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Master Thesis in Physics
60 ECTS-credits
Masrur Morshed Nahid
Department of Physics
Umeå University
In Quest of Printed Electrodes for Light-emitting
Electrochemical Cells: A Comparative Study between
Two Silver Inks
Masrur Morshed Nahid
Supervisor: Andreas Sandström
Examiner: Ludvig Edman
Master Thesis in Physics 60 ECTS-credits
The Organic Photonics and Electronics Group (OPEG), Department of Physics, Linnaeus
Väg 20, Umeå University, SE-901 87 Umeå
For your suggestion, supervision, guidance, support and encouragement, thank you very much
Andreas Sandström
Ludvig Edman
My heartfelt gratitude goes to
Amir, Christian, Jenny, Jia, Nikolai, Roushdey, Shi
as well as to
Mamun, Shibbir, and my soul-mate, Rima
This thesis presents a comparative study between two silver nanoparticle inks that were deposited
using a Drop-on-Demand (DoD) inkjet printer, aiming at finding a functional ink that can be used
to print electrodes in Light-emitting Electrochemical Cells (LECs). To achieve this, a DoD inkjet
printer was installed and an acquaintance with the printer was attained. Among the two inks, one
was employed as received while the other was reformulated, and successful deposition of both the
inks was observed. During the reformulation process, it was seen that the highly volatile
tetrahydrofuran (THF) solvent can be used to improve the ink properties, in contrast to what is
recommended. After that, the inks were deposited on UV-ozone treated glass substrates, sintered at
an elevated temperature under ambient conditions, and their specific resistances and thicknesses
were measured. Finally, the inks were used to print the anode in a structured sandwich-cell LEC.
The performance comparison was conducted by observing the emitted light of the LECs. The
results indicate that the reformulated ink performs better, probably due to the lower silver
concentration that results in flatter surface, which in turn effectively alleviates shorts.
Purpose of the Thesis ............................................................................................................................... 1
DMP-2800 Inkjet Printer: An Introduction .......................................................................................... 2
Hardware Configuration of the machine ....................................................................................... 2
Dimatix Drop Manager Software ................................................................................................... 3
DMP-2800 Inkjet Printer: An Overview .............................................................................................. 6
Advancement of the Printing Technology .................................................................................... 6
The PZT-MEMS Device Theory.................................................................................................... 8
Functional-Fluid Characteristics ..................................................................................................... 8
Waveform Basics .............................................................................................................................10
Printed Features: Resolution Parameters, Drop-Size and Limiting Factors...........................12
Ag-inks: Optimizing, Jetting and Sintering ..........................................................................................15
Difference between the inks ..........................................................................................................15
Optimizing an Ink into a Functional Fluid ..................................................................................16
Adjusting the Jetting Parameters ...................................................................................................17
Jetting the Inks.................................................................................................................................17
Sintering Ag Inks on Glass Substrates .........................................................................................19
Ink Characterization ................................................................................................................................21
Theory: Specific Resistance Measurement...................................................................................21
Experimental setup and Measurement Conditions ....................................................................21
Results and Discussions .................................................................................................................23
Performance in LECs .............................................................................................................................26
Theory: Working Principal of LECs ............................................................................................26
Making Sandwich-cell Structured LECs ......................................................................................28
Printing the Bottom Electrodes ............................................................................................28
Preparing the Active Material and Drop-casting................................................................28
Drying the Active Material and Evaporating the Top Electrode ....................................30
Experimental Setup and Measurement Conditions....................................................................30
Results and Discussions .................................................................................................................31
Comparison at a Glance .........................................................................................................................34
Conclusion ................................................................................................................................................35
Future Prospects ......................................................................................................................................36
10 Bibliography ..............................................................................................................................................37
Master Thesis in Physics
60 ECTS-credits
Masrur Morshed Nahid
Department of Physics
Umeå University
1 Purpose of the Thesis
The Organic Photonics and Electronics Group (OPEG) at the department of physics of Umeå
University has recently acquired a Drop-on-Demand (DoD) material deposition inkjet printer. It will
allow new avenues forward regarding design, fabrication, and development of flexible electronic
devices. One such device is the Light-emitting Electrochemical Cell (LEC), a complex entity that
combines the sciences of organic chemistry and solid state physics, and which has been extensively
researched in the OPEG labs.[1-7] Today, this research is primarily focused on solution processable
light-emitting polymers and electrolyte systems, but a different aspect, by no means less crucial, is
the required electrodes that connect the LEC to an external power-supply,[6, 8] and finding methods
of applying these using solution based processes. Though tremendous effort has been aimed worldwide at finding highly conducting materials with high transparency, no obvious replacements for
current vacuum deposited electrodes exist. The ink-jet method has the potential to solve some of
these issues, especially when a DoD deposition technique is used, since it allows for a precise
deposition of a variety of materials thus allowing clever electrode designs to be employed. The
DMP-2800 DoD material deposition inkjet printer (FUJIFILM Dimatix Inc., USA) has been
procured for this very reason: depositing nano-sized metallic particles with high accuracy allowing
highly conductive and functional LEC electrodes.
The focus of this thesis is to compare two types of inks comprising nano-sized silver particles. This
was done by installing and employing a DoD DMP-2800 inkjet printer to deposit the inks. The inks
were evaluated by looking at the physical characteristics of printed Ag-traces. In addition, this thesis
encompasses a comparative study of the performance of LEC devices in which the printed
electrodes were employed as the anode. To achieve these objectives, an acquaintance with the DMP2800 was attained followed by a necessary ink formulation study where one of the Ag-ink was mixed
with various additives to make it compatible with the printer. The inks were deposited on UV-ozone
treated microscopic glass substrates and sintered, after which the specific resistance and the
thickness were measured. In addition to this, a change in appearance of one of the inks was reported
while stored in air. After that, the inks were also used to make electrodes in LEC devices by
sandwiching a drop-casted organic light-generating material between printed Ag-electrodes and an
evaporated Al cathode.[9, 10] A constant external voltage bias was applied to light up the devices
and to study their performances. In addition, this thesis contains practical guidelines on how to best
utilize the printer and the inks, and possible future projects are proposed.
2 DMP-2800 Inkjet Printer: An Introduction
The DMP-2800 is a software controlled DoD inkjet printer that allows the user to deposit fluid
materials on an A4-sized substrate (210 mm x315 mm) using a piezo-based inkjet cartridge. The
complete system is shown in figure 1. This table-top printing device comprises a print-head, ink
cartridges, a vacuum controlled substrate holder, two cameras, a stepper motor controlled x, y, and z
stage, and a computer with pre-installed software. The individual parts of the printer and the
software will be described in more detail below.
Figure 1: Dimatix Materials Printer, DMP-2800 (FUJIFILM Dimatix Inc., USA), and the PC that is used to
control the printer.
2.1 Hardware Configuration of the machine
The print-head consists of disposable cartridges with a maximum reservoir-capacity of 1.5 ml of
user-fillable fluid, as shown in figure 2a. Each cartridge has 16 Micro-Electro-Mechanical System
(MEMS) based nozzles, placed in-line at a distance of 254 µm apart from each other. The diameter
of each nozzle, the drop size generated through that nozzle, and the operating frequency of the
jetted fluid depend on the cartridge type. The two types of cartridges that are compatible with the
DMP-2800 are DMC-11601 and DMC-11610, which contain 9 µm and 21 µm diameter nozzles, and
produce nominal drops of 1 pl and 10 pl (±20% adjustability), with a maximum operating frequency
of 15 kHz and 60 kHz, respectively. The print-head also comprises of a built-in heater with a
maximum heating capability of 70°C (±1°C variability).[11]
Figure 2: a) DMC-11610 Cartridge, with the white reservoir and the MEMS controlled nozzle module separated
from each other. The nozzles are placed in the blue area shown in the inset. b) Print-carriage with the installed
cartridge, on top of the perforated and heatable platen and the cleaning station (at the left).
The substrate-holder, seen in the lower part of figure 2b, is a perforated metal platen connected to a
vacuum pump. It has a built-in heater able to heat the platen up to 60°C (±2°C uniformity), and can
hold up to 25 mm thick substrates. The substrate is placed on top of the platen and the platen is
scanned in the x and y-direction to achieve a raster-style printing.
The fiducial camera is mounted on the cartridge and it is used to align the substrate on the platen
and to inspect the printed pattern. It can be used to measure the size of the printed drops directly,
important when determining the print resolution. The software controlling the camera contains a
feature for measuring the head angle (saber angle), which permits the user to verify whether the
manually set head angle is correct. Also, it contains several features that help the user to fix the
offset of the placed substrate, to align with the printing axes, to save photos in .bmp format or to set
a print reference/print origin of the pattern. Particularly, these features help the user to keep track of
the pattern when a new substrate replaces an old one, when a cartridge with a new fluid is
introduced, or when a new print operation is launched.
The drop-watcher camera is a stroboscopic, built-in deposition observation system that allows the
user to inspect the drop formation at the nozzle/air interface. The camera image on the monitor
screen is a 150-fold magnification of about 210 mm x 170 mm, so that it represents an actual area of
about 1.4 mm x 1.1 mm.[11] The user can watch the drops in fixed static positions (image-like) as
well as under motion (video-like) when they are ejected from the nozzles. Using the drop watcher,
the drop velocity can be measured manually using the velocity markings displayed on the monitor.
Photos and videos of the process can be saved in the .bmp and .avi format, respectively.
The cleaning station comprises disposable cleaning pads that are used to clean the nozzles of the
cartridge (see figure 2b). Three methods of cleaning can be performed: purge, blot and spit. Purge is
used to ensure that all the channels in the cartridge are filled and free from air bubbles, blot is used
to remove any drops formed beside the nozzles, and spit is used to remove any clogging formed at
the nozzle orifice. These software-driven cleaning methods can be run individually or can be
combined as a cleaning cycle. Typically, a cleaning cycle consists of purging and blotting for a few
seconds. If the fluid used is prone to clogging, spitting is also added to the cycle.
2.2 Dimatix Drop Manager Software
The Dimatix Drop Manager is the PC-based Graphical User Interface (GUI) application software of
the DMP-2800 inkjet printer that allows the user to control it by means of a USB- and a video-in
cable. The main screen of this PC-user interface software (see figure 3) consists of three pull-down
menus: ‘File’, ‘Tools’, and ‘Help’; four segments: ‘Install Cartridge’, ‘Select Pattern’, ‘Load/Unload
Substrate’, and ‘Print Set-up’; three tabs: ‘Drop Watcher’, ‘Fiducial Camera’, and ‘Run Cleaning
Cycle’; and two navigating tabs: ‘Back’ and ‘Next’.
Figure 3: Main screen of the Dimatix Drop Manager software.
Whenever a new ink cartridge is installed, the cartridge settings window (see figure 4) is used to
input and establish the correct parameters with the help of the drop-watcher camera. The window
contains three tabs: ‘Waveform’, ‘Cartridge’, and ‘Cleaning Cycles’. The ‘Waveform’ tab (see figure
4a) contains the ‘Jetting Voltage’ buttons for all the 16 nozzles. These buttons allow the user to
regulate the voltage of each nozzle individually (in the range of 0 to 40 V). This individual voltage
regulation is particularly important because the velocity of the drop formed at a nozzle is a function
of voltage applied to that particular nozzle. This tab also contains a ‘Tickle Control’ on/off button
(with frequency adjustability) that enables and controls the low amplitude pulse that is given to the
nozzles periodically to move the meniscus slightly but not to eject a drop. The ‘Cartridge’ tab (see
figure 4b) contains four buttons: ‘Cartridge Temperature (°C)’ for controlling the jetting temperature
(in the range of ambient to 70°C), ‘Meniscus Vacuum’ for controlling the meniscus pressure (in the
range of 0 to 6 inches of water), ‘Jets to Use’ for selecting the adjacent jetting nozzles, and ‘Cartridge
Print Height’ for setting the distance of the print-head above the substrate (in the range of 0.25 mm
to 1.5 mm). The ‘Cleaning Cycles’ tab (see figure 4c) contains four buttons that allow the user to
maintain and create cleaning cycles before, during, and after the printing action as well as when the
printer is idle.
Figure 4: Cartridge settings window showing a) Waveform tab, b) Cartridge tab, and c) Cleaning Cycles tab.
The edit button in the ‘Waveform’ tab of the cartridge settings window opens the waveform editor
window, as can be seen in figure 14. This window consists of two graphs: ‘Jetting waveform’ and
‘Non-Jetting Waveform’, which allows the user to adjust the whole jetting process (the drop
formation, velocity, drop-size etc.) with the help of the drop-watcher camera. Clicking a segment in
the jetting or non-jetting waveform enables the user to adjust the required parameters in that
The ‘Pattern Editor’ option can be accessed through the ‘Tools’ pull-down menu of the main screen
window. This enables the user to make patterns with a desired resolution by setting the drop spacing
(in µm) that is consistent with the head angle, substrate-fluid pair, and the drop size. The buttons in
the window allow the user to draw patterns by portraying/canceling rectangular segments with the
help of a preview window. Also, in this section, the user can fix the reference point/print origin,
print a repetitive array of the designed pattern, and set the number of layers that the printer should
reprint automatically over the same pattern. The Dimatix Drop Manager software can import the
.bmp images and can process those images into pattern files through the ‘Pattern Editor (Bitmap
Images)’ window. This window also comprises different sections and buttons that allow the user to
watch and work with the imported image systematically.
The print set-up segment in the main screen window allows the user a final affirmation of all the
required parameters before a printing job starts and to confirm/cancel the printing. This window
summarizes all the required fields and allows the user to set the substrate thickness, jetting
temperature, the platen temperature, and to toggle the substrate holder vacuum pump on/off.
3 DMP-2800 Inkjet Printer: An Overview
The DMP-2800 is a DoD printer that is designed in the bend-mode configuration, as shown in figure
6, where the print-head is equipped with a piezoelectric transducer, which allows the user, depending
on the cartridge used, to create and eject 10 pl or 1 pl nominal drops by applying a time varying
voltage signal that is converted into translational motion by the receiving transducer. In practice, the
liquids employed must have properties that fulfill those of the so called ‘functional fluid’. The ink,
and the substrate used, brings performance limits such as a minimum size of individual drops and a
minimum line width when making a continuous trace. However, even with an ideal ink, the DMP2800 has mechanical limits that restrict the deposition to a maximum of 5080 drops per inch with a
minimum drop size of 5 μm at a head-angle of 1.1˚.
3.1 Advancement of the Printing Technology
The first crude inkjet device was patented by William Thompson in 1858.[13] Since then, inkjet
printing has matured and developed into a versatile and promising drop deposition technique.
However, even though the concept has improved over the 150 years it has existed, the principal
function still remains the same: the formation and deposition of droplets with the desired volume
and jetting velocity from both Newtonian and non-Newtonian fluids. Various methods have been
employed to achieve this, but most are found within two major categories: the Continuous Ink Jet
(CIJ) technology and the DoD technology. Though both technologies emerged commercially in the
1960s[14], scientists and commercial printer-manufacturers still find interest in both of them. In
spite of the fact that both technologies have developed over time, none can be said to completely
eclipse the other as each still got its own advantages. In CIJs, streams of ink droplets are formed by
the Rayleigh instability. These droplets are ejected under pressure through a nozzle with a typical
velocity of 10 ms-1 and a frequency of 20-60 kHz. A schematic of the drop ejection mechanism of
CIJ technology is shown in figure 5a. The nozzle is subjected to a voltage bias that imparts a charge
on each drop as it is formed. After ejection, each drop is subjected to a further voltage bias that
imparts a deflection of the drop to an angle proportional to the induced charge. Since by definition,
CIJ printer jets the ink continuously, a majority of the drops is not deflected for printing and only a
fraction of the ejected drops is actually used. The non-printed drops are collected in a gutter where a
pump is used to re-circulate the drops to the ink chamber. Though, this technology permits
relatively long distances between the nozzle and the substrate, no nozzle-clogging, and offers the
fastest inkjet printing, it still suffers from several drawbacks, such as the need for high-pressure
maintenance to supply the ink to the nozzle orifice, the complicated hardware needed to
synchronize the breakup of the drops when more than one nozzle is used, using only a fraction of
the ink to print, continuous re-circulation of the non-printed drops to limit the amount of waste
etc.[13, 15] On the other hand, in DoD technology, ink droplets are formed by propagating a
pressure pulse in the fluid held in a chamber. A schematic of this mechanism is shown in figure 5b.
In this case, when the pressure is more than a threshold limit, a drop is ejected. In the absence of the
pressure, the ink is held in the chamber because of the surface tension of the fluid. Also, a static
pressure is maintained to make sure that the meniscus at the orifice is stable. Hence, by definition,
the drops are ejected on-demand, as can be seen from the schematic. In this case, the drop
deposition is achieved by positioning the substrate under the nozzle before ejection of a drop.
Though DoD printers are operated at a lower frequency, typically 1-20 kHz, they offer a practically
uncomplicated, economically favored, and fairly straightforward method that makes the process a lot
easier and hence more favorable, especially when small amounts of expensive inks are employed.[16,
Figure 5: Schematics showing drop ejection mechanism of a) CIJ technology and b) DoD technology (piezo-actuator
In order to generate pressure to the actuator, several schemes are used in DoD based printers.
Among them, the two most common schemes are thermal and piezo based printers. In thermal
inkjet printers, the pressure is generated by vapor bubbles which are created by the local heating of
the ink. This limits the diversity of the ink as well as the durability of the print-head. In comparison,
piezo-actuator based inkjet printers can print almost all liquids while the printed drop volume ranges
from nanoliters to a few picoliters. Another advantage of the piezo inkjet printers over the thermal
printers is that the piezo materials can be used in different deformation modes, which allows for
large design flexibility. The most realistic designs are squeeze-mode, bend-mode, push-mode, and shearmode.[14] Figure 5b and 6 exemplify the squeeze-mode and the bend-mode design configurations,
Figure 6: Schematic showing drop ejection mechanism in bend-mode design configuration.
3.2 The PZT-MEMS Device Theory
This piezo-based DoD inkjet is based on the coupling between the electrical regime and the
mechanical domain through the piezo-electric actuator, and the coupling between the acoustic
regime and the fluid-dynamics domain through the drop formation mechanism. The electromechanical coupling is achieved using MEMS technology, while the acoustic-fluid dynamics
coupling is achieved by tuning the input voltage waveform that deforms the fluid chamber. The
combination of these two mechanisms facilitates the print-head of the DMP-2800.
In the bend-mode design, the piezo material is etched with each of the channels (fluid chambers) in
such a way that the externally applied electric field aligns in the direction parallel to the polarization
of the piezo material. The piezo material which is used here is lead-zirconate-titanate ceramics,
Pb(Zr0.53Ti0.47)O3 (PZT). Each channel of the print-head is actuated by the PZT, i.e. the systematic
deformation of the PZT causes the suction of the ink into the chamber (from the reservoir) as well
as the jetting of the ink through the nozzle (as a single droplet). The schematics shown in figure 7
visualize this process. This channel-PZT combination needs to deform as a single unit and this
deformation needs to be synchronized to the applied electric field. In order to accomplish this, each
channel-PZT unit of the DMP-2800 print-head is constructed using single crystalline silicon. Since
the thermal expansion coefficient of silicon is close to that of PZT, the combination of the two
materials ensures that the entire unit expands relatively uniformly and without stress under any
thermal load. Also, other inherent properties like the chemical resistivity, the single-crystal structure,
the lightness, as well as the stiffness make silicon an excellent choice as an integral part in the printhead.
3.3 Functional-Fluid Characteristics
The functional fluid (the ink) is a material that must be compatible with the printer, and certain
criteria need to be fulfilled for a fluid to be functional. This is due to the physics of the drop
formation, i.e. jetting the drops out of the nozzle, which essentially is very complex as it depends on
the forces involved in the fluid-statics and the fluid-dynamics as well as on the geometry and the
material properties of the fluid chamber. The schematic of figure 7 illustrates what happens when
the forward and reverse pressure in invoked in the chamber. The fluidic forces, e.g. viscosity, surface
tension, inertial force, compressibility etc., dominate the fluid-flow upon invoking the forward
pressure in the chamber. Also, the pressure becomes attenuated and reflected because of the
geometry and the material of the chamber. Thus, a spatial propagation of the fluid as a function of
time is realized. Near the nozzle, other factors, such as fluid-air interaction, surface tension,
temperature, capillary forces etc., make the propagation function even more complicated. As a
result, drops are formed as illustrated by the schematic in figure 7a. Again, just after forming the
drop, the nascent fluid is needed to pull back at the right time to break-off the drop and thus, a
backward pressure is also needed. Figure 7b illustrates the result when a sufficient backward
pressure is invoked. Hence, in order to form the drop of the functional fluid, this pressure must be
sufficient enough so that it can force the fluid to overcome the fluidic forces, impart momentum to
the fluid to jet the drop with a required velocity, and can work in the opposite direction to pull-back
the nascent fluid at the right moment to break-off a droplet.
Figure 7: Schematics illustrating working principle of drop-formation: a) when the forward pressure is invoked, and b)
when the backward pressure is invoked. Note that the fluid flows in the opposite directions, depending on the directions
of the invoked pressure, as indicated by the arrows.
In case of the DMP-2800, the actuator can generate the required back-and-forth pressure for fluids
with certain properties. In order to be compatible with the mechanical-electrical system of the
printer as well as with the dimensions of the print-head (i.e. nozzle, nozzle spacing), the functional
fluids must have properties that fall within a defined window. The fluid can be aqueous or solventbased, and both solutions and particle suspensions can work. For good performance, the fluids
should have a viscosity of 10-12 cps (0.01-0.012 pascal-sec) at the jetting temperature, though it is
possible to jet the fluid with a viscosity as high as 30 cps (0.03 pascal-sec). Also, for the desired
performance, the functional fluid should have a surface tension between 28-42 dynes/cm (0.0280.042 N/m) at the jetting temperature, though fluids having a surface tension as high as 60
dynes/cm (0.06 N/m) can be jetted. Additionally, to prevent the fluid-drop from drying at the
nozzle/air interface, fluids having a low evaporation-rate and a boiling point higher than 100°C are
preferable.[12] The fluid is preferably filtered before use to remove large agglomerates, fibrous
particles, or gels. Also, a pH-value between 4 and 9 is recommended. For some fluids, especially
aqueous-based, degassing might be necessary to remove any dissolved gas which could inhibit
The DMP-2800 inkjet printer is developed to jet functional fluids that have the aforementioned
properties, but fluids outside this range can also be jetted, albeit with lower jetting performance. In
some cases, the fluids need to be reformulated to achieve properties closer to those of the functional
fluid. This is necessary when the viscosity, surface tension and/or evaporation-rate of the original
fluid do not fall within the defined window of the functional fluid. This is normally achieved by trial
and error, employing additives in different ratios to change the properties of the fluid, and testing
the performance using the drop watcher. Additives involve (but are not limited to): surfactants, such
as carboxylates; solvents, such as tetrahydrofuran; and/or humectants, such as glycol. Simultaneous
manipulation of the jetting waveforms, the temperature, and the meniscus pressure while
characterizing the velocity and the drop-formation, are important during the trials. Other influencing
factors that need careful consideration are the cleaning cycle, non-jetting waveform, fluid-substrate
pair, letting the ink settle in the cartridge for a specific time before installing it in the machine, and
keeping the nozzle-areas of the cartridge clean etc. Though the reformulation of the ink may result
in lower performances in the firing frequency, drop velocity, drop formation and sustainability, it
should create spherical drops of sufficient volume without any tailing effect. As an example, figure 8
displays drops that were formed with a reformulated ink at only 2 kHz firing frequency, but which
exhibits spherical drops jetted at a ~7 ms-1 velocity without any tailing effect.
Figure 8: Stroboscopic drop formation photos captured by the drop watcher camera showing a) the tailing effect at ~30
µs, just after the drops come out from the nozzles and b) fine spherical drops without any tailing effect at ~100 µs
ejected at a velocity of ~7 ms-1.
3.4 Waveform Basics
The waveform gives the user control over the printing mechanism. The user can change the
parameters, e.g. jetting frequency, voltage, amplitude level, slew-rate, and pulse-duration, which
results in a change of the acoustic pressure acting on the fluid. This in turn changes the process of
formation and break-off of the droplets out of the nozzle. The user needs to develop the waveform
in parallel with the fluid. The typical basic waveform, or firing cycle, is divided into three/four
segments as shown in figure 9, where each segment has three adjustable properties: slew-rate, level,
and duration. However, as shown in figure 9a, the waveform also comprises a segment 0, but it is
actually connected to segment 4; naming it differently is done only for the sake of understanding the
waveform mechanism in a systematic and efficient manner. The level (in percentage) is the
amplitude of the applied voltage to the operating nozzle that determines how far the transducer is
bending, the slew rate (in a scale of 0 to 2) is the slope of the applied voltage that determines how
fast the transducer is bending, and the duration (in µs) is the time of the applied voltage that
determines how long the transducer will stay in that position. During segments 1 and 2, the drop is
formed and jetted, while the last two segments define the drop break-off and the resetting of the
unit for the next cycle.
Figure 9: a) Schematic of a jetting waveform with different segments (not in scale) and b) screenshot showing an
example of the jetting waveform as it can be seen in the waveform editor window.
As illustrated in figure 9a, a voltage is applied at the beginning, i.e. segment 0 and 4, so that the
transducer is warped slightly. The starting of the firing cycle is represented by segment 1. At first,
when the firing starts, the transducer is reset back to its neutral state (relaxing state) by applying 0 V
(0% level), as can be seen at segment 1 and the red segment of figure 9b. At this state, the fluid
chamber achieves its maximum volume and fluid is pulled in through the inlet, while the meniscus is
pulled inward at the nozzle orifice, as demonstrated earlier by figure 7b. The next phase, segment 2,
is the main drop ejection phase where the transducer is pushed to its maximum state by applying
100% of the applied voltage, as shown in the schematics as well in the screenshot. At this state, the
fluid chamber reaches its minimum volume and the fluid is pushed out of the nozzle orifice, helped
additionally by acoustic effects (see figure 7a for further demonstration). The slew-rate and the time
duration define the timing of the firing of the fluid. Just after the firing pulse, the recovery phase is
applied in segment 3 and 4 where the transducer is pulled back to a partially relaxing position. At
this state, the fluid chamber gets a partial volume, the chamber is decompressed and the fluid is
partially refilled for the next cycle.
In order to get a higher firing velocity, the slew-rate is recommended to be lower in segment 1 and 2
and higher in segment 3 and 4. Initially, a higher voltage is also recommended which can be
subsequently lowered when a satisfactory drop formation is observed. Additionally, since the first
two segments have the most impact on the velocity and the drop formation, the parameters of these
segments are needed to be dealt carefully while the parameters of the last two segments are merely
needed for the fine tuning of the drop formation.
Also, depending on the fluid used, a non-jetting waveform is needed. This waveform works in the
same way as described above but it is executed continuously to keep the nozzle ready for the firing
cycle. For non-jetting waveforms, the voltage amplitude is set at a lower level so that the ink in the
chamber is subjected to a dynamic pressure, without causing a drop to be ejected. It is also explained
in a later section and is shown in figure 15.
3.5 Printed Features: Resolution Parameters, Drop-Size and Limiting Factors
The printed features of the DMP-2800 printer depend on various factors: fluid and substrate
characteristics, fluid-substrate interaction (adhesiveness), sintering conditions of the fluid, print-head
temperature as well as substrate temperature, changing-viscosity of the fluid, drop-volume, head
angle (saber angle), and drop-size on the substrate. Factors related to the fluid and substrate
characteristics are porosity, surface energy and surface-smoothness of the substrate, the
adhesiveness between the fluid-substrate pair, surface tension, viscosity, and compressibility of the
fluid etc. These factors determine the properties like fluid-flow over the substrate surface, strength
of the adhesive bond, wet-film formation etc. Since these parameters only depend on the fluid and
the substrate, they need to be resolved before the printing operation. Also, factors related to the
sintering conditions are temperature, method etc. These parameters determine the properties of the
sintered material. Since these factors are inherent to the fluid used, they also need to be resolved
before the printing operation. In addition, changing-viscosity of the fluid, jetting temperature and
platen temperature can also affect the printing features. This is due to the fact that the fluid may be
blended with surfactants, solvents, and/or humectants, which might require tuning of temperature
as well as meniscus pressure. Since these issues are to be faced while tuning the drop formation, they
need to be resolved before characterizing the printed feature.
For a particular fluid-substrate pair and jetting parameters, the resolution of the printed pattern
depends directly on the drop-size and the head-angle (saber angle). As the schematics in figure 10
illustrate, the printer carriage and the platen move in such a way that the printing operation is done
in a raster-style manner; the carriage moves horizontally (x-direction) while the platen moves
vertically (y-direction). Since the printing nozzles are situated in a single line, the jetting nozzles
move over the platen following a single line in the x-direction, as shown in see figure 10a. As the
drops form in a single line following a raster-style printing, the user-set head-angle fixes the line to
move at a certain angle with respect to the x-direction, as can be seen from figure 10c, which lowers
the effective spacing between the nozzles. This results in the partial overlap of the drops that
ultimately defines the print resolution. For a certain fluid-substrate pair, the user needs to determine
the drop-size and in order to find out the drop-size, a recommended printing pattern, called ‘testpattern’, is printed while the head-angle is kept at 90°, i.e. perpendicular to the direction of the
cartridge movement, as illustrated by figure 10b. This results in a series of drops on the substrate.
The user needs to inspect these drops with the fiducial camera and to measure the radius of the
drops with the on-screen distance measuring feature. According to a chart given by FUJIFILM
Dimatix Inc.[11], this radius value corresponds to a specific saber angle that in turn corresponds
with the resolution of the printed pattern (in drop per inch values). This procedure is further
exemplified in figure 16.
Figure 10: Schematics showing the raster style printing that explains the print resolution when the head-angle is kept
at different angles with horizontal direction: a) at 0°, b) at 90° and c) at an angle in between. Note that only three
nozzles and a single cartridge-sweep are shown in this illustration.
After measuring the drop-size, the user needs to insert the value in the pattern editor window and to
set the corresponding head angle manually for investigation. The user needs to align the angle
accurately, since an error here will distort the printed pattern. Hence, an experiment should be
performed upon every change in head angle, where a printed trace in the y direction is inspected (see
figure 11b). If the line consists of tilted line segments, the head angle needs to be adjusted.
Additionally, a trace in the x direction is recommended, to ensure that the drops are ejected at a
sufficient rate to achieve the sufficient spatial resolution (see figure 11a). As an example, when the
experiment was performed in search for the possible finest resolution of the printed pattern that
could be achieved with one of the Ag-inks on the glass substrate, line breaking and waviness were
observed. In this example, horizontal and vertical lines of different widths were printed while the
head-angles and drop-sizes were varied. The features can be seen from these experiments, where the
head angle was fixed at 5.6° and the drop-size was fixed at 25 µm.
Figure 11: Lines printed with an Ag-ink illustrating the different features encountered while fixing the resolution of
the pattern with the head angle fixed at 5.6° and the drop-size fixed at 25 µm; showing a) horizontal lines of 5 µm
to 25 µm width and b) a vertical line of 40 µm width. Note that the photos were captured by the fiducial camera
before sintering, just after the printing operation; that the widths were defined at the pattern editor window before
printing; and importantly, that the head-angle was set manually.
The printed pattern, a single line for example, is determined by the user-defined deposition
parameters. Since a series of drops make a line on the substrate, the parameters in this case are the
same as mentioned above. In addition to those, there are other factors that restrain the printed
pattern. Since the drops overlap differently depending on the drop-size and the head-angle, the
width of the line in general can be affected; more commonly it causes ‘scalloping’ or ‘waviness’ at
the edge of the line (see figure 12a). Also, the fluid may bead up and the line may break into
individual spots (see figure 12b). When attempting to print thin lines, the user faces the fact that the
waviness at the edges causes the line to break as the line-width reaches its minimum limit. Figure 12a
shows beading of drops just after the printing operation and figure 12b shows the waviness because
of this beading effect that in turn breaks the line. For this reason, the optimization between the
surface tension of the fluid, surface properties of the substrate and the beading effect of the fluid is
necessary. Hence, depending on the fluid-substrate pair and the sintering condition, the user needs
to fix the drop-size first and then use a trial-and-error approach to establish the minimum linewidth.
Figure 12: Single line of Ag nano particles (printed with Ink#1) deposited on the glass substrate (photos were
captured by the fiducial camera) illustrating the waviness and the beading effects a) just after the printing operation and
b) a few seconds later. Note that the photos were taken before sintering.
4 Ag-inks: Optimizing, Jetting and Sintering
This thesis-work comprises a systematic study of two different types of Ag-inks in order to compare
their physical characteristics and their performances as the bottom electrodes of structured
sandwich-cell LECs. These inks are: DGP-40TE-20C (ANP Co. Ltd., S. Korea)[19] and TEC-CO011 (InkTec Co. Ltd., S. Korea).[20] Hereafter, the former will be referred to as Ink#1 and the latter
as Ink#2. Pictures of the inks are shown in figure 13.
Ink#1 Ink#2
Figure 13: Ink#1 and Ink#2 as seen a) in the manufactures’ supplied bottles and b) in the glass vials (~2ml). Note
that Ink#1 was supplied in the glass container and Ink#2 was supplied in the black plastic container. Also note that
the black ‘absorbent’ appearance of Ink#1 and the ‘transparent water-like’ appearance of Ink#2.
4.1 Difference between the inks
The differences between these inks should be noted. Ink#1 comprises ligand-capped metallic Agparticles in a polar solvent (triethylene glycol monoethyl ether, TGME), which provide a high
binding strength to the metal core and results in a stable ink. This ink is manufactured specifically
for deposition on glass substrates using inkjet printers, such as the DMP-2800. On the other hand,
Ink#2 comprises Ag nanoparticles in an organic matrix that contains solvents, polymeric
compounds and dispersants. This ink is designed for plastic substrates, and optimized for spray or
dip-coating. Table 1 presents the details of the inks.
Product No.
Manufactured for
Recommended Substrates
ANP Co. Ltd., S. Korea
ITO glass, Bare glass
InkTec Co. Ltd., S. Korea
Coating (dipping/spray)
Price (per gram)
Dispersion Matrix
Ag content (wt %)
Particle-size (nm)
Surface tension (dynes/cm)
6.6 US $ (approx.)
Polar solvent- triethylene glycol
monoethyl ether (TGME)
0.4 US $ (approx.)
Organic CompoundUnknown
Viscosity (cps)
Supplied in (see figure 13a)
Plastic Bottle (Black)
Appearance (see figure 13b)
Black, ink-like
Transparent, water-like
Storage condition
Sintering condition
~180˚C, 30-45 min on glass, in
~120˚C, 3-15 min on
plastic, in air
Table 1: Details of the inks.[19, 20]
4.2 Optimizing an Ink into a Functional Fluid
Since Ink#1 demonstrates all the required properties in order to be used as the functional fluid, it
was employed as received. However, Ink#2 required a reformulation to jet with the DMP-2800
since the properties e.g. viscosity did not fall in the designated window. Though this ink is made
particularly for spray- and dip-coating on plastics, it was observed that the adhesion with glass
substrates was high enough to result in satisfactory conductive films following sintering. Being
inspired from this fact, Ink#2 was reformulated and optimized into a functional fluid for jetting
purposes. In doing so, a trial-and-error study was performed where several different solvents were
added to the original ink in order to make it a functional fluid. In this study, the core focus was the
tuning of viscosity and surface tension.
The best jetting performance was observed when tetrahydrofuran (THF) was mixed with Ink#2 in a
ratio of Ink#2 : THF=3 : 1 (vol/vol) and subsequently jetted at 30°C cartridge temperature and at
4.0 inch water meniscus pressure. Having 0.48 cps viscosity and 28 dynes/cm surface tension, and
appearing as a colorless-liquid, THF gave the best results by lowering the viscosity and the surface
tension of the original ink. Though the surface tension of Ink#2 falls within the designated window,
the viscosity does not. In addition, THF has a boiling point of 66°C that gives an advantage in
printing with this Ink#2-THF mixture if the platen temperature is kept at ~60°C. This is because of
the fact that the platen temperature causes almost instantaneous evaporation of the THF after the
drop being placed on the glass substrate, leaving only the traces of Ink#2 which consequently turns
into Ag-traces after sintering. It is important to note that even though the recommendation for the
functional fluid is that a boiling point of more than 100°C should be used, this study demonstrated
otherwise. It is evidenced that adding solvents with lower boiling point and high evaporation rate
can be advantageous, provided that the substrate temperature is kept near to the solvent’s boiling
point. The solvent may facilitate the optimization of the fluid and the jetting performance, but if it
evaporates quickly on the substrate, then the deposited ink can be unaffected during sintering. This
is particularly true when thin lines are printed, since a faster drying time alleviates the beading effect
and line breaking
4.3 Adjusting the Jetting Parameters
The 10 pl DMC-11610 cartridges were exclusively used for the jetting of both the inks. Though 1 pl
cartridges allow jetting with higher velocities than 10 pl cartridges, the 1 pl cartridges were not
included in this particular thesis work, and the focus was instead placed on the comparative study of
the ink properties and their performances as electrodes in a LEC configuration. Hence, jetting inks
using 1 pl cartridges, and printing complicated and challenging print patterns, are left for future
Both inks were filtered through a 0.45 µm Teflon filter and kept in glass-vials under ambient
conditions, as shown in figure 13b. The ink-filled cartridges were kept for more than 1 hour and a
few initial cleaning cycles were carried out before jetting. In case of both the inks, the respective
waveforms were optimized for spherical drop formation with minimized tailing effects at a jetting
velocity of 5-7 ms-1. The drop watching facility was used to watch the drops as they formed, while
the jetting and non-jetting waveforms and other jetting parameters (voltage of the nozzles, jetting
temperature, meniscus pressure, number of jets to use, and cleaning cycles at the start/during the
print operation) were tuned and saved for future use. Figure 14 exemplifies the adjustment
environment of the jetting of an ink (Ink#2).
Figure 14: Screenshot showing the drop formation parameters with the drop watching camera view, taken while jetting
an ink. Note that spherical drops were ejected at ~8 ms-1velocity.
4.4 Jetting the Inks
Ink#1 was jetted at a 32°C cartridge temperature and at 4 inches water meniscus pressure, with the
cartridge kept at a height of 0.5 mm from the substrate. A cleaning cycle of 1 sec purging and 1 sec
blotting was utilized in all the printing. The drops were jetted at a maximum jetting frequency of 5
kHz, while the velocity was maintained at between 5-7 ms-1. The best jetting performances were
achieved with the single firing cycle of 12.3 µs with the 4-segment jetting waveform, with the nonjetting waveform maintained at 60% voltage (see figure 15a). At segment 1 of the jetting waveform,
7% voltage with a slew-rate of 0.8 was applied for 3.3 µs while at segment 2, 100% voltage was
applied for 4.8 µs with a slew-rate of 0.38. At segment 3 and 4, 60% voltage was applied for about
4.2 µs so that the operating nozzle could initiate the next cycle. Likewise, Ink#2 was jetted at the
same meniscus pressure and the same cleaning cycle was maintained, though the cartridge
temperature was 30°C and the cartridge height was 0.25 mm from the substrate. The maximum
jetting frequency was 2 kHz with the velocity maintained at between 5-7 ms-1. In this case, the single
firing cycle duration was 14.9 µs, as can be seen by figure 15b. The best performances were achieved
by using a 3-segment jetting waveform while the non-jetting waveform was maintained at 47%
voltage. It should be noted that in the case of both the inks, the applied voltage and the slew-rate
were almost identical in segment 1 as well as in segment 2, but the durations were not. For Ink#2,
the duration in segment 1 was about 6 times lower than that of Ink#1 but it was double in segment
2. This implies that Ink#1 needed more time to refill the ink chamber but fired faster, while Ink#2
filled the chamber quickly but needed more pressure to fire. Also, Ink#2 required more time to
complete a firing cycle: about 2.6 µs more than that of Ink#1.
Figure 15: Adjusted jetting and non-jetting waveforms of a) Ink#1 and b) Ink#2; the highlighted part of the curves
are the firing segments (segment 2). Note that the duration of the firing segment in Ink#2 is double to that of Ink#1.
After adjusting the waveform, the print resolution was needed to be fixed before any pattern could
be printed. The drop size was determined by printing the test pattern and measuring the drop size
using the fiducial camera and the on-screen distance measuring feature, as exemplified by figure 16a.
The measured drop-size was inserted in the print pattern window and the corresponding head angle
was set manually. Some patterns, a single line for example, were printed and the features were
inspected carefully. Since the errors due to the radius measurement and head angle setting were
unavoidable, this procedure was followed unless a satisfactory performance was achieved. Examples
of these trails are illustrated in figures 11 and 12. Figure 16b shows the narrowest-line that could be
achieved without any waviness and segmentation. The minimum width achieved by Ink#1, at a 6.8°
head angle and 30 µm drop-radius, was 50 µm with a resolution of ~850 dpi. On the other hand, the
minimum width achieved by Ink#2, at a 5.6° head angle and a 25 µm drop-radius, was the same as
that of Ink#1 but with a slightly higher resolution, ~1000 dpi.
Figure 16: Print resolution experiment of Ink#1 on the glass substrate where a) drops of ink#1 on the glass
substrate are seen (captured by the fiducial camera) b) 50 µm line-width (the minimum) was achieved with Ink#1.
Note that the photos were taken before sintering. Also note the line-width mentioned here is the width that was
inserted in the pattern editor window.
Since the inks and the printing environment may show a slight variation from time to time, the
jetting performances of both inks were checked before performing any print operation; and if
deemed necessary, the printing parameters and waveforms were recalibrated to restore adequate
jetting performance. The user may choose any number of consecutive nozzles to perform the print
operation as long as the velocities of the drops formed at different nozzles are similar (see figure 8b
or figure 14). In case of these inks, though the waveforms were adjusted using a row of nozzles, only
one nozzle was actually employed for the print operation. This pragmatic approach allowed for the
unique opportunity to watch only a single drop formation and a very swift waveform recalibration,
and importantly, this approach offered the opportunity to get rid of the unavoidable mechanical
error due to a manually-set head-angle. This one-nozzle approach does however suffer greatly for
more complex patterns as the printing time will be prolonged.
4.5 Sintering Ag Inks on Glass Substrates
Microscopic glass slides (Thermo Scientific, Menzel-Gläser, Germany) with a size of 76 mm x 26
mm x 0.25 mm were used as substrates. A piece of A4-size paper was placed underneath the glass
slides to cover all holes in the vacuum platen. In order to have the surface smooth and clean and to
enhance the adhesion angle between the surface and the fluid, the substrates were UV-ozone treated
for 10 min, particles removed by a pressurized air-gun, and then wiped by a piece of cloth before
being placed on the platen. The platen was kept at ~60°C for both inks. This was done for Ink#1 as
it was observed that the line breaking due to the beading effect is less pronounced at ~60°C than at
room temperature. On the other hand, for Ink#2, keeping the platen at ~60°C helped THF to
evaporate very fast as it impinges on the platen. Immediately after the printing operation, the glass
substrates were placed on a hot plate and the printed traces were sintered in air at an elevated
temperature. Ink#1 was sintered at ~180°C for more than 45 min and Ink#2 was sintered at
~120°C for 15 min. In case of Ink#1, the ligands (e.g. thiols, polyelectrolytes, polymers, or
polyethylene glycol) and Ag-particles are bonded together. When the heat is applied, the solvent
evaporates and the particle-ligand bonds are broken. This leads to a direct physical contact between
the Ag-particles. High conductivity is achieved after sintering through the formation of percolation
channels, rather than through the complete collapse of the nanoparticles into bulk metal.[21] The
sintering process for Ink#2 is different. Ink#2 is a transparent, ‘non-particle-type’ ink and the
organic dispersant of this ink is designed so that it remains in the liquid phase as a coating of the Agparticle; but when heat is applied, the organic components and solvents evaporate. The Ag-particles
sinter at the edges, so that a continuous metallic layer can form.[22, 23]
The sintering processes were observed in both cases. The temperature of the hot plate was increased
gradually from 60°C to either ~180°C (Ink#1) or ~120°C (Ink#2). In case of Ink#1, the ‘beading
effect’ was observed as soon as the drops were deposited on the glass substrate and ash-black traces
were seen while the printing operation was going on. When the substrate was placed on the hot plate
and the temperature was raised gradually, the printed traces remained the same throughout the
observation period with no visual difference observed, i.e. the ash-black traces did not change
appearance during the sintering process. On the other hand, the traces made by Ink#2 demonstrated
an interesting feature, where a transition from ‘liquid transparent traces’ to ‘non-transparent solid
metallic traces’ took place, as shown in figure 17. The printed traces were not visible at the time of
the printing (at ~60°C), though ‘liquid transparent traces’ on the glass substrate could be detected
after printing if the substrate was inspected at a close distance (see figure 17a). When the substrate
was placed on a hot plate and the temperature was raised gradually, the traces appeared first as black
lines (see figure 17b-c), and then the formation of the Ag-layer was observed as metallic silver with a
slight yellow tint (see figure 17d).
Figure 17: Photographs of Ink#2-printed traces when sintered for more than 15 min, taken at different temperatures:
a) at ~60°C, b) at ~90°C, c) at ~100°C and d) at ~120°C. In addition, this complex feature exemplifies the fact
that Ink#2 was optimized properly.
5 Ink Characterization
Characterizations of the inks were performed at room temperature and ambient pressure following
the heat-induced sintering, during which the inks had formed conductive Ag-traces on the glass
substrate. These characterizations encompass specific resistance measurement and thickness
measurement of the printed traces. In addition, the physical appearance of the liquid Ag-inks when
stored in air was also observed.
5.1 Theory: Specific Resistance Measurement
Ohm’s law states V=IR, where I is the current between two points of a conductor, V is the voltage
difference between the two points, and R is the resistance. If the temperature is kept fixed, the
resistance R of a 3-dimensional Ohmic conductor depends on the dimensions only i.e. R∝ , where
L is the length and A is the cross-section area, being the product of the width W and the thickness, t
(i.e. A=Wt), as illustrated by the schematic in figure 18. The proportionality constant of this relation
is called the specific resistance ρ. This is an intrinsic property of a material that only depends on
temperature. For pure metallic Ag at 20°C, the specific resistance is ρ =1.59 µΩ-cm (i.e. ρ =1.59*108
Ω-m). Using the equation, R= , the specific resistance of the material can be obtained by
measuring the resistance R of a 3-dimensional sample and plotting it as a function of L/A. The
slope of this plot will be the specific resistance ρ.
Figure 18: Schematic of the 3-dimensional arrangement of a sample.
5.2 Experimental setup and Measurement Conditions
Though a 4-point probe instrument could be used to measure the sheet resistance of the printed Ag
films directly, a different procedure was employed in this thesis, as a 4-point instrument may easily
scratch the printed films on the glass substrate. The 4-point probe technique further requires a
‘uniform surface’ of specific area which is quite impractical for the jetted inks since a larger area may
result in a non-uniform surface after sintering. Therefore, to measure the specific resistance of the
Ag-traces on the glass substrates, a new set of two pair of probes was designed (see figure 19b), so
that a constant current could be applied through one pair of probes, while the resulting voltage at
the sample contact-points was measured with the other pair of probes. However, the new probes act
independent of each other, and the distance between them cannot be determined with great
accuracy. Determining the sheet resistance of a film directly using the new probes is therefore
difficult. However, they are very useful for determining the resistance of thin lines.
The probes were connected to an Agilent 34401A digital multi-meter (Agilent technologies Inc.,
USA), and a LabView® program (National Instruments Corp., USA) was designed (see figure 19c-d)
to control the resistance measuring setup. All samples (see figure 19a) were fabricated with only one
print sweep. Extra drops were deposited manually using a syringe at the end points of a trace after
printing (but before sintering) in order to facilitate the connection between the sample and the
probes. Three lengths were printed with each ink: L = 2 cm, L = 3 cm and L = 4 cm. Each samplelength was printed in 10 different widths: from 50 µm to 1 mm. Hence a total of 60 samples (3 x 10
x 2 = 60) were prepared, as can be seen by figure 19a. Each sample was characterized with the
aforementioned LabView-Agilent-probe setup. 20-25 readings were recorded for each sample, and
the average was used as the effective resistance R of a single sample. Though L and W were defined
in the pattern editor window before printing and be deposited on the glass substrate almost with the
same dimensional precision, variations were observed due to variations of the drop-size, waviness of
the printed traces, the adhesion between glass-ink pairs, and the sintering mechanisms. To
circumvent these variations, several cross-sectional surface profiles were measured at different
points of each sample (see figure 18) using the DektakXT Stylus Surface Profiling System (Bruker
Corp., USA), as shown in figure 19e-f. These surface profiles were exported to Origin® 8.5
(OriginLab Corp., USA), where the areas under each profile curve could be calculated. The nonideal trace was then modeled by a perfect straight rod, with a cross sectional area A given by the
average of several surface-profile areas. Finally, all R and A values for a specific L were plotted on
an ‘R versus L/A’ graph using Origin® 8.5. A linear fitting of the slope of the plotted data gave the
specific resistance ρ. Thus, three specific resistances for the different L values were obtained for
each of the inks. In addition, the average thickness t was obtained using the DektakXT, Stylus
Surface Profiling System, and the physical appearances of the Ag-inks were observed for over a
month under ambient conditions and duly documented.
Figure 19: Characterization experiment, showing a) samples printed on the glass substrate after sintering, b) designed
probes, c) front-panel, and d) back-panel of the designed LabView® program, e) DektakXT, Stylus Surface
Profiling System (Bruker Corp., USA) and f) the surface profile acquired by the profilometer.
5.3 Results and Discussions
The specific resistances at different L obtained for Ink#1 and Ink#2 are shown in figure 20. The
measured specific resistance of Ink#1 falls in the range of 10-19 µΩ-cm, and for Ink#2 in the range
of 5.4-13.8 µΩ-cm. In comparison with the specific resistance of bulk Ag (1.59 µΩ-cm at 20°C),
Ink#1 shows 6-10 times higher sp. resistance while Ink#2 shows 4-8 times higher sp. resistance.
The manufacturers claim that the specific resistance of the Ag-traces (after sintering) to be 5-9 µΩcm and 6 µΩ-cm, respectively, close to what is observed.
The difference between the measured values and the vendor specified value might be a
measurement artifact: due to the manually deposited drops at the ends of each line that may increase
the length L (see figure 19a), due to the positioning of the two points at the profilometer that may
overestimate the width W (see figure 19f), and due to insufficient data points in the linear fitting (see
figure 20a-f).
The thickness of the traces printed by Ink#1 spans a range of 0.3-0.5 µm (i.e. 300-500 nm), and for
Ink#2 the range is 0.08-0.1 µm (i.e. 80-100 nm). The average thickness of Ink#1-printed traces is
thus ~4 times higher than that of Ink#2, as indicated further by the difference in colors in the
respective 3D scans, shown in figure 21b and 21d. A hypothesis is that when THF was mixed with
Ink#2 in a ratio of Ink#2: THF=3:1, the Ag content lowers to ~7.5 wt% from the original (10
wt%), which results in ~4 times lower Ag content than Ink#1. Also, the print-resolutions of both
the inks are almost the same, which signifies the fact that the drops jetted with the inks are almost
identical in volume. Hence, it can be approximated that having ~4 times higher Ag content than
Ink#2, Ink#1 results in ~4 times thicker traces than its counterpart. In addition, it was observed
that the peak thickness of Ink#1-printed profiles is at least twice that of Ink#2-printed profiles, as
evidenced by figures 21a and 21c that show the peak-values of the respective profiles as obtained by
the profilometer. The peak thickness of each profile was taken into particular consideration, because
sandwich cell LECs suffer from the possibility of experiencing shorts in between the electrodes,
with a more uneven line being more sensitive to short circuits than an even line.
Furthermore, the physical appearences of the inks were observed. Though Ink#1 did not show any
change in its appearance, Ink#2 demonstrated an interesting property as it changed its liquid
appearance from clear-transparent to red-brown during the first week of storage. It continues to
change to a darker reddish up to 3-4 weeks, and therafter return to a clear transparent state after 5-6
weeks, as shown in figure 22. Since the detail of the ingredients of the ink is unknown, the reason
behind this appearance-change is difficult to pinpoint. Though no precipitation was observed, there
may be an interaction with light that results in the change of appearance. This hypothesis is
supported by the fact that the manufacturer supplied the ink in a black-plastic bottle, as shown
previously in figure 13a. To improve repeatability, all the printing operations discussed in this thesis
were performed with ‘fresh’ inks. No experiment was performed to characterize how inkjetted traces
are influenced by this appearance-change.
Figure 20: Specific resistance measurement plots: ‘R versus L/A’, showing the specific resistances of Ink#1 (20a,
20c, 20e) and Ink#2 (20b, 20d, 20f) for the three lengths: (a-b) L=2 cm, (c-d) L=3 cm and (e-f) L=4 cm,
Figure 21: Surface profiles and 3D photos of a-b) Ink#1-printed and c-d)Ink#2-printed traces. Note that the color
differences in the 3D photos (figure 21b-d) are due to the thickness of the traces, illustrating the fact that Ink#1 trace
is thicker than that of Ink#2.
Figure 22: Physical appearances of the inks. Ink#1 displays no change after being stored in air for 4 weeks, while
Ink#2 demonstrates a distinct shift of its color: i) ‘fresh’, ii) after 2 weeks, and iii) after 4 weeks.
6 Performance in LECs
The primary objective of this thesis-work was to find an inkjet compatible Ag-ink that is functional
as an electrode in a LEC. Though performance can be measured in terms of specific resistance, as
discussed in the previous sections, compatibility of the inks with the electrochemical nature of the
LEC is essential. Additives in the inks, about which nothing is known, might react during the
reduction and oxidation of the LEC and might result in poor, or no, light emission. In order to
compare the two inks, it is therefore essential that their performances as electrodes in the sandwichcell structured LECs are measured.
6.1 Theory: Working Principal of LECs
In order to understand the working principal of LECs, the analogous description of its doped
inorganic semiconductor device counterpart is helpful to start with. Simply put, when an external
voltage is applied, holes/electrons are injected at the anode/cathode, a process that is facilitated by
placing a p-doped material next to the anode, and an n-doped material next to the cathode. The
interface between the p-doped and the n-doped regions is called a p-n junction, and here electrons
and holes can recombine under the formation of excitons. The decay of the excitons can result in
the emission of radiation. If the frequency of this radiation, which depends on the energy gap
between the conduction band and the valance band of the material, falls within the visible region,
the radiation is seen as light. Thanks to the π-conjugated polymer theory, conjugated polymers,
polyacetylene for example, operate analogously. Though a polymer is typically a non-crystalline,
three-dimensional entity composed of chains with finite length which results in an energy band
scheme that is essentially very complex, one can still approximate it with a material having a valance
and conduction band. In organic electronics, the collection of energy levels corresponding to the top
of the valance band is referred to as HOMO and the bottom of the conduction band is referred to
as LUMO. This comparison is illustrated by the schematics shown in figures 23a and 23b. These
polymers, when powered by an external power supply, can emit light through the recombination of
electrons in the LUMO and holes in the HOMO. Like inorganic semiconductors, the polymers’
electrical properties can be manipulated by doping, for example, by chemical reduction/oxidation
using a redox agent, or through electrochemistry by adding an electrolyte so that electrons/holes are
added to the LUMO/HOMO bands and subsequently subjecting the polymer-electrolyte mix to a
potential bias.[24, 25]
In the basic configuration of the LEC, the semiconducting polymer and the electrolyte, hereafter
referred to as the active material, are sandwiched between two electrodes, as shown in the schematic
of figure 23. Figure 23b illustrates what happens in the absence of an external power supply. The
energy bands i.e. LUMO and HOMO are not subjected to any voltage bias and are therefore
illustrated as flat lines. In this state, no charge injection takes place since the HOMO is filled and
electrons do not have enough energy to reach the LUMO. Immediately after applying a potential
bias, as indicated by the inclined lines of the LUMO and HOMO of figure 23c, no significant
injection of electrons/holes occur as the energy barrier is still too large for efficient tunneling,
assuming that all the active material is subjected to a constant potential gradient. However, the
applied potential allows for ion migration throughout the active material, pushing positively charged
ions towards the cathode and negatively charged ions towards the anode. Gradually, these ions will
screen the electrostatic potential from the electrodes, and eventually form electrical double layers in
the vicinity of the electrodes, as shown in figure 23d. Hence, the width of the energy barriers
between the electrode and the active material decreases, which enables significant electron/hole
injection into LUMO/HOMO by tunneling, as shown in figure 23e. These injected and
subsequently charge-compensated electrons and holes reduce and oxidize the polymer, respectively,
which in turn results in a significant increase of the conductivity of the active material. These
electrochemical doping progresses continue until the two doping fronts meet in the center region
under the formation of a p-n junction, as shown in figure 23f. It is at the p-n junction that light is
Figure 23: Schematics, illustrating the working principal of the LEC at different states.
6.2 Making Sandwich-cell Structured LECs
The sandwich-cell LEC was made according to the schematic shown in figure 24. The active
material was sandwiched between printed Ag-electrodes on a glass substrate, and a thermally
evaporated Al-film.
Figure 24: Schematic of sandwich-cell structured LEC.
Printing the Bottom Electrodes
The bottom electrode of the sandwich-cell LEC was printed on the UV-ozone treated clean glass
substrates in the same fashion as described in the previous sections. To compare the performance of
the two inks, the structure of the LEC was kept fairly simple. Two lines with the same dimensions
were printed side-by-side, using ink #1 for line 1 and ink #2 for line 2. Hereafter, this arrangement
will be referred to as ‘electrode pair’. Several samples of electrode pairs can be seen in figure 25a and
25c. In order to print the bottom electrodes, a 20 mm long and 70 µm wide line was printed and
sintered with Ink#2. After that, Ink#1 was used to print another line of the same length and width
parallel to the first one on the same substrate, at a distance of 2-3 mm from the first one. Since it
was observed that Ink#2 can withstand a 180°C temperature without any influence on the
conductivity, this extra curing of Ink#2 was assumed to not affect the results. As can be seen in
figures 25a and 25c, these two printed lines were connected together using syringe-deposited drops
and conductive tape to facilitate the use of the measuring probes. This is further demonstrated in
figure 26 and 27a where it can be seen that an electrode pair is connected with the external probes
by the means of the conductive tape.
Preparing the Active Material and Drop-casting
The active material solution comprised Superyellow (SY, Merck, PDY-132), poly(ethylene glycol)
dimethacrylate (PEG-DMA, Sigma Aldrich) and potassium trifluoromethanesulfonate (KCF3SO3,
Sigma Aldrich). SY was dissolved in toluene by using a magnetic stirrer and an elevated temperature
of 50°C (323 K) for 24 hours while PEG-DMA and KCF3SO3 were dissolved in cyclohexanone.
Dissolving and mixing the materials was performed under ambient conditions, and all solutions were
made using a solid material content concentration of 10 mg/ml. These solutions were mixed in a
mass ratio of SY:PEG-DMA:KCF3SO3=1:0.5:0.1 that resulted in the desired active material; a glass
vial that contains the blended active material as can be seen in figure 25b. Spin-coating of the active
material at a rate as low as 800 rpm (for 60 sec) was tested (and yielded films with an average
thickness of 0.15-0.2 µm), but unfortunately was found to regularly result in shorts between the Alfilm and the printed Ag-lines, as exemplified by figure 26. Hence, drop casting of the active material
solution was tested instead, as depicted in figure 25b. A glass pipette was used to drop-cast the active
material onto the printed electrodes. The glass substrate was placed on a flat surface and the active
material was deposited with the pipette-made drops by moving over the substrate from one side to
another in a slow manner, and returning to the beginning for the next sweep. 3-4 sweeps were
needed for each substrate. Since the aim of this process is to have a film as uniform as possible, the
velocity of the sweeping motion over the substrate was maintained constant. In addition, the process
was performed very carefully so that all the samples on a substrate were covered, but no drops were
deposited out of the substrate, as evidenced by figure 25c. Also, whenever an air-bubble was
formed, it was removed using the pipette. After completing the drop-casting, the substrate was dried
for 15-20 min in air before it was mounted onto a shadow-mask (see figure 25d). Figure 25c shows
the drop-casted material during drying. The material dried first at the edges of the substrate, as
indicated by a color shift. The center of the substrate remained wet for the longest period. The
average thickness of the drop-casted layer was measured with the surface profile and found to be
0.3-0.4 µm.
Figure 25: The fabrication of sandwich-cell LECs with printed electrodes showing a) electrode pairs on glass
substrates, b) active material ink in a material mass ratio of SY: PEG: KTF=1:0.5:0.1, c) drop-casted active
material on top of the electrode pairs and d) samples mounted with the shadow-mask so that an evaporated Al-film
can be made with dimensions defined by the shadow-mask.
Figure 26: An electrode pair of LECs experiencing shorts between the Al-film and the printed Ag-lines when the
active material was spin-coated.
Drying the Active Material and Evaporating the Top Electrode
After mounting the samples on the shadow mask, the arrangement was transferred to a hotplate set
to ~70°C, and left to dry for 14-15 hours. This drying was performed inside a glove box with
nitrogen atmosphere containing less than 1 ppm oxygen and water; hereafter referred to as the ‘wet
box’. After drying, the samples were transferred to a thermal evaporation chamber (Univex 350,
Oerlikon, Leybold Vacuum, Germany) positioned in another glove box, also filled with nitrogen
atmosphere but completely solvent free; hereafter referred to as the ‘dry box’. In the evaporation
chamber, an Al-film was deposited (Al, 99.999%, Umicore) on top of the active material, with a 76
mm x 9 mm area defined by the shadow mask (see figure 25d). The thickness of Al-film was
controlled to 0.09-0.1 µm. The active material is now sandwiched between the Ag-printed bottom
electrode and the Al top electrode.
6.3 Experimental Setup and Measurement Conditions
Thanks to the open structure of the printed Ag-traces, light from the LEC can escape through the
Al electrodes and the glass substrate, in the direction of the arrows shown in the schematic of figure
24. The electrode pair was tested right away in the dry box while applying a voltage bias between the
printed Ag-electrode and the evaporated Al-electrode. Since both the electrodes in the electrode pair
were connected, both of them experienced the same voltage bias. The only difference between the
two LECs is the ink from which the Ag electrodes were fabricated, and consequently it is
straightforward to attribute observed differences in turn-on time, brightness etc. to the ink selection.
A Keithley-4200 Semiconductor Characterization System (Keithley Instruments Inc., USA) was used
to apply a constant voltage of 5 V and to measure the current as a function of time. The probes
(Signatone, CA) inside the dry box were connected to the Ag-and Al-electrodes. The light emission
was documented by taking photos with a camera (Canon EOS 50D) equipped with a macrolens
(Canon Macro Photo Lens MP-E 65 mm 1: 2.8) placed inside the dry box, by maintaining the same
settings (f/4, 3 sec exposure time, ISO-3200, 65 mm focal length) during the whole experiment. The
photographs were taken consistently as the experiment was carried out, using the camera
controlling-software DSLR Remote Pro-Remote Capture Application for Canon EOS Digital S.
Since the exposure time of the camera was 3 sec, the timing may suffer an error but it had almost no
effect on the study.
6.4 Results and Discussions
The experimental set-up is shown in Figure 27a. Figure 27b demonstrates an electrode pair as a
reference where Ink#1 and Ink#2 are indicated clearly; all the following pictures in this section are
presented in this order.
Ink#1 Ink#2
Figure 27: Performance comparison experiment, showing a) experiment setup in the dry box and b) two Ag-traces in
an electrode pair configuration as seen from the opposite side of the glass substrate. Note the difference in color of the
printed lines. Electrodes printed with Ink#1 are darker than those printed with Ink#2.
First, performance comparisons regarding the turn-on time of the LECs were conducted. Here, 0
sec refers to the time when a constant voltage bias (5 V) was applied to the electrode pair. The turnon time is defined as the time at which visible light could be seen with the above mentioned settings
of the camera. Figure 28 signifies the turn-on time of both the LECs where it can be seen clearly
that the turn-on time differs with about 40 sec (see figure 28a-b). Ink#1 LECs are slower to turn on
compared to Ink#2 LECs. A careful inspection of figure 28a-b shows that Ink#2 starts ‘glowing’ at
10 sec while Ink#1 needs at least 50 sec.
Second, performance comparisons regarding the brightness of the LECs were conducted. Referring
to all the data presented in figure 28, it can be seen that the light coming out from Ink#2 LECs is
brighter than its Ink#1 counterpart. A careful inspection of figure 28e-f shows that at ~200 sec,
almost all the areas of Ink#1 LEC emitted light but with less brightness than the Ink#2 LEC.
Third, performance comparisons regarding the color/appearance of the printed traces were
conducted. Referring to figure 28, it can be seen that the light comes out from both sides of the
electrodes, as seen by the Ink#2 LEC in figure 28b. However, because of the brightness, it seems
that the light is emitted as single line, as seen by the Ink#2 LEC in figure 28d. In contrast, a careful
inspection shows that Ink#1 LECs never demonstrate such an appearance of single-line emission.
This indicates that Ink#2 LECs are brighter than Ink#1-made LECs, and that the concept of solid
silver traces as semi-transparent electrodes could work in a homogenous light emitting device. The
hypotheses are that the wider the electrodes, more of the light is blocked in this particular
configuration of the LEC, and the colors/appearances of the electrodes help/hinder the light in
exiting the device. In the case of Ink#1, the ‘ash-black’ and ‘absorbent’ appearance of the electrode
(see figure 27b) hinders the light to come out while in the case of Ink#2, its appearance became
advantageous; the ‘silver-like’ and ‘semi-transparent’ appearance of the electrode helps the light to
escape the device, as evidenced by figure 28.
Ink#1 Ink#2
Ink#1 Ink#2
Ink#1 Ink#2
Ink#1 Ink#2
Ink#1 Ink#2
Ink#1 Ink#2c
Figure 28: Performance comparison of LECs showing photos (f/4, 3 sec exposure time, and ISO3200) taken at a)
10 sec, b) 50 sec, c) 100 sec, d) 150 sec, e) 200 sec, and f) 300 sec.
Fourth, it was observed that in some cases, Ink#1 LECs did not emit light at all while Ink#2 LECs
demonstrated the expected emission. Figure 28 illustrates this fact; though both the LECs comprises
to the same electrode pair, Ink#1 LEC did not emit any light whereas the Ink#2 LECs did. The
hypotheses are that the electrode printed with Ink#1 could be broken so that it was not a functional
device at all, and the thickness of the electrode printed with Ink#1 is too large for this particular
configuration of LECs. This later fact implies that the drop volume of Ink#1 is so big that the
printed line protrudes through the active material layer to make direct contact with the Al-film. The
thickness measurement provides indications in support of this hypothesis since the measurement
showed that the average printed thickness of Ink#1 is ~4 times greater than that of Ink#2. Also,
when the largest thicknesses of the respective ink-profiles were considered, it came out that Ink#1 is
at least twice as thick as its counterpart. Consequently, this raises the possibility of making direct
contact, i.e. a short circuit, with the top electrode in the sandwich-cell configuration.
Ink#1 Ink#2
Ink#1 Ink#2
Figure 29: Electrode pair demonstrating a) an Ink#2 LEC shining while the Ink#1 LEC is not working at all
and b) none of the LECs are shining. Inset of 29b shows the electrode pair under illumination. Note that throughout
the course of these experiments, it was never observed that an Ink#1 LEC emitted light while an Ink#2 LEC did
Fifth, performance comparisons regarding the Ag content of the inks were conducted. Referring to
figure 29, it can be seen that solely the Ink#2 LEC is emitting light (see figure 29a) or that none of
the LECs in an electrode pair are emitting (figure 29b). In performing the experiments, it was
observed that the Ink#2 LECs always demonstrated light emission when an electrode pair was
working. In contrast, it was never observed that an Ink#1 LEC was emitting while an Ink#2 LEC
did not. The hypotheses are that the electrode pair was not made properly, the active material was
not drop-casted properly, breaking off/scratching of the devices may happen during handling etc.
When only Ink#2 LECs are emitting but not Ink#1 LEC, the most probable explanation is the
thickness. Ink#1 electrodes are thicker than Ink#2 electrodes, as its ink consists of ~30% Ag
particles which results in rigid and filled traces after sintering. In comparison, Ink#2 consists of 10%
Ag particles and the printed traces are accordingly less thick than its counterpart. In the case of this
particular configuration of the LEC, Ink#1 shows more possibility in protruding through the active
material layer than Ink#2, even when drop-casting, as evidenced by figure 29. Hence, the data
indicates that a higher loading of Ag particles could be a disadvantage that ultimately diminishes the
performance of the LEC, particularly in the case of the sandwich-cell configuration.
7 Comparison at a Glance
This section covers the comparison between the Ag-inks at a glance. The following table
summarizes all the specifics about the inks as they were studied in this thesis.
Jetting temperature, meniscus
Max. jetting frequency (kHz)
(using 10 pl cartridge)
Jetting velocity (ms-1)
Single firing-cycle (μs)
Drop-size (μm), Head-angle,
resolution (dpi)
Min. line-width (μm)
Substrate temperature (while
Sintering condition
32˚C, 4 inch-water
30˚C, 4 inch-water
30, 6.8˚, 850 (approx.)
25, 5.6˚, 1000 (approx.)
Ink-appearance following 5-6
weeks storage in glass vial in
Measured specific resistance after
sintering (µΩ-cm)
Specific resistance compared with
bulk Ag (at 20˚C)
Manufacturers’ claim on specific
resistance after sintering (µΩ-cm)
Thickness on the treated glass
substrate (μm)
Turn-on time (at 5 V)
Sandwich-cell configuration:
electrode’s appearance on the
glass substrate
Sandwich-cell configuration:
homogenous light emission
No change
~180°C, more than 45 min
in ambient
Appearance change while sintering No change
Sandwich-cell configuration:
possibility of making direct
contacts i.e. short circuits
~120°C, more than 15 min in
liquid transparent phase to solid
metallic phase
Water-like to reddish-brown in
3-4 weeks and to water-like
again in 5-6 weeks
6-10 times higher
4-8 times higher
Slower (~50 sec)
Less bright
Ash-black, absorbent;
hinders the light to come
Shows less homogeneity;
never appears as a single
Demonstrates more
possibility because of its
higher Ag content
Faster (~10 sec)
Silver-like, semi-transparent;
helps the light to come out
Table 2: Specifics about the inks and comparison at a glance.
Shows better homogeneity;
appears as a single line
Demonstrates less possibility
because of its lower Ag content
8 Conclusion
The thesis reveals that Ink#2 is better than Ink#1, as the electrode of the sandwich-cell LEC
comprising an Ink#2 bottom anode emits more light with a faster turn-on time compared to a
device comprising an Ink#1 anode. Also, this work ascertains that the specific resistances of the Agtraces printed with both the inks are only 4-10 times higher than that of bulk Ag. Most importantly,
considering the high price of Ink#1, Ink#2 offers the opportunity of making printed electrodes in a
highly cost-effective way.
Though the work demonstrates that both the inks can be jetted with the inkjet printer DMP-2800,
Ink#2 requires a reformulation. However, the results indicate that this is possible and presents a
viable method of getting satisfactory results. It is shown that Ink#2:THF = 3:1 (vol:vol) results in
improved jetting performance. Though it was recommended that the solvents used for the
functional fluid should have low evaporation rates with high boiling points (more than 100°C), this
thesis work verifies otherwise, as evidenced by the successful jetting of an ink mixed with a highly
volatile, low boiling point solvent like THF (boils at 66°C). In fact, the addition of THF is
advantageous if the substrate temperature can be kept close to its boiling point, and an improved
resolution of the printed features is demonstrated.
Finally, this thesis work puts a question mark on a commonly expected feature regarding the
percentage of the metallic content of an ink. Is a higher metallic content always preferred? Here, it is
shown that Ink#1 contains 3 times more Ag-particles and makes ~4 times thicker traces than
Ink#2. However, such thick printed traces demonstrate a higher probability for short circuited
devices by protruding through the active material layer, and the LECs made with this ink emit light
with less homogeneity than its counterpart. Hence, this work suggests that the high metallic content
ink is not the preferred choice for sandwich-cell LECs.
9 Future Prospects
As demonstrated in this work, the jetting of Ag nanoparticle-based inks with the inkjet printer
provides a unique opportunity to make printed electrodes for LECs. LECs were fabricated in a
sandwich-cell configuration with the bottom anodes ink-jetted in a single-line configuration. A
future investigation can aim for printing electrodes with more complicated patterns using other
kinds of available cartridges, which should be of interest for, e.g., large-area LEC configurations.
Printing electrodes for other configuration of LECs e.g. the planar-cell configuration, can also be a
possibility. As evidenced by this work, the printed electrodes can protrude through the active
material, even when a thick drop-cast active layer is used. One way to avoid this problem is to spincoat a PEDOT:PSS layer on top of the electrodes in the sandwich-cell configuration. Hence, a
future experiment and comparison study could include an extra layer of PEDOT:PSS on top of the
inkjetted Ag anode. The future studies could also focus on the addition of suitable additives to
Ink#1 since no study was performed on this regard. In addition, the future study could encompass
the study on finding the reasons behind the observed color change of Ink#2 and could look for the
performance deterioration due to this change. As this thesis work did not focus on using different
substrates and their treatment, investigations can also be carried out regarding the effects of the inksubstrate properties and the ideal conditions for Ag sintering. Moreover, this comparison study
concludes that the reformulated Ink#2 performs well, and since this ink is much cheaper than
Ink#1, working with Ink#2 is recommended. Finally, it is suggested that research should be
performed on the formulation, and subsequent printing, of other conductive inks like graphite and
graphene inks, conductive polymers like PEDOT:PSS[26], small-molecule light-emitters,[27] which
could pave the way to the realization of a large-area LEC devices manufactured entirely by an inkjet
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