Proceedings of the 15th

IEEE International Conference on Nanotechnology

July 27-30, 2015, Rome, Italy

Improved Alignment and Crystallinity of TIPS-

Pentacene Thin Films by Off-Center Spin Coating

Deepak Bharti and Shree Prakash Tiwari

Department of Electrical Engineering, Indian Institute of Technology Jodhpur, Rajasthan, India, 342011.
Email: sptiwari@iitj.ac.in

Abstract— A comprehensive study for crystal alignment of casting or dip coating methods due to various other factors
TIPS-Pentacene by an off-center spin coating has been presented. involved such as concentration of solute, magnitude of
In a normal center spin coating method, the centrifugal force on centrifugal force (spin speed, acceleration, and spin time), and
the grains is multidirectional which results into crystals aligning solvent evaporation. The direction of this centrifugal force has
in multiple directions depending on the location on the sample. been ignored until recently when Yuan et al. [18] presented a
However in an off-center spin coating method where the samples study in which a concept of off-center spin coating (OCSC)
are kept at a distance away from the center, a unidirectional was introduced. Sample to be deposited was kept away from
centrifugal force in the direction of the sample causes all the the center to subject the solution on the sample under a
grains to align nearly in the direction of this force. The spin speed
unidirectional force. This unidirectional force causes solute
was the paramount factor influencing the overall grain size,
crystals to make an aligned assembly in the direction of force.
whereas the overall alignment depends on the off-center distance.
All the films in these experiments were found to have very large However, there are no reports presenting a comprehensive
crystal sizes, ranging up to 5 microns. In addition, films formed study of the effect of the off-center distance and the spin speed
by off-center method were found to be more crystalline than the on the morphology and crystallinity. TIPS-Pentacene is a
center spin coated film and show a metastable crystalline promising organic semiconductor known for its high hole
polymorph. mobility and crystalline nature [19-21]. Application of new
strategies to improve crystallinity and alignment in TIPS-
Keywords—Crystal Alignment; spin coating; TIPS-Pentacene Pentacene films are required for advancement of this field.
In this work, effect of spin parameters and distance from
I. INTRODUCTION center on the morphology of TIPS-pentacene were
Organic thin-film transistors (OTFT) are explored for their comprehensively studied for OCSC method. The process was
application in the backplane driving circuitry of displays [1], optimized to achieve aligned grains of TIPS-Pentacene. Also,
sensors [2, 3] and radiofrequency identification cards (RFIDs) the effect of initial acceleration was explored. The spin speed
[4, 5]. Performance of OTFT primarily depends on the was shown to be a parameter dictating the overall grain size
structure and properties of the active material, which is an whereas the off-center distance was found to affect the overall
organic semiconductor. Alignment of crystals of organic alignment. In addition, various OCSC deposited films were
semiconductors has been a challenging goal to achieve for found to be more crystalline than normal spin coated films.
higher performance in the devices. Many studies have been OCSC films also show a metastable crystalline polymorph,
performed to explore the various factors affecting the favorable for charge transport in OTFTs.
alignment [6, 7]. Application of external force is one of the
usual methods to align crystals. Normally, it is difficult to
obtain semiconductor films with high degree of crystallinity
and desired alignment due to three dimensional growth of
crystals [8]. Several groups have tried organic semiconductor
crystal alignment using strategies such as rubbing alignment
[9], magnetic alignment [10] and meniscus-guided coating
methods such as zone casting [11] and dip coating [12]
solution-shearing [13], droplet-pinned crystallization [14],
electrostatic spray deposition [15], slot-die coating [16], and
volatility-controlled deposition [17]. However most of them
need special apparatus arrangement. Also, most of them
employ drop casting or dip coating as the active layer
deposition method, which results into considerably non-
uniform film. Spin coating has been the obvious choice to
ensure the uniformity of the film and large area applicability,
compared to drop casting methods. However, the alignment is Figure 1. Schematic illustration of off-center spin coating method
difficult to attain in spin coating method compared to drop

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 II. EXPERIMENTAL a fixed d, increase in ω leads to increased grain size but at a
TIPS-Pentacene purchased from Sigma-Aldrich was used cost of loss of alignment. With a fixed spin speed Ȧ, increased
without further purification, to form semiconductor films. off-center distance d results into large dispersity of grains.
Heavily doped n-type silicon wafers (resistivity 0.005 ȍ cm)
were used as the substrate. Substrates were ultra-sonicated in
Iso-propyl-alcohol, and cleaned using boiling solvents of tri-
chloro-ethylene, acetone and methanol respectively and were
dried in nitrogen blow. Native oxide on the Si substrate was
not etched to provide the organic thin films a quasi-oxide
platform. A 1.0 wt% TIPS-Pentacene solution in Toluene was
used to spin coat the samples. All solution preparation and
processing steps were performed in ambient air. Figure 1
shows schematic illustration for the OCSC method. Samples
were placed at an off-center distance (d). Thin films formed
were checked for their crystallinity by X-Ray diffraction
(XRD) measurements using D8 Advance from Bruker. The
morphological characterization was performed by atomic
force microscopy (AFM) using XE-70 SPM from Park
Systems.

III. RESULTS AND DISCUSSIONS

Figure 2 shows the AFM images of center spin coated
(CSC) films. Images clearly depict very large grain size, as
large as 5 microns. These images have been taken near the
four edges of the sample to show the different alignment in the
four directions. As the sample has been kept at the center,
direction of centrifugal force at each location is different i.e.
radially outwards, which causes TIPS-Pentacene grains to
follow the direction of the force. In this way, in a single thin
film, grains are aligned in different but location dependent
directions.
Figure 3. TIPS-Pentacene morphology with off-center distance and spin speed
Figure 4 shows AFM images of OCSC films, taken near
the four edges of the sample to show the aligned grains in all
four directions. Centrifugal force on all locations of the
sample will be in a nearly single radial direction away from
the center. Deviation from the single direction of the
alignment will depend on the azimuthal dimension of the
sample. It can be ascertained from the figure that most of the
grains have their larger dimension along the direction of
centrifugal force. Thus all the grains of the film are aligned in
more or less in a single direction. This single direction
alignment will be beneficial for OTFT performance.

Figure 2. Different alignment in different directions with normal center spin

coating method

Figure 3 shows the variation of TIPS-Pentacene

morphology with off-center distance d and spin speed ω. With Figure 4. Unidirectional alignment at different locations with off-center spin
coating method

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Figure 5. Effect of acceleration in initial 10 seconds of coating (a) 20 rpm/sec,
(b) 50 rpm/sec, (c) 75 rpm/sec and (d) 100 rpm/sec. Final speed attained was
1000 rpm at an off-center distance of 1.25 cm for all the cases.
Figure 6. XRD patterns for off-center spin coated films at various off-center
distances.
Figure 5 shows the effect of acceleration in initial 10
seconds. As most of the solvent evaporation takes place in
initial few seconds of the spin duration, spin speed attained
during this period plays very important role in overall
alignment. It can be observed in this figure that an acceleration
of 20 rpm/sec was not sufficient for alignment whereas at the
initial acceleration of 50 rpm/sec a noticeable alignment was
observed. This alignment was again lost probably due to
434
crystal roll-over at higher initial accelerations of 75 and 100
rpm/sec.
XRD patterns for TIPS-Pentacene thin film spin coated at
various speeds and at various off-center distances are shown in
figure 6. From the patterns it can be deduced that OCSC film
is always more crystalline than the CSC film irrespective of
spin spped and off-center distance. A meta-stable crystalline
polymorph for TIPS-Pentacene can also be obtained by OCSC
method as confirmed by samples coated at an off-center
distance of 2.5 cm. These kinetically trapped, non-
equilibirium polymorphs tend to demonstrate a better
performance than equilibirium polymorphs [22]. In addition,
OCSC samples coated at spin speed of 1000 rpm were nearly
of single crystal quality. With increase in spin speed thin film
turns poly-crystalline from a single crystal quality.
IV. CONCLUSION
A detailed study of crystal allignment and crystallinity in
TIPS-Pentacene films by off-center spin coating method was
done. Due to the multidirectional centrifugal force in the
normal spin coating, grains were aligned in several directions,
but in the off-center spin coating, unidirectional centrifugal
force causes grains to align in a single direction. In addition,
crystallinity was also improved for films formed using this
method. The spin speed, off-center distance and speed attained
in first few seconds were demonstrated as the factors affecing
the crystal size and alignment very critically. Thus this slight
change in the coating method results into twoway benefit in
terms of improved crystalline quality and a better alignment.
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