Surface Modification to create Antifouling of Solar Cell

Sunil R Rudagi Rohit Sengar

Student id:1001242020 Student id: 1001105335
Department of Mechanical Engineering Department of Mechanical Engineering
University of Texas – Arlington University of Texas-Arlington
sunil.rudagi@mavs.uta.edu rohit.sengar@mavs.uta.edu

ABSTRACT B. Operating principle of dye sensitized solar cell

The energy output of a solar cell is generally associated with the
sun’s available energy (light intensity).Fouling has a major impact
on the power output of a solar cell. Among these, soiling (dust) is
the major factors that influence the output of solar cell. In this
paper we discuss, Impacts of dust deposition on solar cell, self-
cleaning super hydrophobic surface that can be used as antifouling
coating. We also discuss, how water repellency arises from the
presence of hydrophobic microstructures at the solid surface,
Theoretical concepts such as wetting models, Contact angle
hysteresis and Curvature and line tension effect are reviewed. We
also discuss the optimal design to be given to a solid surface to
make it robustly water repellent (conceptual design). Self-cleaning
phenomenon in lotus leaf is studied and lotus leaf inspired different
structures and their fabrication techniques using PDMS and Su-8
are reviewed.
Figure 2: Schematic of working principle of DSSC
INTRODUCTION
Nano crystalline TiO2 is deposited on the conducting electrode
A. DYE SENSITIZED SOLAR CELL (photoelectrode) to provide the necessary large surface area to
adsorb sensitizers (dye molecules). Upon absorption of photons,
dye molecules are excited from the highest occupied molecular
orbitals (HOMO) to the lowest unoccupied molecular orbital
(LUMO) states as shown schematically in Figure 2. Once an
electron is injected into the conduction band of the wide
bandgap semiconductor nanostructured TiO2 film, the dye
molecule (photosensitizer) becomes oxidized. The injected
electron is transported between the TiO2 nanoparticles and then
extracted to a load where the work done is delivered as an
electrical energy.

IMPACT OF FOULING

There are three main fouling influence of PV power generation

Figure 1: Schematic of DSSC
The main parts of single junction dye sensitized solar cell are
illustrated schematically in Figure 1. The cell is composed of
four elements, namely, the transparent conducting and counter
conducting electrodes, the nanostructured wide bandgap
semiconducting layer, the dye molecules (sensitizer), and the
electrolyte. The transparent conducting electrode and counter-
electrode are coated with a thin conductive and transparent film
such as fluorine doped tin dioxide (SnO2).
project, the blocking to transmission of sunlight, the increasing
of temperature on the PV performance, and the impact of
transmission of sunlight which caused by surface corrosion.
A. FOULING BLOCKING TRANSMISSION OF
SUNLIGHT
Dust landing on PV panel blocks the light irradiating on the PV
surface and makes the solar PV cells area reduced which can
receive solar energy and makes the uniformity of the light
spread in the glass cover change. The light intensity which
reaches on the PV cells is weakened, so the amount of PV
power generation is decreased.
B. FOULING CHANGE THE TEMPERATURE OF PV
PANELS
Thermal conductivity of dust is very small. A a result PV‘s heat
cannot be quickly distributed to the surrounding air. The
temperature of PV panels constantly rises, the temperature rising
rate of covered part is faster. The efficiency of PV panels is
closely linked to the temperature of solar panels generating. 1
degree Celsius rise in temperature, lower power generation
efficiency about 0.5% [14]. Therefore, dust makes PV panels‘
temperature rise, and it affects the efficiency of PV power
generation.
C. FOULING ERODING OF PV GLASS COVER
The dust is acidic or alkaline. When the moist dust attaches to
the surface of PV glass cover glass, major components of glass
(silica and limestone and other substances) are to work with acid
or alkaline reaction. With the time increasing in acid or alkaline
environment, the glass surface will be gradually eroded. As acid
or alkaline dusts erode the PV glass cover, it reduces the
smoothness of glass cover surface and reflective index is
decreased. Therefore Reflected light intensity increases, and the
refraction light energy is decreased. Reduction in the amount of
photovoltaic power generation.
Figure3: Current–voltage characteristics of CPV module with
various levels of dust accumulation: (a)clean glass
surface;(b)0.85g/cm2 dust; (c)1.85g/cm2 dust; and (d) 5.4g/cm2
dust.
THEORETICAL BACKGROUND
A. SURFACE TENSION
The contact angle of liquid on the solid is determined by the
surface tension of liquid, surface energy of solid, and their
interaction. In a pure liquid, molecules in the bulk of liquid have
interactions with all neighboring molecules so that the net force
should be zero, but the molecules exposed at the surface do not
have interactions on all sides of them to provide a balanced net
force, resulting in the local asymmetry of interactions. The
resulting dissymmetry in the interactions causes pulling internal
force called as the surface tension. Therefore, surface tension of
the liquid changes its geometry to minimize this energy defect,
forming a spherical shape. For a solid substrate, the ‗surface
energy‘ is used to have equivalent meaning of surface tension
for a liquid.
B. WETTING MODELS
Young described the contact angle of a liquid droplet on an ideal
solid substrate (Figure 4(a)). It is determined by the
thermodynamic equilibrium of surface tensions of three
interfaces under the droplet:
(1)
θ is contact angle and γSG, γSL, and γLG are surface tension of
solid-gas, solid–liquid and liquid–gas interfaces, respectively.
On roughened surfaces, there are mainly two different
equilibrium states: Wenzel state and Cassie Baxter state. When a
liquid can fully wet the surface texture, the thermodynamic
equilibrium contact angle of a liquid droplet is described by the
Wenzel model (Figure 4(b)) which is given by:
(2)
Where θw is the apparent contact angle in Wenzel state, θ refers
to Young‘s contact angle; r is a roughness factor, which is
defined as the ratio of actual area of a rough surface to the flat,
projected area.
When a liquid cannot penetrate into the surface texture, the
droplet forms a highly non-wetting regime known as a Cassie-
Baxter (Figure 4 (c)) state. Because of a decrease in the effective
contact area between a surface and a droplet by entrapped air, it
can have low adhesive force. Therefore, compared to Wenzel
state, the droplet in the Cassie state displays a very high contact
angle as well as low hysteresis. Cassie Baxter equation is given
by:
(3)
Or
(4)
Where
Note that the roughness factor r in Eq. (4) is calculated only for
the part of the solid surface that is in contact with liquid. Where,
fsL is the fraction of the solid in contact with the liquid, θC is
effective contact angle in Cassie state.
Figure 4: Schematic diagrams of different wetting regimes: (a)
Young's model, (b) Wenzel model, (c) Cassie- Baxter model
C. CONTACT ANGLE HYSTERESIS
When a droplet is placed on an inclined surface, the droplet can
experience gravitational force so that the shape of the droplet
becomes asymmetric. On the downhill side, the droplet
advances but on the uphill side, the droplet recedes. Therefore,
the contact angle of the droplet on the downhill side is an
advancing contact angle and that of the droplet on the uphill side
is a receding contact angle. The difference between the
advancing angle and the receding angle is called contact angle
hysteresis. Due to the difference of advancing and receding
contact angles, the droplet can stick to the surface against
gravitational force. The difference of cosines of the advancing
and receding angles is given by
( )( ) (5)
The first term in the right-hand part of the equation corresponds
to the contact angle hysteresis of a smooth surface which is
proportional to the fraction of the solid–liquid contact area (1−
). The second term is the effect of surface roughness,
which is proportional to the length of the triple line.
(a) (b)
Figure 5 : Schematics depicting the motion of a liquid droplet on a
declined substrate covered with dirt. (a) When moving on a flat
substrate, where the adhesion between the dirt particles and the
substrate is high, the droplet just passes through. (b) A different
situation occurs on a substrate that is topographically decorated, so
that the dirt particles have difficulty adhering to it. As the liquid
droplet rolls off the substrate, it picks up the dirt particles and
hence cleans the substrate.
A superhydrophobic surface should have a low contact angle
hysteresis to allow water to flow easily along the surface.
Therefore the requirements for a surface to be super
hydrophobic are: 1) contact angle must be to greater than 150
(θ>150°). 2) Low contact angle hysteresis (θadv−θrec<5°). Low
CA hysteresis results in a very low water roll-off angle (the
angle to which a surface may be tilted for roll-off of water).
D. CURVATURE AND LINE TENSION EFFECT
Atoms at a curved solid surface have fewer bonds than at a flat
surface. Therefore, the energy depends on the radius of
curvature. The curvature dependence of the surface energy is
characterized by the Tolman's length δ, normally of the
molecular scale. The surface tension of a curved drop's surface
with the radius R is related to that of a flat surface is given by
(6)
( )
In a similar manner, molecules at the edge have fewer bonds
than those at the surface, which leads to excess energy
proportional to the line tension τ J/m. The line tension is
related to the Tolman's length, as an edge with a small radius R
yields excess energy αR×2δγ/R, where α is the angle of the
edge. When divided by the circumference length of the edge α
R, the line tension is
(7)
Taking into account the contact line effect, for a droplet with
radius R is given by
⁄
(8)
Where is the contact line tension, and is the value given by
the Young equation.
Hydrophilic to hydrophobic for a hydrophilic surface, the
contact angle increases with an increase of fLA. At a high value
of fLA, a surface can become hydrophobic. Using the Cassie–
Baxter equation, the value of fLA at which a hydrophilic surface
could turn into a hydrophobic one is given as.
(9)
CONCEPTUAL DESIGN OF HYDROBHOBIC SURFACE
There are three parameters necessary to define such topography,
namely the post radius b, the post height h and the pitch p of the
array. These structures can be made by etching, or by casting,
allowing us to independently set these three parameters,
typically in the range of 1–100 mm.
d one[ equation ]. The critical radius for a Cassie drop is thus of
Figure 6: water-air interfaces below a drop are curved (Cassie
state), owing to the curvature of the drop (or to the pressure
applied to the drop, if there is any). We characterize the lowering
of the interface below the top of the posts by a length d.
For regular arrays of long and dilute, cylindrical posts (b<<h
and b<<p), the roughness simply is
⁄ (10)
Hence, a second natural parameter is the ratio between the
top and bottom surface areas, which is also the post density. It
can be written as
(11)
drop, we can recall that the energy gained by a spherical drop
when it is placed on a substrate is
( ) (12)
This energy gain is different in a Wenzel or in a Cassie state.
From this relationship; we learn that the state of lower energy is
that of one with larger radius i.e. of smaller contact angle.
A comparison between the cosines given by equations (2),(4)
and (11) thus tells us the state of lower energy. For example, a
Cassie state will be favored provided that that
is
(13)
In the limit , this condition can be rewritten as
⁄| |, which implies roughness factors larger than 2–3 (the
Young contact angle is commonly in the range of 110–120, for
hydrophobic compounds Using equation (10), we thus find that
the pillar height must exceed the ratio , which implies a
large aspect ratio h/b (larger than 1/2 ).
Secondly, the liquid–vapor interface itself is curved, either
because of a pressure applied on the drop (a dynamical one, for
example, in the case of an impact), or simply owing to the shape
of the drop, which is curved at a large scale. The interface
curvature (figure (6)) should scale as ⁄ , while the drop
curvature increases as 1/R. Hence, the depth of penetration (d)
of the interface inside the texture should obey the
relationship ⁄ the smaller the drop, the larger d. If this
quantity becomes of the order of the pillar height h, a solid–
liquid contact should nucleate on the bottom of the substrate and
propagate if the Cassie state is of lower energy than the Wenzel
the order of ⁄ (much larger than p, if h<p). This quantity can
be made very small (robust Cassie state) either by making h
large or by reducing the different sizes p and h—a reduction in
size affects the resistance of the Cassie state, which might
explain the existence of such very small scales in many natural
materials.
SUPERHYDROPHOBICITY IN LOTUS LEAF
Some biological materials possess excellent surface wettability
and exhibit a superhydrophobicity-induced self-cleaning
property. Among the variety of self-cleaning biomaterials, the
lotus leaf, is one of the most promising. Water droplets falling
onto the leaves bead up and roll off. Rainwater washes dirt from
the lotus leaves so that they are self-cleaning.
Figure 7: (a) Large-area SEM image of the lotus leaf surface (23).
Every epidermal cell forms a papilla and has a dense layer of
epicuticular waxes superimposed on it. (b) Enlarged view of a
single papilla from panel a. (c) SEM image of 3D epicuticular wax
tubules on lotus leaf surfaces, which create nanostructures (3–5).
(d) Water droplets roll easily across the lotus leaf surface and pick
up dirt particles, demonstrating the self-cleaning effect.
Lotus leaf surfaces possess randomly distributed micropapillae
with diameters ranging from 5 μm to 9 μm (Figure 7a). On
every papilla, fine branch-like nanostructures with diameter of
approximately 120 nm have been observed (Figure 7b).
Multiscale structures provide air pocket formation, resulting in
the lowest contact area between lotus leaf surfaces and water
droplets. Furthermore, hydrophobic three-dimensional (3D)
epicuticular waxes with a tubule structure have also been found
on lotus leaf surfaces (Figure 7c). Micronanoscale hierarchical
structures and hydrophobic epicuticular waxes confers a high
water contact angle and a small sliding angle, exhibiting
superhydrophobic and low-adhesion characteristics. The water
contact angle and sliding angle of lotus leaves are approximately
160◦ and 2◦, respectively. Water droplets on their surface are
almost spherical and can roll freely in all directions and then
pick up dirt particles (Figure 7d). A very high static water
contact angle and a very low sliding angle are essential for
achieving superhydrophobicity-induced self-cleaning.
FABRICATION OF OPTICALLY TRANSPARENT PDMS
ARTIFICIAL LOTUS LEAF FILM USING
UNDEREXPOSED AND UNDERBAKED PHOTORESIST
MOLD.
Polydimethyl-siloxane (PDMS) seems to be an ideal material for
fabricating a optically transparent artificial lotus leaf film for
several reasons: first, it has a low surface energy of 19.8
mJ/cm2; it shows high optical transparency throughout the
ultraviolet and visible wavelengths; and it is well known for
precise replication of inverse images of a mold structure. In
addition, PDMS has extremely low Young‘s modulus (< 4MPa)
which makes the PDMS an ideal material for flexible artificial
lotus leaf film application to conform to arbitrary shaped
nonplanar surfaces.
A. DESIGN
Underexposed and Under Soft-Baked PR Mold
(a) (b) (c)
Figure 8: Conceptual schematic diagrams of the PR mold after
developing. (a) Conventional lithography. (b) Underexposure
condition. (c) Underexposure and under soft-bake condition.
In a conventional photolithography, it is highly desirable to have
near vertical sidewall in the patterned PR as shown in Fig. 8(a).
Underexposure condition in photolithography may not provide
enough irradiation to cause photochemical conversion of
dissolution inhibitor which may result in undesirable well-
shaped PR pattern Fig. 8(b). Significant under soft-bake
condition allows PR to retain good amount of solvents which
greatly increase the dissolution rate of the PR during
developing, i.e., the more residual solvent contained in the PR,
the higher the dissolution rate. Therefore, under soft-bake
condition, PR may be readily attacked by the developer in both
exposed and unexposed regions, which in turn results in
undesirable extremely poor patterning. However, once optimal
under softbaking condition is combined with underexposure
condition, it may create extremely unique hierarchical micro-
/nanoscale patterns in one-step photolithography Fig. 8(c),
converting this normally undesirable pattern into our benefit.
Replicating inverse image of this irregular-shaped PR mold
using PDMS may provide an unprecedented simple way of
creating a highly optically transparent extremely flexible
superhydrophobic thin film for a variety of applications.
B. FABRICATION
To prove this hypothesis, AZP4620 positive PR has been used
for creating the underexposed under soft-baked PR mold. The
thick AZP4620 PR mold is started with a standard spin coated
deposition (3000 r/min expected thickness of 14μm) on a Si
substrate; then it is soft baked in a convection oven at 88 °C for
5 min. Another layer of the PR is processed with the same
condition as the first layer and the double-layer thickness
became 43±2μm due to the viscous nature of the first PR layer.
The third layer deposition process (700 r/min) made the triple-
layer PR thickness to 103±3μm; then it is soft baked in a
convection oven at 88 °C for 30 min. Although baking time for
each layer is 30, 35, and 40 min, amount of evaporation of
solvents in each PR layer is not proportional to the baking time.
Intentionally the first and second layers was baked for only 5
min to retain good amount of solvents in those layers. The final
layer is baked for 30 min to evaporate most of the solvents in
the third layer. While solvents in the third layer are evaporated,
some of the solvents in the first and second layers would also be
evaporated, but the solvent evaporation rate for the first two
layers is much lower than that of the third layer. Next, the PR is
exposed under a UV light source, but with significantly
underexposure condition Fig. 9(b). Then, the PR sample is then
developed by AZ400K diluted (1:3) developer [ Fig9 (c)] to
form the underexposed underbaked PR mold. Next, PDMS
(RTV615A) is mixed with a curing agent with a weight ratio of
10:1. This PDMS mixture is placed in a desiccator and is de-
gassed under vacuum condition until no bubbles appeared. De-
gassed PDMS is carefully poured over the PR mold to cover the
whole surface area and minimize the introduction of bubbles;
then it is triple spin coated on the PR mold to enhance the
uniformity. After the first and second deposition of PDMS, it is
cured in a vacuum oven for PDMS to fill out the extremely
concave area at 80 °C for 15 min. After the third deposition, the
sample is placed in a convection oven at 65 °C for 30 min.
Finally, AZ 400T PR stripper is used to safely delaminate the
replicated PDMS from the PR mold as shown in Fig. 9(d). The
replicated PDMS sample is cleaned in an ultrasonic bath with
acetone for 1 min and rinsed with DI water.
Figure 9: Process flow for the hierarchical micro-/nano-patterned
PDMS film: (a) spin coating of PR and under soft-bake, (b) UV
underexposure to create a micro/nano combined broccoli-like
PDMS pillar array structures, (c) developing, and (d) soft-
lithography using PDMS.
(a) (b) (c)
(d) (e)
Figure 10: (d) Optical image of the PR mold. (b)–(e) SEM images of
the replicated PDMS artificial lotus leaf.
A combination of exposure dose of 800 mJ/cm2 with 88 °C soft-
baking for 30 min turned out to be the right combination for
reproducible fabrication of hierarchical micro-/nano-scale
textured surface formation in the replicated PDMS. Fig.10 (a)
shows an optical image of the top view of the underexposed
under soft-baked (800 mJ/cm2, 88 °C soft-bake 30 min)
AZP4620 PR mold which shows a very irregular shape inside
the PR mold. Fig.10 (b)–(e) shows SEM images of the unique
broccoli-shaped surface-textured PDMS replicated from the
underexposed under soft-baked AZP4620 PR mold. The
broccoli-shaped pillar structure‘s height is75±5μm due to
significant underbaking and underexposure condition although
the PR thickness is 103±2μm. Since the PDMS baking was
carried out at lower temperatures than PR baking condition, we
expect that the impact of the PDMS baking on the PR topology
is minimal.
ANALYSIS
The surface characteristics of the broccoli shaped replicated
PDMS film from the 88 °C soft-baked (30 min), 800 mJ/cm2
exposure dose AZP4620 PR has the water static contact angles
of 157.7±1°, 160±1°, and 161±0.5° for the 4-, 10-, and 15-μL
droplets, respectively, well above the conventional
superhydrophobicity threshold of water contact angle of 150°.
Water static contact angles of the natural lotus leaf are known to
be 160–170°. The superhydrophobic PDMS film is optionally
further surface modified by a plasma deposition of 100 nm thick
fluorocarbon (FC). The FC-coated superhydrophobic PDMS
shows improved water contact angle in the range of 160–163°.
The sliding angles of the broccoli-shaped surface-textured
superhydrophobic PDMS film are 23.4±0.8°, 14.7±1.3°, and
7.7±0.8° for the 4-, 10-, and 15-μL droplets, respectively. The
FC-coated broccoli-shaped surface-textured superhydrophobic
PDMS film shows significantly lower sliding angles in the range
of 5° and 7.33° for 15- and 10-μL droplets, respectively, while
the natural lotus leaf‘s sliding angle is consistently lower than 6°
regardless of the size of the droplets. The advancing angles were
in the range of 155±0.5°–161.33±0.763° for 1, 2, and 4μL
droplets with the dispense rate of 0.08μL/s. The receding angles
were found to be 123.33±1.3°– 133.33±0.29° for the, 1-, 2-, and
4-μL droplets using the evaporation method. The
advancing/receding contact angles of water droplets on the
natural lotus leaf are known to be approximately 160° and 140°,
respectively..
Figure 11: I–V characteristics of solar cell (solid) and PDMS
coated solar cell (dash).
PDMS BASED SUPER-HYDROPHOBIC THIN FILM. super-hydrophobic SU-8 thin film was in the range of 156° ~
161° (0.025 μL/sec. dispense rate) and the receding angle is
A dense array of replicated PDMS micro lens and PDMS micro measured to be 122° ~ 127°. Optical transparency is found to be
bowls by single and double soft lithography, respectively from 60 ~ 70%, which shows feasibility of the optically transparent
an array of tall and sharp photoresist spikes using their unique applications.
3D diffuser lithography technique is demonstrated. The PDMS
micro bowl array shows water contact angle of approximately
164.6° and low adhesive force, outstanding characteristic for the
self-cleaning thin film applications. Further demonstration is a
robust super-hydrophobic and super-oleophobic surface with
inverse trapezoidal microstructures on PDMS. Here the unique
backside 3D diffuser lithography is used to fabricate a
photoresist mold and PDMS trapezoidal structures are replicated
using soft lithography method (Figure 12). The inverse
transparent and flexible PDMS trapezoidal microstructures have
the following dimensions: pitch distance of 40 μm, diameter of
26 μm at the top, diameter of 15 μm at the bottom. The contact
angle of Teflon coated PDMS trapezoid surface is as high as
153°.
Figure 13: Fig: Fabrication sequence of the nano-patterned
SU-8 micro-pillar array

Figure 12: (a) A schematic diagram of backside 3D diffuser

lithography, (b) SEM image of inverse trapezoid with
magnification (50 μm), (c) with magnification (20 μm), (d)
with magnification (5 μm).

SU-8 BASED SUPER-HYDROPHOBIC THIN FILM

As shown in Figure 13 a dense array of tapered SU-8 micro-

pillar array is fabricated using SU-8 backside exposure method.
Then, it is isotropically dry etched for 10 min. using O2/CF4
(90%: 10%) plasma with a power of 300 W in a microwave
plasma etcher. The top and bottom diameter of the SU-8 micro- Figure 14: Figure 11 SEM images of nano-patterned SU-8
pillar is 50 μm and 85 μm, respectively, and the height is 250 micro-pillar array: (a) after plasma treatment, (b) close-up
μm with a 3°~5° tapered angle (Figure 14a and b). Isotropic view, (c) nano-patterned surface, and (d) plasma treated top
plasma etching process is used to make nano-porous patterns pillar area.
(10 ~ 900 nm) uniformly on the surface of the non-planar micro-
pillar structures (Figure 14c and d). The advancing angle of this
CONCLUSION
The Higher water contact angles and lower sliding angles
showed higher superhydrophobicity in films. Hydrophobic
property was achieved by placing a cushion of air below the
water drop (Cassie state), this was achieved by making surface
rough. Superhydrophobic surface had water contact angles
greater than 150 degree and low contact angle hysteresis less
than 5 degree. PDMS Superhydrophobic film using
underexposed and underbaked condition demonstrated water
contact angles in the range 157-161 degree's. FC coating on top
of this showed slight improvement in water contact angles. The
water contact angles of SU8 superhydrophobic thin film were
found to be same as observed in PDMS superhydrophobic film.
The PDMS film showed noticeably high optical transparency of
90% when compared with 60-70% optical transparency of SU8
thin film.
NEW IDEAS / FUTURE WORK
 Self-cleaning surfaces with self-healing properties can be
developed from self-healing mechanisms observed in some
plants and animals.
 Micro-nano scale cells having a dome shaped can be
fabricated and assembled to create a thin film solar cell.
Such a solar cell will give a rough surface with high contact
angle making itself cleaning. This type of cell will not
require an antifouling coating.
 Micro channels can be used to pump the water. This can
assist in cleaning of surface and also may help in cooling of
the solar cell surface (efficiency is temperature dependent).
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