmrle, R. Angers, Metall. Trans. B 1974, 5, 817.
51 J. R. Greer, R. A. Street, Acta Mater. 2007, 55, 6039.
Chem. 2007, 17, 677.
53 D. Kim, S. Jeong, B. Kyun Park, J. Moon, Appl. Phys. Lett. 2006, 89, 264101.
54 J.-Y. Song, S.-Y. Choi, Displays 2006, 27, 112.
55 T. Kizuka, H. Ichinose, Y. Ishida, J. Mater. Sci. 1997, 32, 1501.
56 K.-S. Moon, H. Dong, R. Maric, S. Pothukuchi, A. Hunt, Y. Li, C. P. Wong, J. Electron.
Mater. 2005, 34, 168.
57 S. B. Fuller, E. J. Wilhelm, J. M. Jacobson, J. Microelectromech. Syst. 2002, 11, 54.
58 http://www.microfab.com/equipment/technotes/technote99-02.pdf
59 T. Murakami, H. Suetsugu, NEC Tech. J. 1999, 52, 11.
60 T. Shinoda, M. Wakitani, T. Nanto, N. Awaji, S. Kanagu, IEEE Trans. Electron Dev. 2000,
47, 77.
61 A. L.Yarin, J. B. Szczech, C. M. Megaridis, J. Zhang, D. R. Gamota, J. Colloid Interface Sci.
2006, 294, 343.
62 S. H. Ko, H. Pan, C. P. Grigoropoulos, C. K. Luscombe, J. M. J. Frchet, D. Poulikakos,
Nanotechnology 2007, 18, 345202.
63 J. Chung, N. R. Bieri, S. Ko, C. P. Grigoropoulos, D. Poulikakos, Appl. Phys. A 2004, 79,
1259.
64 M. Nchter, B. Ondruschka, W. Bonrath, A. Gum, Green Chem. 2004, 6, 128.
65 K. J. Rao, B. Vaidhyanathan, M. Ganguli, P. A. Ramakrishnan, Chem. Mater. 1999, 11, 882.
66 Y. Fang, M. T. Lanagan, D. K. Agrawal, G. Y. Yang, C. A. Randall, T. R. Shrout, A.
Henderson, M. Randall, A. Tajuddin, J. Electroceramics 2005, 15, 13.
67 R. M. Anklekar, K. Bauer, D. K. Agrawal, R. Roy, Powder Metall. 2005, 48, 39.
68 P. Lidstm, J. Tierney, B. Wathey, J. Westman, Tetrahedron 2001, 57, 9225.
69 F. Wiesbrock, R. Hoogenboom, U. S. Schubert, Macromol. Rapid Commun. 2004, 25, 1739.
70 I. Reinhold, Investigation to Alternative Sintering Methods for Inkjet Printed Conductive
Silver Tracks, Diploma Thesis, Eindhoven University of Technology and Technical
University Chemnitz, 2008.
71 C. Gabriel, Sami Gabriel, E. H. Grant, B. S. J. Halstead, D. M. P. Mingos, Chem. Soc. Rev.
1998, 27, 213.
134
72 E. T. Thostenson, T.-W. Chou, Composites: Part A 1999, 30, 1055.

73 P. Mishra, G. Sethi, A. Upadhyaya, Metall. Mater. Trans. B 2006, 37, 839.
74 D. Agrawal, Trans. Ind. Ceram. Soc. 2006, 65, 129.
75 D. K. Cheng, Field and Wave Electromagnetics, 2nd ed., Addison-Wesley Co. Inc., Reading,
MA 1989, p. 369-371.
76 P. O. G. Risman, M. Fagrell, F. Stillesj, WO 2004/105443, 2004.
77 H. Zuckerman, J. Miltz, Packag. Technol. Sci. 1994, 7, 21.
78 S. Magdassi, A. Bassa, Y.Vinetsky, A. Kamyshny, Chem. Mater. 2003, 15, 2208.
79 Y. Matsumoto, Y. Yamaguchi, J. Hombo, T. Hauber, W. Gopel. J. Solid State Chem. 1992,
98, 201.
80 M. J. Renn, WO 2007/070868 A2, 2007.
81 H. Kersten, R. Wiese, G. Thieme, M. Frhlich, A. Kopitov, D. Bojic, F. Scholze, H.
Neumann, M. Quaas, H. Wulff, R. Hippler, New J. Phys. 2003, 5, 93.
82 R. France, R. Short, J. Chem. Soc. Faraday Trans. 1997, 93, 3173.
83 A. Roosmalen, J. Baggermann, S. Brader, Dry Etching in VLSI, Plenum Press, New York,
1991.
84 S. Sinha, Surf. Coat. Technol. 2002, 158, 214.
85 B. Satpati, J. Ghatak, B. Joseph, P. V. Satyam, T. Som, D. Kabiraj, B. N. Dev, in NSC Indo-
German Workshop, New Dehli, 2005.
86 R. Holm, S. Storp, Appl. Phys. A 1977, 12, 101.
87 H. Kersten, H. Deutsch, H. Steffen, G. Kroesen, Vacuum 2001, 63, 385.
88 A. M. J. van den Berg, P. J. Smith, J. Perelaer, W. Schrof, S. Koltzenburg, U. S. Schubert, Soft
Matter 2007, 3, 238.
89 D. Hegemann, H. Brunner, C. Oehr, Nucl. Instrum. Methods Phys. Res. B 2003, 208, 281.
90 M. A. Liebermann, A. J. Lichtenberg, Principles of Plasma Discharges and Materials
Processing, 1st Edition, Wiley & Sons, New York, 1994.
91 D. Soltman, V. Subramanian, Langmuir 2008, 24, 2224.
92 J. Mei, M. Lovell, M. Mickle, IEEE Trans. Electron. Packag. Manuf. 2005, 28, 265.
93 S. L.-C. Hsu, R.-T. Wu, Mater. Lett. 2007, 61, 3719.
94 B. D. Cullity, S. R. Stock, Elements of X-ray diffraction, 3rd Edition, Prentice-Hall, Upper
Saddle River, NJ, 2001.
135
Diamond Viper V550, AGP, 16 MB
5
Microstructures prepared by photo-embossing
Abstract
Photo-embossing is a photolithographic technique for the generation of polymer relief structures
that are created by a deformation of the surface of the film, which is caused by a material flux induced
by a local polymerisation. One of the main problems in photo-embossing is the low aspect ratio of the
formed features, which are typically 0.05 in an inert atmosphere and 0.2 in an ambient atmosphere.
This chapter describes the improvement of the aspect ratio of photo-embossed microstructures by
adding compounds that interfere with the reaction kinetics. Firstly, the addition of t-butyl
hydroquinone (TBHQ) is described. Hereby, the aspect ratio was increased under inert atmosphere to
0.35, which is an improvement of a factor of 7. It is believed that TBHQ behaves as a retarder in the
photopolymer system, when environmental oxygen is absent. TBHQ reduces the rate of polymerisation
by converting acrylate radicals into stable phenol radicals. Since oxygen then has a negative influence
on the formation of relief structures, processing has to occur under an inert atmosphere.
Secondly, the addition of a reversible addition-fragmentation chain transfer (RAFT) agent,
typically used for controlled radical polymerisation, in particular of acrylate monomers, improves the
aspect ratio under an inert atmosphere by a factor of almost 10, up to 0.46. Moreover, the increase is
independent of atmospheric conditions since oxygen inhibition hardly occurs, which is a major
advantage for industrial applications of photo-embossing. The aspect ratio could be improved due to
the controlled acrylate polymerisation upon addition of a RAFT agent. The insensitivity to oxygen
inhibition is related to the ability of the RAFT agents to form stable radicals independent on the
presence of oxygen.
The improved photo-embossed structures offer a simple and versatile alternative for the
production of large-scale/large-area relief structures in thin polymer films and might find potential
applications in microelectronic elements, biosensors and cell growth arrays.
Parts of this chapter have been published: (1) K. Hermans, F. K. Wolf, J. Perelaer, C. W. M. Bastiaansen,
R. A. J. Janssen, U. S. Schubert, D. J. Broer, Appl. Phys. Lett. 2007, 91, 174103; (2) K. Hermans, J. Perelaer,
C. W. M. Bastiaansen, D. J. Broer, PCT/EP2007/007498, Dutch Polymer Institute; (3) J. Perelaer, K. Hermans,
C. W. M. Bastiaansen, D. J. Broer, U. S. Schubert, Adv. Mater. 2008, 20, 3117; (4) J. Perelaer, K. Hermans,
C. W. M. Bastiaansen, U. S. Schubert, PCT/EP2008/056373, Dutch Polymer Institute; (5) K. Hermans, J.
Perelaer, C. W. M. Bastiaansen, U. S. Schubert, D. J. Broer, manuscript in preparation.
Chapter 5
5.1 Introduction
Photo-embossing is a photolithographic technique for the generation of polymer relief
structures.[1-3] The relief structures are created by a deformation of the surface of the film
which is caused by a material flux induced by a local polymerisation.[4-5] This technique offers
a simple and versatile alternative for the production of large-scale/large-area relief structures
in thin polymer films, that find applications in microelectronic elements,[6] biosensors and cell
growth arrays.[7-8]
Standard lithography techniques to create relief structures use light-induced solubility
changes of a polymer photoresist.[9] After a wet-etching step the final structure is developed.
The etching step is a time and cost consuming factor in the production of relief structures and
not favourable in terms of sustainability and environmental effects. In contrast, photo-
embossing does not involve any etching steps, which reduces the number of processing steps
and thereby the production costs. Furthermore, unlike conventional patterning techniques, like
hot-embossing[10-11] or micro-contact printing[12-13] techniques, photo-embossing does not
require expensive moulds and, as a consequence, photo-embossing represents a simple and
relatively inexpensive technique to create a surface relief.
In the photo-embossing process a typical photopolymer consists of a mixture of a polymer
binder, a multifunctional acrylate monomer, and a photoinitiator. The photo-embossing
procedure is depicted in Figure 5.1. In the first step a film of the photopolymer solution is spin
cast onto a substrate, for example glass or a flexible polymer substrate.
(a) (b) (c)
Figure 5.1 Photo-embossing process explained in three steps: the substrate is coated with the solid photopolymer
reactive blend spun from solution (a), exposed to UV radiation through a mask of defined grating size and a
latent image of the mask is formed into the film, which can be developed upon heating (b). After development
the sample is fixed by UV flood exposure (c).
Next, the photopolymer layer is locally exposed with UV light, creating radicals in the
illuminated areas (Figure 5.1b). Due to the solid state nature of the photopolymer, monomer
diffusion to the reactive sites is restricted and polymerisation hardly occurs because the free
138
radicals are captured in an immobile, glassy matrix. After exposure the sample is heated
above a threshold temperature, whereby the sample changes from a solid to a more mobile,
liquid-like state, which enhances diffusion and allows the monomer to polymerise in the
exposed areas. Due to the consumption of the monomer in the illuminated regions, the change
in chemical potential provides a driving force for the monomers in the unexposed areas to
diffuse to the exposed areas. This mass transport creates a volume increase and, consequently,
a deformation of the surface. In the final processing step the sample is fully polymerised by
applying a UV flood exposure at elevated temperatures (Figure 5.1c).
In order to expand the range of applications and to be competitive with other technologies
one of the main problems of the photo-embossing process has to be addressed, which is the
low aspect ratio of the formed features. The aspect ratio, defined as the ratio of the relief
height and width, for photo-embossed relief structures is typically 0.05 in an inert atmosphere
or 0.2 in an ambient atmosphere. It has been found that the material flux, and thereby the
aspect ratio, is highly affected by the polymerisation kinetics[14] and can be optimised by
modifying the rate of initiation by changing initiator content or light intensity.[4]
In this chapter, a method to improve the aspect ratio is described by the addition of
molecules that interfere with the reaction kinetics. The addition of two compounds to the
photopolymer will be discussed; hydroquinones and reversible addition chain transfer (RAFT)
agents. Furthermore, the effect of the atmosphere on the successful usage of these compounds
will be discussed.
5.2 Photo-embossed structures with an increased aspect ratio by addition

of hydroquinones
5.2.1 Introduction
Compounds that interfere with the reactions kinetics, such as inhibitors, are reported to
have a significant influence on the performance of a photopolymer.[15] The reported effects,
however, differ and depend on the type of compound, the photopolymer system and the
processing environment. For example, oxygen has been reported as an effective inhibitor for
radical reactions, which results in oxygen having a negative effect on the performance of a
photopolymer.[16,17] The oxygen molecules react with propagating radicals, forming relatively
nonreactive peroxide radicals that are terminated by reacting with either themselves or other
propagating radicals. As a result, the radical concentration in the activated areas is reduced
139
Chapter 5
and only a small change in chemical potential can be induced by the consumption of reactive
species.
Scattering of UV light and diffusion of reactive species from the exposed to the non-
exposed area also result in a reduced chemical potential between the two areas. Consequently,
diffusion of reactive species from the non-exposed area to the exposed area is hindered, which
results in a smaller contrast between the two areas, hence lower relief structures. It has been
suggested that inhibitors could also have a positive effect on photopolymers by controlling the
undesired reaction of reactive species in the non-exposed areas.[1] Tests, however, that were
performed by adding 4-ethoxyphenol or p-benzoquinone to the photopolymer did not result in
the expected increase in performance for photo-embossing.
Here, a new investigation into improving the aspect ratio of photo-embossed
microstructures is described; the kinetics were tailored by the addition of t-butyl
hydroquinone (TBHQ), which is a well-known inhibitor and/or retarder.
5.2.2 Experimental
Materials
The photopolymer consists of polybenzyl methacrylate (Mn = 70 kDa, Scientific Polymer
Products), which was used as a binder, dipentaerythritol penta/hexa acrylate (Sigma Aldrich),
used as multifunctional monomer, in a 1:1 ratio, and Irgacure 819 (CIBA) as photoinitiator
(5 wt%). The solid materials were dissolved in a 50/50 wt% mixture of ethoxypropylacetate
(Avocado Research Chemicals) and propyleneglycolmethyletheracetate (Aldrich).
For the photopolymer solution preparation, the multifunctional monomer and the solvent were
first mixed in a weight ratio of 1:2. Subsequently, the solution was passed over a silica packed
inhibitor removing column (Aldrich) to remove the 4-methoxyphenol, which is, according to
the supplier, present in the monomer in a concentration of 500 ppm. The monomer/solvent
mixture was mixed with the polymer and photo-initiator in a weight ratio of 30:10:1,
respectively. Finally, t-butyl hydroquinone (Aldrich) was added in different concentrations to
the photopolymer solution (0, 2, 4 and 8 wt%). The total formulation is referred to as
photopolymer solution.
Substrates
Commercially available glass substrates (Marienfield, Lauda-Kningshofen, 5 5 cm) were
thoroughly cleaned by washing subsequently with soap, water, acetone and ethanol.[18] After a
140
second rinsing step with ethanol the glass slides were dried under a flow of air. The
photopolymer was spin coated on the glass substrates (Karl Suss RC8 spin coater, 60 seconds
at 800 rpm) and dried at 80 C for 20 minutes, resulting in a homogeneous layer of 16 m.
Processing
The samples were exposed with USHIO deep UV lamp (UXM-502), which was fitted into an
Oriel arc lamp housing (66902). The intensity was 13 mW cm-2 and all samples were
illuminated for 180 seconds.
A line mask with a 40 m periodicity was placed in direct contact with the sample. The
intensity of lamp was reduced by placing an optical density filter on top of the line mask.
After exposure the masks were removed and the sample was developed by gradually heating
to a temperature of 110 C and keeping it for 10 minutes at this temperature. Finally, a UV
flood exposure was applied for 5 minutes while the sample was at a temperature of 110 C in
order to fix the structures. To prevent oxygen inhibition during exposure, development and
flood exposure, the samples were placed under a protective atmosphere by constant nitrogen
blanketing using a custom-built hot plate. This hot plate was build into an aluminium box
which could be flushed with nitrogen and contained a quartz glass window through which the
samples can be exposed to UV light.
Characterisation
The obtained structure heights were measured with a mechanical profilometer (Tencor
Instruments Alpha-Step 200), which was equipped with a stylus with a 2 m radius and 45
tip angle.
Attenuated total reflection infrared (ATR-IR) measurements were performed using an
Excalibur FT-IR (FTS 3000 MX) that was equipped with a Specac Golden Gate diamond
ATR. A USHIO deep UV lamp (USH-200DP, = 365 nm, I = 1.5 mW cm-2) in an Oriel light
source housing (69054) was used for sample exposure during ATR measurements. The
samples were applied from solution and dried for 10 minutes at 80 C after which they were
cooled to 30 C before starting the measurement.
Scanning electron microscopy (SEM) images were taken using a FEG E-SEM XL30 (Philips,
The Netherlands). The samples were broken parallel to the relief and coated with a thin gold
layer by vapour deposition.
Electron spin resonance (ESR) spectra were measured with a Bruker ESP300 spectrometer at
X-band. The dried films were removed using a razor blade and positioned in a quarts glass
141
Chapter 5
tube. During measurements the tubes were placed under vacuum and exposed to laser light
source ( = 351 nm, I = 10 mW).

The addition of TBHQ suppresses the polymerisation of monomers by converting free
radicals during initiation and/or propagation into less- or non-reactive species. In the case of
very efficient inhibition, polymerisation is halted until all inhibitor is consumed. In the case of
retardation, however, polymerisation occurs but at a reduced rate. The transition between
inhibition and retardation is often somewhat vague and depends on experimental parameters,
such as type of monomers or processing conditions.
By means of attenuated total reflection infrared (ATR-IR) spectroscopy the effect of
TBHQ concentration on the polymerisation kinetics was studied by quantifying the acrylate
conversion real time upon UV exposure. Different amounts of TBHQ were added to the
photopolymer. During the measurements the samples were kept under a nitrogen atmosphere
to exclude the inhibition effect of environmental oxygen. The photo-polymerisation was
initiated 10 seconds after starting the measurement by exposing the samples to a continuous
UV light source. The double bond conversion was determined from peak height changes
associated with the polymerisation.[19] The acrylate conversion is measured at the
corresponding C=C stretch vibration peak at 1635 cm-1. Figure 5.2 shows that the addition of
TBHQ reduces the rate of polymerisation without obtaining an induction period. This
indicates that TBHQ behaves predominantly as a retarder in the photopolymer system upon
photo-polymerisation.
0.8
Relative Acrylate Conversion (-)
0 wt% TBHQ
0.7 2 wt% TBHQ
4 wt% TBHQ
0.6 8 wt% TBHQ
0.5
0.4
0.3
0.2
0.1
0.0
0 1 2 3 4 5
Time (min)
Figure 5.2 Acrylate conversion upon continuous UV exposure initiated after 10 seconds for different
amounts of TBHQ added to the photopolymer. A colour version is available on page 176.
142
Subsequently, the effect of TBHQ on the aspect ratio of photo-embossed structures was
studied. In the exposure step, the photopolymer film was exposed to an exposure dose of 0.19,
0.58 and 1.38 J cm-2 through a line mask with a 40 m period. During exposure, development
and flood exposure the samples were kept under a nitrogen atmosphere. The results are shown
in Figure 5.3.
Aspect Ratio (-) 0.40

-2
1.38 J cm
0.35 0.58 J cm
-2
-2
0.19 J cm
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0 5 10 15 20
wt% TBHQ
Figure 5.3 Aspect ratio as a function of amount of TBHQ added to the photopolymer for, respectively, 0.19,
0.58 and 1.38 J cm-2 mask exposure dose. Lines are drawn to guide the eye.
The results show that the aspect ratio increases with increasing amounts of TBHQ up to a
maximum, of which the position depends on the exposure dose used during the mask
exposure step. Beyond this maximum, the enhanced effect of the TBHQ diminishes. Since the
intensity of the used UV lamp is limited, as well as the exposure time from a practical point of
view, the maximum aspect ratio of the formed relief structures is also determined by the used
setup.
The extent of increase in aspect ratio is further illustrated by scanning electron microscopy
(SEM) images of samples containing different concentrations of TBHQ, as shown in Figure
5.4. Surprisingly, the increase of the height of the structures and their aspect ratio is much
larger than can be achieved by simply reducing the polymerisation rate by reduction of light
intensity or initiator concentration alone.[30] This means that there must be an additional
mechanism explaining the enormous effects of TBHQ which will be elucidated in the
following paragraphs.
143
Chapter 5
(a)
10 m
(b)
10 m
(c)
10 m
Figure 5.4 Scanning electron microscopy (SEM) images of photo-embossed structures with 0 w% (a), 4 w% (b)
and 20 w% (c) TBHQ added to the photopolymer and exposed to 2.4 J cm-2.
In contrast to decreasing the rate of polymerisation by intensity reduction, the presence of

TBHQ only temporarily reduces the number of free radicals by capturing them into less-
reactive species. However, these species are reactivated again during the heating step where
the structures are being formed, thus increasing the concentration of initiating free radicals.
Also, in the absence of TBHQ, the dominant buried radical species for a multi-functional
acrylate are commonly found to be mid-chain acrylate radicals.[20] Although highly reactive,
these radicals have an extreme longevity that is most probably caused by steric effects that
trap the radicals and prevent any further reactions at room temperature. Upon addition of
TBHQ, highly reactive acrylate radicals are transferred to the phenolic compound, thus
creating the stable radical species, acting as a latent initiator. Upon heating, the enhanced
consumption of monomer leads to an increased driving force for diffusion. The formation of
144
the stable phenolic free radical species is further supported by electron spin resonance (ESR)
spectroscopy of samples with 0 or 8 wt % TBHQ added.
Figure 5.5a shows that in absence of TBHQ the ESR signal consist of a complex line
pattern, suggesting the presence of multiple radicals or radicals in different conformations.
The main contribution, however, is ascribed to a mid chain acrylate radical (see inset in
Figure 5.5a), exhibiting hyperfine coupling to two of the four methylene protons, giving rise
to a three-line ESR spectrum. In the presence of TBHQ, however, the ESR signal is different.
The single line spectrum fits the expected signature of a phenol radical (see inset in Figure
5.5b) under conditions of reduced spectral resolution as present in a solid polymer film.[21]
Normalised Intensity (-)
1.0
0.8
(a) Measured
Simulated
0.6
0.4
0.2
0.0
-0.2
-0.4 H2 H2
C C
-0.6
-0.8
O O
-1.0 R
3400 3440 3480 3520 3560 3600

B (Gauss)
Normalised Intensity (-)
1.0
0.8
(b) Measured
Simulated
0.6
0.4
0.2
0.0
-0.2
O
-0.4
-0.6
-0.8
-1.0 OH
3400 3440 3480 3520 3560 3600

B (Gauss)
Figure 5.5 Electron spin resonance (ESR) spectra upon UV exposure of a photopolymer film without addition of
TBHQ (a) and with 8 w% of TBHQ added (b). The black lines represent the measured spectra and the dashed
lines the simulated spectra (aH = 21.0 Gauss (2H)). The insets on the bottom right of the figures (a) and (b) show
the chemical structure of the dominant compound in the spectrum.
145
Chapter 5
When the TBHQ concentration becomes too high, the maximum aspect ratio decreases
again. It is believed that, besides the function of latent initiator, it also contributes to the
termination of the polymerisation reaction. A first indication for this can be obtained from
Figure 5.2, showing that under the same conditions, a higher TBHQ concentration leads to
lower end conversion and thus smaller monomer consumption. Also, as monomer
consumption in the exposed areas is the main driving force for diffusion, a reduction in end
conversion results in less diffusion. This effect can be postponed by choosing a higher
exposure dose, increasing the concentration of the initially captured reactive species. It is this
balance between the initial concentration of reactive species and the end conversion, or the
exposure dose and the TBHQ concentration, that influences the final aspect ratio of the photo-
embossed structures and explains the observations of Figure 5.3.
In summary, it was shown that by adding TBHQ under an inert atmosphere, the aspect
ratio of photo-embossed structures of 0.35 can be obtained, which is an increase by a factor of
7. The positive effect is attributed to the transfer of propagating radical to stabilised species
during the exposure step. These stable radicals are not terminated but instead they act as latent
initiators which can more easily continue polymerisation during the thermal development
step.
5.3 Photo-embossed surface relief structures with an increased aspect ratio

by addition of reversible addition-fragmentation chain transfer
(RAFT) agent
5.3.1 Introduction
In the previous section, a new development in creating high aspect ratio photo-embossed
structures was described by the addition of t-butyl hydroquinone (TBHQ). However, the
presence of atmospheric oxygen still has a significant negative influence on the obtained
aspect ratio, since it inhibits further polymerisation due to the formation of a stable radical
with the TBHQ radicals. As a consequence, no structure will be developed. Although this
problem can be solved by nitrogen blanketing during processing, it is highly interesting from
an application point of view to discover additives or alternative processes that yield high
aspect ratios in all atmospheric conditions including air.
Here, the addition of a reversible addition-fragmentation chain transfer (RAFT) agent to
the photopolymer system and its influence on the aspect ratio of relief structures is described,
146
while using different atmospheric conditions. RAFT agents are well-known for their ability to
confer living/controlled characteristics onto radical polymerisations by creating stable
(dormant) radical species.[22] This is, for example, used to synthesise well-defined
macromolecular architectures, like star, block, or comb shaped copolymers with narrow
polydispersity indices.[23,24,25] In particular, RAFT agents are used to enable controlled
acrylate polymerisation reactions.[26] The mechanism of RAFT is depicted in Figure 5.6 and is
based on the equilibrium between an intermediate stabilised radical A and dormant species B
with a dithioester moiety.[27] Moreover, it is reported that the RAFT mechanism is not
inhibited by oxygen.[28]
Initiation
monomer
I. I. Pn .
Chain transfer
Pn.
S S S . S S S .
II. + R Pn R Pn + R
z z z
monomer
Chain equilibium
Pn.
S S S . S S S .
III. + Pm Pn Pm Pn + Pm
z z z
monomer monomer
B A B
Figure 5.6 Schematic presentation of the reversible addition-fragmentation chain transfer (RAFT)
polymerisation. Within the chain equilibrium compound A represents the intermediate stabilised radical and B
the dormant species.
5.3.2 Experimental
Materials
The photopolymer was prepared similar to as it was described in Section 5.2.2. The RAFT
agents 2-cyanobut-2-yl dithiobenzoate (CBDB), 2-(methoxycarbonyl)prop-2-yl
dithiobenzoate, 2-n-dodecylsulfanyl-thiocarbonyl sulfanyl-2-methylpropionic acid and 2-
phenylprop-2-yl phenyl dithioacetate were used and prepared similar as described in
147
Chapter 5
literature.[29] The RAFT agent to initiator ratio was varied from 0.1 to 4, which equals 0.5 to
10 wt% relative to the blend of polymer, monomer and initiator.
Substrates
The photopolymer was spin coated similar to what was described in Section 5.2.2.
Processing
For illumination an EXFO OmniCure Series 2000 (Photonic Solutions Inc., Ontario, Canada)
UV lamp was used. The intensity was 26 mW cm-2 and all samples were illuminated for
90 seconds.
A rectangular lithographic mask (28 mm 31 mm) that consists of seven parallel sectors
(4 mm 31 mm) was placed onto the sample. Each sector has a line grating with a periodicity
of 40, 30, 20, 15, 10, 8 and 5 m, respectively (dark and transparent areas of the same size).
On top and perpendicular to the line mask a lithographic optical density (OD) mask was
placed in order to change the intensity of the light that reaches the sample. The OD mask also
consists of seven parallel sectors, absorbing 10, 49, 79, 89, 95, 98 and 99% of the light,
respectively.
A custom made hotplate built into an aluminium box with a quartz glass window on top
(through which the sample was illuminated) was used to create a constant inert or ambient
atmosphere. If the experiments were performed under nitrogen atmosphere, the box was
flushed with nitrogen for 5 minutes prior illumination; otherwise the box was disconnected
from the nitrogen. After removal of the masks, the sample was gradually heated to 110 C and
kept for 10 minutes at this temperature. Finally and in order to fix the surface relief structures,
a UV flood exposure was applied for 5 minutes, while maintaining a temperature of 110 C.
Characterisation
Attenuated total reflection infrared (ATR-IR) measurements were performed using an
Excalibur FT-IR (FTS 3000 MX) that was equipped with a Specac Golden Gate diamond
ATR. A USHIO deep UV lamp (USH-200DP, = 365 nm, I = 1.5 mW cm-2) in an Oriel light
source housing (69054) was used for sample exposure during ATR measurements. The
samples were applied from solution and dried for 10 minutes at 80 C after which they were
cooled to 30 C before starting the measurement.
148
Topographic characterisation was performed by white light scanning confocal microscopy

(Surf, Nanofocus, Germany, magnification 20). The profiles were further characterised
using Scanning Probe Image Processor, SPIP software, version 4.1.
5.3.3.1 High-throughput experimentation for identifying the best RAFT agent

The addition of different RAFT agents during the photo-embossing process was
investigated in order to gain control over the acrylate polymerisation, which could lead into an
improvement of the aspect ratio of the formed structures. Hereto, the activating group (Z) and
leaving group (R) of the RAFT agents were altered and the aspect ratios were investigated and
are schematically depicted in Table 5.1.
To minimise the amount of samples and to increase the accuracy of the experiments, a
two-dimensional library has been generated in which the period of the grating structure and
the energy dose were systematically varied over its two axes.[30-32] Hereby libraries of 49
different samples could be created that were characterised by confocal microscopy in a fast
and efficient way.
Table 5.1 Schematic representation of a reversible addition-fragmentation chain transfer (RAFT) agent, where Z
is the activating group and R the leaving group (left). Details of the Z- and R-group for the tested RAFT agents
(right).
* * *
Activating group (Z) * -SC12H25
S S
R
z
* * * *
Leaving group (R) O
COOH
N
O
Figure 5.7 shows the aspect ratio as function of dose for various RAFT agents, obtained
under ambient atmosphere. In general a higher dose results in higher aspect ratios, but not for
all grating sizes that are used. Figure 5.7a shows the relation for 2-cyanobut-2-yl
dithiobenzoate (CBDB) as added RAFT agent. It can be seen that there is an optimum in
aspect ratio of 0.32 for a grating size of 20 m: when smaller or larger grating sizes are used
the effect of the added RAFT agent diminishes. A similar trend can be observed when using
2-(methoxycarbonyl)prop-2-yl dithiobenzoate as RAFT agent (Figure 5.7b). This can be
149
Chapter 5
explained in by the similarity in activating Z-group for both RAFT agents. This functional
group mainly determines the transfer constant of the RAFT agent. Furthermore, the highest
transfer constant was found for a cyanobutyl leaving group and a phenyl activating group.[27]
0.35 0.35
Aspect Ratio (-)

Aspect Ratio (-)
40 m 40 m
0.30 30 m
S S (a) 0.30 30 m O
S S (b)
20 m 20 m
O
15 m N 15 m
0.25 0.25
10 m 10 m
08 m 08 m
0.20 05 m 0.20 05 m
0.15 0.15
0.10 0.10
0.05 0.05
0.00 0.00
1 2 3 4 1 2 3 4
10 10 10 10 10 10 10 10
-2 -2
Dose (mJ cm ) Dose (mJ cm )
0.10 0.10
Aspect Ratio (-)
Aspect Ratio (-)
40 m 40 m
(c)
S
30 m
HOOC
S S
C12H25 30 m
S
(d)
0.08 20 m S 0.08 20 m
15 m 15 m
10 m 10 m
08 m 08 m
0.06 05 m 0.06
05 m
Linear fit Linear fit
2 2
(R = 0.74-0.97) (R = 0.73-0.99)
0.04 0.04
0.02 0.02
0.00 0.00
1 2 3 4 1 2 3 4
10 10 10 10 10 10 10 10
-2 -2
Figure 5.7 Aspect ratio as function of exposure dose for different grating sizes with 2-cyanobut-2-yl
dithiobenzoate (a), 2-(methoxycarbonyl)prop-2-yl dithiobenzoate (b), 2-n-dodecylsulfanyl-thiocarbonylsulfanyl-
2-methylpropionic acid (c), 2-phenylprop-2-yl phenyl dithioacetate (d) as used RAFT agents, under ambient
conditions. The RAFT to initiator ratio was 2. Lines are drawn with a spline fit in (a) and (b) in order to guide
the eye, whereas the dashed lines in (c) and (d) represent linear fits to the data. A colour version is available on
page 177.
In contrast, the RAFT agents 2-n-dodecylsulfanylthiocarbonylsulfanyl-2-methylpropionic

acid (Figure 5.7c) and 2-phenylprop-2-yl phenyl dithioacetate (Figure 5.7d) do not have an
optimum, but show a linear trend between the aspect ratio and exposure dose. The obtained
aspect ratios are all below 0.10 and thus much smaller than for the previously mentioned
RAFT agents. This can be explained by the fact that both a benzyl and an alkyl activating Z-
group have a low transfer constant.[27]
150
Furthermore, Figure 5.7c and Figure 5.7d both show overlapping grating size of 30 and
40 m, which suggests that there must be an optimum grating size between these two values
and higher than the 20 or 30 m for RAFT agents with an aromatic Z-group as activating
group. It is believed that the optimum grating size correlates with diffusion properties, which
is dependent on the transfer constant of the activating group of the RAFT agent.
Strictly speaking, the addition of RAFT agents used in Figures 5.7c and 5.7d decrease the
aspect ratios, while without them aspect ratios above 0.1 were revealed. This implies that
under these circumstances the RAFT agent acts as an radical scavenger and retards the
polymerisation, which reduces the aspect ratio of the final features.
Since RAFT agent CBDB gave the largest aspect ratios, this compound was further
investigated upon different atmospheric conditions and will be described in the next section.
5.3.3.2 Influence of oxygen on the RAFT agent in photo-embossed structures

The effect of oxygen to the system was then investigated by processing in either an
ambient or an inert atmosphere. Figure 5.8 shows the aspect ratio of the photo-embossed
structures as a function of the exposure dose, for both experiments under normal atmosphere
(a) and nitrogen atmosphere (b). For simplicity only the results of the 20 m grating size are
shown, though the trend for the other grating sizes is similar.
Both figures show that the aspect ratio improves with increased amounts of RAFT agent
CBDB, independent of the atmosphere. In order to reach the maximum aspect ratio for an
increased amount of RAFT agent, however, the dose has to be increased as well. If a higher
dose is applied to the system, more radicals are created which decreases the RAFT to initiator
ratio. As a consequence, this leads to a less controlled polymerisation and thus lower aspect
ratios. Therefore, larger amounts of RAFT agent should be added in order to be able to
control the polymerisation and to develop larger aspect ratios. Each curve reveals a maximum
aspect ratio, depending on the dose and the RAFT agent to initiator ratio, after which the
enhanced effect diminishes again. Furthermore, Figure 5.8a indicates that inhibition with
oxygen does not take place when using RAFT agents, which is in agreement to what has been
reported recently by Zhang et al.[28] If an ambient atmosphere is used, the maximum aspect
ratio for each RAFT to initiator ratio is lower than for inert atmospheres. Moreover, higher
doses are required for these maxima, which may be explained by the presence of atmospheric
oxygen in the system, which could have a negative effect on the polymerisation due partial
inhibition.
151
Chapter 5
0.5
Aspect Ratio (-)
0.5
Aspect Ratio (-)

RAFT:INI = 4 RAFT:INI = 4
RAFT:INI = 2 (a) RAFT:INI = 2 (b)
0.4 RAFT:INI = 1 0.4 RAFT:INI = 1
RAFT:INI = 0.5 RAFT:INI = 0.5
RAFT:INI = 0.2 RAFT:INI = 0.2
RAFT:INI = 0 RAFT:INI = 0
0.3 0.3
0.2 0.2
0.1 0.1
0.0 0.0
1 2 3 4
10
1
10
2
10
3
10
4
10 10 10 10
-2 -2
Exposure Dose (mJ cm ) Exposure Dose (mJ cm )
Figure 5.8 Aspect ratio as function of exposure dose for different reversible addition-fragmentation chain
transfer (RAFT) agent to initiator ratios under ambient (a) and inert (b) atmosphere. For better visualization only
the data for the 20 m grating size is shown. Lines are drawn to guide the eye.
To further elucidate the mechanistic details of the polymerisation, the kinetics of the
polymerisation upon UV exposure were investigated by means of ATR-IR spectroscopy. With
this technique, the acrylate monomer conversion is measured in real time. The double bond
conversion was investigated at 1635 cm-1, which corresponds to the C=C stretch vibration
peak of the multifunctional acrylate. Figure 5.9 represents the conversions derived from the
IR spectra for the addition of TBHQ (a) and a RAFT agent (b). Under inert atmospheric
conditions and when TBHQ or a RAFT agent has been added to the system, the curves look
almost identical. However, when looking at the bottom curve in Figure 5.9a, with addition of
TBHQ under ambient atmosphere, the polymerisation is almost halted and no structures are
formed the aspect ratios are smaller than 0.01. In contrast to this, atmospheric oxygen does
not have a negative influence on the formation of the structures when a RAFT agent was
added, since the bottom curve in Figure 5.9b shows a significant conversion in time; however,
there is a significant decrease of the acrylate end conversion and polymerisation rate.[33] The
absence of an induction period for all curves indicates that no inhibition takes place upon
addition of a RAFT agent, also not for TBHQ under an inert atmosphere. However, when
TBHQ is added under ambient conditions inhibition of the polymerisation does take place,
since no structures are formed, whereas it is possible to create surface relief structures under
an ambient atmosphere when a RAFT agent is added. Apparently, the increase of the aspect
ratios with a RAFT agent cannot be explained only with polymerisation kinetics.
152
1.0 1.0

TBHQ:INI = 0:1 (N2) RAFT:INI = 0:1 (N2)
TBHQ:INI = 1:1 (N2) (a) RAFT:INI = 1:1 (N2) (b)
0.8 TBHQ:INI = 0:1 (Air) 0.8 RAFT:INI = 0:1 (Air)
TBHQ:INI = 1:1 (Air) RAFT:INI = 1:1 (Air)
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
0 1 2 3 4 5 0 2 4 6 8 10 12 14 16
Time (min) Time (min)
Figure 5.9 Acrylate conversion measured by real time ATR-IR spectroscopy upon continuous exposure for
varied concentrations and different atmospheric conditions of TBHQ (a) and a reversible addition chain transfer
(RAFT) agent (b).
The increase in aspect ratio using RAFT agents is, however, expected to be due to the
formation of stable radicals that act, after heating, as latent initiators, similar to TBHQ. The
increased initiator concentration is not harmed by the presence of oxygen, since the oxygen
present in the system does not decrease the concentration of RAFT agent. The dormant
species B in Figure 5.6, that undergoes fragmentation in order to react with monomers, has its
intermediate radical positioned at the carbon-atom between the two sulfur-atoms.[34]
Therefore, the RAFT agent remains between the two ends of the propagating polymer chains,
which makes the dormant species rather immobile. The consumption of monomer in the
illuminated areas is enhanced due the presence of RAFT agent; the structure height increases
in the illuminated areas, which increases the features aspect ratios.
In summary, the aspect ratios were improved both in inert and ambient atmospheres with
the addition of a reversible addition-fragmentation chain transfer (RAFT) agent. The
improvement in ambient atmosphere is almost a factor of two, whereas under inert
atmosphere structures with an aspect of 0.46 have been created, which represents an
improvement of almost 10 times. The aspect ratio could be improved due to the controlled
acrylate polymerisation upon addition of a RAFT agent. The fact that the photo-embossing
system is independent of the atmosphere is of particular interest in applications where the
presence of atmospheric oxygen is unavoidable, such as large area applications. Other
applications might be found in biomedical or optical applications where higher aspect ratios
are necessary.[35-37]
153
Chapter 5
5.4 Conclusions
The aspect ratios of photo-embossed microstructures have been improved by the addition
of compounds that interfere with the reaction kinetics. Firstly, adding t-butyl hydroquinone
(TBHQ) resulted in improved relief heights of 0.35, which represents an increase of a factor
of 7. It is believed that TBHQ behaves as a retarder in the photopolymer system, when
environmental oxygen is absent, and reduces the rate of polymerisation by converting acrylate
radicals into stable phenol radicals.
Secondly, by the addition of a reversible addition-fragmentation chain transfer (RAFT)
agent the aspect ratio could be improved as well. However, the increase is independent of
atmospheric conditions since oxygen inhibition hardly occurs, which is a major advantage for
industrial applications of photo-embossing. The aspect ratio could be enhanced due to the
controlled acrylate polymerisation upon addition of a RAFT agent and increased by a factor
of almost 10, to a value of 0.46. The insensitivity to oxygen inhibition is related to the ability
of the RAFT agents to form stable radicals.
The improved photo-embossed structures offer a simple and versatile alternative for the
production of large-scale/large-area relief structures in thin polymer films and finds
applications in microelectronic elements, biosensors and cell growth arrays.
5.5 References
1 J. R. Lawrence, F. T. ONeill, J. T. Sheridan, Optik 2001, 112, 449.

2 C. de Witz, D. J. Broer, Polym. Preprints 2003, 44, 236.
3 O. V. Sakhno, T. N. Smirnova, Optik 2002, 113, 130.
4 C. Witz, C. Snchez, C. W. M. Bastiaansen, D. J. Broer, Handbook of Polymer Reaction
Engineering, Vol. 2 (Eds. T. Meyer, J. Keurentjes), Wiley-VCH, Weinheim, 2005, Ch.19.
5 C. M. Leewis, A. M. De Jong, L. J. van IJzendoorn, D. J. Broer, J. Appl. Phys. 2004, 95, 4125.
6 C. Kim, P. E. Burrows, S. R. Forrest, Science 2000, 288, 831.
7 K. Y. Suh, J. Seong, A. Khademhosseini, P. E. Laibinis, R. Langer, Biomaterials 2004, 25,
557.
8 P. Ghosh, M. L. Amirpour, W. M. Lackowski, M. V. Pishko, R. M. Crooks, Angew. Chem.
Int. Ed. 1999, 38, 1592.
9 H. J. Levinson, Principles of Lithography, SPIE, Bellingham, 2001.
10 M. Heckele, W. K. Schomburg, J. Micromech. Microeng. 2004, 14, R1.
11 H. Becker, U. Heim, Sens. Actuators A 2000, 83, 130.
12 S. Y. Chou, P. R. Krauss, P. J. Renstrom, Appl. Phys. Lett. 1995, 67, 3114.
154
13 L. S. Roman, O. Ingans, T. Granlund, T. Nyberg, M. Svensson, M. R. Andersson, J. C.

Hummelen, Adv. Mater. 2000, 12, 189.
14 T. J. White, L. V. Natarajan, V. P. Tondiglia, T. J. Bunning, C. A. Guymon, Macromolecules
2007, 40, 1112.
15 A. L. Logothetis, J. M. McKenna, J. Polym. Sci., Part A; Polym. Chem. 1977, 15, 1431.
16 P. Ghosh, P. S. Mitra, J. Polym. Sci., Part A; Polym. Chem. 1976, 14, 981.
17 D. Benda, J. uprek, V. ermk, Eur. Polym. J. 2001, 37, 1247.
Chem. 2007, 17, 677.
19 J. E. Dietz, B. J. Elliott. N. K. Peppas, Macromolecules 1995, 28, 5163.
20 E. Selli, C. Oliva, Macromol. Chem. Phys. 1995, 196, 4129.
21 J. Zhu, W.J. Johnson, C.L. Sevilla, J.W. Herrington, M.D. Sevilla, J. Phys. Chem. 1990, 94,
7185.
22 J. Chiefari, Y. K. Chong, F. Ercole, J. Krstina, J. Jeffery, T. P. T Le, R. T. A. Mayadunne, G.
F. Meijs, C. L. Moad, G. Moad, E. Rizzardo, S. H. Thang, Macromolecules 1998, 31, 5559.
23 H. Shinoda, K. Matyjaszewski, Macromolecules 2001, 34, 6243.
24 R. T. A. Mayadunne, J. Jeffery, G. Moad, E. Rizzardo, Macromolecules 2003, 36, 1505.
25 C. Tang, T. Kowelewski, K. Matyjaszewski, Macromolecules 2003, 36, 1465.
26 Y. K. Chong, T. P. T. Le, G. Moad, E. Rizzardo, S. H. Thang, Macromolecules 1999, 32,
2071.
27 G. Moad, J. Chiefari, Y. K. Chong, J. Krstina, R. T. A. Mayadunne, A. Postma, E. Rizzardo,
S. H. Thang, Polym. Int. 2000, 49, 993.
28 Z. Zhang, X. Zhu, J. Zhu, Z. Cheng, S. Zhu, J. Polym. Sci., Part A; Polym. Chem. 2006, 44,
3343.
29 G. Bouhadir, N. Legrand, B. Quiclet-Sire, S. Z. Zard, Tetrahedron Lett. 1999, 40, 277.
30 C. Snchez, B.-J. de Gans, D. Kozodaev, A. Alexeev, M. J. Escuti, C. van Heesch, T. Bel, U.
S. Schubert, C. W. M. Bastiaansen, D. J. Broer, Adv. Mater. 2005, 17, 2567.
31 N. Adams, B. de Gans, D. Kozodaev, C. Snchez, C. W. M. Bastiaansen, D. J. Broer, U. S.
Schubert, J. Comb. Chem. 2006, 8, 184.
32 B.-J. de Gans, C. Snchez, D. Kozodaev, D. Wouters, A. Alexeev, M. J. Escuti, C. W. M.
Bastiaansen, D. J. Broer, U. S. Schubert, J. Comb. Chem. 2006, 8, 228.
33 J. Gao, Y. Luo, R. Wang, B. Li, S. Zhu, J. Polym. Sci., Part A; Polym. Chem. 2007, 45, 3098.
34 D. G. Hawthorne, G. Moad, E. Rizzardo, S. H. Thang, Macromolecules 1999, 32, 5457.
35 S. H. G. Teo, A. Q. Liu, J. Singh, M. B. Yu, J. Vac. Sci. Technol. B 2004, 22, 2640.
36 M. Schirmer, D. Perseke, E. Zena, D. Schondelmaier, I. Rudolph, B. Loechel, Microsyst.
Technol. 2007, 13, 335.
37 B. Sell, A. Snger, G. Schulze-Icking, K. Pomplun, W. Krautschneider, Thin Solid Films
2003, 443, 97.
155
BMW R1100 GS (1994)
6
Inkjet printing of conductive features onto
embossed structures
Abstract
This chapter describes the inkjet printing of a silver nanoparticle ink onto a predefined
topography pattern in a thermoplastic surface. These topographical structures have been embossed
into the polymer surface by means of either photo-embossing or hot-embossing. With the first method
the micro-channels were formed by photo-embossing, as described in Chapter 5, while with the second
method the topographic features were formed by pushing a master into a thermoplastic substrate,
which was held above its glass transition temperature.
Subsequently, droplets of a silver nanoparticle ink were dispensed over the as-formed micro-
channels. As a consequence of capillary forces the micro-channels were filled with the ink and tracks
with an improved resolution were formed. The tracks had widths ranging from 5 to 25 m. Despite a
significant improvement of the aspect ratio of the photo-embossed features the structures were not
sufficiently high and overfilling of the channels occurred. Therefore, most of the experiments were
performed using hot-embossing, where masters with a higher aspect ratio were used.
Several of the as-prepared features were sintered thermally, which resulted in conductive silver
tracks with a conductivity of approximately 20% of the bulk silver value. These relatively high values
obtained may be ascribed to an increased level of silver particle packing, which may be a
consequence of forming the tracks using capillary filling.
Parts of this chapter have been published: C. E. Hendriks, P. J. Smith, J. Perelaer, A. M. J. van den Berg, U. S.
Schubert, Adv. Funct. Mater. 2008, 18, 1031.
Chapter 6
6.1 Introduction
Considerable research into the production of conductive tracks formed either from
copper,[1] gold,[2] or silver[3-8] and using inkjet printing as the method of deposition has been
undertaken frequently. Although conductivity values of 50% of bulk silver and higher have
been obtained,[9,10] the production of conductive tracks has not yet moved away from being a
matter purely of academic interest. This is mostly because one of the limitations of inkjet
printing is its resolution.[11]
As a general rule, a feature obtained by inkjet printing tends to have a width that is greater
than the diameter of the nozzle, as has been described in Chapters 2 and 3. Although an
obvious way of achieving narrower features is to reduce the diameter of the printheads
nozzle, this places rheological constraints on the inks that can be printed.[12] Furthermore,
reducing nozzle size does not take into account the surface energy of a substrate, which has a
significant influence on the final as-printed feature.[11,13]
An effective approach is to create patterns composed of different surface energies on the
substrate, which direct the printed ink into regions of preferential wetting. This approach is
often called pre-patterning. Sirringhaus et al. obtained line widths of 5 micrometers using a
water-based polymer and pre-patterning.[14] Features that are narrower than 5 micrometer
have been obtained using the same approach, and the behaviour of an ink on such a pre-
patterned substrate has been studied.[15]
A drawback in using surface energy pre-patterns with inkjet printing is that those patterns
are not visible afterwards and it removes inkjet printings advantage of being able to fabricate
patterns without the need for masks, since some form of lithography is required to produce
surface energy patterns. Moreover, the need to pre-pattern the substrate increases the overall
processing time and places a restraint on scaling-up to roll-to-roll (R2R) production.
An acceptable answer to this problem may be presented by the use of photo-embossing (as
discussed in Chapter 5) or hot-embossing.[16-18] The principle of hot-embossing involves a
master being pressed for a few minutes into a thermoplastic polymer that has been heated
above its glass transition temperature (Tg). Hot-embossing can produce very fine sized
structures; for example, features with diameters of 25 nm have been fabricated.[16] Hot-
embossed features also offer the advantage that the features can be visibly located after
patterning and that the master can be reused to prepare samples,[19] which helps to minimise
processing times, allows for automated mass-production and therefore enables costs to be
reduced. The procedure for hot-embossing is schematically depicted in Figure 6.1. The
158
Inkjet printing of conductive features onto embossed structures
procedure in Figure 6.1a-b differs from photo-embossing, but the principle of capillary filling
in Figure 6.1c-d is the same.
(a) (b) (c) (d)
Figure 6.1 Schematic representation of the steps to produce capillary filled silver tracks by hot-embossing a
relief structure prior to inkjet printing: a polymer is heated above its Tg and in a controlled manner the master is
pushed into the polymer (a), followed by removing the master from the embossed polymer (b). An inkjet printed
droplet is accurately placed on the formed channel (c), which is filled through capillary forces (d). A colour
version is available on page 177.
Once recessed topography structures have been formed by photo- or hot-embossing, they
can be filled with liquids or inks using capillary forces. When the contact angle is sufficiently
small, the liquid fills as a result of the capillary force of the topography structures compared
to planar surfaces;[20] this is similar to the micro-moulding in capillaries (MIMIC) technique,
developed by Whitesides et al.[21,22] However, structures formed by MIMIC resemble tunnels
that are open at both ends, whereas hot-embossed structures resemble open channels.[23,24]
With the MIMIC technique, structures are filled by placing a drop of liquid at the end of a
channel. This liquid fills, or imbibes, the capillary in order to minimise the interfacial free
energies of the solid/air and solid/liquid interfaces.[22] The imbibition rate greatly decreases
when the liquid does not wet the capillary walls, and is proportional to (/)1/2, where is the
surface tension and is dynamic viscosity.[25] For hot-embossed structures, imbibition occurs
by the progressive filling of corners.[26] For example, in a square channel the imbibition front
moves forward following the lower two corners of the square, as shown schematically in
Figure 6.2 for substrates with a varied interfacial free energy (SV). After a certain distance has
been travelled, these corner regions are connected by a thin film of the wetting liquid on the
flat regions;[21] the bulk of the wetting liquid then follows.[20-22,25]
159
Chapter 6
(c)
(a) (d)
(b)
Low Med High

Figure 6.2 Schematic summary of different spreading regimes observed in micro-moulding in capillaries
(MIMIC). Shapes of the imbibing liquids in capillaries are formed on substrate with a low (a), medium (b,c) and
high (d) interfacial free energy (SV), respectively. Reprinted from ref. [21].
In this chapter, inkjet printing onto surfaces with a predefined topography will be
described. The structures are fabricated either by photo-embossing or by hot-embossing.
Subsequently, droplets of a silver ink are dispensed on top of these fabricated structures,
which are filled by the ink. The inkjet printer which was used for this study allowed the
precise placement of droplets by mechanically positioning the substrate directly underneath
the printhead with a printing accuracy of 1 m.
After the ink was deposited, the tracks that formed were typically 25 m or less in width.
The tracks can be described as being invisible on account of their very narrow width.
Although, an exact value for the minimal visible width is difficult to obtain, a person with
uncorrected vision is unable to differentiate between two narrow features when they are about
15 m apart at a set focal distance.[27]
Conductive tracks were obtained by thermally sintering the silver nanoparticles.
6.2 Experimental
Fabrication of photo-embossed structures
The surface relief structures were prepared similar to what was described in Chapter 5.
However, a different line mask was used: the first line mask consists of parallel lines, which
had a width of 25 m and the interline spacing was 50 m: thus having a pitch of 75 m. A
second line mask had the same line width of 25 m, but an interline spacing of 100 m,
which corresponds to a pitch of 125 m. The resulting relief heights were approximately 1.5
to 2 m.
160
Fabrication of hot-embossed structures

Hot-embossed structures were produced by the controlled pushing of customised and standard
silicon calibration gratings (Mikromasch, Madrid, Spain), referred to as masters, into a
polymer substrate that was heated at least 60 C above its Tg for 3 minutes using a small press
(Tribotrak, DACA instruments, Santa Barbara, USA). The produced hot-embossed structures
were not treated in any other way and were ready for use. The polymer substrates were either
polystyrene (N5000, Shell, The Netherlands; Tg = 100 C), which was heated to 180 C or
polycarbonate (Bayfol, Bayer, Germany; Tg = 205 C), which was heated to 270 C. The
Tribotrak hot press consists of a lower stage and an upper counter-balanced stage that can be
adjusted to accommodate substrates of different thicknesses; both stages are heatable. The
pressure can be controlled by varying the mass applied to the upper stage.
Inkjet printing
Technologies GmbH (Norderstedt, Germany) equipped with either a 70 m or 100 m nozzle
diameter MD-K-140 dispenser. The Autodrop system has a positioning accuracy of 1 m and
a fiducial video camera, which allowed the head to be confidently positioned.
The ink used was a commercially available dispersion that contains 57.4 wt% of silver
nanoparticles in tetradecane (Nanopaste NPS-J, Harima Chemicals, Japan). This dispersion
was typically printed at 115 V and 64 s pulse width when using a 70 m nozzle, while 87 V
and 40 s were used for a 100 m nozzle. All printing was done with a frequency of 200 Hz
and under ambient conditions.
Characterisation and sintering

The contact angles that the silver ink made with the polymer substrate were determined using
a contact angle measuring system (OCA 30, Dataphysics, Filderstadt, Germany). The formed
tracks were imaged and evaluated using optical light microscopy (Axioplan imaging 2, Zeiss,
Jena, Germany) and scanning electron microscopy (FEG E-SEM XL30, Philips, Eindhoven,
The Netherlands).
Sintering was performed by placing the substrates into an oven, set at 200 C, for 90 minutes.
161
Chapter 6
6.3 Results and discussions
6.3.1 Inkjet printing onto photo-embossed structures

The photo-embossed structures, fabricated as described in the previous chapter, can be
seen as micro-channels in a polymer surface. A sequence of droplets of a 6 wt% Harima ink
(the original ink was ten times diluted with tetradecane) was dispensed with a 100 m nozzle
over the photo-embossed structures perpendicular to the direction of the channels.
In Figure 6.3 typical printing results are displayed, indicating that the directing of the ink
into the channels has taken place successfully. The line width is approximately 25 m. The
location of the original placement of the droplet can be seen in Figure 6.3a; the droplet on the
surface has a contact diameter of approximately 250 m; this can be ascribed to the small
contact angle of 5 that the ink forms with the substrate. The micro-channels direct the silver
ink droplet from the top surface into the channels and, subsequently, the ink fills the channel
over a distance of almost 1 mm to each side of the originally printed droplet. Since the pitch is
smaller than the contact diameter of the droplet, it is difficult to address a single channel.
Although single channels could not be addressed when using a line mask with a pitch that
is larger than the in-flight droplet diameter (125 m instead of 75 m), the uniformity of the
ends of the tracks seemed to improve significantly, as shown in Figure 6.3b, but this result
was not reproducible.
One issue that was considered was whether the surface energy of the uppermost region, of
the entire feature, could be tailored so that the ink only wets the walls and floor of the channel
and not the interline exposed surface. In terms of discrete, conductive features this would
greatly reduce the chances of shorts occurring. A simpler solution could be to use a master
with an interline spacing greater than the diameter of the ink droplets, but a method of making
the uppermost surface dewetting may be preferred.
162
(a) (b)
Figure 6.3 Optical microscopy images inkjet printed droplets of diluted Harima silver ink onto photo-embossed
relief structure, which was prepared using a 25/50 (a) and 25/100 (b) line mask. The first number indicates the
line width and the second number gives the interline spacing.
The relatively low aspect ratio of the photo-embossed structures, i.e. the low volume of
the channels, is not sufficient to fill the channels without bulges appearing at the top, which
limits the amount of ink that can be directed into the channels. Moreover, a structure with
corners is preferred for capillary forces.[25]
In contrast to photo-embossing, hot-embossing looks like a more promising technique to
create micro-channels, since channel volume can be tailored easily by altering the aspect ratio
of the master and, moreover, squared structures can be created in stead of round structures,
which are favourable for capillary filling (see Figure 6.2).
Finally, the high sintering temperature that is necessary for sintering the silver
nanoparticles is not compatible here with the used substrate: the PMMA photo-embossed
relief structures have a Tg of approximately 112 C. Therefore, another substrate or ink needs
to be chosen in order to form conductive silver tracks with track width smaller than 25 m.
6.3.2 Inkjet printing onto hot-embossed structures
6.3.2.1 Hot-embossing masters

The two masters that were used to produce the hot-embossed channels are shown in
Figure 6.4. The first master (Figure 6.4a) had a pitch of 42 m and was made up of truncated
triangles, which were 20 m high. The second master (Figure 6.4b) had a 10 m pitch and
was composed of rectangular structures whose height and width was 1.6 m and 5 m,
respectively.
163
Chapter 6
(a) 20 m
(b) 5 m
Figure 6.4 Scanning electron microscopy (SEM) images of the used silicon masters for hot-embossing: 42 m
pitch sloped line master with a structure height of 20 m (a) and 10 m pitch squared line master with a structure
height of 1.6 m (b).
The silver nanoparticle ink was observed to wet both polystyrene and polycarbonate very
well. The contact angle was measured to be 6 on polystyrene and less than 5 for
polycarbonate. The low values of contact angle that the ink formed for both of these
substrates suggest that it is very suitable for forming tracks by the capillary filling method.[20]
The diameter of the as-deposited ink droplet was measured to be 120 m on the non-
structured polymer surface.
6.3.2.2 Conductive silver tracks in hot-embossed channels

The initial experiments involved the inkjet printing of a single ink droplet with a 70 m
nozzle diameter over channels that have been formed by hot-embossing polystyrene with the
42 m pitch master. The ink filled a single channel for a distance of more then 4 mm, as a
consequence of capillary forces. An optical micrograph of the resultant track can be seen in
Figure 6.5.
200 m
Figure 6.5 Optical microscopy image of a single silver nanoparticle track on a hot-embossed polystyrene
structure prepared from a 42 m pitch line master. The original inkjet printed dot is located in the drawn circle.
The top images show the line widths that are measured at the locations marked by the small arrows.
164
One of the most notable features of this track is that it shows little variation in its width
over its total length, as can be seen in the inset images of Figure 6.5. This uniformity of width
is attributed to the capillary filling method, in which ink fills the corner regions first and the
bulk of the liquid follows afterwards.[21] These tracks were also examined using SEM since
there is a decrease in resolution as higher magnifications are used with optical microscopy;
Figure 6.6 shows a typical section of the track. It can be seen from Figure 6.6a that the as-
formed track is straight and little deviation in its width can be seen. The total width of the
feature is about 13 m, with the central track having a width of approximately 6 m; on either
side of this track there are two clear boundary regions. A more detailed investigation was
made as can be seen in Figure 6.6b and c.
(a) 5 m
(b) 5 m
(c) 1 m
Figure 6.6 Scanning electron microscopy (SEM) images of a single nanoparticle track on a hot-embossed
polystyrene structure prepared from a 42 m pitch line master. The images show, respectively, the top view (a)
and side views (b,c).
Figure 6.6b shows a cross section of the dried ink track that formed at the bottom of the
hot-embossed groove; the arrow indicates the highest point that the ink reached, which is
approximately 5 m. It should be noted that the meniscus that the ink formed in the groove is
not known. The thin deposit that is coated on both sides corresponds to the two boundary
regions, which can be seen at either side of the track in Figure 6.6a. It is thought that this
residue does not contribute significantly to the tracks conductivity. A close-up of the tracks
165
Chapter 6
cross-section (Figure 6.6c) confirms that the boundary region material, which was deposited
when the groove was filled with ink, is not very thick. As the ink evaporated the majority of
the dried solids were deposited at the bottom of the groove.
The volume of the formed track was found to be in good agreement with the solids
content of the silver nanoparticle ink, which was calculated from the original weight
percentage given by the supplier and found to be 23 vol%. The volume of the as-formed
central track over a distance of 4.2 mm was calculated and found to be approximately 25 pL.
The original inkjet printed droplet was measured to be 113 pL, which results in a solid content
of 22 vol% ([25/113] 100). The thin covering that was deposited on the walls as the ink
filled the channel and the residue of the original droplet that remained on the uppermost
surface (Figure 6.5, circled region) were neglected. If these values could be included in the
calculation, the value of 22 vol% would be slightly higher. Since the highest point the ink
reached is uniform over the total track and the calculations are in good agreement with the
contents of the ink, it indicates that most of the solvent is still present when the ink finishes
filling the channel. It should be remarked upon that the density of packing of the dried
material is not known, which could also affect the calculated value.
The data that were obtained from the polycarbonate substrates are comparable to the
polystyrene data. This similarity was expected since the contact angle for both substrates is
comparable and the micro-channels are filled by capillary forces.[20] Figure 6.7 shows a
section and an end of the track that was formed in the polycarbonate hot-embossed structure.
The overall width is 13.5 m and the width of the central region is 5.9 m, which compares
favourably to the track that formed in the embossed polystyrene. Both at the end and in the
section, a number of agglomerates can be seen that are most likely formed as the carrier
solvent evaporated.
(a) 5 m
(b) 5 m
Figure 6.7 Scanning electron microscopy (SEM) images of a single silver nanoparticle track on a hot-embossed
polycarbonate structure (a) and the end of the track (b), prepared from a 42 m pitch line master.
166
It was observed that only a small amount of the 20 m high channel was filled when using
a single, dispensed droplet. Therefore, it was thought that a greater amount of filling could be
achieved simply by dispensing multiple droplets. Furthermore, it was expected that this would
lead to an increase in the height of the central region and in the width of the overall feature
since the embossed channels had a finite length of 1 cm. This additional filling was performed
printing droplets parallel to the channels and subsequently by decreasing the dot spacing,
whose effect can be seen in Figure 6.8. For comparison, the smallest values of line width that
were obtained are shown in the insets of Figure 6.5, where only a single droplet was
dispensed. It can be seen that as dot spacing decreases the tracks width increases, as was
expected.
The main reason for increasing the amount of ink added to the channel was to investigate
the possible influence this might have on the electrical conductivity of the tracks. Therefore,
these tracks were thermally converted to silver and measured for resistance. The results are
discussed in the next section.
(a) (b)
(c) (d)
Figure 6.8 Optical microscopy images of silver nanoparticle track widths on a hot-embossed polycarbonate
structure prepared from a 42 m pitch line master formed with different dot spacings of 1 mm (a), 0.5 mm (b),
0.3 mm (c) and 0.2 mm (d), respectively.
6.3.2.3 Conductivity measurements

Conductivity measurements were performed on the thermally sintered tracks. The results
are shown in Table 6.1; it can be seen that the resistance per mm decreases as more ink has
been used to fill the channels, i.e. the closer together the deposited droplets the wider (and
higher) the track and the lower the resistance.
167
Chapter 6
Table 6.1 Influence of dot spacing on electrical properties.

Dot spacing Track width Resistance Resistivity
-1
(mm) (m) ( mm ) ( m)
-8
1 9.8 8.3 9.1 10
-8
0.5 10.5 6.3 8.6 10
-8
0.3 12.8 3.3 8.0 10
-8
0.2 17.2 1.7 8.5 10
The resistivity of the tracks was calculated using the equation:
= R A/ l (6.1)
with the lines resistance R, its length l , and its cross sectional area A.[4]
The value of resistivity is similar for the four samples, as might be expected since the
same ink was used. Moreover, the value of resistivity for these tracks is about 5 to 6 times the
bulk silver value, which corresponds to 20 to 17% of the conductivity (1/) of bulk silver,
respectively. The value is quite favourable when compared to the value that was obtained in
Chapter 4; where the same ink and sintering method was used and a conductivity of only 5%
of bulk silver was found.
The higher values obtained from this method are ascribed to an increased level of silver
particle packing, which may be a consequence of forming the tracks using capillary forces.
Magdassi et al. found that tightly packed, unsintered silver nanoparticles exhibited
conductivities that were 15% of bulk silver.[28]
6.3.2.4 Line structures with improved resolution in polycarbonate

Tracks with a higher resolution were formed using a 10 m pitch squared line master
(Figure 6.4b). It was not possible to only address a single track since the 10 m pitch is much
smaller then the ink droplet; although, a simple solution could be using a customised master
that consists of more widely spaced lines. Figure 6.9 shows the result of dispensing one ink
droplet over the 10 m pitch polycarbonate channels; the position of the initial droplets
landing can be observed to the left of the channels. The droplet subsequently spreads through
six tracks over a distance of approximately 2 mm.
168
100 m
Figure 6.9 Optical microscopy image of multiple silver nanoparticle tracks on a hot-embossed polystyrene
structure prepared from a 10 m pitch line master. The original inkjet printed dot is located in the drawn oval.
A more detailed look is shown in Figure 6.10. Initially, the tracks appear to have a similar
appearance to those which formed in the 42 m pitch channels (Figure 6.7); in that they have
a central region between two boundary regions. However, the length of the tracks in the hot-
embossed polycarbonate structures are shorter than those in polystyrene structures. It is
suggested that the strength of capillary forces tends to decrease with an increasing slope angle
of the channels,[26,29] therefore the obtuse angle between the channels wall and floor may
have contributed to the reduced length.
(a) 5 m
(b) 5 m
Figure 6.10 Scanning electron microscopy (SEM) images of multiple silver nanoparticle tracks on a hot-
embossed polystyrene structure (top) and the end of the track (bottom), prepared from a 10 m pitch squared line
master.
169
Chapter 6
In summary, conductive silver tracks were produced that were narrower than 30 m. This
was achieved by making hot-embossed features, which were prepared by the controlled
pushing of a master into polystyrene or polycarbonate substrate that was held at temperatures
above their Tg. Droplets of a silver nanoparticle ink were dispensed over the as-formed
channels using an inkjet printer. The ink filled the channel as a consequence of capillary
forces and was observed to form tracks with a uniform width. A range of tracks were
produced by alteration of the dot spacing. Tracks with different morphologies were obtained
by using different masters.
The tracks were then thermally sintered to produce conductive silver tracks. The
resistance per unit length of the tracks was found to decrease for the tracks that were filled to
a higher degree. Furthermore, the resistivities of the tracks were found to be 5 to 6 times the
bulk silver value. These relatively good values are ascribed to an increased level of silver
particle packing, which may be a consequence of forming the tracks using capillary filling.
6.4 Conclusions
A new method for improving the resolution of inkjet printed tracks has been described by
printing on top of predefined topography structures in a thermoplastic surface. These
topographical structures have been embossed into the polymer surface by means of either
photo-embossing or hot-embossing.
The first method uses the micro-channels as they were formed by photo-embossing, while
the second method uses a technique to prepare topographic features in a polymer substrate by
pushing a master into a thermoplastic substrate, which was held above its glass transition
temperature.
After pre-patterning the substrate an inkjet printer was used to dispense droplets of a silver
nanoparticle ink over the as-formed patterns. Subsequently, the pattern directs the ink in a
selective manner into the as-formed channels as a consequence of capillary forces, which
results in minute tracks with an improved resolution. The tracks had widths ranging from 5 to
25 m.
Several of the as-prepared features were sintered thermally, which resulted in conductive
silver tracks with a conductivity of approximately 20% of the bulk silver value. These
relatively high values may be due to an increased level of packing of the silver particles,
which may be a consequence of using capillary filling to form the tracks.
170
6.5 References
1 T. Cuk, S. M. Troian, C. M. Hong, S. Wagner, Appl. Phys. Lett. 2000, 77, 2063.
2 S. Molesa, D. R. Redinger, D. C. Huang, V. Subramanian, Mat. Res. Soc. Symp. Proc. 2003,
H8.3.1, 769.
3 A. L. Dearden, P. J. Smith, D.-Y. Shin, N. Reis, B. Derby, P. OBrien, Macromol. Rapid
Commun. 2005, 26, 315.
4 S. B. Fuller, E. J. Wilhelm, J. M. Jacobson, J. Microelectromech. Syst. 2002, 11, 54.
5 J. B. Szczech, C. M. Megaridis, D. R. Gamota, J. Zhang, IEEE T. Electron. Pack. 2002, 25,
26.
7 D. Kim, J. Moon, Electrochem. Solid State Lett. 2005, 8, J30.
8 K. J. Lee, B. H. Jun, T. H. Kim, J. Joung, Nanotechnology 2006, 17, 2424.
9 J. Perelaer, A. W. M. de Laat, C. E. Hendriks, U. S. Schubert, J. Mater. Chem. 2008, 18, 3209.
12 H. P. Le, J. Imaging Sci. Technol. 1998, 42, 49.
13 P. C. Duineveld, J. Fluid Mech. 2003, 477, 175.
Science 2000, 290, 2123.
15 J. Z. Wang, Z. H. Zheng, H. W. Li, W. T. S. Huck, H. Sirringhaus, Nature Mater. 2004, 3,
171.
16 S. Y. Chou, P. R. Krauss, P. J. Renstrom, Appl. Phys. Lett. 1995, 67, 3114.
17 L. S. Roman, O. Ingans, T. Granlund, T. Nyberg, M. Svensson, M. R. Andersson, J. C.
Hummelen, Adv. Mater. 2000, 12, 189.
18 J. R. Lawrence, P. Andrew, W. L. Barnes, M. Buck, G. A. Turnbull, I. D. W. Samuel, Appl.
Phys. Lett. 2002, 81, 1955.
19 N. Stutzmann, T. A. Tervoort, C. W. M. Bastiaansen, K. Feldman, P. Smith, Adv. Mater.
2000, 12, 557.
20 T. Pfohl, F. Mugele, R. Seeman, S. Herminghaus, ChemPhysChem 2003, 4, 1291.
21 E. Kim, G. M. Whitesides, J. Phys. Chem. B 1997, 101, 855.
22 E. Kim, Y. Xia, G. M. Whitesides, Nature 1995, 376, 581.
23 R. Seemann, M. Brinkmann, E. J. Kramer, F. F. Lange, R. Lipowsky, PNAS 2005, 102, 1848.
24 M. L. Chabinyc, W. S. Wong, K. E. Paul, R. A. Street, Adv. Mater. 2003, 15, 1903.
25 M. Dong, I. Chatzis, J. Colloid Interface Sci. 1995, 172, 278.
26 G. Mason, N. R. Morrow, J. Colloid Interface Sci. 1991, 141, 262.
27 F. W. Campbell, D. W. Green, J. Physiol. 1965, 181, 576.
28 S. Magdassi, M. Grouchko, D. Toker, A. Kamyshny, I. Balberg, O. Millo, Langmuir 2005, 21,
10264.
29 T. T. Huang, D. G. Taylor, K. S. Lim, M. Sedlak, R. Bashir, N. S. Mosier, M. R. Ladisch,
Langmuir 2006, 22, 6429.
171
172
Colour figures
Colour figures
(a) I - Piezo move outwards
(b) II - Negative waves travel outwards
(c) III - Waves reflect and one reverses
(d) IV - Waves arrive at centre

when piezo contracts
(e) V - Wave is magnified and

drop ejected
Figure 1.6 Schematic representation of the acoustic wave propagation through a glass capillary used in
piezoelectric drop-on-demand devices.
Mn = 1.5 kDa Mn = 124 kDa
Mn = 16.8 kDa Mn = 236 kDa
Mn = 60.6 kDa Mn = 545 kDa
Figure 2.7 Three-dimensional images of dried droplets on a substrate from a polystyrene/toluene solution with a
varied polymers Mn value. Shown are from top to bottom and left to right, polystyrene with a Mn value varied
between 1.5 and 545 kDa.
173
Colour figures
(b) (c) (d)
Figure 3.2 Line width and height as function of dot spacing for inkjet printed Cabot silver nanoparticles at room
temperature onto glass substrates (a). Three-dimensional white light interferometry images of the lines inkjet
printed with a dot spacing of 80, 100 and 120 m, respectively (b,c,d).
0.8
Absorbance (-)
(a) 0.7 (b) glass + polyurethane + disperse red

glass + polyurethane
glass
0.6
0.5
0.4
0.3
0.2
0.1
10 mm
0.0
350 400 450 500 550 600 650 700 750 800
Wavelenght (nm)
Figure 3.7 A photograph of the inkjet printed colour gradients by addition of 0.5 wt% Disperse Red to the 40
wt% polyurethane dispersion (a). UV-VIS spectra of inkjet printed 40 wt% polyurethane films with and without
the addition of 0.5% wt Disperse Red onto cleaned glass slides (b).
Droplet height (m)
12
(b) 74 C
60 C
(c)
10 52 C
41 C
33 C
8 25 C
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Droplet width (m)
Figure 3.10 Dried droplet width and height as function of the substrate temperature (a). The influence of
substrate temperature on droplet profile formation of two droplets (b). Three-dimensional images (c) of a single
droplet printed at 33 C (lower) and 60 C (upper). All droplets were printed on cleaned glass slides.
174
Colour figures
(a) (b)
Figure 3.18 Cross-sectional image and 3D image of inkjet printed silver tracks on polyarylate films using a dot
spacing of 5 m (a) and 25 m (b). The substrate was heated to 60 C and five layers were printed on top of each
other.
Figure 4.2 Schematic illustration of a silver nanoparticle with carboxylic acid as capping agent.
(a) (b)
X Y
E field H field
175
Colour figures
(c)
Z
X
Figure 4.12 Electrical (a) and magnetic field (b) distributions in a sectoral circular resonator (normalised values,
vector length and colour proportional to magnitude, solid line represents the boundary of the cavity). Magnitude
of the electrical field in a cross-section at half-height of the contemplated cavity geometry (c) (logarithmic
depiction). Reprinted from ref. [70].
Conductance ( )
0.30
-1
0.25 (a) (b)

0.20
0.15
0.10
0.05
0.00
0 100 200 300 400 500
Time (s)
Figure 4.13 Conductance as function of time for the microwave sintering of silver tracks (a) printed onto a
polyimide substrate (b).
0.8
0 wt% TBHQ
0.7 2 wt% TBHQ
4 wt% TBHQ
0.6 8 wt% TBHQ
0.5
0.4
0.3
0.2
0.1
0.0
0 1 2 3 4 5
Time (min)
Figure 5.2 Acrylate conversion upon continuous UV exposure initiated after 10 seconds for different
amounts of TBHQ added to the photopolymer.
176
Colour figures
0.35 0.35
Aspect Ratio (-)

Aspect Ratio (-)
40 m 40 m
0.30 30 m
S S (a) 0.30 30 m O
S S (b)
20 m 20 m
O
15 m N 15 m
0.25 0.25
10 m 10 m
08 m 08 m
0.20 05 m 0.20 05 m
0.15 0.15
0.10 0.10
0.05 0.05
0.00 0.00
1 2 3 4 1 2 3 4
10 10 10 10 10 10 10 10
-2 -2
0.10 0.10
Aspect Ratio (-)
Aspect Ratio (-)

40 m 40 m
(c)
S
30 m
HOOC
S S
C12H25 30 m
S
(d)
0.08 20 m S 0.08 20 m
15 m 15 m
10 m 10 m
08 m 08 m
0.06 05 m 0.06
05 m
Linear fit Linear fit
2 2
(R = 0.74-0.97) (R = 0.73-0.99)
0.04 0.04
0.02 0.02
0.00 0.00
1 2 3 4 1 2 3 4
10 10 10 10 10 10 10 10
-2 -2
Figure 5.7 Aspect ratio as function of exposure dose for different grating sizes with 2-cyanobut-2-yl
dithiobenzoate (a), 2-(methoxycarbonyl)prop-2-yl dithiobenzoate (b), 2-n-dodecylsulfanyl-thiocarbonylsulfanyl-
2-methylpropionic acid (c), 2-phenylprop-2-yl phenyl dithioacetate (d) as used RAFT agents, under ambient
conditions. The RAFT to initiator ratio was 2. Lines are drawn with a spline fit in (a) and (b) in order to guide
the eye, whereas the dashed lines in (c) and (d) represent linear fits to the data.
(a) (b) (c) (d)
Figure 6.1 Schematic representation of the steps to produce capillary filled silver tracks by hot-embossing a
relief structure prior to inkjet printing: a polymer is heated above its Tg and in a controlled manner the master is
pushed into the polymer (a), followed by removing the master from the embossed polymer (b). An inkjet printed
droplet is accurately placed on the formed channel (c), which is filled through capillary forces (d).
177
Summary
Summary
The goal of the work presented in this thesis is the combined use of inkjet printing and embossing
techniques to fabricate microstructures. The thesis is divided into two sections. The first part (Chapters
1 to 4) describes a bottom-up procedure using inkjet printing to fabricate microstructures onto
polymeric substrates, whereas the second part (Chapters 5 and 6) describes hot-embossing and a new
technique called photo-embossing for the creation of surface relief structures, that are filled using an
inkjet printer to improve resolution.
The introduction offers a literature survey that describes the history and recent achievements in the
inkjet printing field. Inkjet printing has developed from only producing text and graphics into a major
topic in current research and development.
Chapter 2 describes the behaviour of ink droplets both in-flight as well as upon impinging the
substrate, which are discussed in order to understand the basics of successful inkjet printing. For
equally-sized droplets of a dilute polystyrene solution, a linear relationship, which decreased, was
observed between the dried droplet diameter and the printing height. Whereas, increased
concentrations revealed an initial exponential decay in the dried droplet diameter, which stabilized at
greater heights. At higher concentrations and heights, the polymer is believed to form a skin on the
surface of the inkjet printed droplet, which causes inhibition of the in-flight evaporation of the solvent.
The size-selective segregation of monodisperse silica particles in drying droplets was also studied. It
was observed that the particles sediment as close as possible towards the periphery; the actual distance
between the location of segregated particles and the contact line increases with increasing particle size.
The third chapter describes inkjet printing of functional materials. A polyurethane dispersion was
inkjet printed to fabricate three-dimensional structure with single layers having a height of
approximately 10 m. Secondly, an aqueous TiO2 nanoparticle ink was printed that gels above a
certain temperature. Droplets and lines with improved morphological control and resolution were
achieved using this thermal gelation effect. Defect-free straight lines could be printed on hydrophobic
surfaces, which is impossible with regular inks due to the dewetting nature of these substrates. Finally,
the resolution of directly inkjet printed lines of silver nanoparticles on polymer substrates that have a
lower surface energy than common polymer substrates was improved: lines with a resolution down to
40 m were printed.
After depositing silver nanoparticle inks, a thermal sintering step is required in order to render the
particles conductive, which is discussed in Chapter 4. Polymer substrates can usually not withstand
high temperatures and, therefore, require a low temperature during the sintering process. Two new
techniques are discussed that sinter in a selective way so that the polymer substrate is not affected.
These techniques are exposure to microwave radiation and argon plasma. With the former technique,
the sintering time was shortened by a factor of 20 and three minutes were sufficient for sintering.
Furthermore, the presence of conductive antennae further promotes sintering and times of 1 second are
178
Summary
sufficient to obtain pronounced nanoparticle sintering. The second technique uses exposure to argon
plasma; a process that shows a clear evolution starting from a sintered top layer into bulk material.
Chapter 5 describes a new technique called photo-embossing. This method represents a
photolithographic technique for the generation of polymer relief structures that are created by a
deformation of the surface of the film, which is caused by a material flux induced by a local
polymerization. One of the main problems in photo-embossing is the low aspect ratio of the formed
features. Chapter 5 describes the improvement of the aspect ratio by adding compounds that interfere
with the reaction kinetics, such as t-butyl hydroquinone (TBHQ) and reversible addition-fragmentation
chain transfer (RAFT) agents. By adding these compounds the aspect ratios were significantly
improved up to a factor of almost 10.
The last chapter describes the inkjet printing of a silver nanoparticle ink onto a predefined
topography pattern in a thermoplastic surface. These topographical structures have been embossed into
the polymer surface. Subsequently, droplets of a silver nanoparticle ink were dispensed over the as-
formed micro-channels. As a consequence of capillary forces the micro-channels were filled with the
ink and tracks with an improved resolution were formed. The silver tracks had widths ranging from 5
to 25 m.
In general, it can be concluded that inkjet printing represents a highly suitable technique for
systematic and statistical studies, since multiple equally sized droplets can be dispensed into a matrix,
which subsequently can be analysed. Furthermore, inkjet printing is capable of preparing high-
resolution conductive features on or into polymer substrates. Together with inkjet printing, (ink)
materials can be saved, since the ink is only dispensed on demand. It is, however, necessary to tune the
polymer substrate as well the conductive inks properties. Alternative and selective sintering methods
open new routes to produce conductive features on common polymer foils that have a relatively low
glass transition temperature.
In combination with different embossing techniques inkjet printing could lead to a higher
resolution and more continuous overall processing of electronic devices on flexible substrates in the
future. The improved photo-embossed structures offer a simple and versatile alternative for the
production of large-scale/large-area relief structures in thin polymer films.
179
Samenvatting
Samenvatting
Het doel van het onderzoek dat gepresenteerd wordt in dit proefschrift, is het combineren van
inktjet printen en embossing technieken. De thesis is verdeeld in twee secties. Het eerste gedeelte
(hoofdstuk 1 tot en met 4) beschrijft een bottom-up procedure waarbij inktjet printen gebruikt wordt
om microstructuren op polymeer substraten te creren. Het tweede gedeelte (hoofdstuk 5 en 6)
beschrijft hot-embossen en een nieuwe techniek, genaamd foto-embossen, die snel en eenvoudig relif
structureren in polymeer substraten kunnen creren.
De introductie van dit proefschrift geeft een literatuur overzicht van zowel de historie als de
recente toepassing op het gebied van inktjet printen. Inktjet printen heeft zich namelijk ontwikkeld van
een productiemethode voor tekst en plaatjes tot een belangrijke techniek voor onderzoek en
ontwikkeling.
Hoofdstuk 2 beschrijft het gedrag van inkt druppels tijdens de vlucht en na de landing op het
substraat; kennis van dit gedrag is immers essentieel voor het bereiken van de gewenste
printresultaten. In eerste instantie werd een lineair afnemend verband tussen de druppel diameter en de
printhoogte gevonden voor identieke geprinte druppels van een verdunde polystyreen oplossing met
een identiek volume. Echter bij een hogere polymeer concentratie werd een exponentieel verval van de
druppel diameter waargenomen, dat een constante waarde bereikt bij grotere hoogtes. Dit afwijkende
gedrag bij hogere concentraties en hoogten wordt toegeschreven aan een dunne polymeerlaag die zich
aan de binnenkant van de druppel vormt, waardoor verdamping van het oplosmiddel gereduceerd
wordt. Tevens werd de grootte-afhankelijke segregatie van monodiperse silica deeltjes in drogende
druppels bestudeerd. Dit liet zien dat deeltjes zo dicht mogelijk bij de contact lijn sedimenteren, maar
dat de uiteindelijke afstand tot de contact lijn afhangt van de deeltjes grootte; de afstand tussen de
locatie van de gesedimenteerde deeltjes en de rand van de druppel neemt toe bij toenemende deeltjes
grootte.
Het derde hoofdstuk gaat over het inktjet printen van functionele materialen. Een polyurethaan
dispersie werd geprint om driedimensionale structuren met een laagdikte van 10 micrometer te
creren. Tevens werd geprint met in water opgeloste TiO2 nanodeeltjes, welke boven een bepaalde
kritische temperatuur een gel vormt. Druppels en lijnen met verbeterde morfologie en resolutie werden
verkregen middels dit gelatie effect. Bovendien kunnen hiermee defect-vrije, rechte lijnen geprint
worden op hydrofobe oppervlakken, wat met normale inkten onmogelijk is door de slechte
bevochtiging van deze substraten. Als laatste kon de resolutie verbeterd worden van geprinte lijnen
van zilver nanodeeltjes op polymeer substraten met een oppervlakte energie lager dan meer gangbare
polymeer substraten: lijnen met een resolutie van 40 micrometer werden geprint.
Na het printen van inkten met zilver nanodeeltjes is een thermische sinter stap nodig om de
aanwezige deeltjes geleidend te maken: dit proces wordt in hoofdstuk 4 besproken. Polymeer
substraten zijn normaal gesproken niet bestand tegen hoge temperaturen en vereisen daarom een lage
180
Samenvatting
procestemperatuur tijdens het sinteren. Twee nieuwe technieken worden besproken die het sinteren
plaats laten vinden zonder dat het polmeer substraat vervormt: blootstelling aan microgolf straling of
blootstelling aan een argon plasma. De eerste techniek verkort de sintertijd met een factor 20,
waardoor drie minuten voldoende zijn voor het sinterproces. Bovendien heeft de aanwezigheid van
geleidende antennes een versnelde werking op het sinterproces; in plaats van drie minuten bleek
sintering al na 1 seconde te hebben plaatsgevonden. De tweede techniek, het blootstelling aan plasma,
liet een duidelijk evolutie zien van een gesinterde toplaag tot bulk materiaal.
Hoofdstuk 5 beschrijft een nieuwe techniek genaamd foto-embossen. Dit is een fotolithografische
techniek om relif structuren in polymeren te maken door een flux van materiaal te veroorzaken ten
gevolge van een lokale polymerisatie. En van de problemen van foto-embossen is de lage aspect ratio
van de gevormde structuren. Hoofdstuk 5 beschrijft het verbeteren van de aspect ratios van deze
middels foto-embossen verkregen structuren door het toevoegen van componenten die de reactie
kinetiek benvloeden, zoals t-butyl hydroquinon (TBHQ) en zogenaamde reversible addition-
fragmentation chain transfer (RAFT) agents. Door het toevoegen van deze componenten kon de aspect
ratio verbeterd worden met een factor van bijna 10.
Het laatste hoofdstuk behandelt het inktjet printen van zilver nanodeeltjes op een van te voren
gedefinieerde topografie in een thermoplast. Deze topografische structuren zijn aangebracht door
middel van embossing in een polymeer substraat. Vervolgens worden druppels van een inkt die zilver
nanodeeltjes bevat over de gevormde microkanalen geprint. Als gevolg van de capillaire krachten
vulden de microkanalen zich met de inkt en ontstonden lijnen met een verbeterde resolutie. De lijnen
hadden een breedte in de orde van 5 tot 25 micrometer.
In het algemeen kan geconcludeerd worden dat inktjet printen een zeer geschikte techniek is voor
systematische en statistische onderzoeken, omdat meerdere identieke druppels geplaatst kunnen
worden in een matrix, die achtereenvolgens geanalyseerd kan worden. Verder is inkjet printen in staat
om geleidende structuren met een hoge resolutie te maken op of in een polymeer substraat. In
combinatie met inktjet printen kan materiaal bespaard worden, omdat de inkt alleen geprint wordt
waar en wanneer het nodig is. Het is echter noodzakelijk om de eigenschappen van het polymeer
substraat en van de geleidende inkten op elkaar af te stemmen. Alternatieve en selectieve sinter
methoden openen nieuwe wegen om geleidende structuren te fabriceren op veel gebruikte polymeer
substraten met een lage glasovergangstemperatuur.
In combinatie met verschillende emboss technieken kan inktjet printen tot een hogere resolutie
leiden en in de toekomst tot een meer continu produktie proces voor elektronische apparaten op
flexibele substraten. De verbeterde foto-emboss structuren bieden een simpel en toegankelijk
alternatief voor het op grote schaal en op grote oppervlakten produceren van relif structuren in dunne
polymeer substraten.
181
Nomenclature
Nomenclature
Symbol Full expression Unit
Latin letters
- Pulse width s
a Dried droplet diameter m
A Area m2
B Magnetic field vector T
c Speed of light m s-1
C Concentration g mol-1
d Diameter m
d Penetration depth m
D Contact diameter m
D Electric displacement vector C m-2
e Elementary charge C
E Energy J
E Electric field vector N C-1
f Frequency s-1
h height m
H Magnetic field vector A m-1
i Imaginary unit 1
I Intensity W m-2
J Current density vector A m-2
K Boltzmann constant J K-1
K Kuhn-Mark-Houwink-Sakurada parameter cm3 g-1
l Length m
m Mass kg
M Molar mass Da
n Number -
Oh Ohnesorge number -
P Pressure Pa, bar
P Power W
r Radius m
R Correlation coefficient -
R Resistance
Re Reynolds number -
t time s
T Temperature C
v Velocity m s-1
V Potential V
V Volume m3
We Weber number -
x Distance m
X Mole fraction -
Z Fromm number -
Z Impedance
182
Nomenclature
Greek letters
Spreading factor -
Surface tension N m-1
Permittivity F m-1
Viscosity Pa s
Contact angle
Wavelength m
Permeability H m-1
Charge density C m-3
Density kg m-3
Resistivity m
Conductivity -1 m-1
Relaxation time s
Angular frequency rad s-1
Operators
Partial derivative -
Curl -
Divergence -
Superscripts
Real part
Imaginary part
* Complex
Subscripts
0 In-flight, initial
A Advancing
e Electron
float Floating
g Glass transition
i Ion
k Kinetic
lv Liquid-vapour
max Maximum
n Number averaged
r Relative
R Receding
s Surface tension
sl Solid-liquid
sp Spreading
sv Solid-vapour
v Viscous
w Weight averaged
183
Nomenclature
Prefixes
Symbol Prefix Short scale 10n Decimal
Y Yotta- Septillion 1024 1 000 000 000 000 000 000 000 000
Z Zetta- Sextillion 1021 1 000 000 000 000 000 000 000
E Exa- Quintillion 1018 1 000 000 000 000 000 000
P Peta- Quadrillion 1015 1 000 000 000 000 000
T Tera- Trillion 1012 1 000 000 000 000
G Giga- Billion 109 1 000 000 000
M Mega- Million 106 1 000 000
k Kilo- Thousand 103 1 000
h Hecto- Hundred 102 100
da Deca- Ten 101 10
- - One 100 1
d Deci- Tenth 10-1 0.1
c Centi- Hundredth 10-2 0.01
m Milli- Thousandth 10-3 0.001
Micro- Millionth 10-6 0.000 001
n Nano- Billionth 10-9 0.000 000 001
p Pico- Trillionth 10-12 0.000 000 000 001
f Femto- Quadrillionth 10-15 0.000 000 000 000 001
a Atto- Quintillionth 10-18 0.000 000 000 000 000 001
z Zepto- Sextillionth 10-21 0.000 000 000 000 000 000 001
y Yocto- Septillionth 10-24 0.000 000 000 000 000 000 000 001
Abbreviations
ATR Attenuated total reflection

BuAc Butyl acetate
CA Contact angle
CBDB 2-Cyanobut-2-yl dithiobenzoate
CFT Critical flocculation temperature
CIJ Continuous inkjet
DoD Drop-on-demand
DPG Dipropylene glycol
ESR Electron spin resonance
FT Fourier transform
IR Infrared
LASER Light amplification by stimulated emission of radiation
LCST Lower critical solution temperature
MIMIC Micro-moulding in capilaries
MOD Metallo-organic decomposition
OD Optical density
OFET Organic field effect transistor
OLED Organic light emitting display/diode
OTFT Organic thin film transistor
OTS Octadecyl trichlorosilane
PC Polycarbonate
PDI Polydispersity index
PEDOT Poly(3,4-ethylenedioxythiophene)
184
Nomenclature
PEN Polyethylene naphthalene

PET Polyethylene terephthalate
PI Polyimide
PMMA Poly(methyl methacrylate)
PS Polystyrene
PSS Poly(4-styrenesulfonate)
PTFE Polytetrafluorethylene
PU Polyurethane
PVME Poly(vinylmethylether)
PVOBA Poly(vinyloxy-4-butyric acid)
R2R Roll-to-roll
RAFT Reversible addition-fragmentation chain transfer
RFID Radio frequency identification
SEM Scanning electron microscopy
TBHQ t-Butyl hydroquinone
TEM Transmission electron microscopy
TGA Thermogravimetric analyses
TIJ Thermal inkjet
UV Ultraviolet
VIS Visible
vol Volume
wt Weight
XRD X-ray diffraction
185
186
Curriculum vitae
Curriculum vitae
Jolke Perelaer werd geboren op 20 oktober 1979 in Neerijnen. Na het behalen van het gymnasium
diploma aan het Johan de Witt Gymnasium in Dordrecht, begon hij in 1998 aan de opleiding
Scheikunde aan de Universiteit Utrecht. Zijn afstudeerproject werd uitgevoerd in de groep van
professor Gerard van Kooten met als onderwerp het synthetiseren van organometaalcomplexen
gebaseerd op nieuwe brugliganden met terpyridine en pincer functionaliteiten. Dit resulteerde in 2004
in het doctorandusdiploma, met lof.
In februari 2005 begon hij zijn promotieonderzoek aan de Technische Universiteit Eindhoven onder
leiding van professor Ulrich S. Schubert. De belangrijkste resultaten van dit onderzoek staan
beschreven in dit proefschrift.
Jolke Perelaer was born in 1979 in Neerijnen. After finishing his gymnasium degree at the Johan de
Witt Gymnasium in Dordrecht, he started in 1998 with the chemistry program at the Utrecht
University. His undergraduate research concerning the synthesis of organometallic complexes based
on new bridging ligands with terpyridine and pincer moieties was performed within the group of
professor Gerard van Kooten. This resulted in 2004 in the Master of Science degree, with distinction.
In February 2005 he started with his Ph.D. work under supervision of professor Ulrich S. Schubert at
the Eindhoven University of Technology. The most important results of this work are described in this
thesis.
187
List of publications
this work is included in the thesis

o this work is not included in the thesis
Refereed publications:
2009
Jolke Perelaer, Patrick J. Smith, Erwin van den Bosch, Stephen S.C. van Grootel,
Peter H.J.M. Ketelaars, Ulrich S. Schubert
The Spreading of Inkjet Printed Droplets with a Varied Polymers Molecular Weight on a Dry
Solid Substrate
Macromol. Chem. Phys. 2009, in press.
Jolke Perelaer, Patrick J. Smith, Mike M.P. Wijnen, Erwin van den Bosch,
Rebecca Eckardt, Peter H.J.M. Ketelaars, Ulrich S. Schubert
Droplet Tailoring Using Evaporative Inkjet Printing
Macromol. Chem. Phys. 2009, DOI:10.1002/macp.200800537.
2008
Jolke Perelaer, Antonius W.M. de Laat, Chris E. Hendriks, Ulrich S. Schubert
Inkjet Printed Silver Tracks: Low Temperature Curing and Thermal Stability Investigation
J. Mater. Chem. 2008, 18, 3209-3215.
Jolke Perelaer, Ko Hermans, Cees W.M. Bastiaansen, Dirk J. Broer, Ulrich S. Schubert
Photo-embossed Surface Relief Structures with an Increased Aspect Ratio by Addition of a
Reversible Addition-Fragmentation Chain Transfer (RAFT) Agent
Adv. Mater. 2008, 20, 3117-3121.
Chris E. Hendriks, Patrick J. Smith, Jolke Perelaer, Antje M.J. van den Berg,
Ulrich S. Schubert
Invisible Silver Tracks Produced by Combining Hot-Embossing and Inkjet Printing
Adv. Funct. Mater. 2008, 18, 1031-1038.
Jolke Perelaer, Patrick J. Smith, Chris E. Hendriks, Antje M.J. van den Berg,
Ulrich S. Schubert
The Preferential Deposition of Silica Micro-particles at the Boundary of Inkjet Printed
Droplets
Soft Matter 2008, 4, 1072-1078.
188
Thijs H.J. van Osch, Jolke Perelaer, Antonius W.M. de Laat, Ulrich S. Schubert
Inkjet Printing of Narrow Conductive Tracks on Untreated Polymeric Substrates
Adv. Mater. 2008, 20, 343-345.
2007
Ko Hermans, Florian K. Wolf, Jolke Perelaer, Cees W.M. Bastiaansen,
Rene A.J. Janssen, Ulrich S. Schubert, Dirk J. Broer
High Aspect Ratio Surface Relief Structures by Photo-Embossing
Appl. Phys. Lett. 2007, 91, 174103.
o Marcella Gagliardo, Jolke Perelaer, Frantiek Hartl, Gerard P.M. van Klink,
Gerard van Koten
Mono- and Heterodimetallic FeII and RuII Complexes Based on a Novel Heteroditopic
4-{Bis(phosphanyl)aryl}-2,2:6,2-terpyridine Ligand
Eur. J. Inorg. Chem. 2007, 2111-2120.
Antje M.J. van den Berg, Antonius W.M. de Laat, Patrick J. Smith, Jolke Perelaer,
Ulrich S. Schubert
Geometric Control of Inkjet Printed Features using a Gelating Polymer
J. Mater. Chem. 2007, 17, 677-683.
Antje M.J. van den Berg, Patrick J. Smith, Jolke Perelaer, Wolfgang Schrof,
Sebastian Koltzenburg, Ulrich S. Schubert
Inkjet Printing of Polyurethane Colloidal Suspensions
Soft Matter 2007, 3, 238-243.
2006
Jolke Perelaer, Berend-Jan de Gans, Ulrich S. Schubert
Ink-jet Printing and Microwave Sintering of Conductive Silver Tracks
Adv. Mater. 2006, 18, 2101-2104.
189
Patents
2009
o Ingo Reinhold, Rebecca Eckardt, Chris E. Hendriks, Jolke Perelaer, Ulrich S. Schubert
Method for generation of electrically conducting surface structures, device and use
PCT/EP2009/09000375.7, Dutch Polymer Institute.
2008
Jolke Perelaer, Mark Klokkenburg, Ulrich S. Schubert
Method for Generation of Electrically Conducting Surface Structures, Apparatus Therefore
and Use
PCT/EP2008/08021042.0, Dutch Polymer Institute and TNO.
Jolke Perelaer, Ko Hermans, Cees W.M. Bastiaansen, Ulrich S. Schubert

Process for Preparing a Polymeric Relief Structure
PCT/EP2008/056373, Dutch Polymer Institute.
2007
Ko Hermans, Jolke Perelaer, Cees W.M. Bastiaansen, Dirk J. Broer
Process for Preparing a Polymeric Relief Structure
2006
Method for Generation of Metal Surface Structures and Apparatus Therefor
Non-refereed publications
2008
Jolke Perelaer, Chris E. Hendriks, Ingo Reinhold, Rebecca Eckardt, Thijs H.J. van Osch,
Ulrich S. Schubert
Inkjet Printing of conductive silver tracks in high resolution and the (alternative) sintering
thereof
Proceedings of the 24th International Conference on Digital Printing Technology and Digital
Fabrication 2008, 697 (Pittsburgh, USA).
190
2007
Inkjet Printing and Microwave Sintering of Conductive Tracks on Polymer Substrates
Proceedings of the Printing Future Days 2007, 37-40.
Submitted papers
Jolke Perelaer, Mark Klokkenburg, Chris E. Hendriks, Ulrich S. Schubert

Microwave Flash Sintering of Inkjet Printed Conductive Tracks for Roll-2-Roll Applications
o Peter Krber, Joseph T. Delaney, Jolke Perelaer, Ulrich S. Schubert

Reactive Inkjet-Printing of Polyurethanes
Ingo Reinhold, Chris E. Hendriks, Rebecca Eckardt, Johannes M. Kranenburg,

Jolke Perelaer, Reinhard R. Baumann, Ulrich S. Schubert
Argon Plasma Sintering of Inkjet Printed Silver Tracks on Polymer Substrates
o Jolke Perelaer, Chris E. Hendriks, Antonius W.M. de Laat, Ulrich S. Schubert

One-step Inkjet Printing of Conductive Silver Tracks on Polymer Substrates
Manuscripts in preparation
Ko Hermans, Jolke Perelaer, Cees W.M. Bastiaansen, Ulrich S. Schubert, Dirk J. Broer
Improving the Performance of Photopolymers by Adding Kinetic Interfering Compounds
o Josue J.P. Valeton, Ko Hermans, Cees W.M. Bastiaansen, Dirk J. Broer, Jolke Perelaer,
Ulrich S. Schubert, Gregory P. Crawford, Patrick J. Smith
Conductive Silver Features Obtained at Room Temperature using Spin-coating and Inkjet
Printing
Jolke Perelaer, Ulrich S. Schubert

Inkjet Printing: From Graphical Arts to a state-of-the Art Research Technique
191
Acknowledgements
Acknowledgements
Finally, the last pages of the thesis to be finished. Writing the acknowledgement is probably the
largest piece of senseless work one can do: firstly, probably over 90% of those who receive this book
will only read the acknowledgements (to check if they are mentioned here) while the rest is skipped,
despite this part takes only less than 10% of the total work that has been invested into this thesis.
Secondly, if one needs to thank every individual that cooperated during the last years within my
research, I would have failed expressing my gratitude during or right after the research. Therefore, I
rather not give the impression to say as they do in Brabant: Houdoe en bedankt.
Nevertheless, according to the standards and since everybody expect an acknowledgements chapter
here, I will summarise some words of appreciation. Before starting though, I would like to sincerely
express my apologies to those who are not mentioned here: you might not have been important enough
during the last years.
Eerste Promotor, Prof. Dr. Ulrich S. Schubert, Laboratory for Macromolecular Chemistry and
Nanoscience (SMN), I would like to thank you for supporting my research during the last four years
and for being a good example that a full time professor can also be a respected sales manager at the
same time. This combination not only gives the luxury of having high-tech equipment around but also
enough money to support cooperation projects.
Secondly, I would like to thank all members of the defence commission: Prof. Dr. Dick Broer (Philips
Applied Technologies and Eindhoven University of Techology), Prof. Dr. Reinhard Baumann
(Institute for Print und Media Technology, Chemnitz University of Technology, Germany), Prof. Dr.
Schlomo Magdassi (Casali Institute of Applied Chemistry, Hebrew University of Jerusalem, Israel),
Prof. Dr. Vivek Subramanian (Department of Electrical Engineering and Computer Science,
University of California, Berkeley, U.S.A.) and Dr. Ton de Laat (Philips Applied Technologies,
Eindhoven, the Netherlands). I am very honoured to have such impressive committee members in the
defence board.
Lots of respect goes to the two post-docs who guided me during the PhD, unfortunately only for
short times, but I would like to thank: Dr. Berend-Jan de Gans (now at Evonik, Essen, Germany) and
Dr. Patrick Smith (currently at the Institute of Microsystem Technology, University of Freiburg,
Germany). Dear Patrick, thank you for being my co-promoter! After we have worked together in
Eindhoven, we continued working together when you have settled in Freiburg. I admire your
capabilities both friendly as well as professional. I wish you, Kate and little Gwen a very happy and
prosperous life all together!
Although not officially being a Post-doc in the group, Ton de Laat has supported me a lot during the
research. Most of the times he answered all my questions with Philips did that already 10 years ago.
192
Acknowledgements
Nevertheless, together we managed to publish all results, independently of the age of the results.
Ton, hartelijk dank voor de feedback op mijn proefschrift en dat je in de commissie zit.
Innovative thinking is a continuous drive for the Dutch Polymer Institute and, therefore, they
are greatly acknowledged, including their financial support. Furthermore, Microdrop Technologies
(Norderstedt, Germany) is also acknowledged for cooperation.
The Polymer in Communication Technology (PICT) group of the Eindhoven University of
Technology, and in particular Kees Bastiaansen and Dick Broer, I would like to thank for enthusiast
and nice cooperation. In particular, Kees B. I would like to thank for support and discussions.
Furthermore, all the colleagues at PICT Id like to thank for cooperation and coffee. Colleague PhD
Ko Hermans I thank for working together during the four years first with photo-embossing, and later
with inkjet printing. Good luck with your defence!
Continuously, the SMN-group in Eindhoven is greatly thanked for all the support and nice
moments, including the group-trips, coffee and lunch breaks. Furthermore, the strongly fluctuating
Inkjet Group Id like to thank for the good research and keep up the good work! Also the Jena-side
of SMN is thanked for the good spirit. In particular, Anja Teige thank you for your trouble.
Excellent work and help I had from a significant collection of students who helped me with the
research, including Caoxia Hu, Thijs van Osch, Ludo Koen, Mike Wijnen, Erwin van den Bosch,
Stephen van Grootel, Ingo Reinhold and Peter Krber. Their work made this thesis a lot thicker. In
particular, I wish Thijs many safe kilometres on the motorbike. Furthermore, Ingo, I wish you all the
best: it started with some small talk during the Inkjet Workshop 2007, but ended with a klares 1.0
for your diploma thesis in Eindhoven. Good luck, wherever around the world youd like to go. And
thanks for introducing me to the word Daumenkino; the result is added to the bottom of the pages in
this thesis. Furthermore, Volker Gerling (http://www.daumenkinographie.de) is acknowledged for a
live demonstration of Daumenkino.
I would also like to thank all external collaborators from outside TU/e. Firstly, the Fontys
Hogeschool Applied Science, lectoraat Functional Polymer, in particular Peter Ketelaars and Jan
Bernards: they stimulated their students to do their thesis in inkjet printing together with TU/e, which
also resulted in two papers so far! Secondly, the Holst Centre, in particular Mark Klokkenburg, Marcel
Tijdink and Peter Kruijt, for their great knowledge and expertise. Furthermore, Ashok maestro
Shridhar (Unversity of Twente) is greatly acknowledged for fruitful discussions and experiments, and
good beer times. Stephan Jahn (Institute for Print und Media Technology) for good times in Chemnitz!
Validus Technologies a spin-off company in inkjet printing from the TU/e and in particular
193
Acknowledgements
Robert Vrancken, Nico Verloop and Thijs Meier, I would like to thank for Friday afternoon
experiments and wish you all the best for the future.
Kind-heartedly, I would like to mention those who are normally not mentioned too often. Here, I
focus on the technical staff of the SMN-group: Rebecca Eckardt, Martin Fijten, Chris Hendriks, Renzo
Paulus, Hanneke Lambermont-Thijs and, formerly, Antje van den Berg. Basically, they should be seen
as the backbone of the group. With their infinite support they keep the instruments running and thus
the research going. In particular, I would like to thank Chris for all microscopy measurements and for
the good times, during and after work: Chris, er zijn weinig momenten waarop jij blad voor de mond
neemt, wat ik je niet altijd in dank afgenomen heb, maar doorgaans kan ik je kritische blik op mijn
werk en persoonlijkheid enorm waarderen. Jammer dat je geen PhD wilt doen, want ik vind je er een
goede kandidaat voor ook al vind je jezelf vaak maar een simpele HBOer! Ook Pauline wil ik
bedanken voor de mooie SEM plaatjes. Samen met Raf wens ik jullie een gelukkige toekomst!
Rebecca, you have a strong driving force for good research, which I appreciate very much. Thanks
also for enjoyable moments at the Hannover fairs and I wish every woman was driving like you drive!
Renzo, wanneer gaan we Jekkers kijken? Martin, ook al ben je Limburger ja, die was te makkelijk
Hanneke, Meta en Hans bedankt vooral voor de ontspannen momenten in kantoor en tijdens het
koffie drinken in de ochtenden.
Heel graag wil ik ook Antje van den Berg bedanken. Niet alleen voor de fijne samenwerking, maar
vooral voor de vriendschap die in de jaren ontstaan is. Ik betwijfel of ik de plaatsnaam Sint
Michielsgestel ooit correct uit kan spreken. Daarnaast heb ik genoten van alle culturele avondjes uit
naar de schouwburg of bioscoop. Ik wens jou en Rob een hele fijne toekomst samen.
Oh, almost forgotten I want to thank Claudia, Tina, Christina, Manuela, Remzi, Hans and
Christoph for the nice RPK courses in Utrecht. Furthermore, a big thanks goes to Tamara Druzhinina,
not only for the help with Daumenkino, but also for the nice conversations.
Ultimately, my big respect goes to Emma Eltink: zonder jou was ik denk ik de vier jaar niet
doorgekomen. Vooral voor de filosofische en psychologische onderwerpen van het leven konden we
elkaar goed vinden. Ik wil je bedanken voor alles wat je gedaan hebt in de afgelopen vier jaar: je bent
een geweldige vrouw!
Verder wil ik graag mijn dank betuigen aan Wasil Maslow voor het uitspreken van de woorden
half gebakken brood wordt nooit lekker. Deze wijze woorden hebben mij destijds geholpen de keuze
te maken om een promotie onderzoek te starten.
194
Acknowledgements
Allicht, Dispuut Machinatio Capitis, ofwel d Heeren dispuut van Nederlands mooiste stad
Utrecht heb ik slechts n ding te zeggen: driewerf hoezeee! Heeren, bedankt voor het bestaan en het
brengen van zoveel mooie momentjes: Nieuwkoop, Servi, Utrecht, Zuid-Afrika, WVS, Canada,
Rolde, etc
Natuurlijk wil ik ook mijn vrienden bedanken zij die het zijn, weten wie ik bedoel en dus hoef ik
geen namen te noemen voor al de momenten dat we over werk konden praten, maar vooral die
momenten dat we ontspannen onderuitgezakt juist over alles behalve werk konden praten. Dat laatste
is misschien wel belangrijker geweest.
Juist, en zoals altijd eindigt een dankwoord met de meest belangrijkste personen voor auteur. Mijn
ouders Charles en Joeky wil ik mijn innige dank betuigen. CP, met jou kon ik regelmatig over het
onderzoek praten, de ene keer onder een sterrenhemel in Luxemburg, de andere keer met een fles
(goede) whisky. Joeky, dank je wel voor het geven van een goede start en verdere stabiliteit in mijn
leven. Ik kan mijn grote dank nauwelijks verwoorden, dus verwijs ik naar een zinnetje van Harrie
Jekkers (uit: Papa, 1997):
kiezen kun je nooit voor de ene man en vrouw,

dat maakt ze zo bijzonder, want zij kozen voor jou.
Ook wil ik mijn broer Ibo hier noemen, waar je ook bent, in mijn gedachten ben je er altijd.
Und... Felice, hoi Liebste, ich mchte mich vor allem bei dir bedanken: nicht nur dass du da bist,
sondern auch dass du das Beste bist was mir je passiert ist. Endlich werden wir nicht mehr so weit
voneinander entfernt sein. Apropos, kennst du einen acrostychon?
195

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Please check the document version of this publication:

Citation for published version (APA):

Download date: 27. May. 2017

prof.dr. U.S. Schubert

Technische Universiteit Eindhoven, 2009

Cover design by Jolke Perelaer and Felice Kroworsch

Printed at PrintPartners Ipskamp, Enschede, The Netherlands

Klein Orkest, Over de Muur (1984)

Met diploma's en een yuppie pak, heb je misschien meer kans,

Normaal, Kwestie van Balans (1991)

4.3.2 Experimental ................................................................................................................. 114

6.3.2.1 Hot-embossing masters ..........................................................................................163

Manneke Pis (Brussels, Belgium)

1.1 A historical overview

When applying an acoustic energy, the frequency of the mechanical vibrations is

Undeflected Deflected Unvibrated Acoustic Piezo Electrostatic Thermal

Binary Multiple Top shooter Side shooter

Bend Shear Push Squeeze

Figure 1.5 Classification of inkjet printing technologies, adapted from [45].

1.2 Working principle of piezoelectric printheads

(a) I - Piezo move outwards

(b) II - Negative waves travel outwards

(c) III - Waves reflect and one reverses

(d) IV - Waves arrive at centre

(e) V - Wave is magnified and

Pulse width (s)

90 100 110 120 130

1.3 Fluid dynamics

1.4 Aim and outline of the thesis

1 J. A. Nollet, W. Watson, Philos. Trans. 1749, 46, 368.

24 M. Naiman, US Patent 3,179,042, 1965.

57 K. A. M. Seerden, N. Reis, J. R. G. Evans, P. S. Grant, J. W. Halloran, B. Derby, J. Am.

2.2 Influence of the printing height

2.2.3 Results and discussion

Droplet velocity (m s ) 4.0

Toluene 0 24.7 0.599 0.006 97.6 2.37 63.4 <5

2.3 The behaviour of inkjet printed droplets of polymer solutions on a dry

2.3.3 Results and discussion

2.3.3.1 Molar mass influence on droplet spreading

2.3.3.2 Comparison of the maximum spreading diameters

1.50 0.06 4.49 0.04 89.84 3.44 3.75 4.64 3.76

Mn = 1.5 kDa Mn = 124 kDa

Mn = 16.8 kDa Mn = 236 kDa

Mn = 60.6 kDa Mn = 545 kDa

Droplet diameter (m)

2.4 Preferential deposition and size-selective segregation at the boundary

2.4.3 Results and discussion

2.4.3.1 Contact angle dependency of a drying droplet

i) ii) iii) i) ii)

2.4.3.2 Coffee drop effect with monomodal PMMA latex suspensions

2.4.3.3 Coffee drop effect with monomodal silica particles

Finally, this can be written:

0.165 20 160.6 0.9 158.8 171 4

Finally, the size-selective segregation of silica based particle populations in drying

1 E. Tekin, P. J. Smith, U. S. Schubert, Soft Matter 2008, 4, 703.

8 Y. Yoshioka, G. E. Jabbour, Synth. Met. 2006, 156, 779.

43 S. Magdassi, M. Grouchko, D. Toker, A. Kamynshny, I. Balberg, O. Millo, Langmuir 2005,

75 B.-J. de Gans, S. Hoeppener, U. S. Schubert, Adv. Mater. 2006, 18, 910.

(a) (b) (c) (d)

Line width (m)

Line height (m)

(b) (c) (d)