Wetting Behavior of Textured Silicon Surfaces-An Experimental Study 2020-2021

Wetting behavior of textured silicon surfaces- an experimental study 2020-2021
Chapter 1
Introduction
Micro Electro Mechanical Systems (MEMS) is a technology that combines miniaturized

mechanical and electronic components with the improvement in nanotechnology, and has grown
rapidly over the last few decades due to its small size, high throughput, high integration
capability with electric circuit, low unit cost and excellent performance and hence finds its
market in vast number of areas including sensors, accelerometers, resonators, switches,
gyroscopes, relays, micro valves and pumps. Due to well-established design and fabrication
processes related to IC technology, the MEMS gadgets / devices are conventionally made of
Silicon (Si), but the main disadvantage is that silicon has poor tribological properties. The most
important components or functional elements in MEMS are the micro sensors and micro
actuators, apart from the miniaturized structures and microelectronics. Sensors and actuators are
categorized as “transducers”, which are devices that convert energy from one form to another.
Sensor based MEMS are commercially available, as they have only sensing elements; while
actuator based MEMS are devices having relative motion, and they are not yet being
commercialized due to high friction between two surfaces which hinders the smooth movement
and long term reliability due to poor tribological solutions.
The physical dimension of MEMS devices may vary from one micron to several
millimeters. As the MEMS device shrivels, every force related with the gadget /device downsize
with the size. For instance, downsizing the MEMS principle length from a solitary millimeter to
a solitary micrometer delivers a lessened volume by a component of a billion and diminished
territory /surface by an element of a million. Consequently, at the smaller scale, the surface to
volume proportion develops with scaling down, and surface forces (for example, meniscus
forces, viscous drag, surface tension, friction and adhesion) are required to build a thousand
times more than the forces corresponding to the volume, (for example, inertial and
electromagnetic strengths); in simple surface forces dominates the volume forces, thus
decreasing the performance and subsequently the life of the micro devices. Wettability
commonly referred as an important surface property, is another issue affecting the tribological
Department of Mechanical Engineering, UVCE Page 1

properties at the micro/nanoscale. The degree to which the solid surface repels a liquid has
evoked many industries and academic researches to

Work in the field of microfluidics, thin-film technology, aerospace components, anti-corrosive,

anti-snow sticking and self-cleaning surfaces applications. The wetting of the solid surface by the
liquid behavior depends on two main properties of the solid surface under study: the surface
energy of the top molecular layer and its surface morphology. Certain studies mention that
hydrophobicity can be achieved only by modifying the chemical composition by lowering
surface energy [2 -10]. However for super hydrophobicity, surface morphology has a significant
effect on wettability [11] where the air gets trapped in between the liquid and the rough surface.
Thus super hydrophobicity arises from the combination of low surface energy materials and
hierarchical or multiscale structure with micro and nano features [12, 13]. Nature has gifted us
the combination of these two properties for liquid super repellency in the form of plant Leaves
[14] (lotus, Indian canna, knotweed, and taro leaf) and in some insect wings like dragonfly,
butterfly, cicada, damselfly, and legs of a water strider.
Two distinct regimes occur when a liquid droplet is placed on micro patterned surfaces. If
a droplet penetrates into the gaps of the micro pillar termed as wetted regime (static water
contact angle WCA < 90°), while if the droplet sits on top of the micro pillar supported by
entrapped air then it is known as non-wetted regime (WCA > 90°). Wetted regimes usually
occurs on hydrophilic surfaces as they possess high surface energy, supporting high friction and
adhesion. On the contrary, non-wetted regimes occur on hydrophobic surfaces as they possess
low friction and low adhesion because of low surface energy [18].
There is enormous research been conducted by measuring static contact angle on artificial
roughened surfaces referred to as micro patterns, 3D negative fingerprint and honeycomb
textured surface were fabricated on SU8 coated silicon surface to produce a WCA of 81° and 95°
respectively [15], Replicated epoxy micro pillars of cylindrical type created by soft lithography
provides a CA of 151° [16], SU8 micro pillars of square shape were fabricated on silicon by UV
lithography achieves a WCA of 131° [17], Micro/Nano grooves of varying pitch on silicon
wafers by photolithography techniques produces a max contact angle of 48° [18], SU8 microdot
patterns were fabricated by polymer jet printing on silicon samples by varying the distance
between the dot (pitch) and found that SU8 textured surfaces have shown lower contact angle
compared to spin-coated samples (SU8/Si) because of increased exposure of silicon surface [19].

Nano patterns of PMMA with three different aspect ratios (holding time) were fabricated on
silicon surfaces using simple capillary force lithography produced a contact angle of 99° [20].
Silicon micro pillars and channels were fabricated using photolithography and deep reactive ion
etching (DRIE) Techniques produces a WCA of 59 and 63 respectively [21] .
Apart from the geometric parameters being mentioned, there are other factors influencing
the wetting behavior, one such is the orientation of the pillars. To the best knowledge of the
author, the effect of contact angle on the arrangement of micro pillars in an array has not been
investigated before; apart from the effect of hollow geometries in comparison with solid
geometries. The micro patterns used in the study are an array of circular and square pillars of
both solid and hollow cross-section, with uniform height and constant cross-section area,
arranged in two different arrangements (chain-type and zig-zag type) at a varying pitch. If the
pillars in the adjacent row are opposite to each other then it’s termed as chain type arrangement
(figure 2a-d), and if the pillars are staggered in such a way that every pillar is in the middle of the
two pillars of the adjacent rows (figure 2e & f), then the arrangement is said to be zig-zag. But in
the zig-zag arrangement, the contact angle measurement depends on the direction of viewing as
the patterned surface is no longer Isotropic. This direction dependency called anisotropic wetting
behavior can be observed in some natural surfaces like in the case of rice leaves [22], which has
the capability to control the water movement in a particular direction [23]. Hence in this paper
care was taken to view the static contact angle in the vertical direction (y) and is only been
reported (figure 6), as the wetting behavior was slightly different in the horizontal direction (x)
[24].
1.1 History of this journal paper

The idea of surface texturing is inspired by nature. Shark skin, for instance, boosts swim
speed by cutting the drag force; therefore, the skin suits of Olympic athletes have v-shaped
grooves called rib lets which mimic the texture of shark skin. The gecko foot is another example
from nature that inspired many adhesive systems. Many studies have investigated the effect of
surface texturing on the performance of a variety of mechanical systems. It was found that
surface texturing has great potential for improving the tribological performance in terms of
reducing the wear, friction, and lubrication consumption.

1.2 Surface Texturing Parameters

Different texture parameters, such as shape, size, density, depth, and orientation, or a
combination of these parameters, control the effectiveness of the surface texture on tribological
performance.
In general, surface texture may be positive, in that it protrudes out of the surface, or
negative, such as dimples or holes. It can also be made up of continuous grooves, channels, or
undulations. It can be discrete shapes, such as circular, square, triangular, or hexagonal, that are
distributed evenly or randomly. Positive surface textures are used extensively in micro-electrical
mechanical systems (MEMS), and magnetic hard disks to decrease the friction by decreasing the
area of contact. Negative texturing, which is the focus of the current study, is mostly employed
in automotive components, and in machining tools and punches for metal forming processes.
1.3 Benefits of Surface Texturing

The role of the surface texturing in improving the tribological properties varies based on the
contact conditions, whether they are hydrodynamic (full), mixed, boundary, or dry conditions. In
the case of the full or mixed lubrication conditions, the micro-craters serve as micro-
hydrodynamic bearings that increase the hydrodynamic pressure due to asymmetric pressure
distribution, therefore the load carrying capacity increases. In mixed lubrication conditions, this
additional lift in hydrodynamic pressure alters the balance between hydrodynamic and boundary
lubrication, consequently the number of the asperities in contact decreases, and friction and wear
decrease. In boundary lubrication these craters act as lubricant reservoirs for the continuous
retention of lubricant, and for dry sliding the surface texture acts as wear debris traps so that
plowing decreases. Consequently, abrasive wear and friction are reduced.
1.4 Optical lithography

Optical lithography or UV lithography, is a process used in microfabrication to pattern,
parts of a thin film or the bulk of a substrate (also called a wafer). It uses light to transfer
a geometric pattern from a photomask (also called an optical mask) to a photosensitive (that is,
light-sensitive) chemical photoresist on the substrate. A series of chemical treatments then
either etches the exposure pattern into the material or enables deposition of a new material in the

desired pattern upon the material underneath the photoresist.
A single iteration of photolithography combines several steps in sequence. Modern

cleanrooms use automated, robotic wafer track systems to coordinate the process. The procedure
described here omits some advanced treatments, such as thinning agents or edge-bead removal.
 Cleaning
If organic or inorganic contaminations are present on the wafer surface, they are usually
removed by wet chemical treatment, e.g. the RCA clean procedure based on solutions
containing hydrogen peroxide. Other solutions made with trichloroethylene, acetone or methanol
can also be used to clean.
 Preparation
The wafer is initially heated to a temperature sufficient to drive off any moisture that may
be present on the wafer surface, 150 °C for ten minutes is sufficient. Wafers that have been in
storage must be chemically cleaned to remove contamination. A liquid or gaseous "adhesion
promoter", such as Bis(trimethylsilyl)amine ("hexamethyldisilazane", HMDS), is applied to
promote adhesion of the photoresist to the wafer. The surface layer of silicon dioxide on the
wafer reacts with HMDS to form tri-methylated silicon-dioxide, a highly water repellent layer
not unlike the layer of wax on a car's paint. This water repellent layer prevents the aqueous
developer from penetrating between the photoresist layer and the wafer's surface, thus preventing
so-called lifting of small photoresist structures in the (developing) pattern. In order to ensure the
development of the image, it is best covered and placed over a hot plate and let it dry while
stabilizing the temperature at 120 °C.
 Photoresist application
The wafer is covered with photoresist by spin coating. Thus, the top layer of resist is
quickly ejected from the wafer's edge while the bottom layer still creeps slowly radially along the
wafer. In this way, any 'bump' or 'ridge' of resist is removed, leaving a very flat layer. Final
thickness is also determined by the evaporation of liquid solvents from the resist. For very small,
dense features (< 125 or so nm), lower resist thicknesses (< 0.5 microns) are needed to overcome
collapse effects at high aspect ratios; typical aspect ratios are < 4:1.

The photo resist-coated wafer is then prebaked to drive off excess photoresist solvent,
typically at 90 to 100 °C for 30 to 60 seconds on a hotplate.
 Exposure and developing

After prebaking, the photoresist is exposed to a pattern of intense light. The exposure to
light causes a chemical change that allows some of the photoresist to be removed by a special
solution, called "developer" by analogy with photographic developer. Positive photoresist, the
most common type, becomes soluble in the developer when exposed; with negative photoresist,
unexposed regions are soluble in the developer.
A post-exposure bake (PEB) is performed before developing, typically to help

reduce standing wave phenomena caused by the destructive and
constructive interference patterns of the incident light. In deep ultraviolet lithography,
chemically amplified resist (CAR) chemistry is used. This process is much more sensitive to
PEB time, temperature, and delay, as most of the "exposure" reaction (creating acid, making the
polymer soluble in the basic developer) actually occurs in the PEB.
The develop chemistry is delivered on a spinner, much like photoresist. Developers

originally often contained sodium hydroxide (NaOH). However, sodium is considered an
extremely undesirable contaminant in MOSFET fabrication because it degrades
the insulating properties of gate oxides (specifically, sodium ions can migrate in and out of the
gate, changing the threshold voltage of the transistor and making it harder or easier to turn the
transistor on over time). Metal-ion-free developers such as tetramethylammonium
hydroxide (TMAH) are now used.
The resulting wafer is then "hard-baked" if a non-chemically amplified resist was used,
typically at 120 to 180 °C] for 20 to 30 minutes. The hard bake solidifies the remaining
photoresist, to make a more durable protecting layer in future ion implantation, wet chemical
etching, or plasma etching.
 Etching
In etching, a liquid ("wet") or plasma ("dry") chemical agent removes the uppermost
layer of the substrate in the areas that are not protected by photoresist. In semiconductor
fabrication, dry etching techniques are generally used, as they can be made anisotropic, in order

to avoid significant undercutting of the photoresist pattern. This is essential when the width of
the features to be defined is similar to or less than the thickness of the material being etched (i.e.
when the aspect ratio approaches unity). Wet etch processes are generally isotropic in nature,
which is often indispensable for microelectromechanical systems, where suspended structures
must be "released" from the underlying layer.
The development of low-defectively anisotropic dry-etch process has enabled the ever-
smaller features defined photo lithographically in the resist to be transferred to the substrate
material.
 Photoresist removal
After a photoresist is no longer needed, it must be removed from the substrate. This
usually requires a liquid "resist stripper", which chemically alters the resist so that it no longer
adheres to the substrate. Alternatively, photoresist may be removed by a plasma
containing oxygen, which oxidizes it. This process is called ashing, and resembles dry etching.
Use of 1-Methyl-2-pyrrolidone (NMP) solvent for photoresist is another method used to remove
an image. When the resist has been dissolved, the solvent can be removed by heating to 80 °C
without leaving any residue.
 Bosch process
It is pulsed or time-multiplexed etching, alternates repeatedly between two modes to achieve

nearly vertical structures
The Bosch process uses a fluorine based plasma chemistry to etch the silicon, combined with
a fluorocarbon plasma process to provide sidewall passivation and improved selectivity to
masking materials. A complete etch process cycles between etch and deposition steps many
times to achieve deep, vertical etch profiles. It relies on the source gases being broken down in a
high-density plasma region before reaching the wafer, which has a small but controlled voltage
drop from the plasma. This technique cannot be performed in reactive ion etch systems (RIE), as
these have the wrong balance of ions to free radical species. This balance can be achieved in
high-density plasma systems (HDP). The most widely used form of HDP uses inductive coupling
to generate the high-density plasma region so is known as ‘inductively coupled plasma’ (ICP).
Sulphur hexafluoride (SF6) is the source gas used to provide the fluorine for silicon etching. This

molecule will readily break up in high-density plasma to release free radical fluorine. The
sidewall passivation and mask protection is provided by octofluorocyclobutane (c-C 4F8), a cyclic
fluorocarbon that breaks open to produce CF2 and longer chain radicals in the high-density
plasma. These readily deposit as fluorocarbon polymer on the samples being etched. The profile,
etch rate and selectivity to the mask material are all controlled by adjusting the etch step
efficiency, the deposition step efficiency or the ratio of times of the two steps. The process is
relatively insensitive to the exact nature of the photoresist, to the extent that it does not need hard
baking of the resist prior to etching. In fact, it is best to avoid high temperature bakes of resist, as
this causes variation in the resist profile, which can cause mask recession problems on certain
structures.
 Wet etching
The first etching processes used liquid-phase ("wet") etchants. The wafer can be
immersed in a bath of etchant, which must be agitated to achieve good process control. For
instance, buffered hydrofluoric acid (BHF) is used commonly to etch silicon dioxide over
a silicon substrate.
Different specialized etchants can be used to characterize the surface etched. Wet
etchants are usually isotropic, which leads to large bias when etching thick films. They also
require the disposal of large amounts of toxic waste. For these reasons, they are seldom used in
state-of-the-art processes. However, the photographic developer used for photoresist resembles
wet etching.
As an alternative to immersion, single wafer machines use the Bernoulli principle to

employ a gas (usually, pure nitrogen) to cushion and protect one side of the wafer while etchant
is applied to the other side. It can be done to either the front side or back side. The etch chemistry
is dispensed on the top side when in the machine and the bottom side is not affected. This etch
method is particularly effective just before "backend" processing (BEOL), where wafers are
normally very much thinner after wafer back grinding, and very sensitive to thermal or
mechanical stress. Etching a thin layer of even a few micro meters will remove micro cracks
produced during back grinding resulting in the wafer having dramatically increased strength and
flexibility without breaking.
After fabrication of the model is done the model is checked for any imperfection in
fabrication using Atomic force microscopy.
1.5 Atomic force microscopy
FIGURE 1. Block diagram of atomic force microscopy
Atomic force microscopy (AFM) or scanning force microscopy (SFM) is a very-high-resolution

type of scanning probe microscopy(SPM), with demonstrated resolution on the order of fractions
of a nanometer, more than 1000 times better than the optical diffraction limit The AFM has three
major abilities: force measurement, imaging, and manipulation.
For imaging, the reaction of the probe to the forces that the sample imposes on it can be
used to form an image of the three-dimensional shape (topography) of a sample surface at a high
resolution. This is achieved by raster scanning the position of the sample with respect to the tip
and recording the height of the probe that corresponds to a constant probe-sample interaction
(see section topographic imaging in AFM for more details). The surface topography is
commonly displayed as a pseudo color plot.
 Working principle
As shown in Figure 1 the AFM consists of a cantilever with a sharp tip (probe) at its end
that is used to scan the specimen surface. The cantilever is typically silicon or silicon nitride with
a tip radius of curvature on the order of nanometers. When the tip is brought into proximity of a
sample surface, forces between the tip and the sample lead to a deflection of the cantilever
according to Hooke's law. Depending on the situation, forces that are measured in AFM include
mechanical contact force, van der Waals forces, capillary forces, chemical bonding, electrostatic
forces, magnetic forces (see magnetic force microscope, MFM), Casimir forces, solvation forces,
etc. Along with force, additional quantities may simultaneously be measured through the use of
specialized types of probes (see scanning thermal microscopy, scanning joule expansion
microscopy, photo thermal micro spectroscopy, etc.).
 Applications
The AFM has been applied to problems in a wide range of disciplines of the natural
sciences, including solid-state physics, semiconductor science and technology, molecular
engineering, polymer chemistry and physics, surface chemistry, molecular biology, cell biology,
and medicine.
1.6Goniometer
The static sessile drop method. The sessile drop contact angle is measured by a contact
angle goniometer using an optical subsystem to capture the profile of a pure liquid on a solid
substrate. The angle formed between the liquid–solid interface and the liquid–vapor interface is
the contact angle. As shown figure 2 Contact angle measurement the droplet is placed on the
substrate, which is then gradually tilted. The advancing angle is measured at the front of the
droplet just before the droplet starts to move by using goniometer as shown in figure 3. The
receding contact angle is measured at the back of the droplet, at same time point.

FIGURE 2. WATER DROPLET CAPTURED BY GONIOMETER
FIGURE 3. GONIOMETER
1.7 Wenzel and Cassie-Baxter Model
FIGURE 4. WENZEL AND CASSIE BAXTER MODEL
A model shown in figure 4 explains how rough surfaces affect the contact angle of liquid
droplets on solid surfaces. A liquid droplet introduced on to a solid surface starts to spread until a
specific contact angle is attained, depending on surface tension of solid liquid, solid air and
liquid air interfaces. In Wenzel state, a droplet of liquid immerses into the surface texture has
opposed to Cassie-Baxter state where it rests upon the surface texture. This eliminates air liquid

interface against surface. The Cassie-Baxter model is widely used to predict the apparent contact
angles obtained on composite super hydrophobic interfaces.
Chapter 2
Literature Survey
The literature survey is a proof essay of sorts. It is a study and review of relevant
literature materials in relation to the topic considered.
L.Y. Jonathan.et.al [35] studied different lubrication techniques using PFPE lubricant, viz
dip coating and vapour deposition and compared with Localized-Lubrication which has been
proposed as a novel method of lubrication to offers long term wear durability for microsystems,
and concluded that delivering a fixed amount of PFPE lubricant locally (Loc-Lub) onto the
specified location has proven effective apart from reducing the friction coefficient and
preventing excessive wear, as the other techniques when used affects the functionality of certain
portion of the microsystem device such as pads and electrical contacts. Hence Loc-Lub can be
adapted to any MEMS devices without any surface modification to retain functionality. The
application of PFPE as the lubricant in between the metal surfaces have found susceptible to
catalytic degradation and may cause corrosion due to fluorine presence. Hence Jonathan.et.al in
his further studies investigated the effectiveness of Multiply-alkylated Cyclopentanes (MAC)
lubricant by comparing with PFPE in his method of lubrication (Loc-Lub) and found that
improved friction and wear properties were obtained. The main reason is that MAC is extremely
cohesive that separates two surfaces from direct contact, and they show high thermal stability
and have the feasibility to coat onto various surfaces.
Sirpuram and Stephens [36] addressed the effects of different texture shapes of positive
and negative texturing. Square, diamond, circular, triangular and hexagonal shapes were
modeled, with different area densities under a hydrodynamic lubrication condition. Two
objectives were sought in this study, the effects of the shape and the texture areal density on the
coefficient of friction and leakage rate. They concluded that the shape of the texture has an
insignificant effect on the friction coefficient; however, it had a great impact on the leakage rate.
The square pattern provided the worst leakage rate, and the triangular pattern gave the best

leakage rate. In addition, the texture areal density affects the minimum friction coefficients,
which were obtained at 20% and 80% of the areal texture coverage for the positive and negative
texturing, respectively.
Kligerman and Etsion [37] developed a theoretical model to identify the most significant
parameters under hydrodynamic sliding conditions, specifically for mechanical seals. Based on
the findings of an earlier study that promoted evenly distributed micro-textured patterns in order
to increase the load carrying capacity, hemispherical dimples arranged in a rectangular layout
were modeled. This study suggested that an optimal texture size could be found based on
lubricant properties, pressure difference across the seal, and the areal density of the texture.
Tnder [38] proved analytically that a micro textured region can replace a macro feature,
such as step or inclined plane, in creating hydrodynamic pressure in sliding seals. The role of
either the macro feature or the proposed micro textured area is to decrease the friction which the
entering flow to the seal encounters. In this analytical study, grooves oriented perpendicularly to
the flow
Direction was modeled, as well as square and circular discrete dimples. All texturing designs
showed improvement in the hydrodynamic pressure and the leakage rate.
Kovalchenko et al. [39] looked into the effects of laser surface texture on the lubrication
regime transition. Specifically, the effects of the sliding speed, normal pressure, and the lubricant
viscosity on the friction were tested. A pin-on-disk apparatus was used in this case, and the laser
surface texturing had more impact on friction in cases of higher normal loads, higher sliding
speed, and higher viscosity.
Pettersson and Jacobson [40] studied the effects of the surface texturing of coated silicon
under boundary and dry sliding conditions. Etched silicon samples were coated with either TiN
or DLC. This study showed the critical impact of the material interaction under oscillating
sliding by a ball slider. Two texturing designs were investigated, grooves and square dimples as
shown in Figure 5. The results of this study were compared to untextured samples. Under
boundary lubrication conditions, the DLC coating with square dimples showed stable low
friction behavior, while the grooved texture showed high friction. The textured TiN coating

behaved differently and showed unstable friction behavior on all texturing patterns. In dry sliding
conditions, the DLC coating showed high friction when compared to the untextured surface.
DLC has self-lubricating properties where a thin low friction tribofilm was formed on the
surface. When the DLC coated sample was textured, the sharp edges of the pores scraped off the
thin tribofilm causing the fluctuations in the friction behavior. On the other hand, the TiN
textured samples showed low friction with both the square and groove patterns.
FIGURE 5. Textured squares and grooves by Patterson and Jacobson
Summary
The failure of MEMS devices is dependent on the poor tribological performance and
adhesion issues of the structures in the system. Few methods are been studied to relieve the
tribological issues (viz Thin organic films, Topography and chemical modifications, Dual film
coatings) and the following are the important outlines from the study:
 Thin films which acted as protective lubrication coatings in many applications, have poor
durability because of the lack of tribological contributions of mobile molecules, like low
shear strength, replenishment and trapping among micro-asperities.
 Tailoring the surface topography and chemically modifying have gained a momentum in
improving the tribological performance, due to reduced area of contact between the surfaces
under sliding which changes the wetting interface behavior, traps wear debris thereby
reducing plowing effect.
 A dual film coating which includes the lubrication synergy of solid and liquid combination
has become a most popular design concept to improve the life of the lubrication coatings and
thereby registers for better load carrying capacity in MEMS devices.

Chapter 3
Experimental Methodology
3.1Fabrication of Silicon Micro patterns

P-type polished silicon of orientation, with a thickness of 525µm, was used as a substrate
(procured from Prolyx microelectronics pvt ltd – India). Single crystal silicon used traditionally
as a structural material is hydrophilic in nature. In this study, micropatterns on a silicon wafer
were fabricated using direct-write lithography and deep reactive ion etching (DRIE) technique,
as they provide the freedom of shapes with high resolution, smooth surface without any burrs
[25]. Figure (6) shows the steps involved in the fabrication process. As an initial step, silicon
wafer as received were cleaned sequentially with piranha (H2SO4 & H2O2 in 3: 1 ratio) solution
at 90°C for a duration of 10 min to remove any contamination followed by dipping in dilute
hydrofluoric acid (DI water and HF in 50:1) for 30 seconds for native oxide removal, finally the
samples were dried with nitrogen gas and the excess moisture on the wafer surface was removed
by keeping the wafer on the hot plate at 110°C for 10 min. The cleaned wafers were then spin-
coated with positive photoresist (AZ-4562) and prebaked at 110°C for 75 sec. micro patterns
(array of pillars distributed in a square of 10x10mm size on 4 inch silicon wafer) of different
geometries by varying the pitch (space between two adjacent pillars) and arrangement (chain and
zig-zag) were designed using CleWin software, and the same was developed on the photoresist
using a mask less direct write lithography tool (Heidelberg Instrument).
DRIE was done as per the Bosch process using two gases (SF6 and C4F8) in a switched/
cyclic process to obtain patterns on the silicon wafer. Finally, the photoresist was removed, and
the patterned wafer was sequentially cleaned in acetone, isopropyl alcohol and DI water followed
by blowing it with nitrogen gas. The wafer was then diced to 10x10mm sample, and each sample
has an array of different geometry features fabricated on it for a varied pitch (45, 55, 65 &
75µm). Table 1 briefs us the details of sample geometries, dimensions and the distance between
the consecutive pillars (pitch).
3.2Surface characterization
Goniometer (Holmarc Opto mechatronics Pvt Ltd) was used to determine the contact
angle measurement by gently landing a droplet of de-ionized water (DI) on the test sample from
the micro syringe attached to it. Prior to contact angle measurement the samples were immersed
in acetone, isopropyl alcohol sequentially and finally washed with DI water and dried by
blowing nitrogen gas. A droplet of 5μl volume (diameter of a spherical droplet is around 2.1 mm
[26]) was chosen to ensure that the droplet size is comparatively larger than the dimensions of
the patterns on the sample. Care was taken to place the droplet on the surface at zero velocity
without causing the water droplet to penetrate in between the pillars. The data specified are the
average of five readings taken at different locations on the test sample at room temperature, and
the standard deviations was calculated and were indicated as error bars.
Optical Microscope (Olympus BX61) and Optical Profilometer (Talysurf CCI - Taylor
Hobson Precision) was used to examine the exact shape of the micro pattern geometry on the
fabricated samples. Figure (7) illustrates the 2D optical images and figure (8) shows the surface
profile and 3D images of an array of different geometry patterns at 45μm pitch fabricated on the
silicon sample.
Table 1: Dimensions and Geometry of patterns

Feature Dimensions of Cross-section area Height of the Pitch in µm (P)
pillar in µm of pillars in µm2 pillar in µm (H)
(A)
Solid Circle D = 31.5
Hallow Circle Do = 36,Di = 18 780 14 -15 45,55,65 &75

Solid Square S = 28
Hallow Square So = 32,Si = 16
FIGURE 6. Schematic diagram of creating micro patterns

FIGURE 7. Optical microscopic 2D images of patterns with 45 μm Pitch (P).(a) Solid circle—chain
type, (b) hollow circle - chain type, (c)solid square—chain type, (d) hollow square—hain type, (e)
hollow circle- zig-zag type, (f) hollow square—zig-zag type.

FIGURE 8. Optical Profilometer images of surface profile and 3D images of patterns with 45μm
Pitch. (a, b) solid circle - chain type, (c, d) hollow circle - chain type, (e, f) solid square - chain type,
(g, h) hollow square - chain type, (i, j) hollow circle—zig-zag type, (k, l) hollow square—zig-zag
type.
Chapter 4
Result and Discussion
Wettability governed by topography has a strong influence on properties of a textured
surface, in this study contact angle of the water droplet on the sample is measured to obtain an
understanding of the effect of geometry (micro pattern) and its arrangement. Hence a
comparative study is been made as follows.
4.1 Solid patterns (Chain type) and Hollow patterns (Chain type)
Figure (9) shows the static contact angle as a function of varying pitch for an array of
patterns (solid circle, hollow circle, Solid Square, and Hollow Square). In this case, both solid
and hollow pillars are arranged in a chain type. The graph plotted shows that texturing the silicon
surfaces has an effect on the contact angle, as un-textured silicon surfaces have 64° contact angle
[27]. Interestingly solid pillars have shown a different plot compared to hollow pillars for both
the geometries (circular and square patterns). Hydrophobicity (WCA > 90°) is achieved for all
pitches in case of solid pillared patterns, compared to hollow pillared which experiences both
hydrophilic (WCA < 90°) and hydrophobic surface properties. There was no super
hydrophobicity (WCA > 150°) seen in any of the samples as there was only topography
modification without any chemical modification of the surfaces. If a water droplet is landed on
the textured samples consisting of pillars arranged in a square grid as in case of chain type, the
maximum drop of the droplet occurs in the center of the square formed by four pillars or in
between the two pillars which are diagonally across [26] as shown in figure (10a).
In the case of all micro pillared surfaces of chain type (solid or hollow) at the lowest and
largest pitch, the contact angle is less compared to the intermediate pitch, this is in accordance
with [28] that the droplet bounces off on all micro pillared surfaces except on the ones fabricated
with lowest and highest pitch. This could be due to minimal gap between the pillars in case of
lowest pitch (P-45) which is not sufficient for a droplet to bounce [28], as there is minimum/no

possibility for air to interfere in between the liquid and solid interface so as to support the liquid
droplet. Another reason could be the effect of sharp edges on the pillars at lowest pitch as
compared to flat surfaces [26, 29]. Whereas at largest pitch (P-75) there is sufficient space
between pillars, such that the liquid droplet penetrates partially/fully between the pillars leaving
minimum/no air pockets. In other words the droplet is unable to pull the penetrated liquid and
leads to non-bouncing [28]. Also in some cases if the pitch is large, the droplet might not touch
the bottom of the cavities, the droplet becomes unstable as it would have entered metastable state
resulting in a transition from cassie baxter to wenzel regime [28, 30].
At intermediate pitch (P-55 and P-65) the contact angle is more in all pillared patterns
because there is a possibility of air been entrapped in between the liquid and solid surfaces. Also
due to sharp corners experienced by solid square-patterned surfaces (SS—CT); for all pitch, the
contact angle values are less compared to solid circle patterned surfaces (SC—CT). Therefore for
solid circular patterns, the optimum pitch is at P-65, which leads to more contact angle compared
to P-55. Also, we can observe from figure (9), that there was a sudden drop in contact angle from
P-55 to P-65 in case of solid square patterns, and the droplet which was bouncing (due to more
contact angle) lost its stability after few seconds. This is in comparison with square pattern of
hollow cross-section at pitch P-65, which has resulted in more contact angle. The inner and outer
profile of hollow square have supported the droplet resulting in more contact angle at an
optimum pitch P-65, while for solid square at the same pitch the droplet was not supported and
instead the droplet becomes unstable.
As described earlier from figure (9), hollow patterned surfaces experience both
hydrophilic and hydrophobic characteristics. The hydrophilic state is achieved at the lowest pitch
(P-45) as well as at the highest pitch (P-75), whereas at intermediate pitch (P-55 and P-65) the
patterned surfaces experience hydrophobic state. Hollow pillars experience a sudden transition
from wetting to non-wetting and non-wetting to wetting [28] at the lowest and highest pitch as
compared to solid pitch, and the reason would be due to the fixed gap (figure 10(c)), in addition
to space (pitch) provided between pillars. The fixed gap and the variable space (pitch) between
the pillars assists in both hydrophilic and hydrophobic transitions. The combination of a fixed
gap and lowest pitch, fixed gap and largest pitch between pillars have led to the lowest contact

angle (hydrophilicity), whereas intermediate pitch in combination with fixed gap leads to
hydrophobicity. The values of contact angle at the intermediate pitch for hollow patterned
surfaces are more compared to solid pillars, this is due to the addition of a fixed gap making the
water droplet to bounce on the pillars. Therefore hollow pillars at varied pitch enhance both
hydrophilic and hydrophobic characteristics compared to solid pillars. As described the sharp
corners in the solid square have reduced the values of contact angle in comparison with solid
circular patterned surfaces, whereas the same sharp corners that occur at both inner and outer
surfaces/ profiles of the hollow square (HS—CT) have increased the contact angle in comparison
with hollow circular patterns(HC—CT). Therefore hollow square-patterned surfaces at P-65
have produced more contact angle (WCA = 144) compared to all other patterned surfaces having
the same area of cross-section.
FIGURE 9. Static contact angle of Solid (chain type) and Hollow (chain type) patterns as a function
of varied pitch.

FIGURE 10. Droplet of water suspended on a Chain type patterned surface, (a) Plan view shows
the location of a maximum droop, (b) Side view of section S-S if the patterned surface consists of
solid pillars[26], (c) Side view of section S-S if the patterned surface consists of hollow pillars(chain
type).
4.2 Hollow patterns (Chain type) and Hollow patterns (Zig-zag type)
Figure (12) presents the static contact angle values at a varying pitch for hollow patterns of
chain type (CT) and zig-zag type (ZZT) arrangement. In chain type arrangement both
hydrophobic and hydrophilicity can be noticed for both the geometries, whereas in zig-zag
arrangement except for hollow circle at highest pitch, all the values obtained are in the
hydrophobic zone. In case of chain type arrangement, the adjacent row of pillars are opposite to
each other as shown in figure (10(a)), hence the maximum droop is at the intersection of the
diagonals formed by four pillars in a square grid (distance between the diagonals is √2P, where P
is pitch between the adjacent pillars); whereas in zig-zag arrangement the adjacent row of pillars
is shifted by half the pitch, hence the maximum droop occurs at the intersection of diagonals
formed by four pillars placed in a parallelogram. There are two diagonals, minimum and the
maximum as shown in figure 11(b),(c))for section S-S and S’-S’ from the figure (11(a)). As
mentioned earlier, WCA for a zig-zag arrangement is viewed in the vertical direction (y), and
hence from the plot, we can observe that the WCA values are decreased as the pitch increases;
this is because of the large distance between the pillars diagonally = ((13/4)) P, where the
liquid-air interface is destabilized leading to the formation of the solid-liquid interface due to
capillary and gravitational forces [26]. From this, we can observe that the arrangement of
pillars/patterns in an array plays a predominant role in the measurement of the water contact
angle. Also, the highest contact angles can be achieved by hollow square as compared to the
hollow circle in both the arrangement, as the air pockets exists in the sharp corners in case of
hollow squares at both inner and outer surface and this could be the valid reason for a water
droplet to bounce on the pillars[31].
From the above study been observed, when a water droplet falls on a roughened/micro
patterned surfaces, the wetting behavior of a liquid can be explained either by the Wenzel model
or by Cassie Baxter model.

According to Wenzel model, when a water droplet completely wets the textured surfaces;
the contact angle is given as
where θw is the WCA on the

micro-patterned surface in Wenzel state, r is the surface roughness factor which is defined as the
ratio of the actual area of a rough surface to the projected area., and θ is WCA on a flat surface of
the same material (Young’s contact angle).
In contrast, the patterned surfaces (except hollow geometries at lowest and highest pitch
in case of chain type arrangement) have a larger contact angle compared to bare silicon which
experiences hydrophilicity (WCA < 90°). This indicates that the WCA on micro patterned
surfaces is characterized by the Cassie-Baxter model rather than the Wenzel model [32].
Therefore according to Cassie-Baxter model, for a liquid droplet that sits on top of the micro
pillar supported by entrapped air have low adhesive force, and the contact angle is given as
Where θc is the WCA

on the micro-patterned surface in cassie baxter state, fs is the fraction of the solid in contact with
the liquid droplet, hence the equation shows that the contact angle increases as the solid fraction
decreases in Cassie state. However in few studies, the liquid droplet partially enters the patterned
surface leading to an intermediate wetting model [31, 33] and this could be evaluated by
measuring the sliding angle [32]. Thus texturing is an effective way to improve the wetting
behavior by reducing the surface real area of contact, and further can be enhanced by combining
with chemical modification [15, 18, and 34].

FIGURE 11. Droplet of water suspended on a Zig-zag type patterned surface. (a) Plan view shows
the location of a maximum droop (b) Side view of section S’-S’ if the patterned surface consists of
hollow pillars (zig-zag type), (c) Side view of section S-S if the patterned surface consists of hollow
pillars (zig-zag type).
FIGURE 12. Static contact angle of Hollow patterns of chain and zig-zag type arrangement as a
function of varied pitch.

Chapter 5
Conclusion
An investigation on the effect of texture geometry and its arrangement in an array was
carried out using a droplet of DI water under static conditions. Circular and square were the
geometries selected for fabricating patterns with both hollow and circular cross-sections. The
patterns were arrangement in both chain type and zig-zag type. Author concluded that the
texturing has an effect on contact angle measurement. At the varying pitch in the chain-type
arrangement, solid patterns have resulted in hydrophobicity, whereas hollow patterns experience
both hydrophilic and hydrophobicity; the addition of a fixed gap could be a valid reason. Hollow
square in the chain-type arrangement has a large contact angle (WCA = 144°) at pitch 65μm
compared to other geometries and cross-section, this may be due to existence of air pockets at
the sharp corners that occur at both inner and outer surfaces, which makes the water droplet to
bounce on the pillars leading to less adhesive force. Pattern arrangement plays a crucial role, zig-
zag arrangement has WCA less than the chain type arrangement for hollow patterns, and this is
because of forces influenced by gravitation and capillary at large diagonal distance between the
pillars leading to the homogeneous solid-liquid interface.

References
[1] Kumar K M, Shanmuganathan P V and Sethuramiah A 2018 Tribology of silicon surfaces: a
review Materials Today: Proceedings 5 24809–19
[2] Nishino T, Meguro M, Nakamae K, Matsushita M and Ueda Y 1999 The lowest surface free
energy based on− CF3 alignment Langmuir 15 4321–3
[3] Cha K H and Kim D E 2001 Investigation of the tribological behavior of octadecyl
trichlorosilane deposited on silicon Wear 251 1169–76
[4] Satyanarayana N, Sinha S K and Ong B H 2006 Tribology of a novel UHMWPE/PFPE dual-
film coated onto Si surface Sens. Actuators, A 128 98–108
[5] Ma J Q, Pang C J, Mo Y F and Bai M W 2007 Preparation and tribological properties of
multiply-alkylated cyclopentane (MAC)– octadecyl trichlorosilane (OTS) double-layer film on
silicon Wear 263 1000–7
[6] Minn M and Sinha S K 2008 DLC and UHMWPE as hard/soft composite film on Si for
improved tribological performance Surf. Coat. Technol. 202 3698–708
[7] Saravanan P, Satyanarayana N and Sinha S K 2013 Self-lubricating SU-8 nanocomposites
for microelectromechanical systems applications Tribol. Lett. 49 169–78
[8] Panjwani B, Satyanarayana N and Sinha S K 2011 Tribological characterization of a
biocompatible thin film of UHMWPE on Ti6Al4V and the effects of PFPE as a top lubricating
layerJ. Mech. Behav. Biomed. Mater. 4 953–60

[9] Minn M, Soetanto Y S and Sinha S K 2011 Tribological properties of ultra-thin

functionalized polyethylene film chemisorbed on Si with an intermediate benzophenone layer
Tribol. Lett. 41 217–26
[10] Chen H, Zhang X, Zhang P and Zhang Z 2012 Facile approach in fabricating
superhydrophobic SiO2/polymer nanocomposite coating Appl. Surf. Sci. 261 628–32
[11] Ogihara H, Xie J and Saji T 2013 Factors determining wettability of superhydrophobic
paper prepared by spraying nanoparticle suspensions Colloids Surf., A 434 35–41
[12] Verho T, Korhonen J T, Sainiemi L, Jokinen V, Bower C, Franze K and Ras R H 2012
Reversible switching between superhydrophobic states on a hierarchically structured surface
Proc. of the National Academy of Sciences 109, 10210–3
[13] Papadopoulos P, Mammen L, Deng X, Vollmer D and Butt H J 2013 How
superhydrophobicity breaks down Proc. of the National Academy of Sciences 110, 3254–8
[14] Guo Z and Liu W 2007 Biomimic from the superhydrophobic plant leaves in nature: Binary
structure and unitary structure Plant Science 172 1103–12
[15] Wang Y, Wang L, Xue Q, Yuan N and Ding J 2010 A facile method to improve tribological
properties of silicon surface by combining nanogrooves patterning and thin-film lubrication
Colloids Surf., A 372 139–45
[16] Myint S M, Minn M, Yaping R, Satyanarayana N, Sinha S K and Bhatia C S 2013 Friction
and wear durability studies on the 3D negative fingerprint and honeycomb textured SU-8
surfaces Tribol. Int. 60 187–97
[17] Ebert D and Bhushan B 2012 Durable Lotus-effect surfaces with hierarchical structure using
micro-and nanosized hydrophobic silica particlesJ. Colloid Interface Sci. 368 584–91
[18] Milionis A, Bayer I S, Fragouli D, Brandi F and Athanassiou A 2013 Combination of
lithography and coating methods for surface wetting control In Updates in Advanced
Lithography. IntechOpen
[19] Tay N B, Minn M and Sinha S K 2011 Polymer jet printing of SU-8 micro-dot patterns on
Si surface: optimization of tribological properties Tribol. Lett. 42 215
[20] Yoon E S, Singh R A, Kong H, Kim B, Kim D H, Jeong H E and Suh K Y 2006
Tribological properties of bio-mimetic nano-patterned polymeric surfaces on silicon wafer
Tribol. Lett. 21 31–7
[21] Singh R A, Pham D C, Kim J, Yang S and Yoon E S 2009 Bio-inspired dual surface
modification to improve tribological properties at small-scale Appl. Surf. Sci. 255 4821–8
[22] Feng L, Li S, Li Y, Li H, Zhang L, Zhai J and Zhu D 2002 Super ‐hydrophobic surfaces:
from natural to artificial Adv. Mater. 14 1857–60

[23] Wu D, Wang J N, Wu S Z, Chen Q D, Zhao S, Zhang H and Jiang L 2011 Three ‐level
biomimetic rice‐leaf surfaces with controllable anisotropic sliding Adv. Funct. Mater. 21 2927–
32
[24] Cassie A B D and Baxter S 1944 Wettability of porous surfaces Trans. Faraday Soc. 40
546–51
[25] Wang X and Kato K 2003 Improving the anti-seizure ability of SiC seal in water with RIE
texturing Tribol. Lett. 14 275–80
[26] Bhushan B and Jung Y C 2008 Wetting, adhesion and friction of superhydrophobic and
hydrophilic leaves and fabricated micro/ nanopatterned surfacesJ. Phys. Condens. Matter 20
225010
[27] Kashaninejad N, Chan W K and Nguyen N T 2012 Eccentricity effect of micropatterned
surface on contact angle Langmuir 28 4793–9
[28] Patil N D, Bhardwaj R and Sharma A 2016 Droplet impact dynamics on micropillared
hydrophobic surfaces Exp. Therm Fluid Sci. 74 195–206
[29] Nosonovsky M and Bhushan B 2005 Roughness optimization for biomimetic
superhydrophobic surfaces Microsyst. Technol. 11 535–49
[30] Bhushan B, Jung Y C and Nosonovsky M 2010 Lotus effect: surfaces with roughness-
induced superhydrophobicity, self-cleaning, and low adhesion Springer Handbook of
Nanotechnology (Berlin, Heidelberg: Springer) pp 1437–524
[31] Luo C, Xiang M and Heng X 2012 A stable intermediate wetting state after a water drop
contacts the bottom of a microchannel or is placed on a single corner Langmuir 28 9554–61
[32] Bae K J, Yao W, He Y and Cho Y R 2017 Wetting behavior of liquids on micro-patterned
polymer surfaces fabricated by thermal imprinting Korean Journal of Metals and Materials 55
624–31
[33] Li Z, Wang J, Zhang Y, Wang J, Jiang L and Song Y 2010 Closed-air induced composite
wetting on hydrophilic ordered nanoporous anodic alumina Appl. Phys. Lett. 97 233107
[34] Zhao W, Pu J, Yu Q, Zeng Z, Wu X and Xue Q 2013 A novel strategy to enhance
micro/nano-tribological properties of DLCfilm by combining micro-pattern and thin ionic liquids
film Colloids Surf.,
[35] Jonathan, L. Y., V. Harikumar, N. Satyanarayana, and Sujeet K. Sinha. "Localized
lubrication of micromachines: a feasibility study on Si in reciprocating sliding with PFPE as the
lubricant." Wear 270, no. 1 (2010): 19-31.
[36] Siripuram, R.B. and L.S. Stephens, Effect of deterministic asperity geometry on
hydrodynamic lubrication. Journal of Tribology, 2004. 126(3): p. 527-534.
[37] Kligerman, Y. and I. Etsion, Analysis of the hydrodynamic effects in a surface textured
circumferential gas seal. Tribology Transactions, 2001. 44(3): p. 472-478.
[38] Tnder, K., Inlet roughness tribodevices: Dynamic coefficients and leakage. Tribology
International, 2001. 34(12): p. 847-852.
[39] Kovalchenko, A., O. Ajayi, A. Erdemir, G. Fenske and I. Etsion. The effect of laser surface
texturing on transitions in lubrication regimes during unidirectional sliding contact. 2005:
Elsevier Ltd.
[40] Pettersson, U. and S. Jacobson. Influence of surface texture on boundary lubricated sliding
contacts. 2003. Stockholm, Sweden: Elsevier Ltd.

Wetting Behavior of Textured Silicon Surfaces-An Experimental Study 2020-2021

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Wetting Behavior of Textured Silicon Surfaces-An Experimental Study 2020-2021

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Wetting behavior of textured silicon surfaces- an experimental study 2020-2021

Micro Electro Mechanical Systems (MEMS) is a technology that combines miniaturized

Department of Mechanical Engineering, UVCE Page 1

Department of Mechanical Engineering, UVCE Page 2

Work in the field of microfluidics, thin-film technology, aerospace components, anti-corrosive,

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1.1 History of this journal paper

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1.2 Surface Texturing Parameters

1.3 Benefits of Surface Texturing

1.4 Optical lithography

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desired pattern upon the material underneath the photoresist.

A single iteration of photolithography combines several steps in sequence. Modern

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 Exposure and developing

A post-exposure bake (PEB) is performed before developing, typically to help

The develop chemistry is delivered on a spinner, much like photoresist. Developers

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It is pulsed or time-multiplexed etching, alternates repeatedly between two modes to achieve

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As an alternative to immersion, single wafer machines use the Bernoulli principle to

1.5 Atomic force microscopy

FIGURE 1. Block diagram of atomic force microscopy

Atomic force microscopy (AFM) or scanning force microscopy (SFM) is a very-high-resolution

Department of Mechanical Engineering, UVCE Page 11

FIGURE 2. WATER DROPLET CAPTURED BY GONIOMETER

1.7 Wenzel and Cassie-Baxter Model

FIGURE 4. WENZEL AND CASSIE BAXTER MODEL

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Department of Mechanical Engineering, UVCE Page 13

Department of Mechanical Engineering, UVCE Page 14

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3.1Fabrication of Silicon Micro patterns

Table 1: Dimensions and Geometry of patterns

Hallow Circle Do = 36,Di = 18 780 14 -15 45,55,65 &75

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Hallow Square So = 32,Si = 16

FIGURE 6. Schematic diagram of creating micro patterns

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Department of Mechanical Engineering, UVCE Page 19

Department of Mechanical Engineering, UVCE Page 20

Department of Mechanical Engineering, UVCE Page 21

Department of Mechanical Engineering, UVCE Page 22

Department of Mechanical Engineering, UVCE Page 23

where θw is the WCA on the

Where θc is the WCA

Department of Mechanical Engineering, UVCE Page 24

Department of Mechanical Engineering, UVCE Page 25

Department of Mechanical Engineering, UVCE Page 26

Department of Mechanical Engineering, UVCE Page 27

[9] Minn M, Soetanto Y S and Sinha S K 2011 Tribological properties of ultra-thin

Department of Mechanical Engineering, UVCE Page 28

Department of Mechanical Engineering, UVCE Page 30

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