Spin Coating of PH3T/PCBM on Silicon Wafer

Samarth A Begari Vishnu Prasad Aditya Mantri

20BEC0756 20BEC0789 20BEC0778

Abstract— Spin coating is a procedure used to deposit
uniform thin films to flat substrates. Usually a small amount of
coating material is applied on the center of the substrate, which
is spinning at a particular RPM. The substrate is then rotated at
high speed in order to spread the coating material by centrifugal
force. A machine used for spin coating is called a spin coater, or
simply spinner. Factors such as rotational speed, acceleration,
and fume exhaust contribute to how the properties of coating.
In our project, we determine the different layers of thickness
which differ along with the rotational speed. It varies 50 nm
onwards. Commonly used materials, poly(3- hexylthiophene),
P3HT, and phenyl-C61-butyric acid methyl ester, PCBM are
used here in spin coating. Spin coating is widely used in micro
fabrication of functional oxide layers on glass or single crystal
substrates using solgel precursors, where it can be used to create
uniform thin films with nano scale thicknesses. Here, P3HT
coated silicon wafers can be used in solar cells to increase the
efficiency and make it highly reproducible since the thermal
treatment of P3HT/PCBM films prepared from Chlorobenzene
solution results in a decrease of the charge transfer yields. The
improved performance of solar cells is therefore attributed to
optimization of the morphology, in particular molecular order
in the P3HT regions.
Keywords- Spin Coating, film thickness, P3HT/PCBM
study has been initiated. An accurate theory of spin coating
would permit better design and control of the process in its
various applications. Decades of industrial production have
shown that the depositions of thin photoresists films, which
constitute the main utilization of the spin coating process, are
quasi- perfectly controlled. However, any progress in
developing mathematical models should be probably more
helpful in the case of heat resistant dielectric insulating films
(polyamides or other materials). In contrast to the photoresists
which are often low molecular weight materials dissolved in
low boiling solvents at low concentration, polyimide
precursors are high molecular weight polymers. These
materials are supplied in organic solvents boiling at
temperatures close to 200°C at concentration, levels (10–
20%). This implies that spin analytical models will be based
on sophisticated equation taking in consideration a number of
physical parameters.
III. METHODOLOGY
Spin coating generally involves the application of a thin film
(a few nm to a few um) evenly across the surface of a substrate
by coating (casting) a solution of the desired material in a
solvent (an "ink") while it is rotating.

I. INTRODUCTION
Spin coating is currently the predominant technique employed
to produce uniform thin films of photosensitive organic
materials with thickness of the order of micrometers and
nanometers. The pioneering analysis of spin coating was
performed more than fifty years ago by Emil et al who
considered the spreading of a thin axisymmetric film of
Newtonian fluid on a planner substrate rotating with constant
angular velocity. In many cases the coating material is
polymeric and is applied in the form of a solution from which
the solvent evaporates. Spin coating was first studied for
coating of paint and pitch. Spin coating is one of the most
common techniques for applying thin films to substrates. It is
used in a wide variety of industries and technology sectors.
The advantage of spin coating is its ability to quickly and
easily produce very uniform films, ranging from a few
nanometres to a few microns in thickness. The use of spin
coating in organic electronics and nanotechnology is
widespread and has built upon many of the techniques used in
other semiconductor industries. It also has some differences
due to the relatively thin films and high uniformity required
for effective device preparation, as well as the need for self-
assembly and organization to occur during the casting process.
In this project we aim to introduce general spin coating
concepts and also describe some of the specific techniques 1. First the substrate is coated in the ink containing the
useful in organic electronics and nanotechnology. Along with molecules dissolved in a solvent (1).
that we are going to determine the rotational factor which 2. Then the substrate is rotated at high speed and the
differs the thickness of the layer accordingly and can be majority of the ink is flung off the side (2).
viewed with the help of the Atomic Force Microscope. 3. Airflow then dries the majority of the solvent,
leaving a plasticised film (3)
II. MODELING OF SPIN COATING 4. Before the film fully dries to just leave the molecules
First, Even though spin coating has been universally used in on the surface (4).
the semiconductor industry long before, hardly any theoretical
The rotation of the substrate at high speed (usually >10
rotations per second = 600 rpm) means that the centripetal
force combined with the surface tension of the solution pulls
the liquid coating into an even covering. During this time the
solvent then evaporates to leave the desired material on the
substrate in an even covering.
1. A small molecule in a solvent is first dispensed
across the substrate and as the solvent begins to
evaporate this produces internal currents (1).
2. The droplet shrinks in size with the internal currents
depositing molecules at the receding edges (2).
3. By slowing down the evaporation rate it is possible
to have highly ordered films produced at the edges
(3).
4. However, the coating across the surface is usually
high uneven with a typical "coffee staining" effect
(4).
For most applications the most important consideration is
the thickness of the film that is produced during spin
coating.
KEY STAGES OF SPIN COATING
The physics of spin coating can be effectively modeled by
dividing the whole process into four stages sketched in the
Figure below, which are deposition, spin-up, spinoff and
evaporation of solvents. The first three are commonly
sequential, but spin-off and evaporation usually overlap.
Stage 3(flow controlled) and stage 4 (evaporation
controlled) are the two stages that have the most impact on
final coating thickness.
2
A. DEPOSITION
During this stage, solution is allowed to fall on rotating
substrates from microsyrings and the substrate is accelerated
to the desired speed. Spreading of the ion takes place due to
centrifugal force and height is reduced to critical height. This
is the stage of delivering an excess of the liquid to be coated
to the surface of the substrate a portion of which is
immediately covered or “wetted”. In this stage liquid can be
deposited in different ways (a) as a heavy rain that inundates
the entire disk; (b) as a bolus at the center or around the
perimeter of hole if the center has been cut out, the liquid then
spreading over the rest of the disk, or (c) as a continuous
stream at the center, or all the way around the inner perimeter,
the liquid then flowing outward over the entire disk, or (d) as
a continuous stream from an elevated delivery port that
moves racially over the disk. No matter what way is used the
amount of liquid deposited through excessive is limited and
this stage ends when delivery ceases.
B. SPIN-UP
The second stage is when the substrate is accelerated up to its
final, desired, rotation speed. This stage is usually
characterized by aggressive fluid expulsion from the wafer
surface by the rotational motion. Because of the initial depth
of fluid on the wafer surface, spiral vortices may briefly be
present during this stage; these would form as a result of the
twisting motion caused by the inertia that the top of the fluid
layer exerts while the wafer below rotates faster and faster.
Eventually, the fluid is thin enough to be completely co-
rotating with the wafer and any evidence of fluid thickness
differences is gone. Ultimately, the wafer reaches its desired
speed and the fluid is thin enough that the viscous shear drag
exactly balances the rotational accelerations.
C. STABLE FLUID OUTFLOW
The third stage is when the substrate is spinning at a constant
rate and fluid viscous forces dominate fluid thinning
behavior. This stage is characterized by gradual fluid
thinning. Fluid thinning is generally quite uniform, though
with solutions containing volatile solvents; it is often possible
to see interference colors “spinning off ”, and doing so
progressively more slowly as the coating thickness is
reduced. Edge effects are often seen because the fluid flows
uniformly outward, but must form droplets at the edge to be
flung off. Thus, depending on the surface tension, viscosity,
rotation rate,etc., there may be a small bead of coating
thickness difference around the rim of the final wafer.
Mathematical treatments of the flow behaviour show that if
the liquid exhibits Newtonian viscosity (i.e. is linear) and if
the fluid thickness is initially uniform across the wafer (albeit
rather thick), then the fluid thickness profile at any following
time will also be uniform.
D. EVAPORATION
When spin-off stage ends the film drying stage begins.
During this stage centrifugal outflow stops and further
shrinkage is due to solvent loss. This results in the formation
of thin film on the substrate. The fourth stage is when the
substrate is spinning at a constant rate and solvent
evaporation dominates the coating thinning behavior. In this,
the rate of evaporation depends on two factors (a) the
difference in partial pressure (actually chemical potential) of
each solvent species between the free surface of the liquid
layer and (b) the bulk of the gas flowing nearby. During the
evaporation stage the suspended or dissolved solids may
grow so concentrated at the liquid surface as to form a high
viscosity, low diffusivity layer or solid skin.
IV. INFLUENCE OF RESIST FILM THICKNESS
The resist film thickness given for a certain spin speed holds
for sufficiently long spin times, when the resist spin-off is
completed. As the figure below shows, the spin times
required to attain the final film thickness increases with the
resist viscosity. Low spin speeds also increase the time for a
constant resist film thickness.
Resist film thickness and remaining solvent concentration
after different long spin coating for a thin(left) and thick
resist (right) before (black) and after (blue) softbaking
This time-dependency not only allows the film thickness to
be adjusted for spin speed, but also the spin time. For thin
films (approx. < 10 μm), the spin times should always be
„sufficiently long‟ to make the result more reproducible. The
remaining solvent concentration in the resist film also
impacts on its thickness. During coating, the solvent
concentration drops and saturates at a value of approx. 15-25
% which depends on the film thickness and is higher for
thicker films. The subsequent softbake reduces the remaining
solvent concentration to values of typ. 5 %. A high ambience
solvent saturation in the spin coater reduces the attained resist
film thickness due to a suppressed solvent evaporation from
the resist. Therefore, the first few wafers of a coating series
might reveal a slightly higher film thickness as compared to
wafers subsequently coated with a certain amount of fresh
resist in the spin-coater. In this case, coating some dummy
wafers at the beginning of a coating series would be
beneficial by means of constant resist film thicknesses.
V. PROCEDURE
P3HT and PCBM that will be added in 1:1 ratio in
chlorobenzene. It is kept over the magnetic stirrer for about
40 minutes and solution is added continuously in small
amounts. After p3ht is dissolved completely then the solution
is dyed with red color to showcase the layer property. • P3ht
- poly(3-hexylthiophene-2,5-diyl). Commonly known as
P3HT. Used due to its’ good solubility and high hole
mobility.
P3HT concentration is taken between 5-10 gm/L and RPM
between 2-5,000 to get a layer thickness of less than 100 nm.
Phenyl-C61-butyric acid methyl ester, PCBM, is the best
solvent for P3HT hence it is used here. The solution is now
divided into two equal parts to: 1. Spinning and coating; 2.
Coating and spinning. For 2000, 3000, 4000, 6000, 7000,
8000 rpm and the thickness were measured for each.
VI. RESULTS
Spin coating of P3HT/PCMB on 2000RPM(50X) 2000RPM(50X) 3000RPM(100X)
Plastic substrate of thickness 50nm
3000RPM(200X) 4000RPM(50X) 4000RPM(100X) 5000RPM(50X)
VII. CONCLUSION
The advantages of spin coating are the simplicity and relative
ease with which a process can be set up, coupled with the thin
and uniform coating that can be achieved. Due to the ability
to have high spin speeds the high airflow leads to fast drying
times, which in turn results in high consistency at both
macroscopic and nano length scales. With increase in RPM,
the thickness of the film also increases as seen under
AFM.
This P3HT/PCMB coated wafer can be used in solar cells to
increase the efficiency. The disadvantage of spin coating is
that it is an inherently batch (single substrate) process and
therefore has a relatively low throughput compared to roll-to-
roll processes. The fast drying times can also lead to lower
performance for some particular nano-technologies (small
molecule OFETs for example), which require time to self-
assemble and/or crystallize.
Despite these drawbacks, spin coating is usually the
starting point and benchmark for most academic and
industrial processes that require a thin and uniform
coating.
VIII. REFERENCES
[1] Growth and Characterization of Pure and Doped SnO2 Films for H2 Gas
Detection Chang-Hung LinˈWei-Che ChangˈXiaoding Qi
[2] Fundamental understanding and modeling of spin coating process : A
review‟ by Niranjan Sahu.
[3] Bornside, D. E., Macosko, C. W., & Scriven, L. E. (1987). MODELING
OF SPIN COATING. Journal of imaging technology, 13(4), 122-130.
[4] Hall, D. B., Underhill, P., & Torkelson, J. M. (1998). Spin coating of thin
and ultrathin polymer films. Polymer Engineering & Science, 38(12),
2039-2045.