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1 - Coffee-Ring-effect Based Self-Assembly Mechanism For All-Inkjet Printed Organic Field Effect Transistors
1 - Coffee-Ring-effect Based Self-Assembly Mechanism For All-Inkjet Printed Organic Field Effect Transistors
Genehmigte Dissertation
Doktoringenieur
Dr.-Ing.
vorgelegt von
Gutachter:
Prof. Dr.-Ing. Arved Carl Hübler
Prof. Dr. rer. nat. Dr. habil Ulrich Sigmar Schubert
Thema
Coffee-ring-effect based self-assembly mechanism for all-inkjet printed
organic field effect transistors with micron-sized channel length
Seitenzahl: 164
Anzahl der Abbildungen: 86
Anzahl der Tabellen: 21
Anzahl der Literaturzitate: 229
——————————————————————————
Schlagworte:
coffee ring effect, OFET, small gap electrodes, inkjet printing,
minimization of channel length, model, PTFE, evaporation mechanisms,
polymer transistors, dewetting, self-assembly
I
Abstract
Due to the increasing interest in low-cost, lightweight, and wearable technologies,
flexible and printed electronics has become an intensive field of research during the
last two decades. This research is mainly focused on the development of solution-
processed organic materials, the evolution of diverse appropriate printing technolo-
gies and the enhancement of electronic device performance. Compared to conven-
tional electronics, printed technologies allow for cheaper and easier processing but
much poorer resolution, which results in comparatively large organic field effect tran-
sistor (OFET) channel lengths of a few ten microns. Reducing the channel length
requires the use of additional methods such as wetting-based [SvWFS05, Sch11]
and non-printed approaches [KPG+ 07, BNVC13]. The minimization of the chan-
nel length is crucial in order to obtain higher frequencies and increasing currents.
Therefore, overcoming the resolution limitation is one of the challenging topics in
the field of printed electronics.
In this thesis, a new approach for the realization of fully inkjet-printed small-
channel OFETs is investigated. For this purpose, a piezoelectric Drop-on-Demand
(DOD) inkjet printer with 10 pl printheads is employed. This approach involves a
self-aligned, dewetting-based technique for the reproducible fabrication of source and
drain electrodes with homogeneous and well-controllable channel lengths down to 4
µm. For the realization of these electrodes, a water-based, hydrophobic nanoparticle
(NP) dispersion is initially printed and dried at room temperature in order to spon-
taneously form a thin hydrophobic twin-line of few microns due to the so-called coffee
ring effect (CRE) [DBD+ 97, DBD+ 00]. This mechanism is responsible for the mi-
gration of the NPs from the center to the edge of the printed line during evaporation.
An alcohol-based silver NP ink is subsequently printed on the hydrophobic lines and
self-aligned to split into two separated source and drain electrodes. Dispersions with
different materials such as polytetrafluoroethylene (PTFE) and fluoroplastic NPs,
different particle sizes and concentrations are evaluated in order to optimize the
twin line deposition and the dewetting of the silver ink. Optimum dispersions are
printed, then characterized on untreated polyethylene naphthalate (PEN) foils and
oxygen plasma treated dielectrics such as cross-linked poly-4-vinylphenol (c-PVP)
and cross-linked polymethyl methacrylate (c-PMMA).
To evaluate the influencing parameters on the twin-line deposition, a model is
developed for the calculation of the printed rivulet width and the electrode gap,
which is determined by the width of the hydrophobic ring. These dimensions are in-
vestigated as functions of the printing parameters, NP concentration, line geometry,
and wetting properties. Multiple simulations are used to determine the influence of
each parameter on the twin-line deposition and calculate the critical channel length,
below which the dewetting of the conductive ink on the hydrophobic line is no more
III
IV
possible. Based on the simulation results, the optimum parameters are used to
control the gap between the printed source and drain electrodes.
The underlying mechanism is finally employed for the realization of fully inkjet-
printed OFETs on plastic substrates with small channel lengths and a bottom gate
bottom contact configuration (BGBC). For this purpose, a silver NP ink is used
for the electrodes, a PTFE NP dispersion is printed on c-PVP and a small-molecule
6,13-Bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) solution is used for the
semiconducting layer. Multiple small-channel OFET arrays are furthermore fabri-
cated with a good reproducibility of the channel length and a high yield, which
proves the industrial applicability of the proposed approach.
Kurzfassung
Die Integration kostengünstiger, leichter und tragbarer Technologien gewinnt zuneh-
mend an Interesse. Dies führt kontinuierlich zu einer rasanten Zunahme der For-
schungsaktivitäten im Bereich der flexiblen und gedruckten Elektronik. Der Fokus
liegt hierbei überwiegend auf der Entwicklung organischer Materialien, Herstellung
von geeigneten Druckverfahren und Verbesserung der Leistungsfähigkeit gedruckter
elektronischer Bauteile. Ein ausschlaggebender Vorteil der gedruckten gegenüber
der konventionellen Elektronik liegt darin, dass sie eine preiswerte und einfache
Prozessierung ermöglicht. Die Beeinträchtigung dieser jungen Technologie ist im-
mer noch die schwächere Auflösung, welche zur Erstellung von organischen Feldef-
fekttransistoren (OFETs) mit vergleichbar größeren Kanallängen von einigen zehn
Mikrometern führt. Die Reduzierung der Kanallänge erfordert die Verwendung
zusätzlicher Hilfsmethoden z.B. oberflächenspannungsstrukturiertes Drucken [Sch11,
SvWFS05] oder “non-printing”-Technologien [KPG+ 07, BNVC13]. Die Minimierung
der Kanallänge ist entscheidend, um höhere Frequenzen und Ströme zu erzielen.
Daher ist die Optimierung der Auflösung ein wesentlicher Parameter, um die Tech-
nologie weiter zu entwickeln.
Die vorliegende Arbeit stellt ein neu entwickeltes Verfahren zur Realisierung von
All-Inkjet-gedruckten OFETs mit kleinen Kanallängen dar. Hierbei wird ein Drop-
on-Demand (DOD) Inkjet-Drucker mit 10pl-Druckköpfen eingesetzt. Dieses Ver-
fahren basiert auf einem oberflächenspannungsabhängigen Ansatz für die repro-
duzierbare Erstellung von Source- und Drainelektroden mit homogenen und kon-
trollierbaren Kanallängen bis 4 µm. Beim Erstellen dieser Elektroden wird zuerst
eine wasserbasierte Dispersion mit hydrophoben Nanopartikeln gedruckt und bei
Raumtemperatur getrocknet. Während der Trocknungsphase wird der sogenan-
nte Kaffeeringeffekt (CRE) zu Nutze gemacht [DBD+ 97, DBD+ 00]. So führt der
CRE zur Migration der Nanopartikeln vom Zentrum bis zum Rand der gedruck-
ten Struktur. Diese gerichtete Migration bewirkt eine spontane Erstellung einer
dünnen hydrophoben Doppellinie mit einer Breite von nur wenigen Mikrometern.
In einem weiteren Schritt wird eine alkoholbasierte Silbernanopartikeltinte über die
hydrophobe Linie gedruckt. Aufgrund der niedrigen Oberflächenenergie der darunter
befindlichen hydrophoben Linie, teilt sich die leitfähige Tinte in zwei voneinander
getrennte Strukturen, die zunächst als Source- und Drainelektroden eingesetzt wer-
den. Um dieses Verfahren zu optimieren, werden im Rahmen dieser Arbeit Dis-
persionen mit verschiedenen hydrophoben Materialien wie Teflon- oder fluoroplas-
tische Nanopartikeln unterschiedlicher Partikelgrößen und Konzentrationen unter-
sucht. Die optimale Dispersion wird darauffolgend auf unbehandelten PEN-Folien
und sauerstoffplasmabehandelten Dielektrika wie vernetztem Poly-4-Vinylphenol (c-
PVP) und vernetztem Polymethylmethacrylat (c-PMMA) gedruckt und anschließend
V
VI
charakterisiert.
Um den Einfluss verschiedener Parameter auf dieses Verfahren zu evaluieren,
wurde ein Modell für die Berechnung der Breiten der gedruckten Struktur und
der getrockneten hydrophoben Doppellinie, die den Elektrodenabstand bestimmt,
entwickelt. Diese Dimensionen werden in Abhängigkeit verschiedener Druckparameter,
Nanopartikelkonzentrationen, Liniengeometrien und Benetzungseigenchaften unter-
sucht. Zunächst werden Simulationen durchgeführt, um den Einfluss von jedem
Parameter auf die Doppellinienentstehung zu bestimmen. Dieses Modell ist eben-
falls erforderlich für die Berechnung der kritischen Kanallänge, unter welcher keine
Entnetzung der leitfähigen Tinte auf der hydrophoben Linie mehr möglich ist. Die
gewonnenen Simulationsergebnisse bzw. die optimalen Parameter werden für die
Kontrolle des Abstands zwischen den Source- und Drainelektroden beim Drucken
eingesetzt.
Das beschriebene Verfahren wird zur Realisierung von All-Inkjet-gedruckten OFETs
mit kleinen Kanallängen auf Plastiksubstraten in einer Bottom-Gate-Bottom-Contact-
Konfiguration (BGBC) verwendet. Die benutzten Materialien bestehen aus einer
Silbernanopartikeltinte für die Source-, Drain- und Gateelektroden, c-PVP für das
Dielektrikum und TIPS-Pentacen für den Halbleiter. Multiple OFET-Arrays wer-
den zum Schluss mit hoher Reproduzierbarkeit der Kanallängen und hoher Ausbeute
gedruckt, um die industrielle Anwendbarkeit des vorgestellten Verfahren zu zeigen.
Preface
VII
Contents
1 Introduction 1
IX
X Contents
Bibliography 121
List of symbols
XIII
XIV Contents
∆t drying time s
◦
T temperature C
◦
Tchuck printer chuck temperature C
◦
Tcuring ink curing temperature C
T oF500µm time of flight at a traveling distance of 500 µm s
◦
TT IP S curing temperature of TIPS-pentacene C
◦
∆T vertical temperature gradient between substrate and C
drop surface
Uth threshold voltage V
UDS source/drain voltage V
UGS gate/source voltage V
v(r) average speed of fluid flow m s−1
Vd droplet volume of hydrophobic NP dispersion pl
Vd,0 reference droplet volume pl
Vd,Ag printed droplet volume of silver ink pl
Vp nanoparticle volume µm3
Vw volume of water in the formulation µL
VL liquid volume µm3
VR ring volume µm3
w width of coffee ring µm
wcrystals average TIPS-pentacene crystal widths µm
wriv rivulet width µm
wriv,0 reference rivulet width µm
wriv,1D rivulet width of a single droplet line (1D) µm
wriv,method2 rivulet width as calculated in Method 2 µm
wriv,Ag rivulet width of printed silver ink structure µm
wriv,Layout rivulet width in the printing layout µm
wriv,M ethod1 rivulet width as calculated in Method 1 µm
w4 width of triangular coffee-ring geometry µm
wO width of circular coffee-ring geometry µm
Wch channel width µm
We Weber number
WAg width of printed silver ink structure µm
∆x drop spacing µm
4x0 reference drop spacing µm
4xAg drop spacing of printed silver ink µm
4xP V P drop spacing of printed c-PVP µm
4xT IP S drop spacing of printed TIPS-pentacene µm
X input array of simulation (7-dimensional vector)
X0 reference input vector
XVI Contents
Abbreviation Description
XVII
XVIII Contents
Abbreviation Description
P3HT Poly(3-hexylthiophene-2,5-diyl)
Pani Polyaniline
PE-CVD Plasma-Enhanced Chemical Vapor Deposition
PEDOT:PSS Poly(3,4-ethylene-dioxythophene):poly(4-styrene-
sulfonate)
PEN Polyethylene Naphthalate
PET Polyethylene Terephthalate
PGMEA Propylene Glycol Monomethyl Ether Acetate
PMMA Polymethyl Methacrylate
PMMF Poly(melamine-co-formaldehyde)methylated
PPy Polypyrrole
PS Polystyrene
PTAA Poly(triarylamine)
PTFE Polytetrafluoroethylene
PVDF Polyvinylidene Fluoride
PVP Poly-4-vinylphenol
PZT-bimorph Piezoelectric Bimorph
QSCV Quasi-Static Capacitance Voltage
R2R Roll-To-Roll
RMS Root-Mean-Square
RT Room Temperature
S Source
SAM Self-Assembled Monolayer
SDL Single Droplet Line
SEM Scanning Electron Microscopy
SMU Source-Monitor Units
TCL Three-phase Contact Line
TCO Transparent Conductive Oxide
TFT Thin Film Transistor
TGBC Top Gate Bottom Contact
TGTC Top Gate Top Contact
TIPS-pentacene 6,13-Bis(triisopropylsilylethynyl)pentacene
VRH Mott’s Variable Range Hopping
Chapter 1
Introduction
Diverse requirements such as flexibility, high performance, low-cost manufacturing,
rapid processing, lightweight, and low-temperature fabrication have been pushing
the electronic device industry to develop new technologies and materials. This con-
tributed to the flourishing of a highly interdisciplinary technology and science field:
flexible electronics.
The development of flexible electronics dates back to the 1960s [WS09] starting
from the first flexible solar cell arrays [HS65, PKM63] to the first flexible thin film
transistors (TFTs) developed by Brody et al. in 1968 [BP68]. One decade later, the
chemistry Nobel prize laureates Shirakawa et al. succeeded in discovering the first
highly conductive polymer, polyacetylene [SLM+ 77, Nob00]. This succession of dis-
coveries was the major trigger for the rapid development of the research in the field of
printed and organic electronics within the last decades. Different solution-processed
materials have undergone development and allowed for new printing methods [Kla06]
to be applied in electronic components and industrial applications such as RFID-tags
[SFC+ 05, GCL+ 14], sensors [PH12, WW13, BBG+ 16], flexible displays [KAEN+ 13],
solar cells [HTZ+ 11, LLOZ+ 13], active matrix imaging [SKI+ 05, NKK+ 08], ultra-
sonic mapping [KSN+ 10], electronic skin [SS09] and textile integration [PJ03].
The global revenues for products using printable, flexible, and wearable electronics
in 2016 are estimated at US$26.9 billion with an annual increase of 31.8% since 2010
[Kal17]. This market is dominated by OLED and conductive ink, however, it shows
a significant growth potential of smaller segments emerging from R&D such as logic,
memory and thin film sensors [DH15]. Among these segments, the market of printed
and thin film transistor circuits consists of more than 500 organizations working
on the development of printed transistors and memories [HD13]. First commercial
products in this field are for example the roll-to-roll (R2R) printed organic memories
produced by ThinFilm Electronics for smart consumables, brand protection, or toys
and games [Thi11]. Another example product is the flexible plastic e-paper display,
which is developed by Dresden Electronics [Dre15] and based on organic thin film
transistor (OTFT) technology from Plastic Logic [Pla17].
As a fundamental backbone of electronic circuits, OFETs including OTFTs are
used for example in complementary inverters [LCCR12, BKK+ 13] and ring oscil-
lators [HSK+ 11, SKJ+ 12] or even as sensors [KDB+ 13, GZJ+ 15, MSMDRM14].
Despite the versatility of its applications and advantages including flexibility and
low-cost processing, OFETs suffer from different limitations, which hamper their
commercialization. These problems are firstly related to the materials: the low car-
1
2 Chapter 1
rier mobility µ of organic semiconductors affects the output currents, the switching
speed and the on/off current, which leads to a lower performance. This is due to
the weak van der Waals bonding between π-conjugated molecules in these semicon-
ductors compared to covalently-bonded inorganic semiconductors, which results in
electronic band narrowing and charge carrier localization [And58]. The reported
values are at most between 0.01 and 10 cm2 V-1 s-1 [NHS+ 11, CJC+ 11] compared to
mobilities around 1000 cm2 V-1 s-1 in crystalline silicon transistors [Nea02]. Further-
more, the fast degradation of organic dielectrics is responsible for higher operation
voltages, higher hysteresis, and more instability in air or under stress, which results
in a short lifetime of the transistors [Fic04]. In addition to problems caused by
material limitations, OFET performance is also affected by dimensional limitations
related to the resolution of printing technologies. An ideal OFET configuration re-
quires a short channel length Lch and a minimum gate to source/drain overlap length
Loverlap . This necessitates an accurate control of the printing quality of the solution-
processed materials and a precise layer-to-layer registration capability. Hence, im-
proving the semiconductor mobility µ and overcoming the resolution limitation by
minimizing Lch and Loverlap are desirable to achieve a high operation speed of OFETs
[KKJS12, UNS+ 11] according to the following expression of the transistor frequency
fT [GM90, BDLHP94]:
gm µ · UDS
fT = = , (1.1)
2πCG 2πLch (Lch + 2Loverlap )
where gm , CG , and UDS are the transconductance at the operating point, the gate
capacitance, and the voltage applied between source and drain electrodes, respec-
tively.
This thesis focuses on the development of OFETs with a small channel length. Dif-
ferent methods to downscale Lch have been reported (see. section 2.4.3). Generally,
these methods necessitate additional and expensive “non-printing” steps such as pho-
tolithography [SKF+ 00, NZCS07] or laser technology [KPG+ 07, BNVC13], which
generally provide a precise structuring but can damage organic materials during ex-
posure or development of the photoresist. Therefore, downscaling the channel length
is more challenging when it is realized only by means of printing technologies such
as Inkjet. For example, the printing heads of the piezoelectric DOD inkjet printer
DMP 2800 used in this work eject drops with a volume of 10 pl, which leads to a
large drop diameter of around 50 µm on common polyethylene terephthalate (PET)
or PEN substrates.
Within the framework of this thesis, a novel technology for the fabrication of
source and drain electrodes with channel lengths down to 4 µm is presented. This
approach is based on employing the coffee ring effect for the realization of small
hydrophobic twin-lines from printed hydrophobic NP dispersions. This evaporation
mechanism has received growing interest in recent years due to its wide range of ap-
plications, especially in the health care field such as nanochromatography [WCSH11],
analysis of blood diseases [BSLS11] and biomarker detection [TBE+ 14]. Electronic
applications such as inkjet printing of transparent electrodes [ZZX+ 13] and via-hole
interconnections [KSFS01] were reported as well. The coffee ring effect was also
3
recently used for the realization of small-channel OFETs by combining inkjet tech-
nology with laser structuring [SWAS10] or lithography [WCZ+ 14]. The uniqueness
of the proposed approach in this thesis consists of employing the coffee ring effect for
a completely printed (all-inkjet) realization of tunable small-channel OFETs, which
is correlated to a high applicability of this method thanks to its simplicity, rapid pro-
cessing, and low costs. In addition to this, the proposed approach shows flexibility
in terms of OFET configuration and material choices and can be adopted for other
printing techniques. In this work, the influence of different printing parameters and
properties of used materials are studied and investigated based on the development
of a theoretical model, which is mainly employed for the calculation of the coffee-ring
dimensions. The optimum parameter combination is then calculated and adopted
experimentally for the control of the channel length and subsequently for all-inkjet
printing of small-channel OFETs.
This thesis is organized in 6 chapters: Chapter 2 provides explanations of the
fundamentals related to this work e.g. printing technologies, surface properties,
evaporation mechanisms, and OFETs. Its last section reports a review of the
literature about the methods used for the realization of small-channel OFETs. The
third chapter presents experimental details used in this work, namely materials,
methods, and characterization techniques. The twin-line deposition of hydropho-
bic NP dispersions is studied by analytical modeling and simulations in chapter 4.
Influencing printing parameters and material properties derived from this chapter
are investigated experimentally and discussed in chapter 5. Optimum results for
the realization of small-channel OFETs are applied in chapter 6. The final chapter
consists of concluding remarks and suggestions for future work.
Chapter 2
Fundamentals and state of the art
From a bare substrate to a final printed device, a sequence of pretreatments, printing
steps, drying steps, and characterizations is undergone by the used materials. In or-
der to have a better understanding of these mechanisms, this chapter presents an
overview on inkjet printing and explains fundamentals related to surface proper-
ties and evaporation mechanisms. The last section is dedicated to printed OFETs:
Brief explanations of the principle and the most important parameters are given.
Moreover, a review of most common materials and methods for the realization of
small-channel OFETs is presented.
5
6 Chapter 2
Flexography
piezo inkjet printing (s. Section 2.1.1), which is the method adopted in this work.
Inkjet printing is a digital, additive, and mask-free “direct write printing” method,
by which a fixed quantity of liquid phase materials is ejected accurately according to
a predefined layout and without any intermediate carrier for the printed information
[K+ 00]. In this technique, drops are ejected with a controllable volume from nozzles
and deposited on an underlying substrate, in order to form a dot-matrix pattern.
Generally consisting of a laboratory setting, inkjet printing is adequate for initial
research and development tests. However, it can also be adapted to high-volume
production techniques such as R2R methods [WLG+ 11].
An ejected drop undergoes five typical phases: ejection, flight, impact, spreading,
and finally drying [KLC13]. Improving the printing quality means an optimization
of the drop behavior within these phases. Here, different challenges concerning the
fluidic properties are encountered [Che11]: A constant drop volume and a straight
flight direction are required for homogeneous and reproducible printed lines. This
requires a stable flow during the transition from liquid channels to single drops.
Typical problems here are undesirable satellites, double ink stream, and nozzle clog-
ging, especially by using colloidal inks instead of soluble inks. These problems can
be avoided by optimizing ink properties such as viscosity and surface tension with
respect to the appropriate choice of the printhead and printing parameters. De-
gassing and filtering are also crucial for the minimization of air bubble formation
and removal of undesirable particle agglomerations in the fluid.
Once deposited, the interaction of various parameters related to ink, substrate,
printing, and drying conditions is responsible for the deposition morphology of the
jetted drop [SS08, Dui03]. For example, the surface energies of ink and substrate
define the wettability of the printed drops (s. Section 2.2.1). A low wettability (high
contact angle (CA)) inhibits a continuous line formation or leads to irregular bulge
formation if a high liquid amount is printed. In contrast, a high wettability (low
CA) leads to a high drop spreading and generally to uncontrollable line geometry.
These wetting properties can be manipulated by proper surface treatments or use
2.1 Inkjet printing 7
of additives (s. Section 2.2.2). After impact and spreading, the control of drying
mechanisms is crucial for the final deposition morphology (s. Section 2.3). A typical
observed phenomenon here is the coffee ring effect, which is responsible for the
migration of ink solute to the edge of printed lines during evaporation (s. Section
2.3.1). In addition to the drying conditions at the drop vicinity, ink properties
such as solvent boiling point [PM06, SLO11], thermal conductivity [RKD+ 07], and
particle concentration [Dee00] have an important influence on the coffee ring effect.
Controlling these properties is able to induce Marangoni flows [HL06] oppositely to
the CRE and can be efficiently used in order to reach a better thickness uniformity.
As previously mentioned, the optimization of the printing quality requires the
investigation of the first phases, namely ejection and flight. These two phases are
mainly influenced by the choice of the inkjet printing method: continuous or drop
on demand (s. Fig. 2.1). For continuous inkjet printing, the printer generates
charged small drops continuously and orients them according to the preferred image.
The periodic drops are ejected with a controllable volume by adjusting the drop
velocity and using an electrostatic field, which activates the nozzle periodically and
controls the flight direction. In contrast, DOD printers generate drops only when
they are required to print a dot from the predefined layout. The main advantages of
this method are the small drop size, the high placement accuracy, and the efficient
material usage [WLG+ 11]. DOD printing has two main subdivisions: thermal and
piezoelectric. In addition to these methods, there are other smaller subdivisions such
as electrostatic and acoustic DOD inkjet printers [Le98]. The next section provides
a detailed description of the piezoelectric DOD inkjet printing.
the creation of the required deformation. Fig. 2.2: Piezoelectric DOD inkjet printing.
As described in Fig. 2.3, the applied
waveform controls the mechanical deformation of the piezoelectric element and con-
sequently the liquid flow. A waveform typically consists of four segments, which
are characterized by three properties: duration, level, and slew rate [FUJ08]. The
“start”-segment can be considered as one of the four segments as it is connected to the
fourth segment. The DMP 10 pl printheads used in the current work (DMC-11610)
have a single row of 16 nozzles with a spacing of 254 µm. For a better resolution of
the printed features, 1pl printheads (DMC-11601) can be used with the same DMP
2800-printer. For the 10pl- and 1pl- printheads, the applied voltages vary between
0 and 40 V. The level of each segment in the waveform corresponds to a percentage
of the applied voltage and determines the liquid volume of the pumping chamber.
This means that each voltage change corresponds to a change of the liquid volume
in the chamber and leads to a different drop volume. The slew rate of each segment
defines the speed of the volume change and has therefore an important influence on
the jetting quality. As shown in Fig. 2.3 the piezoelectric bimorph (PZT-bimorph)
is electrically activated by the electric field caused by the applied voltage. The po-
sition of this PZT-bimorph defines the liquid volume in the pumping chamber. The
operating principle of the PZT-bimorph is described as follows:
Standby mode: A bias voltage is applied to depress the fluid chamber and the
PZT-bimorph is slightly deflected. For this step, a high surface tension and a
low pressure are favorable to avoid ink dripping out of the nozzle [Cal01].
Fluid drawing mode: The applied voltage is decreased to zero in order to bring
the PZT-bimorph back to a neutral straight or relaxed position, then followed
by a hold-time. Consequently, the fluid is drawn into the pumping chamber
from the ink reservoir and the chamber is filled up to its maximum volume.
The liquid in the chamber pulls the meniscus at the nozzle and makes it ready
for jetting.
Drop ejection mode: This phase initiates the drop formation. The slope steep-
ness of the firing pulse provides the energy required for the initial ejection.
2.1 Inkjet printing 9
a) b) c) d)
voltage
voltage
voltage
voltage
start
start
start
start
1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4
Figure 2.3: Waveforms and schematic illustration of PZT-motion and fluid flow at
different modes of piezoelectric inkjet printing. a) Standby mode, b) Fluid drawing
mode, c) Drop ejection mode, d) Recovery mode [FUJ08]. Active segments are high-
lighted in red for each mode.
10 Chapter 2
where d is the characteristic length equal to the diameter of the nozzle aperture of
the DOD printheads and ρ, γ, and η are the density, surface tension, and viscosity
of the liquid, respectively. According to the prediction of Fromm, Z has to exceed 2
in order to enable a drop formation for DOD printheads. Later, a refinement of this
condition to 1 < Z < 10 was reported by Derby et al. in [DRS+ 00, RD00] where
Z = 1 is the limitation related to the ink viscosity and Z = 10 is the value at which
satellite drops are formed instead of single ones. According to the DMP-2800 user
manual [FUJ08], following requirements have to be fulfilled by the fluid: a viscosity
η between 10 and 12 cps at jetting temperature, a surface Tension γ between 28 and
33 dynes/cm and a density ρ greater than 1000 kg/m³.
The fluid properties are not only important for the optimization of jetting quality
but also for the control of liquid spreading after impacting the substrate. For
example, it is shown in [PSvdB+ 09] and [PSW+ 09] that the final shape of the
printed structures is influenced by the fluid viscosity, which is dependent on the
solute concentration. The influence of the liquid’s physical properties will be inves-
tigated in the model developed in Chapter 4 in order to predict the final geometry of
the printed hydrophobic NP dispersion. For the control of the interaction between
the ejected fluid and the underlying substrate, it is important to study the surface
properties and define the appropriate methods for their modification.
2.2.1 Wetting
The periphery of the contact area between the deposited liquid and the underlying
substrate is defined by the three-phase contact line (TCL). At this line, the CA
between the substrate and the tangent to the liquid-vapor interface determines the
degree of the wetting, also known as wettability. Depending on the value of this
angle, the generic terms hygrophilic and hygrophobic were suggested by Marmur
[Mar08] for low and high CAs, respectively. The use of the prefix hygro here is
related to its meaning in Greek, namely “liquid”. In case of water, a surface is called
hydrophilic if the water CA is low and hydrophobic if the water CA is high. The
wetting behavior of the drop on a given substrate is defined based on following cases
(s. Fig. 2.4):
2.2 Surface properties 11
a) b)
Liquid
Gas
θ θ
Substrate Substrate
Figure 2.4: Three-phase-systems with CAs of a) θ > 90◦ (dewetting) and b) 0° < θ < 90◦
(partial wetting).
a) γLV b)
σLV
θY θY σSV
γSV
Substrate γSL Substrate
σSL
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where γSV , γSL , and γLV are the interfacial tensions at the solid-vapor, solid-liquid,
and liquid-vapor interfaces, respectively and θ is the CA (s. Fig. 2.5.a). The
thermodynamic equilibrium is reached by fulfilling the following minimum energy
condition, also known as Young equation:
σSV − σSL
cos θY = , (2.3)
σLV
where σSV , σSL , and σLV are the interfacial energies at the solid-vapor, solid-liquid,
and liquid-vapor interfaces, respectively and θY is the Young contact angle (s. Fig.
2.5.b). The conditions in 2.2 and 2.3 can only coincide in case of an ideal solid
surface [MM13]. In fact, if the diffusion equilibrium at the solid-liquid-interface is
absent, the three-phase-system can fulfill the mechanical equilibrium condition in
2.2 and be far from the thermodynamic equilibrium [RF04]. Generally, the solid
surface heterogeneity is unavoidable in praxis. This leads to CA variability, which is
responsible for unreproducible CA measurements (s. Section 5.3.1). The CA is also
influenced by the surface roughness [NIHS98]. For example, Bico et al. [BMQ99]
reported that a combination of hydrophobicity and high surface roughness leads
to superhydrophobicity. In this case, the deposited water drops, also called “pearl
drops” remain nearly spherical on the substrates.
The nature of the physical or chemical reaction depends on the plasma energy level,
gas feed, and nature of polymeric materials. Plasma is composed of two types of
gases:
Inorganic gases such as argon (Ar), helium (He), hydrogen (H), nitrogen (N),
and oxygen (O). These gases are responsible for the creation of a non-polymer-
forming plasma and lead to the following reactions [Ina96]:
– Implantation of atoms, which is a recombination between the radicals
activated from gas molecules and generated at the polymer surface.
– Radical generation, which means the abstraction of hydrogen from the
polymer chains or chain scission of the polymer chains.
– Etching reaction, which means a degradation of the polymer surface. A
molecule is formed by a chemical reaction, which takes place between the
solid atom (from the substrate to be etched) and gas atoms then removed
from the substrate.
Depending on plasma power and gas feed, a wide range of surface modifications
from hydrophilic to hydrophobic can be achieved. The use of plasma treatment and
polymerization is essential in the field of printed electronics. It is important not
only to remove contaminants from the polymer surface but also to tune its surface
energy or deposit new polymers. For example, oxygen plasma treatment is general-
ly used for a better hydrophilization of the substrate [LH10] [GLK+ 10]. For the
same purpose, ultraviolet (UV)/ozone (O3 ) [LSH+ 08b] [LC12] [LSH+ 08a] is used to
enhance the surface energy of the polymer surface. In case of surface hydrophobiza-
tion, plasma polymerization is usually used in printed electronics for the deposition
of thin hydrophobic layers such as fluorinated materials (e.g. carbon tetrafluoride
CF4 [SvWFS05] and octafluorocyclobutane C4 F8 [KO10]) or hexamethyldisilazane
(HMDS) [TS11]. It is also possible to tune the surface energy of the substrate by
modifying the amount of oxygen in a gas mixture with fluorinated materials such as
CF4 /O2 [ITS+ 08] or C4 F8 /O2 plasma [KKCO11].
2.2.2.2 Coatings
Similarly to plasma polymerization, polymer layers can be deposited by the use
of different methods such as spin coating or dip coating. These coatings consist
of hydrophilic or hydrophobic materials. Examples of coatings used in the field of
printed electronics are: Fluorocarbon (FC), which is a hydrophobic coating generally
14 Chapter 2
processed in the form of an FC-solution and deposited by spin coating and self-
assembled monolayers (SAMs), which result of physical or chemical forces leading
to the formation of a one molecule thick layer of material that bonds to the substrate
in an ordered way.
a) b) c) z
Figure 2.6: Evaporation modes of a drop on a substrate: a) constant contact area mode,
b) constant contact angle mode, and c) mixed mode.
Constant contact area mode: At this stage, the first particles migrate to the
edge of the drying drop due to the coffee ring effect, which is going to be
explained in detail in the next section. This migration results in the formation
2.3 Evaporation mechanisms 15
Structure
Particle hydroxya-
PS - PS PS PS
material patite
Particle size 60 nm - 1 µm 1 µm 60 nm -
DI+ Sur-
Dispersant DI ISO DI ISO DI
factant
ODT-
Substrate Titanium PDMS Glass Glass Titanium
treated
Source [SBMM04][BFA09] [BFA09] [BFA09] [Som04] [TS03]
of a ring at the boundary of the drop, which is responsible for the contact line
pinning. At this stage, the contact area remains constant while the contact
angle keeps on decreasing.
Mixed mode: This stage is a mixture of constant contact area and constant
contact angle modes. This means, that the contact angle and the contact line
decrease continuously.
In case of a pure liquid e.g. distilled water (DI) or isopropanol (ISO), the constant
contact area mode is generally observed at the start of evaporation, then followed by
the dominant constant contact angle mode. A very low concentration of unexpected
contaminants in the liquid can be responsible for slight contact angle differences but
hardly affects these two modes [KAKZ07]. After evaporation, these contaminants
leave a drying pattern consisting of a central bump [KAKZ07]. By the presence of
a solute in the liquid, different other patterns such as single rings, multiple rings,
fingering at the contact line, uniform patterns, or networks of polygons or hexagonal
arrays can be observed after drying (s. Table 2.1). The diversity of these patterns
is mainly related to different evaporation mechanisms such as the coffee ring effect,
the Marangoni flow and the slip-stick-motion, which are going to be explained in
the following sections.
have a dense, ring-shaped structure made of coffee particles along the perimeter.
Similar stains were observed by the presence of a dispersed solute in an evaporating
liquid. Deegan et al. reported, that the CRE is caused by a combination of capillary
flow and contact line pinning. For this phenomenon, three conditions have to be
fulfilled: The initial CA has to be different from zero, the contact line pinning has
to occur at its initial position, and the solvent has to evaporate. These conditions
lead to the replenishment of the liquid evaporating from the edge by liquid from the
interior. Consequently, the resulting outward flow transports the dispersed material
to the edge (s. Fig. 2.7.a). Deegan et al. [DBD+ 97] explained the reduction of
the height h(r) at each point r (s. Fig. 2.7.b) as a function of the evaporative flux
J(r). As explained in Section 2.2.1, the drop maintains a spherical shape in order to
minimize the area of the liquid-vapor-interface and thus minimize its surface tension.
a) Evaporation rate J b)
Capillary flow J
hh v
Substrate r
R
Liquid Solute
Intern © Siemens AG 2014 Alle Rechte vorbehalten.
Figure 2.7: Schematic illustration of the coffee ring effect. a) Flow profile, b) Quantities
responsible for the flow as demonstrated by Deegan et al. in [DBD+ 97].
For a given short time of drying ∆t, the liquid evaporates along the liquid-vapor-
interface due to the rapid interchange of liquid molecules between the surface and
adjacent air and vapor leaves at a rate per unit area J(r). This lost volume of liquid is
represented in Fig. 2.7.b by the orange color. In the annular gray region, the volume
represented by the blue color is smaller than the volume removed by J(r) there (heavy
arrows). For this reason, the fluid flows outwards with a depth-averaged speed v(r) in
order to compensate the deficit volume, shown with horizontal stripes. In [DBD+ 00],
Deegan presented a model for the prediction of the flow velocity, the rate of the ring
growth, and the solute distribution within the drop. The calculated distribution of
the evaporation flux along the drop surface is not uniform. As shown in Fig. 2.7.b,
the evaporation is enhanced at the edge. This is explained by the greater probability
of an evaporating molecule to escape by its random walk motions when leaving from
the edge than when leaving from the center of the drop. This explains the depen-
dence of the evaporation rate on the surface tension of the substrate as well. As this
surface tension affects the drop curvature (s. Section 2.2.1), the evaporation rate be-
comes higher on hydrophilic substrates and lower on hydrophobic substrates [MM13].
Y. O. Popov [Pop05] refined the model of Deegan and calculated the time evolution
2.3 Evaporation mechanisms 17
of the drying process and the growth of the deposit phase as illustrated in Fig. 2.8.
Within this model, he calculated the ge-
ometry of the coffee rings as functions
of three parameters: initial concentra-
tion of the solute, initial geometry of
the drop, and time. For the realization
of this model, he assumed that the in-
ner part of the ring (which means the
boundary between the liquid phase and
the deposit phase) is a vertical wall. Intern © Siemens AG
time
2014 Alle Rechte
However, he reported that experimen- vorbehalten.
tal results show a spread shelf-like inner Fig. 2.8: Time evolution of the deposit phase
part of the deposited rings. growth: side view (left) and top view (right)
[Pop05].
The coffee ring effect is influenced by different parameters, which are going to be
explained in detail in the next section (s. Section 2.3.1.2). One of these parameters
is the concentration of the solute in the evaporating liquid, which can be used to
control the morphology of the final deposit. By printing lines consisting of a low-
concentrated liquid, the CRE can be used to obtain a twin-pair of parallel lines as
shown in Fig. 2.9. This twin-line deposition is used in this thesis for the realization
of continuous hydrophobic pairs of lines from low-concentrated PTFE dispersions.
Different examples of twin-lines are reported in literature mainly for the realization
of thin metallic lines from copper or silver NPs. For example, T. Cuk et al. inkjet-
printed thin copper twin-lines from copper hexanoate NPs dispersed in chloroform
[CTHW00]. By the use of profilometry, they showed that the geometry of the twin-
lines is strongly dependent on the solution viscosity and deposited volume per unit
length.
In addition to copper, twin-line de-
position from silver NPs is reported,
Drop Liquid Particles
mainly for the realization of transparent
electrically conductive structures. For
example, V. Bromberg et al. inkjet-
printed continuous silver lines with a
Evaporation
width of 2 – 8 µm from water disper-
+ CRE
sions with 1 wt. % of 77 nm silver NPs
and showed the dependence of the fi- Twin-line
nal line geometries on substrate wetta-
bility [BMS13]. A comparison between
the drying behaviors on hydrophilic and
Fig. 2.9: Principle of the twin-line deposition
hydrophobic substrates showed a faster
pinning and a higher deposition rate at
higher CA. Scanning electron microscopy (SEM) micrographs of the final deposits
showed the formation of discrete micron-scale islands of NP-monolayers in the inter-
18 Chapter 2
line region. According to [BLN+ 06], these islands nucleate from individual particles
captured by the liquid-vapor-interface during evaporation. At higher CA, Bromberg
et al. reported the formation of line discontinuities, which were denoted as kinks
and explained by a sharp local distortion of the contact line during rivulet formation
[BMS13]. Transparent electrodes based on the silver twin-lines were also inkjet-
printed by Z. Zhang et al. [ZZX+ 13] from silver NPs (40 – 60 nm). The width of
these lines was tuned by the variation of the NP concentration (0.5 – 5 wt. %) and
substrate wettability. For the hydrophobic substrates, their observations showed
that the migration of NPs starts with an initial pinning step, followed by a contact
line motion or slip-stick motion, which means the formation of stripes due to the
recession of the contact line (s. Section 2.3.3). The results on the hydrophilic Glass
substrate showed an immediate self-pinning of the contact line at initial time and a
higher solvent loss at the edge. Compared to hydrophobic substrates, Z. Zhang et
al. reported that the contact area remained constant and the CA decreased linearly
until the end of evaporation [ZZX+ 13]. In addition to this, a better transparency
was achieved at higher hydrophilicity, due to a smaller island nucleation between
the twin-lines. These results prove that a higher hydrophilicity is desired for the
optimization of the PTFE twin-lines within the experimental part of this work.
a) FG b)
F3 Particle Particles
F2 ΔT
F1 F4 Liquid Liquid
Substrate θ
Intern © Siemens AG 2014 Alle Rechte vorbehalten.
Figure 2.10: Influencing parameters on the coffee ring effect. a) Model presented by A.
P. Sommer et al. in [SR05], b) Contact angle and size-dependent segregation of spheric
particles [PSH+ 08].
2.3 Evaporation mechanisms 19
an influence on these interactions. For example, it was shown in [CJS10] that the
relative humidity has an influence on the CA and consequently on the convective
flow presented by F2 . In this context, V. H. Chhasatia et al. showed that the CA
decreases with increasing relative humidity, which results in a higher spreading of
the printed drops and a different deposition pattern. The CA can also be changed by
adding surfactants to the deposited liquid as described previously in Section 2.2.2.3.
Depending on the chemical composition of these surfactants (for example, ionic or
anionic), it is possible to obtain different drying patterns such as rings or arrays
[Dee00].
In addition to the parameters related to liquid properties, the twin-line deposition
is influenced by other parameters related to the particles such as concentration, size,
and shape. The effect of particle size on the final pattern can be observed based on
the evaporation of bidispersions consisting of particles with two different sizes. For
example, A. S. Sangani et al. showed that not all the particles are effective in the
contact line pinning [SLSS09]. For this purpose, they mixed 50 µm particles with 3
µm particles and compared their behaviors within the evaporation time. The drying
pattern showed, that smaller particles migrate toward the drop edge and form a
monolayer of well-ordered particles. However, larger particles migrate toward the
center of the drop or nearly stay immobile and form a multilayer of disordered
particles. Another example in [CS11] shows a size-dependent particle separation
with smaller particles closer to the edge. Here, V. H. Chhasatia et al. studied the
influence of the force F1 presenting the attraction between the particles and substrate
as well. In this context, they proved that a higher substrate wettability leads to
an enhanced contact line pinning and consequently to a better particle separation.
This segregation can be explained by the contact-angle-dependent placement of the
particles as shown in Fig. 2.10.b [PSH+ 08]. This preferential deposition of particles
is caused by the wedge shape, which defines the drop height and position suitable
for the particle size.
Based on the model and parameters cited above, it is possible to control the
CRE and suppress it as well. Suppressing the CRE can be realized by inducing
Marangoni flows (s. Section 2.3.2), which are oppositely directed to the convective
flows responsible for particle deposition at the contact line. It is also possible to sup-
press the CRE by changing the particle shape [YLS+ 13], adding a gelating polymer
[VdBdLS+ 07], or using electrowetting [EADM11].
conventional transparent conductive oxide (TCO) films and have multiple potential
applications in the field of optoelectronics.
In addition to transparent electrodes, different microstructures can be realized
based on the CRE. For example, T. Kawase et al. introduced the concept of the
so-called inkjet-etching in [KSFS01], which means a site-selective removal of a pre-
viously deposited material by the inkjet-printing of a solvent drop. They used this
concept for the realization of via-holes in an insulating layer of PVP by locally dis-
solving this layer with inkjet-printed ethanol drops. The CRE enables the migration
of PVP to the edge of the dissolved area and hence the realization of a thick insu-
lating ring. This technique was extended by B. de Gans et al. for the realization of
other polymer-relief geometries such as grooves, rectangular and circular hole arrays
[dGHS06]. These structures were demonstrated to be useful for the use as reservoirs
and were realized by the variation of the drop spacing. Inkjet-etching was also used
for the realization of refractive microlens arrays by etching of microwells in PMMA
[CLH09]. L. Zhang et al. [ZLZ+ 12] used the concept of inkjet-etching to develop a
new patterning technique for the realization of high-resolution inkjet patterns. This
technique was referred to as coffee-ring lithography, which consists of patterning a
polymer mask layer with an inkjet-printed solvent, coating of a conductive layer,
and finally removing of the polymer mask (with the coffee rings) through a lift-off
process. This enabled the fabrication of graphene electrodes with a small gap of 1 –
2 µm, which were used for the realization of high-resolution OTFTs. By the use of
the same concept but different materials, it was possible to fabricate gold electrodes
with channel lengths down to 700 nm [WCZ+ 14].
In addition to electronic applications, the CRE has multiple medical applications.
For example, it can be used for the analysis of human blood diseases. D. Brutin et
al. [BSLS11] reported different drying patterns of blood drops belonging to healthy
humans compared to blood drops belonging to humans suffering from anemia or
hyperlipidemia. Furthermore, the CRE can be used for nanochromatography in
order to separate biological entities depending on their sizes [WCSH11] (s. Fig.
2.10.b).
Deegan et al. [DBD+ 97] presented their CRE observations and reported that tem-
perature gradients leading to nonuniform evaporation of the liquid were responsible
for the creation of circulating flows. These flows were demonstrated to be driven
by surface-tension gradients and were identified as Marangoni flows. In their ob-
servations, Marangoni flows were interfering with the oppositely directed outward
capillary flow responsible for the CRE but their influence was minor (s. Fig. 2.11).
However, when these Marangoni flows become dominant, they can be used to sup-
press the CRE and hence reach a higher pattern uniformity and homogeneity of the
material distribution after drying [HL06].
2.3 Evaporation mechanisms 21
Convective Marangoni
flows flows
Substrate
Figure 2.11: Influence of convective and Marangoni flows on particle deposition within
evaporation [MRE+ 12].
and the drain electrodes. The induced charge carriers correspond to electrons or
holes for n- or p-semiconductors, respectively. The application of a bias voltage UDS
between source and drain results in a carrier flow, expressed by the measured current
IDS . This current depends on the channel geometry, insulating layer properties, and
semiconductor choice.
The electrical response of OFETs is characterized based on the output (IDS =
f (UDS )) and transfer (IDS = f (UGS )) characteristics (s. Fig. 2.14). The output
characteristic displays a linear regime and a saturation regime. The first regime
corresponds to UDS UGS − Uth and is described by the linear increase of |IDS |
with increasing |UDS | according to the Ohm’s law. In this regime, |UDS | is increased
until approaching |UGS |. At this level, a channel pinch-off occurs and IDS becomes
independent from UDS , which corresponds to the saturation regime.
The output current IDS is calculated based on Shockley-equations [Brü06] as
Wch UDS
IDS = · Ci · µ · UDS · UGS − Uth − , (2.4)
Lch 2
for the linear regime (UDS ≤ (UGS − Uth )) and
Wch
IDS = · Ci · µ · (UGS − Uth )2 , (2.5)
2Lch
for the saturation regime (UDS > (UGS − Uth )), where Wch , Lch , Ci , and Uth are the
channel width, the channel length, the capacitance per unit area of the insulating
layer, and the threshold voltage, respectively. Ci is calculated as follows:
εr ε0
, Ci = (2.6)
dIso
where εr is the relative permittivity and dIso is the insulator thickness. The threshold
voltage Uth is defined as the minimum gate voltage UGS required for the formation
of the conducting channel, which is correlated with a significant increase of IDS . Uth
can be derived geometrically based on the transfer characteristic (s. Fig.p2.14. b)
by extracting the UGS -value corresponding to the intersection point of the |IDS | =
f (UGS ) curve’s tangent and the UGS -axis. The transfer characteristic is also used to
a) b)
IDS √IDS
Linear Saturation regime
regime
UGS
extract the mobility µ, which is defined as the charge carrier drift velocity per unit of
electric field. The mobility is an important parameter for OFET performance due to
its influence on the switching speed and is mainly influenced by the semiconductor
quality (chemical properties and processing)p and its interface with the insulator. It
is derived by the slope calculation of the |IDS | = f (UGS ) curve and is calculated
as
∂IDS L
µlin = · , (2.7)
∂UGS W · Ci · UDS
for the linear regime and
√ 2
∂ IDS L
µsat = · , (2.8)
∂UGS W · Ci
for the saturation regime [BJDLM97].
Depending on the superposition of the OFET layers and the relative position of the
electrodes to the semiconductor, it is possible to define four different configurations:
bottom gate bottom contact (BGBC), bottom gate top contact (BGTC), top gate
bottom contact (TGBC), and top gate top contact (TGTC). A BGBC configuration
is adopted in this thesis in order to deposit the semiconductor in the final step and
avoid its deterioration by undergoing other processing steps.
2.4.2 Materials
OFET layers can be realized by printing inks in form of pastes or liquids on rigid
or flexible substrates. The choice of the ink-substrate system is crucial due to the
influence of material interactions on the quality of printed layers and hence on OFET
performance. A printed inkjet ink consists typically of a vehicle (fluid), a solute,
and additives such as wetting agents and dispersing agents. These components
impact ink properties such as viscosity, stability, and wettability, which together
with substrate properties (e.g. roughness and surface tension) define the three-
phase contact angle. In addition to this, the layer quality is influenced by the drying
process, which results in different solvent evaporation mechanisms and different final
morphologies (s. Section 2.3). An overview of printed OFET materials is given as
follows:
Substrates
Substrate materials can be flexible such as paper, plastic foils, and textiles or rigid
such as glass and silicon. Polymeric substrates are advantageous due to their light
weight and low cost. However, they limit the maximum temperatures used for the
other processing steps due to their low glass-transition temperatures (e.g. 78°C
for PET and 120°C for PEN [MRM+ 05]). The suitability of a specific substrate
to the targeted printed device depends mainly on the treatments associated to the
fabrication process e.g. heat stability processes to control the shrinkage or functional
coatings to control the surface tension. Other parameters such as surface roughness,
2.4 Printed OFETs 25
chemical and moisture resistance have a significant impact on the printed device
performance and hence play a key role in the choice of substrates.
Semiconductors
Electrodes
The material choice for the source and drain electrodes plays an important role in
OFET performance. As these electrodes are used for carrier injection, their working
function is required to be close to the HOMO or LUMO level of the used semiconduc-
tor. In case of p-type semiconductors, applying a negative gate voltage UGS results
in hole injection from the source electrode. This requires the use of an electrode
material whose Fermi level is close to the HOMO of the semiconductor. The quality
of the metal-semiconductor-interface is important in the carrier injection. In fact,
the presence of non-ohmic contacts at this interface results in a high contact resis-
tance and high potential barrier. Electrodes can be made of conductive polymers
such as poly(3,4-ethylene- dioxythophene):poly(4-styrene-sulfonate) (PEDOT:PSS),
polypyrrole (PPy), and polyaniline (Pani) or inorganic materials such as gold and
silver NP dispersions.
Dielectric
An organic dielectric has to fulfill different criteria such as high breakdown voltage
and good quality of the semiconductor-dielectric interface due to its significant influ-
ence on the charge carrier transport. In fact, a low surface roughness of the dielectric
results in higher mobilities as demonstrated by Steudel et al. [SDVDJ+ 04]. The
quality of the interface is not only affected by the morphology of the dielectric but
also its polarity. Indeed, the presence of random dipoles at the dielectric surface in-
creases local polarization effects, which in turn can distort the localized states of the
semiconductor [VOL+ 03]. As higher permittivity dielectrics are associated to higher
polarity, it is possible to optimize the semiconductor-dielectric surface by depositing
an additional dielectric layer consisting of a low-k material [ZHH+ 05]. In addition
to this, minimum structural defects and imperfections of the underlying substrate
are required in order to minimize the dielectric charge trapping and leakage current
[Gup10]. Examples of commonly used organic dielectrics for printed OFETs are
poly(methyl methacrylate) (PMMA), poly-4-vinylphenol (PVP), polystyrene (PS),
and polyvinylidene fluoride (PVDF).
[ADS+ 08]. Based on these methods, further minimizing the electrode gap is associ-
ated to low reproducibility and low yield, which necessitates the use of inkjet printers
allowing the jetting of smaller drop sizes such as sub-femtoliter inkjet printers
[SNZ+ 08] or the investigation of other fully-printed or partially-printed approaches.
The first partially-printed, wetting-based approach was presented by Sirringhaus et
al. [SKF+ 00]. This approach combines inkjet printing with photolithography, which
is used to pattern a polyimide film. The created patterns are protected by a pho-
toresist and O2 -plasma-treatment is applied to hydrophilize the free areas between
the polyimide patterns, which leads to the selective formation of hydrophilic and
hydrophobic regions on the surface. Water-based PEDOT:PSS is inkjet-printed
afterwards. Due to the different surface tensions on the underlying substrate sur-
face, the jetted drops dewet on the hydrophobic structures and spread only on the
hydrophilic areas. A similar approach was presented by Wang et al. [WGZS06]
based on the dewetting of PEDOT:PSS on a nanoimprint lithography-patterned hy-
drophobic PMMA structure. Surface tension based patterning of PEDOT:PSS was
also applied in the approach presented by Fischer [Fis09], where PET foils are first
Corona-treated then selectively patterned in order to create regions with high an low
surface energies. This heterogeneous prestructuring is realized by getting selected
areas in contact with suitable materials, which lead to the decreasing of the sur-
face energy at the contact areas. Consequently, a different wetting behavior of the
sprayed conductive PEDOT:PSS ink is obtained leading to the formation of source
and drain electrodes with gaps down to 10 µm. Similarly, a high surface energy
contrast of 50 mM/m was achieved by Corona-treating PET foils (hydrophilic) fol-
lowed by selective application of a hydrophobic material (CYTOP formulation) at
the non-printed regions [Sch11]. This approach was also successfully applied for the
realization of homogeneous source and drain electrodes with gaps down to 10 µm.
Hydrophobic materials were employed in a different concept presented by Zhao et
al. [ZCS+ 07]. In this approach, the conductive ink is inkjet-printed in a hydrophobic
confinement area, which is realized by a lift-off photolithography pattering of two
neighbored gold electrodes followed by their hydrophobization by the vapor-phase
deposition of a fluorinated SAM on their surface. The conductive ink is printed in
the inter-electrode area, where it spreads until reaching the hydrophobic boundaries.
The repulsion by the hydrophobic surface coating from both sides results in the for-
mation of a nanometer to micrometer sized gap. The wetting-based self-alignment
approach presented by Sirringhaus et al. [SKF+ 00] was developed further to be
adapted to fully-inkjet printed fabrication of small-gap electrodes. For example,
the dewetting of PEDOT:PSS on a hydrophobic HMDS-treated PVP surface was
enhanced by using a 50 µm wide bottom Gate electrode as a mesa structure [TS11].
Another example is presented by Sirringhaus group [SvWFS05] showing nanometer
electrode gaps created based on the slipping of a PEDOT:PSS drop at the boundary
of a neighbored surface-treated PEDOT:PSS structure. Doggart et al. [DWLZ10]
however created hydrophobic structures based on mixing the conductive ink with
organoamine, which forms a hydrophobic boundary at the ink contact line during its
evaporation on the substrate. The created hydrophobic organoamine boundary was
employed afterwards for the dewetting of the conductive ink and the fabrication of 10
28 Chapter 2
µm sized electrode gaps. 5 – 10 µm sized electrode gaps could also be realized by the
use of a micromolded separator as shown by Jeong et al. [JKL+ 11]. A microcapillary
was created in a PDMS mold and filled with PTFE, which was hardened afterwards
and used for the dewetting of the inkjet-printed conductive ink. In addition to the
dewetting-based methods, inkjet-printing was combined with different techniques in
order to realize small-gap electrodes. For example, 1 – 2 µm channel graphene elec-
trodes [ZLZ+ 12] and gold electrodes with channel lengths down to 700 nm [WCZ+ 14]
were fabricated by the use of coffee ring lithography, which was previously explained
in Section 2.3.1.3. Inkjet-printing was also combined with laser-based techniques to
reach channel lengths of 700 nm with femtosecond laser ablation [BNVC13] and 17
µm with selective laser sintering of a gold NP ink [KPG+ 07].
The summarized methods in this section prove the fast developing of inkjet- and
wetting-based methods for the fabrication of small-gap electrodes. Most of these
methods combine inkjet with another more accurate technique to achieve higher
resolutions. Purely inkjet-printed electrode gaps with Dimatix DMP-2800 can be
downsized to 40 µm as mentioned above. Downscaling this gap without using a non-
printing technique is challenging as it is correlated to low reproducibility, low yield, or
difficult processing. The purely inkjet-printed approach presented in this work shows
the possibility of the realization of sub-ten micron electrode gaps in an easy, fast,
and cost-saving way. This approach can be adopted for the realization of tunable
channel lengths and can be adapted to different materials, printing techniques, and
OFET configurations. Prior to the presentation of this method, new wetting- and
non-wetting based approaches are examined and introduced in the next section.
Chapter 3
Preliminary examination of new
approaches for small-gap electrode
fabrication
This chapter presents new approaches for the realization of small-gap (micron-sized)
electrodes. The proposed approaches are examined preliminarily, evaluated based
on their feasibility, and classified into two main categories: wetting-based and non-
wetting-based. After brief description and evaluation, one of the proposed methods
is selected to be investigated within this work.
a) b)
PEN unsintered Ag
channel
PEN ~ 3 µm
Sintered Ag
10 µm sintered Ag 10 µm
Figure 3.1: First observations of a sintered silver NP ink on a PEN substrate. a) Spon-
taneous channel formation at contact line proximity. b) Two neighbored electrodes
separated by the formed micron-sized channel.
29
30 Chapter 3
Based on this interpretation, the deposited thin line at the three-phase contact
line is formed during the first “stick”-step by accumulation of the first migrating
NPs at the printed structure edge and the channel is created by the next (single)
“slip”-motion. The resulted channel can be employed for the realization of small-
gap electrodes. As shown in Fig. 3.1.b, the thin line deposited at the edge can be
used as a boundary to stop the spreading of the second ink structure on the PEN
substrate. Starting from this first experimental investigation, a new approach for
the realization of small-gap electrodes can be presented as shown in Fig. 3.2.
a) b) c)
d) e) f)
Spreading direction
Conductive ink Sintered conductive ink
Conductive ink
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Figure 3.2: New approach for the realization of small-gap electrodes based on the sponta-
neous channel formation at contact line proximity during the sintering of a conductive
NP ink.
a) b) c) Conductive ink
HBPS-
boundary
Ag ink + HBPS Spreading direction
Sintered Ag ink
Figure 3.3: New approach for the realization of small-gap electrodes based on the for-
mation of a high boiling point solvent boundary during curing.
32 Chapter 3
Table 3.1: Examples of HBPSs with corresponding soluble, slightly soluble, and insoluble
solvents. Insoluble solvents can be used as solvent for the second conductive ink. EG
and DMSO stand for ethylene glycol and dimethyl sulfoxide, respectively.
After the spreading (d) and the sintering (e) of the second conductive ink, the
remaining HBPS can be removed by a curing step at a temperature higher than
BPhigh . If the required curing temperature is too high and able to damage the
used substrate, it is possible to remove the HBPS by an additional washing-off step.
Based on the list of materials shown in Table 3.1, a first experimental examination is
realized by the use of glycerine as HBPS and Hydrocarbon as solvent for the second
conductive ink (40 wt% silver NP ink UTDAg40 (UT Dots)). In order to examine
the suitability of these two materials for the proposed approach, a glycerine drop
is printed at the proximity of the hydrocarbon-based ink on an untreated PEN-
substrate as shown in Fig. 3.4.a.
The glycerine drop has a low adhesion on PEN. For this reason the hydrocarbon-
based ink repulses the glycerine drop and displaces it easily on the substrate. More-
over, due to the higher adhesion of the silver ink on PEN, the displacement of the
glycerine drop is accompanied by the spreading of the silver ink at its boundary and
underneath its contact area (s. Fig. 3.4.a). In order to avoid this displacement, the
Hydrocarbon-based
ink droplet 100 µm
3.2.1.2 Spontaneous gap definition between liquid contact line and NPs
Depending on the ink wettability on a solid surface, the NPs deposit at the liquid
edge by leaving a micron-sized distance to the liquid contact line [PSH+ 08] (s. Sec-
tion 2.3.1.2). Fig. 2.10.b shows how the contact-angle-dependent wedge shape of the
printed liquid and the particle size determine together the suitable drop height and
the position for the deposited NP. Similarly to the approach presented in Section
3.2.1.1, the created liquid boundary can be used for the separation of two electrodes
as described in Fig. 3.5.
a) b) c)
Physical boundary
Water-based conductive
Plasma-treated surface nanoparticle ink Water boundary
d) e) f)
Spreading direction
Conductive ink 2 Sintered conductive inks
Conductive ink 2
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Figure 3.5: New approach for the realization of small-gap electrodes based on the spon-
taneous gap definition between liquid contact line and NPs.
In the first step (a) the substrate is plasma-treated in order to enhance the
spreading of the printed inks and a physical boundary is printed in order to be
used as a confinement for the printed inks. A NP conductive ink (for example,
water-based) is printed afterwards for the realization of the first electrode. The
34 Chapter 3
a) 2D colloidal monolayer b) c)
Motion (z)
Substrate
Formation of 1D
3D colloidal dispersion colloidal lines + drying
d) Dewetting direction e) f)
Figure 3.7: New approach for the realization of small-gap electrodes based on the dewet-
ting of a conductive ink on thin hydrophobic lines created by the slip-stick motion
mechanism.
As a result of this motion, the contact line moves in periodic slip and stick events
and parallel one-dimensional hydrophobic thin lines are deposited then dried (c).
Afterwards, a conductive ink is printed on the created lines (d). Due to their
hydrophobicity, the conductive ink dewets and parallel conductive strips are cre-
ated (e). The final curing step results in the formation of parallel electrodes with
nanometer-to-micrometer-scale gaps.
a complete dewetting of the conductive ink and the formation of three electrodes
separated by two micron-sized gaps.
This new approach is illustrated in Fig. 3.9. First, a hydrophobic NP ink is
used to print an array of neighbored drops (a). The merging of these drops is
accompanied by their spreading on the substrate, which results in the formation of
a continuous line (b). During solvent evaporation, the NPs migrate to the edge of
the printed structure (red arrows in (b)) and a hydrophobic ring is formed at its
edge (c). A conductive ink is printed afterwards on the deposited ring (d). Due
to the hydrophobicity of the ring, the conductive ink dewets (e) and splits into two
separated structures. Finally, the conductive ink is sintered and two electrodes with
a controllable micron-sized gap are formed.
a) b) c)
Twin-line
Figure 3.9: New approach for the realization of small-gap electrodes based on the dewet-
ting of a conductive ink on thin hydrophobic lines formed by the coffee ring effect.
39
40 Chapter 4
Δx = 50 µm Δx = 25 µm Δx = 10 µm
Δx
SDL (1D)
Δx
MDL (3D) wriv
L
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Figure 4.1: Layouts used for the printing of SDL (1D) and MDL (3D) structures at
different drop spacings.
simultaneously, then it moves back and restarts jetting after a chuck movement in
negative y-direction. As illustrated in Fig. 4.1, two types of rectangular structures
are defined: single drop line structure (SDL) and multiple drop line structure (MDL).
Both structures can be defined with nD as well, where n is the number of printed
lines. The rivulet width wriv measured after printing is generally different from the
layout due to the significant influence of wetting properties and printing parameters
such as waveform, drop volume, and drop spacing.
The twin-line formation after printing an SDL or an MDL structure is illustrated
in Fig. 4.2.
N nn n
L
n (1 )
L
1D nD x
Figure 4.2: Configurations used for the realization of hydrophobic twin-lines. a) SDL-
structure with a single drop line (1D), b) MDL-structure with 3 drop lines (3D).
Once reached the substrate, the ejected drops merge and spread depending on
the wetting properties of ink and substrate. When the solvent starts to evaporate,
the contact line pinning starts due to the enhanced evaporation at the edge and
4.1 Calculation of the deposit ring volume 41
migration of the first NPs (s. Section 2.3.1). This pinned contact line confines
the remaining liquid and results in a constant contact area within the remaining
evaporation time. For this reason, the coffee ring width w increases with increasing
evaporation time but wriv remains constant. In case of an SDL-structure, a single
nozzle is required for jetting (nnozzles = 1) and the printed volume contains a total
number n1D of drops corresponding to:
L
n1D = 1 + (4.1)
∆x
In case of an MDL structure, more than one nozzle are required (nnozzles > 1). For
the used DMC-11610 printheads, the maximum value of nnozzles is 16. If a higher
number of lines n is preferred, it is necessary to have multiple moves of the printhead
in x-direction, accompanied by chuck movements in y-direction. A single move of
the printhead is generally recommended as it leads to a homogeneous migration of
the NPs to the coffee ring edge. In case of multiple moves of the printhead in x-
direction, the first printed lines start the evaporation during the printing process,
which leads to the formation of a coffee ring with inhomogeneous ring width w and
ring height h. In order to guarantee a homogeneous thickness of the dried coffee ring,
a number n ≤ 16 of single-drop lines is considered in addition to the assumption,
that the total line is printed in a single x-movement of the printhead. By the use of
a drop spacing ∆x and a line length L, an MDL structure contains a total number
N of drops equal to:
L
N = n · n1D = n · 1 + (4.2)
∆x
np = N · np,1d , (4.3)
where np,1d is the number of NPs in a single drop. np,1d is calculated by multiplying
the volume of a single drop Vd by the concentration of NPs per volume CV , which
leads to the following relationship:
np = N · Vd · CV (4.4)
Considering the expression of N in Eq.4.2, the total number of NPs in the ring is
expressed as follows:
L
np = n · 1 + · Vd · CV (4.5)
∆x
The microscopic observations of the water-based hydrophobic NP dispersions showed
a very low island deposition in the interline region. For this reason, it is possible
42 Chapter 4
to simplify the calculation of the deposit ring volume by assuming that all the NPs
reach the edge of the printed line during solvent evaporation. Based on this, the final
coffee ring volume is determined by the distribution of np NPs in the space defined
by the liquid edge. The distribution of the NPs is defined by the packing fraction
p as well. According to [PSP83, PPP84], the first particles reaching the liquid
edge at the beginning of the evaporation migrate with low velocities and create well
ordered, periodic series of hexagonal (p = 74%) and cubic packing (p = 52%). For
these ordered particles, a so-called self-healing effect [SSS02] is responsible for filling
defects in the coffee ring by placing a new particle. This “order” is followed by a
“disorder” due to the so-called rush-hour-effect [MGLS11], which is responsible for
a faster deposition of disordered particles. These particles migrate to the edge with
high velocities and deposit in a mixture of hexagonal and cubic packing. For this
reason, the packing fraction p in this dominant part of the coffee ring is assumed
between 74% and 52%. Considering a particle distribution with a packing fraction
p, the ring volume can be calculated as follows:
np · Vp
VR = , (4.6)
p
where Vp corresponds to the volume of a single NP. By inserting the relationship in
Eq.4.5, the ring volume can be expressed as:
L
n· 1+ ∆x
· Vd · CV · Vp
VR = (4.7)
p
For a better process suitability, it is generally preferred to measure concentrations
in weight percent. That’s why, the concentration of NPs per volume CV is expressed
as a function of the concentration in weight percent C, which is defined as:
Gm
C= , (4.8)
Gw + Gm
where Gm and Gw are the weight of the hydrophobic material (NPs) and the weight
of water in the dispersion, respectively. By assuming that the dispersions considered
for this model are highly diluted, the volume of NPs is considered as negligible
compared to the volume of water in the dispersion. Consequently, the volume of the
dispersion is approximately equal to the volume of water. This allows for expressing
the concentration CV as:
ntotal
CV = , (4.9)
Vw
where ntotal is the total number of hydrophobic NPs and Vw is the volume of water
in the dispersion. The weight of water in the dispersion is calculated as:
Gw = ρw · Vw , (4.10)
where ρw = 1g/cm3 corresponds to the density of water. By combining the expres-
sions in Eq.4.8 and Eq.4.10, Gm is calculated as:
4.2 Calculation of the rivulet width 43
C · ρw · Vw
Gm = (4.11)
1−C
The total number of hydrophobic NPs ntotal in the dispersion is calculated by dividing
Gm by the single particle weight Gp , which is expressed as
Gp = ρm · Vp , (4.12)
where ρm is the density of the hydrophobic particle material. A combination of the
expressions in Eq.4.11 and Eq.4.12 results in the following relationship:
Gm C · ρw · Vw
ntotal = = (4.13)
Gp (1 − C) · ρm · Vp
By combining Eq.4.9 with Eq.4.13, the relationship between CV and C is expressed
as:
C · ρw
CV = (4.14)
(1 − C) · ρm · Vp
By inserting Eq.4.14 in Eq.4.7, the volume of the ring is finally calculated as:
L
n · 1 + ∆x · Vd · C · ρw
VR = (4.15)
p · (1 − C) · ρm
Similarly, Y. O. Popov proved the proportionality between the final deposit ring
and the initial volume fraction of the solute by calculating the time dependent ring
growth [Pop05].
By considering the constant value set for RLayout in each printing layout, the rivulet
width is calculated as:
wriv,Layout = (n − 1) · ∆x + 50 µm (4.17)
As illustrated in Fig. 4.3.a, an MDL-structure consists of an SDL-structure with
a rivulet width wriv,1D followed by overlapping drops with a distance ∆x. By
considering the wetting behavior of the SDL-structure on the substrate, the rivulet
width in Method 1 is calculated as:
a) Method 1 b) Method 2
∆x ∆x
∆x ∆x
n=3 wriv
∆x
2R ≈ wriv,1D
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RL.α
hL
wriv
α
RL
VL = AL · L, (4.22)
which is also equal to:
VL = N · Vd , (4.23)
where N is the total number of drops in the MDL-structure and Vd is the drop
volume. By inserting Eq.4.2 in Eq.4.23, the volume of an MDL-structure is calcu-
lated as:
L
VL = n · 1 + · Vd (4.24)
∆x
Combining Eq.4.22 with Eq.4.24 leads to the following expression of the cross section
area:
1 1
AL = n · Vd · + (4.25)
L ∆x
For a given circle radius RL and a central angle α of the circle segment, the cross-
section area is calculated as:
RL 2
AL = · (α − sin α) (4.26)
2
The circle radius is expressed as:
4hL 2 + wriv,method2 2
RL = , (4.27)
8hL
where the liquid height hL is equal to:
wriv,method2 θ
hL = tan (4.28)
2 2
46 Chapter 4
a) 900 900
h (nm)
h (nm)
600 600
300 300
0 0
0 100 200 300 400 500 419 429 439
x (µm) x (µm)
b) 450 450
h (nm)
h (nm)
300 300
150 150
0 0
0 100 200 300 400 500 446 451 456 461
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x (µm) x (µm)
Figure 4.5: First observations of inkjet-printed PTFE ring deposits on PMMA and PVP.
a) Height profile of an MDL-structure printed on PMMA (n = 7, 4x = 10 µm) with
aspect ratios 300:1 and 9:1 on the left and right side, respectively. b) Height profile of
an MDL-structure printed on PVP (n = 7, 4x = 25 µm) with aspect ratios 600:1 and
13:1 on the left and right side, respectively.
a) w b) Solute Liquid
Substrate
1.
~w/2
L w w
h (~nm) h
h r
2.
w<<R
R
w
hmax
wriv w (~µm) 3.
hmax
4.
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Figure 4.6: Schematic illustration of the triangular model. a) Triangular twin-line cross-
sections formed after evaporation of an MDL-structure. b) Ring growth steps including
the formation of the contact line at the start of evaporation (1), the start of ring growth
(with a gentle slope at the ring’s inner part) (2) until reaching a maximum height hmax
(3) and finally the ring growth by keeping a constant height hmax [Pop05].
By assuming that the triangular cross-section is isosceles, the final ring’s height h
corresponds to the radial position r = wriv
2
− w2 , which means that h is approximated
as follows:
wriv w
h≈h r= − , (4.36)
2 2
and hence corresponds to:
4.3 Geometric approximations of the deposit ring cross-section 49
r
wriv 2 w
riv w 2 wriv
h≈ 2 − − − (4.37)
4 sin θ 2 2 2 tan θ
By the use of the ring volume expression in Eq.4.15 and the relationships in Eq.4.34
and Eq.4.37, the ring width is calculated as:
L
n · 1 + ∆x · Vd · C · ρw
w = q (4.38)
wriv 2 wriv w 2 wriv
4 sin2 θ
− 2 − 2 − 2 tan θ · p · (L + wriv ) · (1 − C) · ρm
L
n·(1+ ∆x )·Vd ·C·ρw
For simplification purposes, a constant A is defined as A = p·(L+wriv )·(1−C)·ρm
. This
leads to the following expression of the ring width:
A
w=q , (4.39)
wriv 2 wriv w 2 wriv
4 sin2 θ
− 2
− 2
− 2 tan θ
w4 wriv 3 A · wriv
− w + w + A2 (4.40)
4 2 tan θ
Triangular_1:
s
wriv = (n − 1) · ∆x + 2 Vd
(Method 1)
θ −cot θ
∆x·
sin2 θ
L
w4 n·(1+ ∆x )·Vd ·C·ρw
4
− wriv 3
2
w + A·wriv
tan θ
w + A2 , where A = p·(L+wriv )·(1−C)·ρm
Triangular_2:
r
1 1
2n·Vd ·( L + ∆x )
wriv = 2 sin θ · 2θ−sin(2θ)
(Method 2)
L
w4 n·(1+ ∆x )·Vd ·C·ρw
4
− wriv 3
2
w + A·wriv
tan θ
w + A2 , where A = p·(L+wriv )·(1−C)·ρm
.
Circular_1:
s
wriv = (n − 1) · ∆x + 2 Vd
(Method 1)
θ −cot θ
∆x·
sin2 θ
4.4 Single parameter simulations 51
L
n·(1+ ∆x )·Vd ·C·ρw
q
w = 2 sin θ · VR
(2θ−sin(2θ))(L+wriv )
, where VR = p·(1−C)·ρm
.
Circular_2:
r
1 1
2n·Vd ·( L + ∆x )
wriv = 2 sin θ · 2θ−sin(2θ)
(Method 2)
L
n·(1+ ∆x )·Vd ·C·ρw
q
w = 2 sin θ · VR
(2θ−sin(2θ))(L+wriv )
, where VR = p·(1−C)·ρm
.
n L C Vd θ p 4x
7 5 mm 0.6 wt% 17.75 pl 25.7° 74% 25 µm or 10 µm
a) 20 b) 20
Δx = 25 µm Δx = 10 µm
15 15 Circular_1
Circular_2
w (µm)
w (µm)
Circular_1
10 Circular_2 10
Triangular_1
Triangular_2
5 Triangular_1 5
Triangular_2
0 0
1 2 3 4 5 6 7 1 2 3 4 5 6 7
n n
a) 4 b) 4
Δx = 25 µm Δx = 10 µm
3 3 Triangular_1
Triangular_1 Triangular_2
h (µm)
h (µm)
2 Triangular_2 2
1 1 Circular_1
Circular_1 Circular_2
Circular_2
0 0
1 2 3 4 5 6 7 1 2 3 4 5 6 7
n n
In each graph, the high similarity of both triangular models as well as both circular
models is remarkable. The graphs of the circular model simulation display relatively
higher values of w and lower values of h compared to the triangular models. This
can be explained geometrically as shown in Fig. 4.11, where the triangular model
is represented by an isosceles Triangle 4 and the circular model is represented
by a circle segment O. Associating these geometries to the previously calculated
triangular and circular models in Section 4.3 necessitates four assumptions:
The triangular and circular geometries have equal areas A4 and AO (A4 =
AO ).
Both geometries have a common edge on their basis, which is located at the
contact line.
The vertex of the isosceles triangle is located at the outer liquid circle segment.
This is due to the assumption in Eq.4.36 used for the triangular model, which
is an evidence that the triangle’s height h4 is higher than the inner circle
segment’s height hO .
The outer liquid circle segment is adjacent to the inner circle segment O (s.
illustration of the circular model in Fig. 4.7).
If the triangle’s width w4 is larger than the inner circle segment’s width wO (Fig.
4.11.a), the resulting triangular area becomes larger than the circular area (A4 >
AO ). Consequently A4 and AO are only equal when w4 ≤ wO , which explains that
the ring’s width is lower for the triangular model compared to the circular model.
a) b)
wΔ > wΟ
Liquid X wΔ < wΟ
AΔ ≤ AΟ
AΔ > AΟ
h h h h
w w w w
wriv wriv
Concerning the influence of the drop spacing, a comparison of the graphs a) and
b) shows higher values of w and h for lower drop spacing. The graphs also show an
increasing width and height of the deposit ring with increasing n, which is predictable
due to the increasing liquid and solute volumes.
The influence of n on the rivulet
width wriv is illustrated in Fig. 4.12 450
Δx = 10 µm, Method 2
for Method 1 and Method 2 as well as
350 Δx = 10 µm, Method 1
4x = 25 µm and 4x = 10 µm. For each
wriv (µm)
drop spacing, the rivulet widths calcu- 250
lated at n = 1 are equal for Method
1 and Method 2. However, for n > 1, 150 Δx = 25 µm, Method 2
the difference of the calculated values Δx = 25 µm, Method 1
50
for Method 1 and Method 2 is small for 1 2 3 4 5 6 7
4x = 25 µm but significant for 4x = n
10 µm. Generally printing an MDL- Fig. 4.12: Influence of n on the rivulet width
structure with a smaller drop spacing wriv . Parameter set: L = 5 mm, C = 0.6 wt%,
results in a higher rivulet width due to Vd = 17.75 pl, θ = 25.7°, p = 74 %.
the higher number of drops in x- and y-
directions and hence higher liquid volume. In the graphs this is noticeable only for
Method 2. For Method 1 starting from n = 5, wriv becomes higher for 4x = 25 µm
compared to 4x = 10 µm, which means that Method 2 is more realistic than Method
1. For this reason the next simulation results are going to be calculated only with
Method 2, which means that only the models Triangular 2 and Circular 2 will be
considered for the next steps.
calculated for the triangular (Ftr ) and circular (Fcir ) models (s. Fig. 4.13). For both
drop spacings, w stabilizes starting from L ' 7 mm which corresponds to Ftr = 3.6%
and Fcir = 3% for 4x =25 µm and Ftr = 2.3% and Fcir = 4.8% for 4x =10 µm.
a) 20 10 b) 20 20
Δx = 25 µm wcir Δx = 10 µm
Start of stabilization 8
x
15 15 15
F = wriv/L (%)
F = wriv/L (%)
wcir
x wtr
w (µm)
w (µm)
6
10 x 10 10
x wtr 4 Fcir
5 Fcir 5 5
Ftr 2 Ftr
0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50
L (mm) L (mm)
Figure 4.13: Influence of the line length L on the ring’s width w for a) 4x = 25 µm and
b) 4x = 10 µm. Parameter set: n = 7, C = 0.6 wt%, Vd = 17.75 pl, θ = 25.7°, p = 74
%.
a) b)
30 Δx = 25 µm 30 Δx = 10 µm
Circular_2
w (µm)
w (µm)
20 Circular_2 20
10 10 Triangular_2
Triangular_2
0 0
0 0.5 1 1.5 2 0 0.5 1 1.5 2
C (wt%) C (wt%)
F P W · T oF500µm · N ozzleArea
Vd = , (4.45)
2
where F P W is the firing pulse width (duration of segment 2 of the waveform as
illustrated in Fig. 2.3) and T oF500µm is the time of flight at a traveling distance
of 500 µm. This means that the drop volume can be tuned not only by changing
the printhead but also by changing the waveform and the time of flight. T oF500µm
in turn depends on the applied waveform, printing parameters (applied voltage,
cartridge temperature, meniscus vacuum), and ink properties such as viscosity and
solute concentration. This shows again that the studied model parameters (in this
case the drop volume Vd and concentration C) depend on each other. However, for
simplification purposes, it is possible to assume here that the change of concentration
does not affect the drop volume. For the 10 pl printheads and printer used in this
work, the voltages can be varied between 0 and 40 V, which leads generally to a
variation of drop volumes in the range of 0 pl to 20 pl. The simulation results in
this range are illustrated in Fig. 4.15.
Similarly to the results shown for the variation of concentration (Fig. 4.14), w
values increase with increasing C and decreasing 4x due to the increasing ring
volume. In contrast to the variation of C, changing the drop volume leads to a
change of wriv not only because of the higher total printed liquid volume but also
because of the higher overlap distances of neighbored drops and the dependence of
56 Chapter 4
a) 20 b) 20
Δx = 25 µm Δx = 10 µm
15 15 Circular_2
w (µm)
w (µm)
Circular_2
10 10
5 5 Triangular_2
Triangular_2
0 0
0 5 10 15 20 0 5 10 15 20
Vd (pl) Vd (pl)
Figure 4.15: Influence of the drop volume Vd on the ring’s width w for a)4x = 25 µm
and b) 4x = 10 µm. Parameter set: n = 7 , C = 0.6 wt%, L = 5 mm, θ = 25.7°,
p = 74 %.
a) 40 b) 1000
Δx = 25 µm
30 800
wriv (µm)
w (µm)
600
20 Wriv
Circular_2 Triangular_2 400 (method 2)
10
200
0 0
0 15 30 45 60 75 90 0 15 30 45 60 75 90
θ (°) θ (°)
Figure 4.16: Influence of the CA θ on a) the ring’s width w and b) the rivulet width
wriv . Parameter set: 4x = 25µm, n = 7 , C = 0.6 wt%, L = 5 mm, Vd = 17.75 pl,
p = 74 %.
4.5 Comparison of parameter influences 57
4.5.1 Principle
First, a 7-dimensional vector X is defined as input array for the simulation. The
single components of X correspond to values of the input variables Xi , which leads
to the following definition of this vector:
Table 4.2: Values used for the single dimensions of the reference vector X0 .
Y0 = f (X0 ) , (4.49)
where f (X0 ) is equal to w0 (X0 ) or wriv,0 (X0 ). These values are listed in Table 4.3:
58 Chapter 4
Table 4.4: Definition of minimum and maximum values for each component Xi .
1 n 7 1 14 -85.7% +100%
2 4x (µm) 25 5 50 -80% +100%
3 C (wt%) 0.6 0 1.2 -100% +100%
4 L (mm) 5 0 10 -100% +100%
5 Vd (pl) 17.75 0 20 -100% +12.68%
6 θ (°) 25.7 0 50 -100% +94.55%
7 p (%) 63 52 74 -17.46% +17.46%
high similarity of the simulation results for both models is remarkable, that’s why,
it is possible to focus on one of these models e.g. Triangular 2 for the simulation
analysis.
a) 100 b) 100
w w
% %
75 w0 75 w0
50 50
25 X i 25 X i
% %
X 0 ,i X 0 ,i
0 0
-100 -75 -50 -25 0 25 50 75 100 -100 -75 -50 -25 0 25 50 75 100
-25 -25
Xi = n Xi = n
-50 Xi = Δx -50 Xi = Δx
Xi = C Xi = C
Xi = L Xi = L
-75 Xi = Vd -75 Xi = Vd
Xi = θ Xi = θ
Xi = p Xi = p
-100 -100
Figure 4.17: Comparison of parameter influences on the ring’s width w for a) Triangu-
lar 2 and b) Circular 2.
These graphs display an insignificant influence of the packing fraction p and line
length L on the ring’s width w. However, they show that it is possible to minimize
w by increasing θ or 4x or decreasing one of the parameters C, n, or Vd . Increasing
θ or 4x can be used to minimize w down to -32% and -29%, respectively and their
corresponding graphs show similar progression with a slight difference of their slopes.
For negative 4ww0
values, the graphs of the parameters C, n, and Vd exhibit higher
slopes and very similar progression. Decreasing these parameters can be used to
minimize w down to -55% for n and -100% for C and Vd .
Despite the high similarity of the percentage change resulting from the minimiza-
tion of C, n, or Vd , these parameters have different influences on wriv as shown in
Fig. 4.18. A negative percentage change of n and Vd results in a percentage change
of wriv down to -55% and -100%, respectively, which is equivalent to the same per-
centage change of w. Similarly, increasing θ or 4x leads to minimizing wriv down to
-33%, which is also very similar to the percentage change of w. However, minimizing
C doesn’t show any influence on wriv , which means that it is the single parameter,
which can be used for the minimization of w without affecting wriv . This result is
very important for the flexibility of the OFET design and low-cost processing as
it can be adopted for the realization of OFETs with different channel lengths by
the use of the same printing layout. In addition to this, minimizing C is not re-
lated to any experimental limitations contrarily to the other parameters. In fact,
minimizing Vd requires the use of printheads with smaller nozzles or decreasing the
applied voltages, which can lead to a different quality of jetting. To ensure a good
printing quality, increasing θ generally requires a higher drop spacing 4x and vice
versa, which means that a simultaneous increasing of both parameters is generally
not favorable.
60 Chapter 4
5.1 Materials
The schematic illustration of the bottom gate bottom contact (BGBC) OFET con-
figuration is presented in Fig. 5.1. The basic processing steps consist of 1) printing
the gate electrode (G) on the PET substrate, 2) printing the dielectric, 3) printing
the hydrophobic twin-lines based on the coffee-ring-effect, 4) printing the source (S)
and drain (D) electrodes by applying a conductive ink, which dewets on the twin-
lines due to their low surface tension, 5) printing of a semiconductor confinement
which is used as a physical boundary to limit the spreading of the semiconductor ink,
which is printed at the final step. Further steps (e.g. surface treatments or removal
of the twin-lines) are going to be added to this basic processing flow depending on
the achieved results.
For the realization of the hydrophobic twin-lines, NP dispersions with variable
NP sizes are tested on different substrates. The choice of dispersion and substrate
material is adopted for the realization of OFETs.
h
61
62 Chapter 5
a) b)
Hydrophobic twin-lines
PET Semiconductor confinement
Semiconductor G
confinement Dielectric
Semiconductor
S D
Dielectric
D S
G
Hydrophobic twin-lines Semiconductor PET
Intern © Siemens AG 2014 Alle Rechte vorbehalten.
Figure 5.1: Schematic illustration of the BGBC OFET configuration realized in this
work. a) Top-view. b) Cross-section.
According to the model calculations realized in Section 4.4.3, achieving small ring
widths requires a minimization of the solid concentration (s. Fig. 4.14). For this
reason, it was necessary to dilute the purchased dispersions with water and thus
downscale the concentration to 0.6 wt%. The choice of water as solvent is due to
its weak Marangoni flows compared to other solvents. This allows convection to
dominate the deposition pattern and hence results in the formation of twin-lines
with a minimum material deposition in the central ring area [HL06].
The three dispersions are filtered by the use of 0.45 µm nylon filters and filled
into DMC-11610 cartridges, which are equipped with 10 pl printheads. The printing
parameters are listed in Table 5.1:
Table 5.1: Printing parameters used for the 0.6 wt% water-based hydrophobic NP dis-
persions.
Voltage 40 V Waveform
Due to the fast evaporation of the water present in the dispersions, the twin-lines
are formed on the printing chuck at 28°C immediately after printing. Next, the
printed structures are cured in an air convection oven for 10 min at 150°C, which is
a relatively low temperature compared to the melting temperature of the NPs. This
latter corresponds to 342 – 345°C for PTFE and 260°C for fluoroplastic NPs due
to their smaller size and lower molecular weight (106 g/mol for fluoroplastic NPs
compared to 108 g/mol for PTFE). These melting temperatures are greater than
the maximum processing temperatures of polymeric substrates (220°C for PEN and
150°C for PET). Curing at 150°C is sufficient to achieve a partial sintering of the
5.1 Materials 63
particles and sufficient adhesion of these NPs on the polymeric substrates. However,
it is important to consider the mechanical and electrical instability of these partially-
sintered films due to the non-melting of the PTFE NPs and possible presence of
solvent residuals after heating. This instability is considered as critical for the charge
carrier transport between the source and drain electrodes by keeping the deposited
twin-lines between the semiconductor and the dielectric layer. However, it can be
considered as advantageous in case of using the twin-lines as sacrificial layer in a
lift-off process, where they are removed easily after the formation of the source
and drain electrodes due to their low adhesion on the underlying dielectric layer (s.
OFET designs in Chapter 7).
Substrates
Voltage 26 V Waveform
voltage
Meniscus vacuum 3 inches H2 O
Cartridge print height 1.5 mm
3.7 µs 3.8 µs 3.3 µs 0.8 µs
Maximum jetting frequency 2 kHz
time
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The substrate used for the realization of OFETs is Melinex ST-504, a polyethylene
terephthalate (PET) foil (DuPont Teijin Films). This substrate has a thickness of
125 µm, is heat stabilized and has a treated side, which provides enhanced adhesion.
Its low CTE of 10 ppm/°C guarantees a high reproducibility of the results, especially
by processing at higher temperatures up to 150°C. The processing temperatures of
PET are lower compared to PEN due to the lower glass transition temperature of
PET (78°C) compared to PEN (120°C) [MRM+ 05]. Being a low-cost material, PET
is generally very attractive for printed electronic applications.
The electrode material used for the OFETs is Cabot CCI-300, which is an alcohol-
based conductive ink containing surface modified ultra-fine silver NPs, with a surface
tension of 30 – 33 mN/m, a solid content of 19 – 21 wt%, and low sintering tem-
peratures down to 100°C. This ink is filtered by the use of 0.45 mm nylon filters,
degassed for around 1 hour in a desiccator, then sintered in an air convection oven
for 30 min at 150°C. The ink is chosen as electrode material due to the low resistivity
of the printed conductive features (bulk resistivity between 4 and 80 µΩ.cm) and
its work function of 5.0 eV [TKM+ 08], which is close to the HOMO level of the
semiconductor used for OFETs. The higher work function of inkjet-printed silver
compared to bulk silver (approximately 4.3 eV) can be explained by the fact that
inkjet-printed silver structures are exposed to air, which leads to their oxidization
[TKM+ 08]. The printing parameters used for this ink are listed in Table 5.2.
Dielectric ink
For the gate capacitance, c-PVP is used as dielectric and processed as described in
Section 5.1.1. It is beneficial to use a cross-linked polymer as OFET dielectric due
to its better properties compared to linear materials (no cross-linking). In fact, the
relatively higher hydrophobicity of the cross-linked polymer compared to the linear
material results in an enhanced long-term stability as mentioned by Matsuguchi et al.
[MSS+ 91]. Moreover, cross-linking improves the insolubility of the dielectric, which
5.2 Modification of the wetting behavior 65
allows the printing of other materials on its top without resulting in its dissolution
[YYFM05].
Semiconductor ink
An organic small molecule p-type 6,13-Bis(triisopropyl-silylethynyl)pentacene (TIPS-
pentacene) is chosen as active semiconductor. The choice of this material is based
on its high reported mobilities up to 0.24 cm2 V −1 s−1 for inkjet printed organic
transistors [LLL+ 08, LCH+ 08]. TIPS-pentacene was developed by a functionaliza-
tion of pentacene and improving its solubility in commonly used organic solvents
[ABEP01]. The solubility of the functionalized semiconductor is modified by func-
tional attached groups, which have a high influence on its processing and perfor-
mance [PPA+ 05]. Due to the high influence of the solvent choice on the crystal-
lization of TIPS-pentacene as well as the performance and stability of the devices
[KLG+ 08], different solvents are tested in this thesis. For this purpose, the semicon-
ducting ink is made of a 1 wt% TIPS-pentacene (Sigma Aldrich) solution based on
one of these four solvents: 1,2-dichlorobenzene (1,2-DCB) (Sigma Aldrich), anisole
(VWR), butylbezene (VWR), and 1,2,3,4-tetrahydronaphthalene (Tetralin, VWR).
The solution is filtered by the use of 0.45 mm nylon filters then printed according to
the same parameters in Table 5.1 except the values of voltage and meniscus vacuum,
which correspond to 28 V and 2 inches of water, respectively. The crystallization
of the semiconductor is optimized by the use of a hydrophobic confinement, which
defines the boundaries of this layer. A design of experiment is used for the variation
of the drop spacing of the semiconductor ink as well as drying temperature and
confinement width. These details are going to be explained in Section 7.3.
Semiconductor confinement
The hydrophobic material chosen for the semiconductor ink confinement is based
on one of the NP dispersions described in Section 5.1.1. The purchased PTFE and
fluoroplastic dispersions are diluted to achieve a solid concentration of 10 wt% and
2 wt % of isopropanol is added for a better jettability. The realized dispersions are
filtered by the use of 0.45 mm filters then printed according to the parameters in
Table 5.1.
The hydrophobic confinement area includes the channel region defined by the gap
between both silver electrodes. The TIPS-pentacene semiconducting ink is printed in
the confinement area, partially on the hydrophobic twin-lines used for the separation
of the electrodes. Due to the high hydrophobicity of the twin-lines, an optimization
of the wetting behavior of the semiconductor ink is required in order to achieve
a good printability as well as good crystal formation. For this reason, different
methods are used for the tuning of the CA of the TIPS-pentacene ink on the under-
lying hydrophobic material. This is realized by the choice of appropriate solvents
and the use of surface modifications based on different plasma-treatments with ar-
gon, nitrogen, oxygen, or hydrogen/argon as feed gas and variable treatment times.
As it is difficult to measure the CA of liquids on the micron-sized deposited rings,
the CA analysis is realized on PET substrates coated with the dispersion material.
The spin coating is realized for 10 s at a rotation speed of 250 rpm followed by 30 s
at 1000 rpm. After spin coating, the substrates are cured for 10 min in an air con-
vection oven at 150°C, then exposed to plasma. This exposure aims to a defluoration
of the coated hydrophobic surfaces by breaking the strong F-C bindings and hence
decreasing the F/C ratio. The defluoration can be described by different chemical
reactions as illustrated in Fig. 5.2.
5.2 Modification of the wetting behavior 67
a) c)
F F F F F NH2 F F F F F
-1F C C C -2F C C C
C C C C C C
F F F F F F F F F F F
b) F F F F F X d) F F F F F F
C C C -1F/-2F C C C C C C C C C
-2F F F
F F F F F F F F F F F
C C C
X -H, -OH F F F
F F F
=O, =NH C C C
Intern © Siemens AG 2014 Alle Rechte vorbehalten. F F F
For example, fluorine atoms can be replaced by amino or other functional groups
[Rot01, Fri12]. In addition to this, unsaturated groups or free bindings can be
created by removing fluor atoms or splitting PTFE chains, respectively.
This difference is relatively small compared to 0.57 for Ar-plasma and 0.89 for N2 -
plasma.
A Balzers LFC 150 machine is employed for this plasma-treatment. The parameters
are listed in Table 5.5:
Table 5.6: Test liquids used for the determination of the substrate surface energy.
5.3.2 Profilometry
A KLA Tencor P-17 Profiler is used mainly for the measurement of the twin-line
profiles as well as surface roughness. This surface profiler is highly sensitive and
provides a repeatability of 0.1% and a reproducibility of 0.25% for steps ≥ 1µm. The
high resolution is achieved by the use of a stylus-based scanning. Depending on head
configuration, different vertical ranges and various stylus forces between 0.05 mg and
50 mg can be programmed. Each measurement requires the definition of following
parameters: scan length (µm), scan speed (mm/s), sampling rate (Hz), applied force
(mg), and vertical range (µm). For the twin-line measurements, the parameters used
are listed in Table 5.7. The measured surface roughness corresponds to the root-
mean-square (RMS) or geometric average deviation of the roughness profile from the
mean line measured in the sampling length. This profiler is used for high precision
measurements, which are included in established silicon technology procedures at
the Siemens AG, Corporate Technology, Research and Technology Center. However,
it is important to consider possible sources of errors by applying this profilometry
method on soft material surfaces, which can have more irregularities or cannot resist
scratching by the stylus point [FR67].
Table 5.7: Parameters used for the measurement of the twin-line height profiles.
71
72 Chapter 6
Q65FA and c-PVP. The first substrate is used as delivered and the second material is
inkjet-printed on PEN substrate and subsequently O2 -plasma-treated. As explained
in Section 5.2.1, improving the wetting properties of water-based dispersions on
hydrophobic untreated c-PVP (measured water CA is equal to 60.2°) necessitates the
use of O2 -plasma-treatment, which decreases the water CA down to 23.7°. Similarly
to the reference vector X0 (s. Table 4.2), the MDL-structures are printed with
n = 7, 4x = 25 µm, L = 5 mm, and Vd = 17.75 pl. The printing results are firstly
characterized by the measurement of the single height profiles as shown in Fig. 6.1.
220 nm 120 nm 90 nm
500 500 500
400 400 400
h (nm)
h (nm)
h (nm)
h (nm)
h (nm)
Figure 6.1: Height profiles of twin-lines on PEN and O2 -plasma-treated c-PVP for dif-
ferent particle sizes: 220 nm, 120 nm, and 90 nm.
These graphs show a higher NP deposition between the twin-lines on PEN com-
pared to c-PVP. This island formation decreases with decreasing NP size and forms
irregular peaks, which are generally higher and denser with increasing NP size. This
irregularity of material deposition is also related to the reproducibility of the results
as well as the amount of NPs migrating to the liquid edge. In addition to this, a
slight difference between the ring heights on the left and right sides is visible.
The high material deposition on PEN compared to c-PVP can be explained by
its higher surface roughness. In fact, due to the absence of a protection layer on the
treated PEN side, slight fissures are formed on its surface through handling. For
this reason the measured surface roughness of 8.83 ± 1.37 nm is higher than the
value cited in the data sheet (2 nm). Consequently, the used PEN substrate has
a higher surface roughness compared to the inkjet-printed c-PVP, whose measured
surface roughness is equal to 2.75±0.35 nm. An increasing surface roughness results
in contact angle hysteresis and slip-stick-motion of the NPs [RVRCCV08], which
explains the sticking of the NPs in the central area of the deposited ring as well as
6.1 Influence of particle size and substrate 73
their irregular deposition. According to [MM13] and [SDJ00], increasing the surface
roughness can be used to suppress the coffee ring effect and hence achieve a higher
homogeneity of material deposition. The NP deposition in the central area of the
ring is also influenced by the NP size, which is shown by the decreasing island
formation with decreasing NP size. This can be explained by the lower attraction
between the substrate and smaller NPs (Force F1 ) in addition to the preferential
deposition of smaller NPs near the drop edge due to the formed wedge shape as
shown for bidispersions in [SLSS09, CS11] and explained in section 2.3.1.2 (Fig.
2.10.a). The force F1 is also affected by the substrate and NP surface tensions. Due
to the equality of the surface tensions for PTFE and fluoroplastic NPs, it is necessary
to investigate the influence of the substrate surface tension on F1 . By assuming that
the functional groups created by O2 -plasma-treatment on the c-PVP surface are
degraded by the liquid present in the printed MDL-structures, it is favorable to
consider the attraction between the NPs and untreated c-PVP. The measured water
CAs on PEN and untreated c-PVP correspond to 37° and 60.2°, respectively, which
means a higher hydrophobicity of untreated c-PVP compared to PEN. According to
the observations realized by Z. Zhang et al. [ZZX+ 13] previously described in Section
2.3.1.1, the contact line of an evaporating dispersion on a hydrophilic substrate is
self-pinned immediately at initial evaporation time and the contact area remains
constant until the end of evaporation. This was explained by the small CA leading
to a higher evaporation rate at the liquid edge compared to the center. However,
the contact line on substrates with higher hydrophobicity is pinned initially then
starts to recede, which leads to a decreasing of the contact diameter and higher
material deposition between the twin-lines. The impact of substrate hydrophobicity
can be confirmed by comparing the behavior of PTFE NPs on c-PVP and c-PMMA,
which has a smoother surface (surface roughness equal to 0.82 ± 0.9 nm) and higher
hydrophobicity. Similarly to c-PVP, it can be assumed that the liquid present in
the MDL-structure degrades the functional groups of the O2 -plasma treatment on
c-PMMA. To get an overview on the hydrophobicity of the compared materials, the
corresponding water CAs are listed in Table 6.1.
The height profiles of the printed MDL-structures on c-PVP and c-PMMA are
shown in Fig. 6.2. Although c-PMMA is smoother than c-PVP, the material depo-
sition in the central area of the ring is much higher compared to c-PVP. Due to the
high hydrophobicity of untreated c-PMMA, the influence of the force F1 becomes
more significant, which minimizes the migration of NPs to the edge. Consequently,
the deposited ring has a smaller height, width, and volume and the drying pattern
on c-PMMA becomes more homogeneous as can be seen in Fig. 6.3.
O2 -plasma-treated untreated
c-PVP 23.7° 60.2°
c-PMMA 26.3° 67.3°
PEN - 37°
74 Chapter 6
Figure 6.2: Height profiles of twin-lines realized by the printing of 220 nm PTFE NP
dispersion on different substrates: a) O2 -plasma-treated c-PMMA and b) O2 -plasma-
treated c-PVP.
a) b)
~5 µm 9 µm
PMMA 50 µm 10 µm
PVP 50 µm 10 µm
The next observation deals with the slight difference of the ring heights between
the right and left side, which can be seen in the height profiles in Figures 6.1 and
6.2 and can be explained in two different ways. The first explanation is related to
the movement of the printhead as explained in Section 4.1.1. In fact, it is favorable
to print the MDL-structures in a single movement, which necessitates in this case
the use of 7 working neighbored nozzles (n = 7). However, if the MDL-structure
is printed with less than 7 nozzles, multiple printhead movements are required. In
this case, the first printed lines can start to evaporate during the printing process,
which leads to a slight difference of the amount of migrating NPs on both sides.
The second explanation is related to the printing layout and thus to the existence
of evaporating structures in the neighborhood of the tested MDL-structure. In this
context, K.-Y. Shin et al. [SLO11] showed that the existence of neighboring parallel
lines results in a morphological change of deposited rings of each structure. For
example, the simultaneous evaporation of three parallel lines results in a symmetric
morphology of the central line, while the left and right lines exhibit higher left and
right peaks in their morphologies, respectively. As the MDL-structures studied in
this section are also printed in parallel to other lines, it is also possible to adopt this
explanation as a reason behind the formation of twin-lines with unequal heights.
A low island formation in the central ring area is favorable first for a better
comparability between theoretical model calculations and experimental results and
6.1 Influence of particle size and substrate 75
secondly for a good printability of the conductive ink. In fact, the presence of
high and large hydrophobic islands can result in discontinuities of the electrodes
and eventually in a high contact resistance due to the presence of less percolating
pathways for the electrons. This means that c-PVP is more suitable to be used as
a substrate material for the twin-line deposition compared to PEN and c-PMMA.
In the next step, the printing results of the three dispersions on c-PVP are
characterized optically by the use of light and scanning electron microscopy (s. Fig.
6.4).
a)
PVP
PTFE
9 µm
PTFE twin-lines
Decreasing nanoparticle size
50 µm 10 µm 2 µm
PVP
b)
11 µm
PVP 50 µm 10 µm
PVP 2 µm
c)
PVP
13 µm
PVP 50 µm 10 µm 2 µm
Figure 6.4: Microscope and SEM images of twin-lines on O2 -plasma-treated c-PVP for
different particle sizes: a) 220 nm, b) 120 nm, and c) 90 nm.
The microscope and SEM images show relatively small islands, which seem to
become thicker with increasing NP size. Consequently, the ring widths increase
with decreasing NP size as shown in the microscope images, where these values
correspond to 9 µm, 11 µm, and 13 µm for particle sizes of 220 nm, 120 nm, and 90
nm, respectively. Although the 90 nm particles show minimum island deposition,
which is advantageous for the silver electrodes, the images in Fig. 6.4.c display
a significant crack formation in the twin-lines. These cracks are not visible in the
120 nm structures but the presence of nm-scaled pores is noticeable. In contrast, the
220 nm twin-lines show a continuous structure, without pores or cracks. The crack
76 Chapter 6
formation was observed before the sintering step, which means that it occurred
within the coffee ring effect during the evaporation on the printing chuck. The
relationship between the crack formation and the particle size can be explained
based on the interaction between adjacent particles, which was represented by the
force F4 in the model of A. P. Sommer et al. [SR05] (s. Fig. 2.10.a). By depositing
a 60 nm polystyrene NP suspension on octyltrichlorosilane (OTS), A. P. Sommer
et al. observed the formation of cracks with radial orientation (which is the same
orientation of the cracks observed for the 90 nm fluoroplastic NPs) in the final
phase of evaporation after the shrinkage of the drop during evaporation. During
solvent evaporation, a volume reduction leads to the formation of a denser structure
[TAP+ 12]. The created stress is distributed throughout the deposited ring and
results in tensile fracture patterns [GS07]. Decreasing the NP size leads to the
formation of a denser structure and a higher interaction between adjacent particles.
In addition to cracks, the voids created due to shrinkage can also have the form of
pores as can be seen in Fig. 6.5. These voids are created within the first drying
step on the printing chuck at 28°C. The subsequent sintering step at 150°C leads
to a propagation and further growth of the pre-existing cracks and pores [GS07,
KKR+ 10].
The created fractures in the hydrophobic twin-lines present different drawbacks
for the reliability of the printed electrodes. The printing results of silver Cabot-CCI
ink on the three dried dispersions are illustrated in Fig. 6.5. The presence of pores
or cracks in the hydrophobic lines does not inhibit the dewetting of the conductive
ink. However, it leads to the formation of small or large silver islands between the
electrodes. Although these silver islands are isolated from each other, a tunneling
between them is possible, which can lead to an electrical transport between them
[TAS+ 03].
Fluoroplastic
PTFE polymer
PTFE
1 µm 2 µm 2 µm
Ag Ag Ag Ag Ag Ag Ag
Figure 6.5: Influence of crack and pore formation on Ag electrodes. SEM pictures (top)
of hydrophobic twin-lines and microscope images of printed Ag electrodes (bottom)
for different NP sizes: a) 220 nm, b) 120 nm, and c) 90 nm.
To sum up, the 220 nm PTFE NPs on O2 -plasma-treated c-PVP showed the best
results compared to PEN and c-PMMA and compared to dispersions with smaller
6.2 Variation of model parameters 77
NPs. The basic criteria for these material choices are minimum island deposition
in the central area of the ring and absence of pores or cracks. Consequently, these
materials can be used for OFET fabrication by choosing c-PVP as dielectric in case
of a bottom gate bottom contact (BGBC) configuration or substrate in case of a
top gate bottom contact (TGBC) configuration. For the second case, c-PVP can be
coated or printed on an underlying substrate such as PEN, PET, or paper. In this
thesis, a BGBC configuration is adopted and the 220 nm PTFE dispersion is printed
directly on c-PVP, which is used as OFET dielectric. The height profile and a SEM-
image of separated electrodes on 220 nm PTFE printed on c-PVP are illustrated in
Fig. 6.6. The complete dewetting of the conductive ink can be clearly seen through
the line morphology in the height profile. The central Ag electrode has a cylindrical
shape due to the high CA of the silver ink on PTFE (80.4°). It is also noticeable
that this central electrode is thicker than both electrodes printed on c-PVP. This
can be explained by the confinement of the ink between both hydrophobic PTFE
lines as well as the presence of hydrophobic islands under silver. As can be seen in
the SEM picture, these islands are also responsible for the higher surface roughness
of silver printed between the twin-lines compared to the silver printed on c-PVP.
After choosing optimum materials for the twin-line deposition, the next experi-
mental part is going to deal with a variation of model parameters by the use of these
materials in order to realize a comparison between theoretical and experimental re-
sults.
a) 400 b)
PTFE PTFE PTFE islands
300 Ag
Ag Ag on PTFE islands Ag
h (nm)
200 PTFE
100
Ag
PVP
0
0 100 200 300 400 500 10 µm
x (µm)
Figure 6.6: Silver electrodes separated by a PTFE line. a) Height profile and b) SEM
image.
n=2
n=3
Overlapping twin-
n=4 lines
n=5
600 µm
Water-based 220 nm PTFE dispersions with 0.6 wt% PTFE and isopropanol con-
centrations between 1 wt% and 10 wt% are mixed then deposited on untreated and
O2 -plasma-treated c-PVP (day 1 and day 3). The corresponding CAs are measured
by the use of the sessile drop technique as described in Section 5.3.1 and the mea-
sured values are displayed in Fig. 6.8. For each isopropanol concentration, the
highest CA is measured on untreated c-PVP and the lowest value is measured on
O2 -plasma-treated c-PVP (day 1).
As expected, the plasma-treated substrate changes its surface tension on the third
day after treatment due to hydrophobic recovery. This explains the slight increasing
of θ on day 3 compared to day 1 for each isopropanol concentration. The resulted
CAs vary between 48.3° and 80° for untreated c-PVP, which proves that increasing
the concentration of isopropanol is not sufficient for a good wettability of the PTFE
dispersions and necessitates the use of O2 -plasma-treatment. The corresponding
microscope images are shown in Fig. 6.9 for θ = 80° and θ = 48.3°.
6.2 Variation of model parameters 79
90
1 wt%
80
2 wt%
70
3 wt% Isopropanol
Contact angle (°)
60
4 wt% concentration
50
5 wt%
40 10 wt%
30
20
10
0
Intern © Siemens AG 2014 Alle Rechte vorbehalten.
c-PVP + O2 (Day 1) c-PVP + O2 (Day 3) c-PVP (untreated)
PTFE
PTFE PTFE
PVP
No treatment / 1 wt% ISO
100 µm PVP 100 µm
θ = 25.7° θ = 16.4°
θ = 24.4°
100 µm 100 µm
O2-plasma (day 1) / 1 wt% ISO O2-plasma (day 1) / 3 wt% ISO O2-plasma (day 1) / 10 wt% ISO
100 µm
Due to the relatively high CA, the printed liquid dewets on untreated c-PVP and
separate drops are formed instead of a continuous MDL-structure. In contrast, θ
varies in the ranges of 16.4° – 25.7° and 27.1° – 35.6° for the first and third day after
O2 -plasma-treatment, respectively. Consequently, the wettability is enhanced and
continuous MDL-structures are formed as shown in Fig. 6.9 for θ = 35.6°, θ = 25.7°,
80 Chapter 6
n = 1, n = 2, n = 3, and n = 7.
These rings show different structures
depending on n. In fact, they exhibit
10
a continuous growth for higher n-values Circular_2
(in this case for n = 7). However, with 8 Triangular_2
decreasing n, the deposited rings show
w (µm)
an increasing formation of pores as well 6
as line discontinuities (kinks). During
the realization of this experiment, it was 4 Experimental
also noticeable that this pore formation
2
increases with increasing drop spacing
as well. These two facts prove that the 1 2 3 4 5 6 7
n
porosity of the ring structure is related
Fig. 6.11: Influence of n on the ring width: com-
to the decreasing volume of the printed parison of experimental results with the models
MDL-structures and hence are resulted Triangular 2 and Circular 2 for 1 ≤ n ≤ 7. Pa-
from its fast evaporation in combination rameter set: 4x = 25µm, L = 5 mm, C = 0.6
with the small amount of NPs present in wt%, Vd = 17.75 pl, θ = 25.7°, p = 74 %.
the liquid.
n=1 n=2
Pores
n=3 n=7
Few/No pores
Continuous PTFE line
10 µm 10 µm
Figure 6.12: Microscope images showing the influence of the number of lines on the
ring structure. 220 nm PTFE NP dispersions printed on O2 -plasma treated c-PVP.
Parameter set: 4x = 25µm, L = 5 mm, C = 0.6 wt%, Vd = 17.75 pl, θ = 35.6°.
Similarly, X. Shen et al. [SHW10] studied the competition between the time
scales of the liquid evaporation and the particle movement in single drops with
small sizes. In this context, they showed that the formation of a continuous ring
structure requires a sufficiently high particle concentration as well as a sufficiently
large diameter of the deposited drop. For lower liquid volumes and lower amount of
particles, the liquid evaporation was faster than particle movement and consequently
the rings could not be formed. According to L. Shmuylovich et al. [SSS02], a defect
present in a deposited ring and formed at a time t0 can be filled at a time t > t0 by a
82 Chapter 6
migrating particle, which was described as self-healing effect. By assuming that the
observed pores are a cluster of one or multiple defects, it is possible to deduce that
the required self-healing effect for the ring continuity could not occur at small n-
values due to the non-presence of an “available” NP to fill the formed defects within
the short time of evaporation.
Circular_2
10
8
w (µm)
6 Triangular_2
4
Experimental
2
0 10 20 30 40 50
L (mm)
Figure 6.13: Influence of the line length on the ring width: comparison of experimental
results with the models Triangular 2 and Circular 2. Parameter set:4x = 25 µm,
n = 7 , C = 0.6 wt%, Vd = 17.75 pl, θ = 35.6°, p = 74 %.
100 µm 100 µm
Pores 10 µm
30 µm 30 µm
Pores
High „island“ deposition
100 µm 50 µm 50 µm
Figure 6.14: Microscope images showing the influence of 220 nm PTFE nanoparticle
concentration C on the twin-line formation. Parameter set:4x = 25 µm, n = 7, L= 5
mm, Vd = 17.75 pl, θ = 35.6°.
example for C = 2 wt%. Similarly to the explanation adopted for small n-values,
the pore formation for small concentrations can also be interpreted by the decreasing
number of “available” NPs, which can fill the defects according to the self-healing-
effect. The formation of a double contact line can be explained by a contact line
motion or slip-stick-motion of the NPs (s. Section 2.3.3), which generally occurs at
small concentrations [SSS02]. In fact, lower concentrations result in lower viscosities,
which lead to the deposition of a small amount of NPs in the contact line and hence
accelerates its depinning [CTHW00].
In summary, the experimental results for the variation of model parameters in-
dicate their influence on the ring width as well as ring structure. Decreasing the
amount of NPs leads to the formation of porous twin-lines, which can be accom-
panied by a slip-stick behavior. This can be seen by decreasing n or decreasing C.
In addition to this, the comparison between theoretical and experimental results
shows high similarity by the use of the model Triangular 2. This means that this
model can be adopted for the prediction and tuning of the ring width starting from
given experimental parameters. However, this model cannot show the limitations
for each parameter such as critical values leading to the formation of pores or ring
discontinuities, which can be considered as an open topic for future research.
of the Cabot CCI-300 ink (4x =25 µm) on hydrophobic twin-lines with different
widths w of 3 µm, 4 µm, 6 µm, and 7 µm. The parameters used for the realization of
these PTFE lines are listed in Table 6.2 and microscopic images of the corresponding
results are shown in Fig. 6.15.
Table 6.2: Parameters used for the realization of PTFE rings with 3 µm≤ w ≤7 µm.
w n 4x C θ
3 µm 4 40 µm 0.4 wt% 35.6°
4 µm 7 40 µm 0.4 wt% 35.6°
6 µm 5 25 µm 0.6 wt% 35.6°
7 µm 6 25 µm 0.6 wt% 35.6°
a) b) unsintered Ag
unsintered Ag
Int 3 µm 4 µm
er
PTFE n
PTFE Partial dewetting
© / Partial dewetting
No dewetting 10 µm 10 µm
Si
e
c) d) PVP
m
sintered Ag
en sintered Ag
s 6 µm 7 µm
A
PTFE
G
Partial dewetting
PTFE
Total dewetting
20 10 µm 10 µm
14
Al
Figure 6.15: Microscopic images showing the wetting behavior of the silver NP ink on
PTFE twin-lines with different widths of a) 3 µm, b) 4 µm, c) 6 µm, and d) 7 µm.
The microscopic images show an improved wetting and increasing bridge formation
of the silver ink with decreasing channel length. In fact, the silver ink shows almost
no dewetting for w = 3 µm. However, it dewets partially on PTFE lines with higher
widths of 4 µm and 6 µm and completely for w = 7 µm. In order to explain these
different wetting behaviors, it is important to study the influence of the material
and printing parameters corresponding to PTFE and silver inks. Twin-lines with
small widths are realized by minimizing the amount of PTFE NPs in the printed
MDL-structures. This can be achieved by decreasing the concentration C, n, or
6.3 Critical channel length 85
L 2
≥ , (6.1)
H 1 − cos θ
where θ is the CA of the liquid ink on the hydrophobic strip. This formula in
addition to the microscopic observations in Fig. 6.15 evidence the existence of a
critical channel length Lcutof f , below which the dewetting of the conductive ink
is no more possible. Equation 6.1 can be adapted to the printing and material
parameters related to PTFE and silver in order to determine Lcutof f , which is going
to be calculated in the following section.
the conductive ink volumes before and after dewetting are equal.
A top-view and a cross-sectional view of the inkjet-printed silver ink structure with
a width WAg and length LAg on a PTFE self-assembled line with a width Lch < WAg
are presented in Fig. 6.17.
86 Chapter 6
a) b)
PTFE twin-lines Ag ink
hriv,Ag
c-PVP
y
x Lch Lch wriv,Ag
Ag MDLs
wriv,Ag LAg
WAg
Figure 6.17: Dewetting of the silver ink on hydrophobic PTFE twin-lines: a) top view,
b) cross-sectional view.
In order to deposit the silver ink layer with a 16-nozzle DMC-11610 printhead,
multiple moves of the printhead in x-direction accompanied by chuck movements
in positive y-direction are required. By assuming that a number nnozzles,Ag ≤ 16
of neighbored activated nozzles is used, the required total number of chuck move-
LAg
ments is around 4xAg ·nnozzles,Ag , where each of these moves is accompanied by two
movements of the printhead. During these movements the dewetting process can be
described in periodic sequences as follows:
Standby mode: Before starting printing, the chuck is located at its initial
position (y = 0) and the printhead as well (x = 0).
Start of printing: The chuck remains at its initial position and the print-
head moves in positive x-direction. During this movement, the activated noz-
zles jet a silver MDL-structure consisting of nnozzles,Ag lines. Each of these
MDL-structures can be approximated by a cylindrical segment with a rivulet
width wriv,Ag and a maximum height hriv,Ag (s. cross-section in Fig. 6.17.b).
Taking into consideration that hriv,Ag (µm-scale) is much higher compared to
the height of the PTFE line (nm-scale) and the geometry of the silver ink
structure is much larger compared to the PTFE line cross-section, it is possi-
ble to suppose that the liquid height of the silver ink cylinder before dewetting
is not affected by the PTFE line height. This means that hriv,Ag is assumed
to be homogeneous before the dewetting (equal ink heights on the substrate
(c-PVP) and PTFE) (s. Fig. 6.18.a). According to Eq.6.1, hriv,Ag is calculated
as:
wriv,Ag θAg,subst
hriv,AG = tan , (6.2)
2 2
where θAg,subst is the CA of the silver ink on the substrate (c-PVP). The silver
6.3 Critical channel length 87
where Vd,Ag and 4xAg are the drop volume and the drop spacing used for the
printing of the silver MDL-structure.
Start of dewetting and return to the initial printhead position: Once finished
the printing of the MDL-structure, the printhead moves in negative x-direction
in order to return back to its initial position. During this movement the
dewetting of silver starts (s. Fig. 6.18.b) and the nozzles are turned off. The
time required for the dewetting of each single silver MDL-structure on PTFE
has not been measured within this work. However, a decreasing dewetting
time with decreasing nnozzles,Ag was observed, which can be explained by the
decreasing liquid volume. In order to assure that the Ag MDL-structure dewets
entirely before starting to print the next MDL-structure, a single nozzle for the
printing of silver is activated (nnozzles,Ag = 1). This has a second advantage
consisting of the minimization of hriv,AG , which is also required for an enhanced
dewetting according to the condition of dewetting in Eq.6.1.
Lch 2
≥ , (6.4)
hriv,Ag 1 − cos θAg,P T F E
where θAg,P T F E is the CA of the silver ink on PTFE. Applying the relationships
expressed in Eq.6.2 and Eq. 6.3 leads to the following expression of the condition of
dewetting:
hriv,Ag
c-PVP c-PVP
a) Before dewetting
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b) After dewetting
Figure 6.18: Dewetting process of a single silver ink MDL-structure on a PTFE line: a)
before dewetting, b) after dewetting.
88 Chapter 6
Lch 4
s ≥ . (6.5)
1 − cos θAg,P T F E
1
2nnozzles,Ag ·Vd,Ag · WAg
+ ∆x1
θAg,subst
sin2
Ag
2
· 2θAg,subst −sin(2θAg,subst )
Simulation 1, which is based on the variation of the silver ink drop spacing
∆xAg between 5 µm and 45 µm. The purpose is to evaluate the influence of
the silver ink volume on the critical channel length.
For PTFE twin-lines printed on O2 -plasma-treated c-PVP substrates, the silver ink
contact angles on PTFE and c-PVP correspond to 80.4° and 7.9°, respectively (s.
list of parameters used for both simulations in Table 6.3). The results corresponding
to Simulation 1 and Simulation 2 are plotted in Fig. 6.19.
Table 6.3: Parameters used for the calculation of the critical channel length.
θAg,subst nnozzles,Ag WAg ∆xAg θAg,P T F E
Simulation 1 7.9° 1 5 mm 5 – 45 µm 80.4°
Simulation 2 7.9° 1 5 mm 25 µm 80 – 130°
a) b)
35 5 µm 20
30 80°
25 15
90°
Lcutoff (µm)
Lcutoff (µm)
20 15 µm 100°
25 µm 10 110°
15 120°
35 µm 130°
45 µm
10 5 θAg,PTFE
∆xAg
5
0 0
0 5 10 15 20 0 5 10 15 20
Vd,Ag (pl) Vd,Ag (pl)
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Figure 6.19: Calculation of the critical channel length as function of the silver ink drop
volume Vd,Ag . a) Variation of the drop spacing ∆xAg (Simulation 1). b) Variation of
the CA θAg,P T F E of the conductive ink on the hydrophobic twin-lines (Simulation 2).
6.3 Critical channel length 89
According to the results plotted in Fig. 6.19.a, the critical channel length decreases
with decreasing drop volume Vd,Ag and increasing drop spacing ∆xAg . This can be
explained by the minimization of the silver ink volume and thus its thickness as
shown in Eq.6.1. The influence of Vd,Ag on Lcutof f shows similar behaviors for drop
spacings between 15 µm and 45 µm and becomes much higher for ∆xAg = 5 µm. For
the 10 pl printheads used in this work, the drop volume can be tuned by varying
the waveform and the voltage applied on the single activated nozzle (0V – 40V)
as shown in Eq. 4.45. By assuming that Vd,Ag = 10 pl, using drop spacings of
25 µm, 35 µm, and 45 µm results in calculated critical channel lengths of 10.95 µm,
9.26 µm, and 8.18 µm, respectively. In order to reach lower Lcutof f -values, a drop
spacing of 35 µm is going to be used for the realization of OFETs and the voltage
applied to the activated nozzle is going to be tuned down to 26 V in order to reach
drop volumes of around 7 pl. Due to possible changes of the temperature or ink
viscosity in addition to printer-related inaccuracies, it is not possible to calculate
the drop volume reproducibly. An approximate drop volume of around 7 pl leads
to a critical channel length of around 6.84 µm for ∆xAg = 35 µm. By showing the
significant impact of the silver ink volume on the dewetting process, this simulation
proves from another side that nozzle area and thus the related printing technology
are crucial factors for the minimization of the channel length. For the same drop
spacing of 35 µm, the use of a 1 pl printhead (DMC-11601) would minimize the
critical channel length down to 2.59 µm. Potential improvement of the dewetting
process can also be derived from the simulation result in Fig. 6.19.b, which shows
a decreasing of Lcutof f with increasing CA of the conductive ink on PTFE. In fact,
replacing the alcohol based silver ink used in this work by a water-based conductive
ink would increase its CA on PTFE up to 120°. For a drop volume of 10 pl and
a drop spacing of 25 µm, this would result in a 49% decreasing of the calculated
critical channel length from 10.95 µm down to 5.55 µm.
The simulation of the critical channel length showed the limitations of the dewet-
ting process proposed for the realization of small-gap electrodes. These limitations
are related to the printing technology (nozzle area of chosen printheads and printing
parameters) as well as material choices leading to different behaviors of the conduc-
tive ink on the hydrophobic material used for dewetting. In the following section,
a lift-off-based approach is introduced in order to overcome these limitations and
reach critical channel lengths down to 4 µm by the use of the same 10 pl printheads.
electrode region. For this purpose, ultrasound cleaning is employed to remove the
PTFE twin-lines by the use of a 1:3 isopropanol-acetone mixture. This solvent
mixture is chosen as etching material as it is suitable for PTFE removal and not
aggressive for the surrounding materials such as silver, c-PVP, and PET-substrate.
The etching step is followed by a 15 min drying step at 150°C in an air convection
oven in order to remove the solvent rests on the sample. The expected final result is
the formation of a PTFE-free and bridge-free pair of silver electrodes. However, the
ultrasound cleaning step showed different results depending on the etching duration
tultrasound as shown in the microscopic image in Fig. 6.20.a. For tultrasound longer
than 6 minutes, PTFE and silver bridges are removed but the silver electrodes are
damaged due to long cleaning duration. In contrast, for tultrasound = 6 min, PTFE
is removed, the bridges are removed, and the silver electrodes are maintained in a
good quality, as can be seen in Fig. 6.20.b.
a) b)
C-PVP
Ag
C-PVP
Ag
PTFE Ag
PTFE Ag
100 µm 100 µm
X 100 µm
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Figure 6.20: Microscope images showing first results of the lift-off-based approach used
100 µm
for the realization of channels with Lch < critical channel length. a) Damaged silver
electrodes due to long ultrasound cleaning duration. b) Good results for tultrasound =
6 min.
Based on these first experimental results, the lift-off-based approach is tested for
the realization of channel lengths equal to 4 µm and 6 µm. For this purpose, the
PTFE twin-lines are printed by the use of the parameters in Table 6.2 and the silver
ink is printed by the use of a drop spacing ∆xAg = 35 µm. The corresponding results
before and after cleaning are displayed in the microscopic images in Fig. 6.21. For
both cases, PTFE twin-lines, silver bridges and residuals are washed-off successfully
by the use of the 1:3 acetone-isopropanol mixture for tultrasound = 6 min.
After microscopic characterization of the inter-electrode region, the proposed ap-
proach is investigated further by the use of SEM microscopy and EDX spectroscopy.
6.3 Critical channel length 91
C-PVP
Ag
PTFE
100 µm
PTFE 100 µm
Ag 100 µm
PTFE 10 µm
PTFE
C-PVP PTFE
PTFE removal PTFE removal
Ag
Ag
Ag
10 µm
100 µm Ag 100 µm 10 µm
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Figure 6.21: Fabrication of 4 µm and 6 µm gap electrodes based on the proposed lift-
off-based approach.
For this purpose, a comparison of the silver electrodes before and after PTFE etching
is realized based on the SEM images shown in Fig. 6.22. Before PTFE removal (Fig.
6.22.a), it is noticeable that both Ag electrodes exhibit different surface roughnesses.
As previously explained in Section 6.1, this is due to the deposition of the silver ink
on two different surfaces: a smooth c-PVP surface and a rough PTFE island surface
in the region between the twin-lines. By the use of the lift-off-process, the PTFE
twin-line etching is accompanied by the removal of the PTFE islands between them,
which results in the formation of silver-free islands as shown in Fig. 6.22.b. More-
over, this figure shows few material residuals in the inter-electrode region, which
could not be observed previously by the use of microscopy. In order to define the
nature of these residuals and explain their formation, a secondary electron emission
spectroscopy is realized in the area highlighted in the SEM picture in Fig. 6.23.
The plotted spectrum shows the presence of a slight silver peak and the absence of
a fluorine peak, which evidences that the few remaining material residuals in the
inter-electrode region are silver and not fluorine residuals. The deposition of these
residuals can be explained by the diffusion of the silver ink through the eventual de-
fects in the PTFE twin lines. These defects can be formed in relationship with the
pore-formation observed for small-channels, generally with channel lengths smaller
than 7 microns. As the sample in Fig. 6.23.a has a channel of 7 – 8 microns, the
PTFE structure should be pore-free. For this reason it is possible to interpret the
formation of silver residuals by the NP size difference between PTFE (220 nm) and
the Cabot CCI-300 silver ink used (25 – 50 nm). In fact, the PTFE NPs are de-
posited in a compact way at the edge of the evaporating MDL-structure during the
coffee ring effect (s. Fig. 6.24.a). This deposition shows an order-to-disorder tran-
sition from the twin-line edge to the center [MGLS11], which is accompanied by a
monolayer to multilayer transition [SLSS09]. Consequently, the PTFE NPs deposit
with different packing densities in an ordered (hexagonal-cubic-order) or disordered
way. These differences result in cavities formed between adjacent NPs and allow
the diffusion of the relatively smaller silver NPs through them as illustrated in Fig.
92 Chapter 6
a)
PTFE islands PTFE islands
Ag
Ag
C-PVP PTFE
PTFE
Outer edge
Inner edge
Ag Ag
10 µm 2 µm
Ag
10 µm
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Ag 5 µm
Figure 6.22: SEM images for Ag electrodes printed on PTFE. a) Without PTFE removal.
b) PTFE removed.
6.24.b. By considering that the outer edge of the PTFE line is thinner and has a
higher NP ordering compared to its inner edge [MGLS11], it is possible to assume
that the diffusion of the silver NPs at the outer edge of the PTFE line is higher,
which leads to a higher formation of silver residuals in this area.
For future research work, potential improvements could be achieved by minimizing
the PTFE NP size to silver NP size ratio. As minimizing the PTFE NP size re-
sults in crack formation during evaporation as previously shown in Section 6.1, it
would be more appropriate to use silver NPs with larger size. Minimizing the sil-
ver residual deposition in the inter-electrode region is highly recommended due to
its direct influence on the OFET performance. First, these conductive residuals
increase the number of percolating pathways for charge carriers, which can result
in a breakthrough, especially by applying high voltages. Secondly, these residuals
result in higher roughness which inhibits the semiconductor crystal growth in the
channel region and results in lower mobilities. Further improvement can be achieved
by minimizing the PTFE island deposition between the twin-lines e.g. by applying
an additional etching step to wash off these islands before printing the silver ink
and consequently create a smooth surface between the twin-lines. As the present
PTFE islands and the silver-free islands (in case of PTFE removal) result in the
presence of less percolating pathways for the electrons, minimizing the formation of
6.4 Electrode fabrication: summary of experimental results 93
islands leads to a higher silver electrode contact resistance and hence a better OFET
performance.
6400
C
Counts
twin-line
Ag 3200
1600
Ag O Ag
Ag-free islands 5 µm F
0
0 2 4 6 8 10
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Figure 6.23: EDX spectroscopy for the inter-electrode region after PTFE removal.
a) b)
C-PVP
PTFE nanoparticles
PTFE line
Silver nanoparticles
1 µm
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Figure 6.24: Silver nanoparticle diffusion through PTFE defects. a) SEM image of a
220 nm PTFE structure. b) Schematic illustration.
150°C. The minimization of island deposition in the central area of the ring and
the absence of pores or cracks was a crucial criterion for the material choices, as it
is favorable for a good comparability between theoretical and experimental results
in addition to its influence on electrode quality and OFET performance. For this
reason and based on the first experimental results, O2 -plasma-treated inkjet-printed
c-PVP was chosen as underlying material for the hydrophobic twin-lines and the
water-based 0.6 wt% PTFE dispersions were chosen for the realization of the small-
channel electrodes.
The next step consisted of the evaluation of the proposed model for the twin-
line deposition by varying the CA θ, the number of lines n, the line length L, and
the concentration C. The CA was tuned between 16.4° and 80° by the variation
of isopropanol concentration in the PTFE dispersions between 1 wt% and 10 wt%
and making use of hydrophobic recovery of O2 -plasma-treated c-PVP substrates.
The corresponding microscopic images displayed a good printability for CAs be-
tween 16.4° and 35.6°. A comparison of the corresponding twin-line widths with
calculated model values showed a higher similarity for the model Triangular 2.
This similarity was also observed by the variation of the number of lines n be-
tween 1 and 7 and the variation of the line length L between 0.1 mm and 50
mm. For low twin-line widths (< 7 µm) realized by decreasing n or C, micro-
scope images showed a tendency to pore formation as well as ink bridge formation.
A model was presented for the calculation of the critical channel length Lcutof f , be-
low which the dewetting of the conductive ink is no more possible. The simulation
results showed an increasing Lcutof f with decreasing conductive ink volume and
evidenced potential improvements of the proposed approach by the use of dif-
ferent printheads with smaller nozzle area or the use of a water-based conduc-
tive ink instead of alcohol-based inks. Finally, a new lift-off-based approach was
proposed for the realization of electrode gaps below Lcutof f by washing off the
conductive material rests in the narrow inter-electrode region. For this purpose,
PTFE twin-lines were ultrasound-cleaned in a 1:3 isopropanol-acetone mixture.
Based on this, silver electrodes with
r
4 µm and 6 µm widths were fabricated. n
Printing of C-PVP
©
SEM microscopy and EDX spectroscopy S O2-plasma-treatment
i
were employed to characterize the inter- e Printing of PTFE dispersion
m
electrode region after the lift-off process e Drying @RT + CRE
n
and showed the presence of few silver s Drying @150°C
A
NP rests there. The electrode fabrica- G Printing of silver ink
tion steps with and without the lift-off 2
0
Sintering of silver ink
process are summarized in Fig. 6.25 and 1 Lift-off
4 Optional
are going to be adopted for OFET fab- A Drying
l
rication in the next chapter.
Fig. 6.25: Electrode fabrication steps.
Chapter 7
Fabrication of small-channel
organic field effect transistors
The previous chapters were dedicated for the description, examination, and op-
timization of a new wetting-based self-alignment mechanism for the realization of
micron-sized electrode gaps. Based on the acquired results in Chapter 6, this chapter
shows the applicability of this mechanism for the realization of fully inkjet-printed,
small-channel OFETs. The process steps are described for two different electrode
fabrication methods: with and without PTFE removal. Besides the electrodes, the
deposition of the dielectric and semiconductor layers is optimized in order to im-
prove the OFET performance. At the end, the different electrode configurations are
compared based on the OFET electrical characterization results.
a) b)
PET
G
Ag
C-PVP
D S
PTFE TIPS-Pentacene
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95
96 Chapter 7
Based on the layout in Fig. 7.1.a, OFETs with a channel length Lch = 8 µm, a
channel width Wch = 4.3 mm and a total area of 10 mm × 3.5 mm are fabricated
by means of inkjet printing. The dimensions used for electrodes and dielectric layer
are fixed for the entire chapter. However, the semiconductor layer dimensions are
going to be updated later (s. Section 7.3.3.2) according to the first results related to
the growth direction of TIPS-pentacene crystals. Details related to the materials,
printing, and drying parameters used for each OFET layer are described in Chapter
5. The fabrication steps are illustrated in Fig. 7.2:
a) b) y
c)
y y
1 mm G x G x G x
1 mm 1 mm
C-PVP
1 mm Ag 2 mm D +O2 S
5 mm 10 mm
Ag
d) e) y f)
y x y
G x G G x
Dewetting Ag
D S D S D S
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AG 2014 Alle Rechte vorbehalten. 4.3 mm TIPS-Pentacene
Figure 7.2: Processing steps used for the fabrication of fully inkjet-printed OFETs. The
deposited layers are a) gate electrode, b) dielectric, c) source and drain contact pads
followed by O2 -plasma-treatment, d) PTFE, e) source and drain electrodes, and f)
semiconductor.
of NPs to the edge of the MDL-structure due to the coffee ring effect. The formed
PTFE twin-lines are cured subsequently for 10 min at 150◦ C. After the drying of
the hydrophobic PTFE twin-lines, the substrate is rotated through 90° in order to
set the PTFE ring perpendicular to the x-direction of the printhead (s. Fig. 6.17).
A 4.3 mm × 500 µm rectangular structure of silver ink is deposited on the PTFE
ring then sintered at 150◦ C (e). The dewetting results in the splitting of the printed
structure into two rectangular electrodes, which are employed as source and drain
(s. Section 6.3.1). The final step (f) consists of the deposition and evaporation of
TIPS-pentacene by the use of a chuck temperature of 60°C.
a) b) 5
1L
4 2L
Ag top electrodes PET
3L
30 mm
3
hcap (µm)
1 mm
1 mm
2
15 mm
5 mm
1
5 mm
C-PVP 0
Ag bottom electrode 10 µm 20 µm 30 µm 40 µm
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Drop spacing (µm)
Figure 7.3: a) Layout used for the realization of neighbored c-PVP capacitances. b)
Dielectric layer thickness as a function of drop spacing and number of layers.
The plotted values correspond to the mean values of the 10 neighbored printed
capacitances. Some irreproducibilities have to be taken into consideration due to the
irregularity of the jetting process and thickness inhomogeneity caused by the coffee
ring effect. This explains the similarity of some results despite the use of different
98 Chapter 7
30 1.2
1L 1L
25 2L 1.0 2L
3L 3L
20 0.8
Ileak [nA/cm²]
Ci [nF/cm²]
15 0.6
10 0.4
5 0.2
0 0.0
10 µm 20 µm 30 µm 40 µm 10 µm 20 µm 30 µm 40 µm
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Drop spacing [µm] Drop spacing [µm]
Figure 7.4: Capacitance and leakage current as functions of the number of layers and
drop spacing for inkjet-printed c-PVP.
parameter sets (e.g. thickness values for 2L and 3L by the use of 4xP V P = 10 µm
or 4xP V P = 30 µm). The plotted results show mean dielectric thicknesses between
0.7 µm and 4.8 µm resulting in capacitance mean values between 2.19 nF/cm² and
25.8 nF/cm². Decreasing hcap is favorable for the increase of Ci , however, it results
in a significant increase of the leakage current. For the highest capacitance Ci =25.8
nF/cm², the mean leakage current corresponds to Ileak = 1.04 nA/cm² and the
possibility of the shortening is very high due to the large drop spacing of 40 µm.
By the use of the same ink composition for c-PVP, a drop spacing of 25 µm, and
two layers, Chung et al. [CJC+ 11] printed 1 µm thick dielectrics and measured a
capacitance of 4.3 nF/cm² and a leakage current of ≤ 0.5 nA/cm². An approximate
value of this thickness can be achieved for 1L and 4xP V P = 20 µm (Ci = 7.94
nF/cm²) or 2L and 4xP V P = 40 µm (Ci = 17.03 nF/cm²) (s. Fig. 7.3.b). Despite
the similarity of the thickness values for both drop spacings, the results show different
capacitance and leakage current values. This can be explained by the change of
pattern fidelity, film quality, and film shape by increasing the drop spacing and
hence decreasing the drop overlap on the substrate [KSS10]. This can also explain
the increase of the standard deviation of Ci and Ileak for higher drop spacings. In
order to achieve good insulating properties and guarantee a good reproducibility,
a drop spacing of 4xP V P = 20 µm and a number of layers NLayers,P V P = 3 are
chosen for the realization of OFET capacitances. This parameter set corresponds to
Ci = 5.03 ± 0.29 nF/cm², hcap = 2.35 ± 0.05 µm, and Ileak = 0.19 ± 0.03 nA/cm².
Moreover, a large rectangular shape of 2 mm × 10 mm is chosen for the dielectric
layer in order to reduce the thickness inhomogeneities caused by the coffee ring effect
by printing the OFET channel area in the central flat region. It is also important
to note that all capacitance, thickness, and leakage current values are measured for
capacitance top electrodes that are printed in the middle flat area of the c-PVP
“coffee-ring”. For a more precise measurement of the relative dielectric constant
7.3 Optimization of the semiconductor deposition 99
εr,P V P , capacitances are fabricated by the use of inkjet printing and spin coating for
the silver electrodes and c-PVP, respectively. Spin coating is used here in order to
achieve better reproducibility and homogeneity of the deposited film. The calculated
relative dielectric constant is equal to εr,P V P = 5.4.
The investigation of the optimum parameter set for the fabrication of the c-PVP
shows mainly the influence of the drop spacing and the number of layers on the
capacitance and leakage current. However, due to the significant influence of the
layer topography on the results, the capacitance is measured for each individual
OFET separately in order to investigate the OFET mobility later. In fact, changing
the dimensions of c-PVP from 5 mm × 5 mm to 2 mm × 10 mm would result
in different distribution of the NPs during solvent evaporation and hence different
thicknesses of the middle “coffee-ring” area.
a) b)
Intern © Siemens
AG 2014 Alle Rechte
vorbehalten.
Figure 7.5: Evaporation of a TIPS-pentacene ink drop and influence of the coffee ring
effect on crystal growth direction. a) Final shape of the dried TIPS-pentacene drop. b)
Microscope image of a TIPS-pentacene drop during evaporation showing the influence
of contact line receding on crystal growth direction.
printer, which is equal to 60°C. After this first drying step, a second annealing step
at a higher temperature is required for the removal of the remaining solvent. Fig.
7.6 shows microscopic images corresponding to dried TIPS-pentacene ink drops after
printing at TT IP S = 60°C and drying for 10 min on the printer chuck (a), followed
by annealing for 10 min at TT IP S = 100°C (b) and 10 min at TT IP S = 125°C(c).
Longitudinal twin boundaries (120 ¯ plane) can be identified for TT IP S = 60°C and
crack formation in the 120 and 210 planes is observed for T > 100°C. According
to J. Chen et al. [CTY+ 06], cracks initiate first on the 210 plane at temperatures
of 80° C – 100° C , then propagate along the 120 plane for temperatures higher than
120° C as a result of expansion from two sides of overlapping crystals. Due to these
cracks, J. Chen et al. reported a decrease of TIPS-pentacene based OFET mobility
by a factor of 50 – 80 %.
In fact, these cracks affect the charge injection at the semiconductor-electrode-
Intern100
© Siemens
µm
AG 2014 Alle
Rechte
Figure 7.6: Influence of the drying temperature on crack formation in TIPS-pentacene
films. The semiconductor is dried for 10 min at 60°C (a), followed by 10 min at 100°C
(b) and 10 min at 125◦ C (c).
7.3 Optimization of the semiconductor deposition 101
interface as well as the charge carrier transport in the channel region [BKHL11].
The influence of drying temperature and crack formation on OFET mobility is in-
vestigated further in the OFET electrical characterization section 7.5.
Intern © Siemens
AG 2014 Alle Rechte
vorbehalten.
Figure 7.7: Influence of solvent choice on the crystal growth of TIPS-pentacene.
“coffee-ring” structure. Fig 7.8 shows three consecutive stages of evaporation. Due to
the coffee ring effect, the evaporation starts at the edges of the printed semiconductor
ink. Consequently, the crystals start to grow from these edges. Ideally, the contact
area of the liquid with the underlying surface should shrink radially leading the
crystals to grow in radial direction until the end of evaporation [LRL+ 12]. However,
due to the high surface tension of the PTFE line, the ink starts to dewet within the
first stage of evaporation (a) and the liquid contact line continues its movement in
parallel to the printed PTFE line (b and c).
a) b) c)
TIPS-Pentacene ink
Contact line motion
PTFE line
Figure 7.8: Three consecutive stages of evaporation and dewetting of a 1,2-DCB based
TIPS-pentacene ink on an untreated dried PTFE line.
The liquid thickness at the central area of the TIPS-pentacene structure is higher
compared to the liquid contact line. According to Eq. 6.1, the dewetting occurs
for low liquid thicknesses. For this reason, the liquid splits continuously at the
vicinity of the moving contact line. Due to this dewetting, the crystals grow in
the same direction as the liquid contact line motion and few, short, and randomly
oriented crystals are located in the channel area. As the quality of the grown crystals
is mainly dependent on the wetting behavior of the semiconductor ink, the next
optimization step of TIPS-pentacene deposition consists of decreasing the contact
angle θT IP S,P T F E . This angle corresponds to the CA of the TIPS-pentacene ink on
PTFE. In order to reduce it, the PTFE surface tension is modified by the use of
different plasma-treatments, as shown in the next section.
related to the high F/C ratio. For this reason, increasing its surface tension requires
breaking the strong F-C bindings, as shown by the different defluoration methods
depicted in Fig. 5.2. Experimental details related to the different plasma-treatments
tested for this purpose are described in Section 5.2.2. The different feed gases used
for plasma-treatments are: argon (Ar), nitrogen (N2 ), oxygen (O2 ), and a mixture
of hydrogen and argon (H2 /Ar). The results are shown in Fig. 7.9. O2 -plasma-
treatment (a) shows a decrease of the surface tension from 4.47 to 2.3 mN m−1 after
10 min. Similarly, K. Ozeki and K.K. Hirakuri [OH08] observed a slight increase of
the water CA on PTFE with increasing O2 -plasma treatment time. This treatment
doesn’t lead to a chemical modification of PTFE but results in the emerging of the
cleaned surface due to the removal of organic contaminants. N2 -plasma (b) consists
of a corona treatment with an atmospheric pressure N2 plasma source. The corona
wire drives with a fixed speed over the samples and takes around 15 s time for each
run. This treatment was tested for up to 3 runs, which corresponds to treatment
times between 15 and 45 s. An exposure within 3 runs results in a slight increase of
the surface tension up to 5.2 mN m−1 . Ar-plasma-treatment (c) is applied for up to
20 min. The surface tension starts to increase significantly after 7 min and reaches
56.7 mN m−1 after 20 min. Nevertheless, this method is not adopted as this surface
tension increasing is accompanied by a physical damage of the treated surface. The
final treatment consisting of Ar/H2 is applied up to 10 min and shows a significant
increase of the surface tension to 53.8 mN m−1 after 5 min. This is equivalent to a
reduction of the water CA from 150◦ to 89.5° and hence can be adopted to improve
the wetting of the TIPS-pentacene ink on PTFE.
a) b) c) d)
60
O2 X 60
N2 X 60
Ar X 60
Ar/H2
Surface tension (mNm-1)
50 50 50 50
40 40 40 40
30 30 30 30
20 20 20 20
10 10 10 10
0 0 0 0
0 2 4 6 8 10 0 15 30 45 0 5 10 15 20 0 2 4 6 8 10
Treatment
Intern time
© Siemens AG(min)
2014 Alle RechteTreatment
vorbehalten.time (s) Treatment time (min) Treatment time (min)
Figure 7.9: Change of the surface tension as function of plasma treatment. The applied
feed gases correspond to a) O2 b) N2 c) Ar, and d) Ar/H2 .
a) b) ∆x = 20 µm ∆x = 10 µm
PEN
PEN
PTFE
PTFE coffe-ring
100 µm
100 µm X 100 µm
a) b)
S
Channel
D
100 µm
Insulator
Crystals PTFE confinement
d) c)
PTFE confinement
S
lup
Channel Lconf
lbottom Cyrstal growth direction
D 100 µm
After printing TIPS-pentacene in the middle area, the crystal growth starts si-
multaneously at the upper and lower PTFE lines of the confinement and continues
in the orthogonal direction in a slowly and well-ordered manner (b). The final step
of evaporation shows a relatively faster receding of the contact line in the lateral
direction, which results in the formation of long crystals perpendicular to the left
and right sides of the confinement (c). In order to avoid this, the confinement design
is updated as shown in (d) by removing the left and right sides. For this updated
106 Chapter 7
design, the distance Lconf between the PTFE lines has a high influence on the fi-
nal crystallization result. For this reason, Lconf is added to the input variables of
the DoE. For the positioning of the OFET channel in the confinement area, two
locations are defined: lup and lbottom for the upper and lower regions, respectively.
This is related to the differences in crystal width and coverage observed between
both regions. Ideally, the crystals from both sides should grow symmetrically and
show very similar behaviors and shapes. However, as the semiconductor drops are
printed with raster scan method, the first printed drop lines (upper region) start to
evaporate earlier compared to the drops printed in the bottom region. The input
parameters and target dimensions of the DoE are summarized in Table 7.1.
Table 7.1: Summary of inputs and outputs of the DoE used for the optimization of the
TIPS-pentacene deposition.
The target dimensions are measured for each parameter combination based on
microscopic images. The optimum parameter combinations for each solvent are
summarized in Table 7.2 and the corresponding crystallization results are displayed
in Fig. 7.12 for anisole (a), tetralin (b), and 1,2-DCB (c).
Compared to anisole and tetralin, the use of 1,2-DCB leads to the highest crystal
coverage and largest crystal width. These values correspond to 87 ± 4 % and 20 ± 3
µm, respectively. In addition to this, the microscopic images of 1,2-DC display a
higher crystal ordering for lup and lbottom . For these reasons, 1,2-DCB is chosen
among the three solvents for the deposition of the semiconductor ink used for the
OFETs.
Table 7.2: Summary of optimum DoE results for anisole, tetralin, and 1,2-DCB.
TIPS-Pentacene crystals
100 µm
100 µm 100 µm
TIPS-Pentacene crystals
100 µm 100 µm
100 µm
Figure 7.12: TIPS-pentacene crystallization results for different solvents by the use of
the open-sided PTFE confinement. The microscopic images correspond to a) anisole,
b) tetralin, and c) 1,2-DCB.
2 Printing of C-PVP
3 Printing of source and drain contact pads
4 O2-Plasma-treatment
5 Printing of PTFE twin-lines + CRE
6 Printing of Source and drain electrodes
‚
7 Ar/H2-plasma-treatment No treatment
Table 7.3: Summary of the parameters used for OFET fabrication (Step numbers are
based on Fig. 7.13).
The common first steps for the three designs consist of printing the silver gate
electrode on untreated Melinex ST-504 PET substrate (1), followed by c-PVP (2),
then source and drain contact pads (3). The surface tension of c-PVP is O2 -plasma-
treated (4) in order to improve the wettability of the water-based PTFE MDL-
structure, which is printed afterwards (5). Due to the coffee ring effect, PTFE
NPs migrate to the edge of the printed dispersion resulting in the formation of hy-
drophobic PTFE twin-lines with a width of few microns. Once printed on top of
these formed PTFE lines, the alcohol-based silver ink dewets and splits into two
separated silver structures, which are sintered consequently and used as source and
drain electrodes (6). The differentiation between the three designs starts in the
following step, which consists of a lift-off-based PTFE-removal (7) (Design 1), an
Ar/H2 -plasma-treatment of the PTFE-channel (7’) (design 2), or further processing
without PTFE-removal (design 3). In the next step, a hydrophobic PTFE con-
finement is printed on the S- and D-electrodes (8) in order to control the crystal
growth direction of the TIPS-pentacene printed in the final step (9). The micro-
scopic images in Fig. 7.14 display the crystal growth on S- and D-electrodes and
channel area for each design. Due to the absence of PTFE in the first design (a), the
7.5 Electrical characterization 109
crystals continue their growth over the channel. Similarly, the crystal growth is not
interrupted in the second design (b) due to the high wetting of the semiconductor ink
on Ar/H2 -plasma-treated PTFE. In contrast, the crystals stop their growth at the
channel boundaries in the third design (c) due the dewetting of the TIPS-pentacene
ink on the hydrophobic PTFE line. This leads to a much lower crystal coverage
compared to the first and second designs. The relationship between crystal quality
in the three designs and the resulting mobility is investigated based on the electrical
characterization realized within the next section.
As mentioned in Section 2.4.1, a BGBC configuration is adopted in this thesis in
order to deposit the semiconductor in the final step. This offers a higher flexibility
for the handling and processing of other OFET layers. Due to the sensitivity of
TIPS-pentacene to higher temperatures (s. Section 7.3.1), adopting a top gate
configuration would require the choice of other conductive and insulation materials,
which can be cured at lower temperatures. In addition to this, the quality of the
semiconductor can be degraded by being dissolved due to the deposition of other
inks on its top. Nevertheless, the proposed electrode fabrication methods are also
compatible for BGTC, TGBC, and TGTC configurations and the processing steps
(such as plasma-treatments) can be adapted depending on the employed materials.
Ar/H2-plasma-treatment No treatment
a) b) c)
TIPS-Pentacene TIPS-Pentacene
TIPS-Pentacene TIPS-Pentacene
TIPS-Pentacene
channel
PVP-channel
PVP-channel Treated PTFE-channel Untreated PTFE-channel
PVP-channel
100 µm 100 µm 100 µm
10 µm
-IDS (µA)
3 30V
20V 0.01
2 30V
1 10V 0.005 20V
-UGS 0V -UGS 10V
0 0 0V
0 10 20 30 40 0 10 20 30 40
-UDS (V) -UDS (V)
b) 9 d) 0.04
UDS= -40V UDS= -40V
0.03
-IDS (µA)
6
-IDS (µA)
0.02
3 0.01
0 0
0 10 20 30 40 0 10 20 30 40
-UGS (V) -UGS (V)
Comparing the IDS -values for both profiles in addition to the corresponding mo-
bilities of 0.01 cm²/Vs for the first curing profile and 0.0013 cm²/Vs for the second
curing profile shows that the additional curing step at 120°C leads to a significant de-
crease of IDS and µ. This is related to the degradation of the semiconductor quality
due to the application of a high curing temperature. As explained in Section 7.3.1
and shown in Fig. 7.6, a crack formation in the 120 and 210 planes is observed for
temperatures higher than 100°C. Starting from 120°C, overlapping crystals undergo
an expansion from both sides leading to the propagation of these cracks along the 120
plane. Consequently, the mobility decreases significantly [CTY+ 06]. However, the
additional curing step at 120°C results in an improved saturation behavior, which
is accompanied by an increasing of the ION /IOF F ratio from 94 to 296. This can be
explained by the evaporation of TIPS-pentacene solvent residuals at 120°C, which
leads to an improved carrier injection at the electrode-semiconductor interface and
hence a lower contact resistance of the electrodes to the semiconductor layer. Due
to the significant decrease of the mobility by applying the additional curing step at
120°C, only Curing profile 1 is adopted for the fabrication of the OFETs.
To explore the influence of design choice and semiconductor processing on OFET
performance, the corresponding output and transfer characteristics are measured
and presented in Fig. 7.16 (TIPS-pentacene cured for 10 min at 60°C).
7.6 Evaluation and discussion 111
-IDS (µA)
-IDS (µA)
20
3 30V
20V 20V 0.01
10 2 30V
1 10V 0.005 20V
-UGS 10V -UGS 0V -UGS 10V
0 0V 0 0 0V
0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
-UDS (V) -UDS (V) -UDS (V)
d) 40 e) 9 f) 0.04
UDS= -40V UDS= -40V UDS= -40V
30 0.03
-IDS (µA)
-IDS (µA)
6
-IDS (µA)
20 0.02
3 0.01
10
0 0 0
0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
-UGS (V) -UGS (V) -UGS (V)
length Lch = 7.13 µm and taking the standard deviation of the experimental values
Lch = 7.91±1.08 µm into consideration, it is guaranteed that the three OFET designs
can be realized with a minimum channel length, which is greater than Lcutof f .
The comparison between the three designs shows the highest mobility for Design 1
with a PTFE-free channel and the lowest mobility for Design 3 with untreated PTFE.
This can be interpreted based on the crystal growth images in Fig. 7.14. The high
hydrophobicity of the untreated PTFE channel in Design 3 results in the dewetting
of the semiconductor ink leading to a low crystal coverage over the channel. In con-
trast, the crystal coverage is highest after PTFE removal in Design 1, which results
in the highest mobility values. By applying Ar/H2 -plasma-treatment in Design 2,
the wetting of the semiconductor ink on PTFE and the crystal growth were enhanced
compared to Design 3, which explains the significant increase of the mobility from
0.0003 ± 0.0003 cm²/Vs to 0.010 ± 0.004 cm²/Vs. However, this improved mobility
is still low compared to the values of 0.035±0.019 cm²/Vs reached in Design 1. This
can be explained based on two factors: different morphology of Ag electrodes and
different quality of the semiconductor-dielectric-interface. Applying Ar/H2 -plasma
in Design 2 leads to an increased surface roughness of the Ag electrodes [Bod15],
which define the dominant surface for crystal growth. Consequently, a higher surface
roughness of the Ag electrodes forces the formation of thinner and shorter crystals
and leads to a lower crystal coverage on the channel region. The different qualities
of the semiconductor-dielectric-interfaces are caused by the deposition of the semi-
conductor on surfaces with different roughnesses. PTFE removal in Design 1 leads
to the deposition of the semiconductor on the c-PVP upper surface with a low sur-
face roughness of 2.58 ± 1.5 nm measured after the lift-off process. This allows the
formation of a smoother semiconductor-dielectric-interface compared to Design 2.
Consequently, higher mobility values are obtained [PPS+ 04] due to the decrease in
voids, defects, and interfacial traps [SDVDJ+ 04] leading to an enhanced molecular
ordering [VAH03].
For the realized measurements, it is important to consider possible factors, which
result in a lower measurement accuracy. Possible factors are the intrinsic accuracy
of the used SMUs and external sources such as setup and measurement settings.
For example, measuring low currents can be severely affected by additional noise
and leakage currents, which are caused by parasitic capacitances and internal leak-
age resistances related to the test fixture (e.g. coaxial cables). In addition to this,
the quality of the unencapsulated organic semiconductor at the top of the mea-
sured devices can be degraded due to its exposition to environmental factors such
as temperature, light, and humidity. Consequently, the mobility values decrease
significantly. From another side, it is also important to consider possible errors
in the calculation of the mobility. In addition to errors related to electrical mea-
surement, errors related to the optically measured values of the channel length and
channel width have to be considered as well. Nevertheless, the calculated mobilities
in this work are comparable to reported values achieved by the use of similar OFET
materials and configurations. In this context, Chung et al. [CJC+ 11] and Kim
et al. [KKC14] reported comparable OFET mobilities of 0.02 cm²/Vs and 0.034
cm²/Vs, respectively by the use of all-inkjet-printed TIPS-pentacene, c-PVP, and
7.6 Evaluation and discussion 113
TGBC TGTC
G G
C-PVP C-PVP
TIPS-Pentacene PTFE S PTFE D
PTFE S PTFE D TIPS-Pentacene
PET PET
Figure 7.17: Schematic illustration of different OFET configurations, where source and
drain electrodes are printed by the use of the coffee-ring-effect based approach pre-
sented in this work.
In terms of contact electrodes, top contact configurations (BGTC and TGTC) al-
low the deposition of the semiconductor on a single surface (dielectric or substrate),
which has the advantage of higher homogeneity compared to bottom contact con-
figurations. However, the hydrophobic twin-lines have to be printed directly on the
semiconductor. As organic semiconductors are usually hydrophobic, printing the
114 Chapter 7
115
116 Chapter 7
persions and O2 -plasma-treated c-PVP substrates was adopted for model evaluation.
The experimental results corresponding to the variation of θ, n, L, and C showed
highest similarity to theoretical results calculated from the model Triangular 2. By
printing an alcohol-based silver NP ink on PTFE twin-lines, a total dewetting was
observed for channel lengths larger than 7 µm. Below this value, a partial dewet-
ting or non-dewetting was observed, which proved the existence of a critical channel
length, below which the dewetting of the conductive ink is no more possible. In
order to predict its value, a model was proposed for its calculation as functions of
printing and material parameters related to the silver NP ink and PTFE disper-
sion (Section 6.3). The simulation of this model showed that the dewetting process
was limited by the adopted printing technology (nozzle area of the printheads and
printing parameters) as well as material choices. In the following section 6.3.3, silver
electrodes with gaps lower than the critical channel length and down to 4 µm could
be fabricated successfully by the use of a lift-off-based approach applied for PTFE
removal.
The acquired results were applied for OFET fabrication in Chapter 7. The adopted
OFET design consisted of a BGBC configuration where silver, c-PVP, and TIPS-
pentacene were used as electrodes, dielectric, and semiconductor, respectively. The
deposition of the dielectric layer was optimized (Section 7.2) by investigating the
influence of the drop spacing and number of layers on the dielectric thickness, ca-
pacitance, and leakage current. The next part (Section 7.3) was dedicated for the
optimization of the semiconductor deposition on c-PVP (after PTFE removal) or
PTFE. First, the influence of the drying temperature of the TIPS-pentacene ink was
investigated (Section 7.3.1) by applying different curing profiles. The corresponding
results showed the formation of cracks in the 120 and 210 planes for temperatures
higher than 120°C. Then, a DoE was applied for the choice of 1,1-DCB among four
different solvents for TIPS-pentacene as it showed the highest crystal coverage and
largest crystal width (Section 7.3.2). Next, different plasma treatments with O2 , N2 ,
Ar, and Ar/H2 as feed gases were tested in order to reduce the hydrophobicity of
PTFE and improve the wettability of the TIPS-pentacene ink on its surface (Section
7.3.3.1). Optimum results were obtained by applying Ar/H2 -plasma-treatment for
10 min, which reduced the water contact angle from 150° to 89.5°. For a better
control of crystal growth, a hydrophobic confinement was printed additionally in
form of two parallel PTFE lines (Section 7.3.3.2). This confinement was employed
to force the grain boundaries between neighbored crystals to be oriented in parallel
direction to the current flow between source and drain electrodes. Based on the
aforementioned optimizations and electrode fabrication methods, three OFET de-
signs with a channel length Lch = 8 µm and a channel width Wch = 4.3 mm were
fabricated and characterized. In Design 1, the lift-off process was used after the
sintering of the dewetted silver ink in order to remove PTFE. For the two other
designs, PTFE was not removed. An Ar/H2 -plasma-treatment was applied on the
PTFE surface to improve the wetting of the TIPS-pentacene ink in Design 2 and no
treatment was applied for Design 3. The different crystal growth behaviors in the
three designs had a significant influence on the electrical characterization results,
which were measured for two different TIPS-pentacene curing profiles: 10 min at
7.6 Evaluation and discussion 117
a) b)
90 nm out
Liquid
θ
Large-sized
hydrophilic Small-sized
nanoparticles hydrophobic 220 nm
nanoparticles 1 µm
Intern © Siemens AG in
2014 Alle Rechte
vorbehalten.
Figure 7.18: a) Size-dependent segregation of NPs leading to the formation of a thin
hydrophobic line near the contact line in parallel to a thicker hydrophilic NP line.
b) SEM image of the coffee ring effect in case of the evaporation of a water-based
bidispersion with 0.2 wt.% PTFE (220 nm) + 0.1 wt.% fluoroplast (90 nm) NPs.
119
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[OKY+ 08] Takahiro Ohe, Miki Kuribayashi, Ryoichi Yasuda, Ami Tsuboi,
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[TAP+ 12] Daniel Tobjörk, Harri Aarnio, Petri Pulkkinen, Roger Bollström,
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Chadha Bali
PERSONAL DATA
WORK EXPERIENCE
2016.01 – 2019.11 Physical design engineer at Intel Corporation, Munich, CRCG (Convergence, RF and
Connectivity Group)
- Mixed-signal static timing analysis
- Digital physical implementation based on RTL2GDS tools and flows
- Chip and block level floor planning, analysis of floor plan options taking into
account timing and area budgets
- Synthesis, constraints, timing analysis and equivalence checking
Place and route, timing closure, power analysis and physical verification
EDUCATION
2011.12 – 2019.06 PhD-student at Siemens AG, Corporate Technology, Research and Technology
Center, Munich and Institute for Print and Media Technology of Chemnitz University
of Technology
2011.03 – 2011.10 Master thesis at Siemens AG, Corporate Research and Technologies, Munich and
Heinz Nixdorf Institute for Medical Electronics of the Technical University of Munich
Topic: Planar circuit design for non-invasive detection of blood glucose (Grade: 1.3)
2010 – 2011.10 Master of Sciences in Electrical Engineering and Information Sciences at the
Technical University of Munich, major in Medical Technologies (Final grade: 1.5)
2009.01 – 2009.05 Exchange semester at the National University of Singapore within LAOTSE program
(Links to Asia by Organizing Traineeship and Student Exchange)
2009.06 – 2009.09 Bachelor thesis at Qimonda AG, Department of Analog/Mixed Signals, Module &
System, Munich and Institute for Electronic Design Automation of the Technical
University of Munich
Topic: Automatic creation of schematic from PCB design
2005.10 – 2010 Bachelor of Sciences in Electrical Engineering and Information Sciences at the
Technical University of Munich, major in Electronics
2004.09 – 2005.06 German language course at the Niedersachsen College Hannover
2004.06 Baccalaureate in Mathematics at the Pioneer High school „Lycée Pilote de Sfax“
LANGUAGES