Particlethinfilm

now dealt with

we
till
films generated by
solution Now we will study about particle
thin films On this cage we move to

dispersion and not solution

First we to discan about what happens

need
when particles are present in a dispersion
Usually when we have particles in a dispersion we

have them dispersed in a disordered way and that

is the classical view of what happens
in a
dispersion

But early simulations suggested that particles in

a dispersion are able to order and crystallise even
when there are no attractions btw the particles
themselves Earlier it was assumed that strong
attractions were needed for crystal units to
order and crystallite
A hard sphere has nearly no attraction and
a steep repulsion potential

The fact that the particles are ordering is

counterintuitive because apparently there is no
reason for them to order

ENTROPY CAN ORDER STUFF

What we can see is that if

we have a high volume fraction of particles
so't and above we will observe that there
is a disorder order transition which is
driven by entropy
Mothe particles are assumed to be hardspheres
with no interactions and no overlapping
possibility during packing

We can easily determine the entropy of a

system just by looking at how many

possible configurations the system might have

There are more ways for the particles to

ordered than to be
arrange in an way
arranged in a disordered way
 ie
whenever we have high
particle canon
a in a

solution the particle fends to arrange in an

ordered way to become crystalline

But why are there more ways to arrange in

the ordered system
This is because when ordered the
will have more independence to
spheres
move around its equilibrium position This is
not available in the disorded way and this
is called translational decrease of freedom

Hence if we have a son with a

volume fraction of particles
very high
even

if there are no interactions b w the

particles themselves Chard spheres they will arrange
in an ordered fashion

Arrangement ordered way is very

in an

useful to prepare functional materials and

hence this is a key area

COFFEE STAIN EFFECT AND ITS PREVENTION

what is coffee stain effect

If we have a solution
and if we
containing particles like a coffee

let it evaporate we can see that upon

evaporation there will be an appearance of

a ring around the edge that a droplet
farm on the surface in which the
particles are localized

the
towardsring
a post
Particles
droplet
forming
it the edge the
on to
coffee around
ready
of evaporation
surface

Formal definition solute redistribution to the 3

contact line of an evaporating sessile drop
How does the coffee stainCoins effect happens
It happens due to capillary
flow

I NI
Note that coffee ring is not necessarily
in any
present in circle shape It can be
complicated shape depending on the shape of
droplet It should assume the projection of
the 3D shape of droplet dispersion

9
Enample
coffeering
effect

COFFEE RING EFFECT IN DETAIL

 c you are drinking coffee

I the coffee spills on a

glass surface
say there is a small drop of the
coffee on the surface

I this drop can be considered as

a dispersion A dispersion with many
particles in it But since dispersion has
a liquid in it and there is enough
it the liquid will evaporate
energy around

41 As the liquid surrounding the particles

evaporate the particle moves within the
dispersion The evaporation flan is always
a constant
flux
evaporative
lightface
So as said the evaporation forces the
particles to move As the particles move they
have certain velocity
a we can

measure this velocity using an instrument

called MPIV Micro particle image velocimetry
6 Where does the particle more The
particles are always seen to move towards
the edges
On the initial phases of evaporation the
particles have a constant velocity
But as the volume of liquid in the droplet
decrease thereby increasing the volume fraction
of the particles there is a steady increase
of particle velocity as measured in MDIV

Now two questions arise

Al why do the particles move towards the edge
The evaporation rate the edges
Contact line is higher Hence there is a
particle transport towards the edges

a why does the velocity of particles increase

after a certain time
The velocity begins to increase
as the droplet becomes thinner
The velocity increase is due to MASS Conservation
As the droplet shrinks an increase in velocity
is needed to maintain the evaporative Hun
 In
v2

where r velocity of particles

h drop height

this velocity varies along the radius of the

droplet and time t

Trait
Feet frail't'd
Tat
remember

Here te is droplet ending time

so as time the ending time te

approaches

Ver increase rapidly and diverges lie it

becomes infinity
v
higher position
with
I mean
higher v varies
hence
heal height of droplet ans local point distance r
fromcentre
U alt velocity that point
in
Derivation given
Refer
pased

what is the consequence of this increase in

velocity

Initially when velocity was lower the

particles moving towards the edges had
enough time to slowly arrange themselves
in an ordered Crystalline array But
as velocity increases the particles arrange
randomly without order because of lack of
time to arrange

disordered
odd

g
 If you ever spill a drop of coffee teal
almost any liquid with something suspended
or dissolved in it you will observe the
coffee ring effect No uniform stain but a

ing shaped stain darker around the edges

Why do we end up with more particles

in the edge than the middle

Let us try to explain it in detail

Lets first understand the material we are
working with to try and learn more about it
so lets understand what coffee is comprised
of

When hot water is poured to the

coffee powder the hot water enters the
coffee ground and extracts oils and other
small molecules from them and then these
oils are what gives flavour to the coffee
The powder remains which is usually filtered
away
But oils E water do not mix Apparently
this is not true in all cases and oil
 and water in coffee is technically a
solution But it cannot be called a solution
in all retrospect There are some oil
drops that are stable and hence coffee can
also be called an emulsion It also
has unfiltered particulate matter which is why
it is also a suspension coffee is really
a solution emulsion and suspension

To understand how the particles end up at the

edge scientists used a suspension of colloidal
particles to study it The colloidal particles are
micron sized plastic spheres this sample is
very much like our coffee

Note that these particles are small enough

That they follow any sort of flow that
is present in the drop as it dries
So they trace down the trajectory of the
water molecules surrounding it But at the
same time they are large enough to be seen
through a microscope

The scientists took a droplet of this

suspension put it on a glans slide and then
 s p mi I l g
they let the drop dry

The first thing they noticed was that the

edge of the droplet became darker and then
finally the edge deepens

They observed that the colloidal particles

are pushed from the middle of the
drop towards the edgesby some force What
was responsible for it why are particles
pushed

The reason is pinned edges and surface

tension
A

Ij n what surface tension is first

Surface tension ultimately comes from the

fact thatSo molecules
are cohesive in
nature they are attracted to eachother
and would prefer to sit very close to
each other
 manga
58888 8 87
molecule is
the
surrounded by hence
molecule and
same energy
stale
ishappy low

molecules
that the
what happens
is inside the
will try to goideally the
in the surface and hence to a surface
bulk of the liquidsettle down lowest
may
will has the
liquid which
shape 3D shape
spherical among any
area ud

But water molecule doesn't rest on a

surface like this

 But instead it rests like this

This is because its not only the

surface tension that matters but also the
adhesion of molecule to the surface
Depending on the infraction the contact
angle can be different
so Lets say this is our colloidal
suspension on the surface

what do you think will happen to this

as it dries

we might think well it evaporates so

the volume goes down and hence the
diameter will go down as well

But in contrast it does not happen

like that

On all cases the edges of the doop gets

pinned which means it does not
move as the drop dries why does that
happen
It is still a mystery in physics Scientists
know that they arise due to a variation
in the wettability of the surface which means
some parts of the surface likes coaler more than
other parts But still there is a lot of
mystery about the enact source
Since diameter is pinned evaporation take
place like this

But as we can see here the edges

has a lot less liquid when compared to
the sides so isn't it supposed to decrease
in volume such that the edges should
flatten out before the middle does

mind Onstuicker
fakrarporation

on that case the droplet should look

something like this

gscrameg
 egg
shape
Ssc

But it does not look that way but it

looks like the one shown before The
season is surface tension

In the fried egg shape would increase the

surface area and the molecules in the
middle would push towards the edges to
minimisethe surface area As it moves it
carries the colloidal particles towards the
edges This is what causes the
coffee stain effect

the

Ii
According to Deegan et Al there are three
requirements for the coffee ring effect

at solvent meets the surface at mon zero

contact angle It must be drop

E
Contact line is pinned to its initial
position

I the solvent evaporates

According to Deegan the evaporation is

faster the edge so liquid must
flow in to compensate Another explanation
can be made using the concept of
surface tension
That
utter famille'd
tougher
Here R radius of the drop
constant as contact line is fined
in the
as any random local point
radius

I Man flux

V on a and t
Note depends

V varies with a because I is different

different positions v edges is higher
 Herent I
to compensate for J

DEWI

JCA Evaporative flux any local point

a distance h from the centre of the
drop
her height the corresponding point
al flow velocity

Note that the evaporative flan Icr reduces

point 9
the height her every

At perimeter all liquid will be removed the

droplet would shrink but the radius of the
drop cannot shrink as the contact line is
pinned To prevent shrinkage liquid must flow
outwards

hat must reduce such that it maintains

the spherical cap structure

I to
maintain
shownwifn
the
him volume
for the removed
cat be
spherical must difference
stripe time
in At to be centre
volume
removed
every
S
But
volume
14g
removed

Evaporation is higher in edges and volume

ten too so to
to be removed is
make up there is a radial flow from
inside to the edges This flow velocity is V9
Of Ja is known Va can be calculated

a depends only on the shape of the

drop

het 46 be vapour canon profile responsible

for diffusion of vapour to air

so IGI D TO
D Diffusivity
04
Inte 8

hea must be constant to

V a

maintain constant Jcr

constant Jcr because same shape of
droplet

As Este

heal decreases to zero

so veal must increase rapidly to maintain
constant Jcr

my
 tater fair
i_

which scientists fend to avoid

However there are a few where the cuamples

was enploited to make functional
phenomenon
materials

coffee'Yingfetiet was to have inkjet

employed
water dispersion of carbon nanotubes
printing of
a

that can arrange on a surface like this

 H sing
coffee
overtaking

we get
do
How

The droplets are initially dropped as first lagers such

that a coffee sing of the following mature

forms

0 0 0 0
drying
Then a second lager is deposited on top after
so that they remain in touch with eachother
and staysconductive

00000
So basically the carbon nanotubes in the water
dispersion arranges an shown above to foam
coffeeringsand create a conductive surface which
is also transparent
There is 81 t transmission best
so we get a transparent conductive film
Conductivity 1560hm sq average respectable

EXAMPLETO Low cost tapwater fingerprinting

Coffeering effect exploited to
was

differentiate btw droplet of water coming

from different parts of the university

what did they do

Water coming from different areas may contain different

mineralconon
they developed a method that combines the
coffee ring effect with crystallisation of the
minerals present inside the water to easily
identify where the water was coming from

As we can see all the droplets look

ii The applications of coffee ing are

we always prefer uniform distribution
very limited and
film and hence we need to find
of particles in
a

ways to avoid coffee ring effect

We can suppress the coffee sing by usually exploiting

the Marangoni effect

 MARE ONIEFFECT
The Marangoni effect
the
refers to a transport phenomena found in
surface of liquids due to difference in surface
tension Marangoni flows
are from regions
of low to region of high surface tension

Eg Take some water in a plate and

some small piecesof paper on top of it
put
The paper floats on the surface due to the
behaves
high surface tension of water which
as a strong blanket a blanket so tight
that all molecules try hard to stay with
each other stretched with a strong contractive
force

blanket
a

surface
fam
Now drop small drop of soap
a

solm in the middle

SOAP is dike water

not It has a
lower surface tension Means the molecules
in soup doesn't want to be with eachother
as much as water'd
Chishersythion
contractile
hitter

ta

drop
s p on a
 d I
soap
Clogalfacetonical
on
É
clower

There is an immediate flow due to

contractile force which
a net higher
propels the soup
molecules from lower to
higher surface tension and eventually flow stops
when they min with eachother

contractile
face
A
set outwards

Another Example of Marangoni effect is wine tears

 Wine tears looks something like this

Wine is somehow seen to crawlup and

drip down like unending tears
what is happening
At the thin film where the surface of the
glass is wet by the alcohol there is
quick evaporation of alcohol forming a
watery mixture this film hence has a
higher surface tension than the bulk Hence
there is a Marangoni flow from the
bulk of the wine and up the glass Then the
tears are constantly fed

Roughly speaking surface tension can be

thought of as the amount of resistance a

surface has towards deformation

Surf la I l

stfu fi
na Ét s

to

I
contractile

Meagher

Hateabm

This demonstrates Marangoni effect

some ApplicatingMaragoniethet

Drying of Silicon
waters after wet processing
a

step
wet
An alcohol vapour is blown to a
surface This leads to a surface tension
 I
gradient which allow the liquid to pull off
completely The alcohol essentially pushes the water
outside

a Crystal growth

of man transfer
Improve the performance

To improve MT surfactants
are added on the surface of the supporting
liquid to induce artificial Marangoni
convection
By of surface tension b w
imbalance

the spreading and supporting liquid the Marangoni

convection is resulted

Artificial Rain

I goniefectinanevaporatingdooklet

Iitfeapitates it undergoes

evaporative cooling this evaporative cooling

causes surface tension gradient due to tempgradient leading
to Margoni stren
It
I So it is not necessary to add soup anything
happens naturally
 Using finite element analysis it is possible to
distribution in the
determine the temperature

droplet due to evaporation

Contact line radius mm

of drop
0.364mm
initial height

when contact angle 400 early times

Decreasingtemp gradient along the height
temp top 2 temp bottom
long conduction path from bottom to top makes top cooler
Cii Increasing temp gradient along the radios
edge temp centre
temp

When contact angle 100

Ci Decreasing temp gradient along the height

temp top L temp bottom

No change with contact angle

 Decreasing temp gradient along the radius
Cii
edge L temp centre
temp
Reversaltake place because longertime higherevalrate lower
Ht
Reversal in gradient is observed

So we can say that as t 9 contact anglet

and there will be a reversal in radial temp
does it occur
gradient Why

At early times the longer conduction path from

the bottom to the top makes the temp
lower the top than elsewhere

At longer times contact angle 100 the faster

rate of evaporation the droplet's edge
makes it cooler there

Ist gradiatindroplet
called Marghoni number Ma
There is something
Ma a T
surface temp
At higher contact angles hisher
higher Marghoni number and there will be
presence of
recirculation

C
 At lower contact angles as evaporation progresses

the surfacetempts lower Marghoni number and

there will not be any recirculation

As soon as the recirculation disappear the

velocity vectors point towards the edge enables
effect
Marangoni the
back to the
suck
to back
particles
centre

Waffarasonistnonvelocitfield
With Marangoni siren the difference
radial direction
in velocity is observed in
considerably

At lower contactangle the Marangoni number

recirculation and
is low or negative so ten
I
 all velocity vectors point towards the edge
and the fluid motion is towards the edge

go any condition the Margoni siren will

have this velocity vector that pushes particles
towards the edges

Suffren the Marangoni stress

comin of surfactants can
Ting radial surface velocity produced
greatly suppress the
by Marangoni siren
can
so presence of the surfactant
suppress

the Marangoni effect

Noted
Overall we can say this

I flow
higher
the
eraparationogatgelocity
pushleft ege
to
 Il dropletd d Effect
evapYatin
But
a
honk
He
sort y
has

my

i
É

Hence overall Marangoni effect prevents

coffee ring
H
But is contaminated with
water
if the
is
surfactants the Marangoni effect
suppressed because it supoen the radial
velocity recirculation
 H
Hence surfactant contamination must be
avoided

Consider

Forms coffee
ring No coffee
ring
H H
Because Marangoni flow Here the Marangoni
is suppressed in water effect is so strong that
due to small interface we can see an inverse
contamination which cannot coffee ring Buildup of
be avoided
1 particles in the centre
ANOTHER STRAIGHTFORWARD WAY TO ELIMINATE
COFFEE RINGS INTERFACE CAPTURE

This is a straightforward method

more
We eliminate the cause that results in coffee
ring
As we know the primary cause is the faster
evaporation rate the edges leading to
internal flow of liquid from the bulk to the
edges to compensate for the losses

If we can raise the temp of drying thereby

increasing the evaporation rate such that
the interface shrinkage rate is higher than
the average particle diffusion rate the
particles will remain trapped the interface
and will not get enough time to migrate
to the edges thereby eliminating the
coffee stain

low
eraplemp

capillary flow
 f

ratewill increase
The faster evaporation

the interface shrinkage rate And as evident the

migrating particles in
vertical evaporation path will

get trapped in the descending interface The

trapped particles behaves as quasi solid layer
a

high comin of solid in liquid that it behaves

as a solid false solid this prevents the
capillary action from pushing the particles to the
edge

Thetevaporation temp larger to induce a

must be
uniform distribution of particles in the drying region
At lower evaporation rates the surface shrinkage
rate will not be large enough to trap all
the particles such that a continious film will be
formed The surface shrinkage rate must be
very large so that most of the particles will get
trapped
Mathematicalenfanation
When interface descending rate particlediffusion rate
No coffee ring

When interface race

descending particle diffusion rate
coffee ring present

Interface shrinking rate Vi

where he original height of droplet

tf total time required to dry

Particle diffusion rate Np 2

ME
where D Diffusion constant
6k3gr
KB boltzmann const
T temperature
viscosity of solvent
N radius
9 hydrodynamic
this study 400C the
tranation occurs But it depends on
Gn
the size of droplet and humidity
So
of the environmenttransition tent
we should determine
experimentally
 Must read

vertically evaporating
liquid carrying particle

ANOMERMETHODqsopp.es
CHANGING THE
rinI i
SHAPE OF PARTICLES USED

In thisstudy it was observed that the

particle shape greatly influence the ability of
the particle to resist the outward capillary
flow that pushes the particles towards the
interface

Hence the experiment was carried out with

different shapes of polystyrene particles 2 1 to
2 3 5 in water
Here a
Ianis
mmk.to
when 271 the particle is anisotropic

The researchers that

anisotropic particles
found
have resistance to outward flow and will
uniformly distribute on the substrate after
drying

why does it happen

As we already know the outward capillary

flow what is responsible for coffeering pushes
particles towards the interfere and edges

when anisotropic particles Cx 1 reaches

the interface they are able to deform the
interface This deformation will lead to
strong inter particle interactions The strong
interactions will lead to the formation of
loosely packed structures agglomerates the
air water interface thus enabling the
formation of a quasi solid lager Thus
the quasi solid nature will prevent the
edge and hence
particles from reaching the
will ensure uniform distribution
dl
 Anisotropic particles get readily interface
trapped more
due to their aspect ratio a higher exposedsurface

int
Under appropriate conditions it anisotropic particles
are mixed with spherical particles it can
still ensure improved uniformity during
deposition

ME
At interface
interaction between 2x interactions b w
anisotropic particles spherical fartides

Why agglomerates radial capillary flow

resist

The energy required to break move the agglomerates

formed by anisotropic particles the interface is
fairly large Hence there is very ten mobility for
such particles

Surface viscosity Bulk viscosity due to

agglomeration interfere leading to larger
resistance to outward flow
what is the issue with spheres

spherical particles on the other hand cannot

deform the interface much Thus they continue
to be pushed to the edge

anisogatiicles
Mt sphericalarticles

whom
body
I
crafting
I
fgnanda

agatteach
edge
amassed
are non crystalline
the

solids not agglomerates gets

that are
interfaceand
organised in
a
stuck uniform
definite lattice pattern hence enables
in the
distribution
body
 Canisoloopity
Clearly as 29
the
uniformity
increase increase
density also
in the
suppression
of
coffee ring

Pmax density edge

density centre
Smild

a major reasons
so we can say there are

II agglomeration toted
Cii interfacial trapping
gym
M
it e

yummy

deform
Imminent
not
spheradoes Yffmains
and
 an
sphere

toeds9iloe
imy.gl anpsdropMoweN

infested

particle dimensions
i
because particle dimensions
can greatly effect the functionality of the
formed thin film

One another method to suppressthe

coffee rings is the use of Acoustic waves

typically 10MHz

Seth
SAWS Surface Acoustic waves can be

generated using an interdigitate d

transducer This can be connected to a
superstate and the droplet can be
allowed to evaporate on top of this surface
This is represented in the figure

what happens
We already know there is an internal
capillary flow that causes the coffee ring
effect the flow can be traced as standing
Capillary waves

As soon as SAW is applied there will

be simultaneously standing acoustic waves and
standing capillary waves in the droplet
The intersection of these waves are called
Nodes The particles get trapped in the
nodes and thus cannot migrate towards the
edge

trapped
since there is absolutely no transport of
the the contact line
particles towards edges

on pins and recedes away

canon
particlepatch
a
At form

IIÉÉ
we can achieve the same

result as above
by applying an
alternating
current instead
So an AC is
given to the substrate Hence
the substrate used must be conductive

AC avoids pinning of the droplets and hence

there will not be a constant contact line
This will prevent the formation of coffeering

The suppression of coffee

ring is due to
reasons
two

4 The AC prevents contact line from pinning

The AC generates internal flow fields
against the capillary flow generated due to
evaporation

when the current is applied we can see

that the droplet shrinks meaning the contact
line gets unpinned
the particles remain in the shrinking liquid
and is still not deposited on the surface The
droplet will keep on shrinking and will
eventually lead to deposition of the particles
centre of the droplet
just in the
The results show that the enact opposite of
coffee ring effect fakes place here The entire
particles are now deposited uniformly in the
centre

By tailoring the frequency of Ac applied it

is

also possible to tailor the density of deposition

ME
Electrowetting means the modification of
the wetting properties of a surface by applying an
electricfield This is the reason why the

contactlineuntin
 COLLOIDAL CRYSTALS
Colloidal crystals are mono dispersed colloids
in which the colloidal particles organize themselves
in long ranged ordered crystals monodispersed
colloids are colloids containing particles of uniform
size

OPALI
Colloidal crystals are also called
opals
colloids
Opals are self assembled monodispersed
spherical

with a long range order

Opals have unique properties in terms of light
propagation Hence it finds application in

optical devices such as photonic band gap

crystals

Colloidal crystals also called opals fair

and
are the best
inverse structures inverse opals
candidates for photonic bandgap materials

Fabrication of Opals are cheaper than

semiconductors
semi con loss

Optical properties of opals can be easily changedby

Changing the size of colloids
cii changing refractive inden of
colloid q
surrounding medium
Ciii Changing the periodicity of lattice points

The challenge is to fabricate a large

flat and uniform opal film which is
considered ideal for all the applications

How to manufacture opal films

There several methods Researches are
are
methods that can
going on to develop
films
give large flat and uniform opal
C DRYING ON A SOLID SUBSTRATE
the most convenient method is drying
on a solid substrate But this method
will not be able to form a uniform
flat opal film on a flat substrate
 is
Of Flat substrate

Hydrophobic Hydrophilic
I water lovingsubstrate
line
shrinking contact y
during drying contact line
pinned
H
H
Shrunkopal film
coffeering
formed
EVAPORATION ON VERTICAL SUBSTRATE
Extension of coffeering

We learnt in the coffee ring

effect that there will
be an ordered arrangement
of particles the
drying front if sufficient
time for ordered
arrangement

is given this will lead

to crystallisation
is the
For a drying droplet the drying front
edge of the droplet so the deposition occurs
 the edge

But in the case above drying front is on top

of the som Meaning top has the highest

evaporation rate So when substrate is
a

dipped depending on the hydrophilicity hydrophobicity

of the substrate the meniscus can move
up down
the solvent evaporates and deposition occurs

However there is a drawback for this

We know that the evaporation front is the

surface of the solvent and deposition
occurs throughout the surface of our
substrate as the solvent surface moves
down during evaporation But this can lead
to difference in particle comin top g
bottom leading to mom uniformity

POSSIBLE SOLUTION
Automate the deposition such that the
substrate is pulled off a detuned
speed
 In the method the concept of coffee ring
is extended such that the localization takes
in the flat substrate instead of edge
place

can
evaporation their

offstage

So for proper deposition either

the liquid must evaporate the substrate must

a
off
be pulled
a solvent must lower
level stage by stage

I
 t
H
Not desirable c Betterton
t
to
Hiatt interface

comin

Noth wemust allow it to evaporate slowly

so that they can get enough time to
arrange and crystallize

Usually Opals have a hexagonal lattice

t
Opal can out of any colloidal particle
be made
as long as they are spherical
The most common is Silica It is easy to

prepare silica particles

or
polymers mainly PS or PMMA

of the size of the particles used to prepare

OPAL is comparable to the size of visible
light we will see the appearance of
a structural colour

Uniform color in an Opal suggests that

the particles are uniformly arranged and are

of similar sizes

OTHER EFFICIENT METHODS TO DEPOSIT PARTICLES

HASURFACK
a ELECTROPHORETIC DEPOSITION

Most deposition methods that involves solvent

evaporation template directed crystallization natural
sedimentation etc are very slow processes The
low formation rate is a key issue in man production
Recentlythe EPD has emerged as a promising
candidate for rapid colloidal crystal film fabrication

Principle The migration of colloidal particles

in a liquid under the influence of
an

electric field and its subsequent deposition

on an

electrode

Thesubstrate is placed inside the electrostatically stabilized colloid

the charged particles The particles

suspension having

will flow to one of the electrode and

arrange on the surface

Why EPD
d No expensive equipment
to
hen time consuming in comparison
 Chemical and physical methods
Easily adaptable to changes in substrate
shape electrolyte composition

MgÉm powder processing

electrophoretic deposition we
For
needto have a suspension The first process is

stabilization of powder

StepI Electrophoretic deposition

The rate is found to
deposition
depend on the voltage used and time for
deposition so it is varied and studied
to
the ideal combination It also depends on the
find anode
angel dist btw cathode g

and the suspension with particles

i
to be deposited
 Catefelectrode

Inededanodel

used a
As shown in the figure they have
down to up coating process This is because
up to down approach can result in
agglomeration

The vertical design of

electrodes
prevents agglomerates
on the coating surface

Range It is the distance btw the cathode

In Com
and anode this case range

Powderprocening

d Sedimentation tests
 sedimentation test
is very important for
powder drocening The particles must not
sediment during deposition Based on the
colloid G liquid certain additives are
added to prevent sedimentation and ensure
stabilization
Surfactants are added in 5m02 Acetyl
eg
acetone to stabilize it from
suspension
sedimentation till 24 hours oo
till thou
Ultrasonification can stabilize the suspension

For electrophoretic deposition prevention of

sedimentation till 10 15 mins is sufficient

Determine particle size distribution

After this particle size distribution is
determined using Dynamic light scattering
This will give the particle size

Deposition is carried out

different ranges voltages and deposition times
 The yield of deposition glowis
determined and the optical conditions are

obtained

changing the deposition time range voltage we

By
the substrate
may control the coating lager on

41 Thermal Annealing Sintering

is done
a high temperature to increase mechanical

strength

ElectrodeMaterial

Platinum is generally preferred for the following

reasons
conductive
it highly
 it ghly
ill Resist high temperatures

AMLI.IE
tophaetic
colloids
deposition to deposit
IT 02 nano on electronically conducting

glass
Usingthe method it is possible to
obtain thick homogenous films suitable
for photovoltaic applications

The good thing about this method is that

it is cheaper when compared to other

Colloidal monolayer
ÉA monolayer made out
of colloids
To obtain this we
assemble colloids on the
air water interface
We will have the monolayer arranged in the
air water interface similar to what spherical
particles do the bottom of a bucket
 Inside the arrangement we can find different
features

boundary
Bluecolor
car dm
while missin cand
redcolors sphere
vacancy ya
gmisains

be willhexasend
There will we
where packingently
Areas packing
Fcc two
perfect good
have there
packing the arrangement

aniern

FABRICIONOFCOLOIDALMONOLAYERS

There are Many methods to fabricate

colloidal monolayer
 Colloidal crystals are having great potential due
to the ability of colloidal particles to arrange
in a symmetric way
Colloidal monolayers consist of a single layer
of colloid Instead of the 3Dimensional arrangement
as seen in colloidal crystals the colloidal
monolayers are 2D

Colloidal Monolayers find excellent applications

lithography can be
in colloidal lithography Colloidal
used to fabricate nanostructures This is way
cheaper than photolithography electron beam lithography

However the resolution achieved is smaller

as of now but still comparable

to fabricate complex it is
nanostructures

important to have non closepacked colloidal

monolayers

what are non close packed monolayers

Here the colloidal spheres in
the 2D arrangement are a distance
from eachother
 How to obtain non close packed colloidal
monolayer

Firstly weshould fabricate a closepacked monolayer

There are several methods to produce closepacked

colloidal monolayer Based on the method the
are classified into two
fabrication techniques

d Direct assembly on substrate

I reassembly on an interface followed by
subsequent transfer to a substrate

I Directassembly

This talks about all the techniques

deposition we have used so far It includes
of
evaporation induced assemblyor like horizontal
deposition vertical deposition rotation induced
deposition like spin coating etc
But there are drawbacks for these methods
when it comes to formation of monolayers that
are uniform flat And large

These methods doesn't give precise control to make

the deposition monolayer
 is
The evaporation driven method
susceptible to coffee ring effect leading to
non uniformity

1 The spincoat is fast and reliable but

the rotation hinders larger
coats

An ideal colloidal monolayer is expected to have

the following properties
41 Flat
1 Uniform
No multilayer
vacancies
41 No cracks
Large area
I cheap

This where the indirect artembly comes into

picture

Preassembly of monolayer On interface followed

by transfer to target substrate

The dareassembly of monolayer is done on a

 parent substrate and then transferred to the
interface of the subphase by immersion or
other technique like injection is done
any
to carefully bring the colloidal monolayer to
the interface
Sodium dodecyl sulfate can be used to promote
crystallisation interface

Now to transfer the monolayer from the

interface to the target substrate we

can use Langmuir Blodgett method

Blodgett method is
The drawback of Langmuir
the crystallisation process is too slow
that
commercial man manufacture
for
The fastest way to transfer this to a

target substrate is by immersing it in the

subphase and slowly picking upthe monolayer

ME
The monolayer can be transferred from the parent
substrate by slowly tilting the substrate the
interface 450angle

I
Is there any other method to transfer mono
lager to the air water interface

Themethod used here in FAU is with the

aid of a Cogstalliser

We add PS Silicaparticles to it using

different techniques usually slow addition using
injection etc
The particlesdo not go into bulk and
localize in the interface as they are
attracted the air water interface

A glass slide can then be used to scoopthem

out Upon drying a structure color
can be obtained

I How to convert closepacked monolayers

into non close packed monolayers
a Mechanical elongation of the substrate
or

Expose the close packed monolayers to

lead
plasma The plasma exposure will
to shrinkage of the particles and hence they

become loosely packed

I Not
We should use Langmuir blodgett method if
ordered
we intend to transfer in an
way or controlled way

Example good monolayer obtained using

of a
Langmuir Blodgett SEM image

vacant
one
only space
 only sp

Using such monolayers we can prepare different

materials by exploiting the monolayer assembly that
already have

Ectualcontrol
AI Non close packed Monolayer fabrication by
etching

As said earlier non close packed

colloidal monolayer are excellent candidates to
fabricate complex nanostructures with very
good resolution
such monolayers can be used as make to
force deposition of particles and to generate
The nanostructures
eg hold can be allowed to evaporate onto the
non closepacked monolayer and then the colloids
can be removed to reveal the nanostructures
The same can be done an angle say
300 to develop other types of nanostructures etc
 etching
discussed etching is carried out
As already
certain power
by using Plasma of
a

a certain flowrate for a certain duration

of time

From results of Vogel Lab

e Plasma power x etching rate

Sow Plasma can produce more etching than
15W Plasma

Orflowrate
Both have
a
etching
Linear
dependency
Lower flowrate is desirable

The etching rate depends on the type of colloidal

particle used

Polystyrene Ps lower etching rate

has a

due to the stabilty provided by the ring

structure
PMMA has a higher etching rate at H
so high difficult to control that it is not
used for colloidal monolayers

stabilityg the colloidal

particle effete
4 Etching gate differs with the substrate used

Insulator substrates will accumulate

charges and
and will repel like charger in the plasma
and hence will reduce etching rate

a semiconductor
Higher etching rate in
like silicon is higher than Glass 5102

etching time vis shape of colloids

e

As we already know as the

colloids
etching process proceeds the spherical
get smaller 9 smaller q stops after
a

certain point
when we look the image from the top
there is no change in shape

However the etching is seen to be not

isotropic when looked from the side

As the etching proceeds beyond a certain

time the spherical particles will turn into
lentil like Structures

lentil
O My
sphere

Ideally etching should be

done until

Final dia
Initial
overall three important aspects must be
taken care of while etching
Things to be taken care of daring etching

1 The diameters of the particle must

decides
be precisely adjusted because that
the geometry g nanostructures

2 The arrangement of particles must not

be hindered to ensure tons range order

Theshape of particles should not

be compromised Spherical particles give
mantmann flexibility to colloidal lithography

9f.tn
ttiscomtromina
Limitation in interparticle distance

Both then limitations are overcome by

the neat method

Non Close packed monolayers using core

shell particles
 This is another method to obtain Non
close
use particles that
packed monolayers We can
have core shell around them to obtain a

Mon Clore hacking

Here we start with particles having a

cone shell around them then we compren them
in a Langmuir Blodgett and we
can obtain
and upon removal of the
a film this way
organic lager we are left with partners on
a

substrate which can then be used for

further processing

Once deposited on the surface the

polymer shells can be removed by
heating This leaves us with
non close packed colloidal monolayers
on the Substrate

Idf
Mang application requires non closepacked
monolayers
Pre assembly of the colloidal particles in
close
oil water interface can provide non

packed monolayers but transferring this to

our

target substrate is not possible without

altering the ordered geometry due to the
capillary forces acting upon drying

Non hexagonal monolayers by soft

repulsion potentials

Typically the monolayers are hexagonally

packed structures but by playing with the

way which
we scoop
up the particles based on
the way we compress the particles we can
have different types of arrangements

In the research work mentioned we

start with colloidal suspension and using

hydrogels it is somicated so that
it have an organic shell around it

i
 sons

Now compressing them with different degrees

by
of compressions we can see that we can

actually observe different geometries in the

monolayer as shown below

Iv

arrangements

Chaika or Line t
we can arrangement
getnongeons
 All these are manipulated using Langmuir
Blodgett

The soft repulsive shoulder refer to

the hydrogels

The soft repulsive shoulder microgels

have attractive interactions with eachother

The combination of attractive microgel microspore

and microsel microsd interaction lead to
the formation of a microgel corona around
the microspheres interface

The complex phase behavior observed in the

presence of microgel can be attributed to
change in geometry as it is not observed
in the absence of microsd
4 Non hexagonalpacking of monolayers by
asymmetric stretching

Asymmetric stretching can be used to obtain

particle arrangements that not hexagonal

are
Hexagonal Non close
close packed packedmonolayer
monolayers of any geometry

The method is described below

The readily accessible hep hexagonal

close packed monolayers are transferred
to the air water interface
Now duringthe process of transfer
of this layer to the target substrate it
induces a controlled purely one
dimensional stretching of the hep
array leading to a variety of
symmetries depending on the transfer
angle and degree of stretching

ME
How to make hydrophobic substrates
 By glass slides with
Shin coating
PS or PMMA

Followed by Annealing 2000C fg

S min

Not
We can confirm the transfer of
monolayer on to the air water interface
with the presence of intense iridescent
colours

The use of asymmetrical stretching to

obtain mon close non hexagonally packed
monolayer is represented in the figure
below
 As evident

The monolayer the air water interface

is perfect hep which is easy to make

The target substrate is hydrophobic in

nature It is dipped an angle and
since it is hydrophobic the meniscus
fall below the substrate surface leading to
a one dimensional any metric stretching

The transferred particles can be immobilized

on the substrate by thermal adhesion

A variety of arrangements can be obtained

based on the stretching factor s and
stretching angle B

The different monolayer arrangements

are given below
 hexagonal centred Oblique
Square rectangular

Complex tessalations from Multiple

depositions

Using multiple deposition cycles it is

possible to obtain very very intricate patterns

The idea is this

Two one dimensional hexagonally packed

monolayers of identical spherical particles
adsorbed a liquid liquid interface
can assemble into a vast array of
micro patterns provided that they are
immobilized into a solid substrate
one after the other
 on H
The first monolayer retains its
low energy hexagonal arrangement
and will act as a template on
to which the second monolayer
is forced to rearrange

The frustration bio the two lagers will

lead to the formation of symmetries
that would never have self
assembled had it been done in
a single step

Using this method we can get

even complex structures
more like
rhomboidal hexagonal herringbone
etc Not just simple rectangular honeycomb
lattices

monolayers of
A Always

different packing fractions

are combined
 COLLOIDAL MONOLAYERS
STRUCTURE TO FUNCTION

Once we form a monolayer on a

substrate we can actually use it to
prepare interesting materials

so we are not limited just by using

silica spheres polystyrene spheres but we
can use them as templates and create
manoporosity we can use them for
colloidal lithography to obtain nanostructure
we on them as a template to deposit metals
and form nanostructures we can also use from
as a mask for eleaing q form nanowivet
VCOLLOIDAL
TEMPLATING E NANO POROSITY

In the research work

Colloida templating was used to
design transparent nanoporus surface
structures
 NANOPOROSITY

i
a

How to create Nanoporosity using colloidal

templating

There are many methods One approach is

to backfill a colloidal monolayer using
a silica precursor to form an

inverse replica that will serve as a

ponces layer
In brief the colloidal monolayer is
assembled the air water interface and
manually transferred onto a solid substrate
 Over this lager silica sol gel precursor
a
is spin coatedThe template colloids are
then burned off by calcination to
obtain the inverse monolayer architecture
Cie Nanoporous material

what can we do with nanopcsa materials

We can do many things we can modify
surface properties
d to make the surface repellent
a lubricant
After fabricating the nanostructures
can be made to lock into the structures
and it will eliminate the pinning
of a second liquid applied to its surface
leading to efficient liquid retellancy
Surface can be made liquid repellent

2 To control surface wettabilty

The simple nanoscale architecture

of the nanopines material fabricated from
colloidal monolayers will give us the
ability to tailor the macroscopic welting
state

We use certain chemicals to functionalise

the inverse monolayer to improve wettability

For intracellular delivery

Nanopera materials are promising

for high efficiency high
platform
viability high throughput intracellular
delivery

The monotones are laser activated

and used for drug delivery

COLLOIDAL LITHOGRAPHY
i NANOSTRUCTURES

has emerged as an interesting

Colloidal lithography

approach to create surface nanostructures in

a cheap and simple fashion

b
 The approach takes advantage of the possibility to
colloidal particles in an order d
arrange
across areas and we can then
fashion large
to create
employ direct evaporation etching
complex nanostructures from the shadowing
effect of the colloidal spheres

some commercial applications of colloidal lithography

we can manufacture chiral crescent

Chiral plasmonic nanostructures are useful for

chiral sensing
Fabietmethodylosy
SttAssembly
We first the colloidal monolayers
assemble

using any of the method we studied whichever

is suitable convenient
The monolayer will always assemble as a
low energy hexagonally closed packed 2D
surface

SIZEREDUCTION
The monolayer has to be made
mom close packed This can be done with any
method we already studied Here plasma
induced size reduction is used

3 Silica deposition
Silica is deposited on the
in a direction
non closepacked PS monolayers
with azimuthal aisle 00

4 evaporation of gold to the surface

This
is done with a

rotating azimuthal angle azimuthal angle 7807

 Directedphysical ion etching
All materials shielded by
colloidal particle stays and the others
the
are removed

Removal of colloids
1 removed
Now the colloids
are

to produce the chiral single crescent array

3 COLLOIDAL ETCHING NANOWIRES

What is colloidal etching

What are nanowires

structures of
Nanowires are
materials having turdenen and diameter in
the nanoscale and an unconstrained length
 Eg of Nanowire Silicon Nanowires

Silicon is a very important material on the

semiconductor industry
If silicon is fabricated as a nanowire it
can become much more versatile By
and
playing with the thickmen diameter
spacing of such of Silicon Nanowires
we

will be able to tailor different characteristics

in say light absorption electron hole recombinational

hydrophobicity etc

But how do we tailor the diameter spacing

in nanoscale
We have to etch parts of the nanowires
But how do we do that
There are several methods but depending
on the resolution method will change

Above 400mm Photolithography

Below 400mm electron beam lithography
 Here electron beam lithography needs
sophisticated equipment and hence is
expensive It is also slow

colloidal lithography can be used instead

and it gives a range till 100mm

Solloidal lithography can be effectively

used to carry out etching colloidal
etching on nanowires to change its
diameter thickness or spacing to manipulate
its properties functionalities

Not
How are Nanowires fabricated

There are three common methods

11 VLS Method Vapor Liquid Solid

This method gives a lot of impurities

Ii Reactive ion etching Needs a clean environment

Ciii MACE Metal assisted Chemical
etching
Here Metal acts as a catalyst to
onidise the silicon material to be etched

so a lager thin film of the metal is

deposited on the silicon material first and
then dipped in the etching son that contains
the onidising agent

M
so MACE t Colloidal etching together can
give the best resolution for vertically
aligned silver nanowires

Example of colloidal etching to fabricate

nanowires with excellent control of nanowire
morphology nanoscale E macroscale diameter
 SKI

on this step we use colloidal monolayer

deposition the silica substrate

we use one of the non close

Then
packing inducing methods like plasmaetching
to produce mom closepacked structures

Now gold the catalyst for oxidisation of

Silica is deposited by any deposition method

The colloids are then burnt away

Now we have circular gold free silicon

exposed region

SHE
Metal Assisted Chemical Etching Mace
MACE is now carried out by dipping
the substrate in an etching som
Etching son has oxidising agent

The silicon unemposed to gold will transform

into silicon nanowires

SKI

Here KOH is the etchant

we the nanowire in Kote for a

of dip
fixed duration the nanowires will become
smaller in dia Using this method we
get excellent dia control
 Here dip etching is used a the
substrate is removed a
predefined
constant rate This can give control
over shape gradient

SummaryoffunctionsofColloidalMonouges

The main things that we can

do with colloidal monolayers are nano porosity

and nanostructures

If we are able to assemble them

on a substrate saywe can prepare a monolayer
made out of polymeric particles polymeric particles
like PS are very useful because they can
be used as a template and then be easily
removed by thermal treatment which means we
just have to bake them in an oven so that
they burn away and do not leave any trace
We can form a nice monolayer of say
Polystyrene particles and then infiltrate the
areas in btw the particles without an inorganic
material like Silica and removing the
particles we can obtain this very controlled
porosity which is very useful because
the
1 it modifies the surface properties of material
a lot so we can change the wettability with
an easy functionalization for eg we can

functionalize it with a self arembled monolayer

with a silane that is hydrophobic and then
we can make this material even more hydrophobic
by adding nanostructures

Cii Another research area we work in

of colloidal monolayers that

are
is use
coreshell
not so closelypacked fabricated using
particles oxysen plasma temperature On the's
hexagonal arrangement of pastilles
case we get a

in the surface that do not touch eachother

and then we can use them as a mask for
deposition of metals
On particular we are working on creating
crescents on surfaces so if we start with a
surface that has hostiles on them we can
 I
deposit a metal from the top and we set
the shade of the particles or we can tilt our
substrate ee have lateral deposition to form moon
like structures or we can use subsegment
deposition cycle to obtain chiral structures

Yhiral structures are used to create sensors

iay C.IN
most important parameters is
One of the
the ordering of the crystal that we can
have So how good our crystal is is a
very important question

Usually when we form a monolayer on a

substrate we end up with many different
domains colour
every different
evident
As different different
a particles
defines of in
arrangement particles
of the
ordering
actions
d
 dived

To Quality of the monolayer several

increasethe
methods have been developed A uniform color
domain is always desirable

C USE OF ULTRASONIC WAVES OR CYCLES OF EXPANSION

CONTRACTION

generate ultrasonic waves inside the

we
we
sub phase here water or can use
do expansion contraction
a trough to of
the monolayer to increase its quality

Results with use of ultrasound

set and
domainslarger
The and a fewin
larger only
eventually
remain
Toman will
sample
the
a NORMAL ACOUSTIC WAVES CAN ALSO BE
USED

acoustic waves can be used

The
during the casting of the particles Air water
interface or afterwards and as we keep
depositing the particles the Quality improves

The size of domain eventually will increase

If we use afrequency that favours the

expansion domain will expand a vice
versa

Hence acoustic waves can control the quality of

a monolayer
 PEROUSTHINFILMS
porous thin film are very useful and there is a

lot of research done on them

Porous thin films
7
IT disordered
I I
eg Inverse eg Mesoperon
opals silica

I Mesoporous Silica

Mesoporous silica is a

Manotechnological advancement comprised

of honeycomb like structure of silica with
a large number of empty channels mesoporous

Manufacture of Mesoporous silica using

micelles
chemistry ofsiligon
silica is condensed from fetraethoxy
silane Eth CHz
Eth CH O
Eth O Si O Eth tetraethoxy silane
teth

When tetraethong silane is presented with water

water can attack silica

Eth o s LL
teth

J
E

O Eth
y
One of the hydrogen atom breaks the bond and
the ethong group become ethanol

O Eth
I
C tho OH HzCha OH
SI
O Eth
ethanol

This does not stop here the OH group in

The above molecule will attack another
tetraethony silane molecule

qtth
Eth Si OH tooth Si O Eth

dEth
H

Eth Si O Si Lotty

The reaction still continues as shown below

Eth
si
 I
Sli O Eth
Otta si o
I
teth
nai

Oft

as water is added and subsequently ethanol

is produced along side

So more silica will be built which is

Si O Si infinitely

Now what happens when we have

micelles in a solution

hydrophobic

Nicely
When we
try to make a thin layer
of silica that is
meroporous we will
use tetraethony silane and surfactants
together

I tetraethony silane represents a silica

precursor ie any compound that will give
silica Si O Si

Manufacture of Mesoperous Silica using evaporation

induced self assembly

d
What we do in this configuration is
that we dip inside the solution of
ethanol water ethanol comes as a
by product from reaction of Tetraetnonysilane
and water a glam water and then we

it out
pull
when we pull it out we wet the
surface with the Solm
As we take it out we are evaporating
our solvent
On the son have a mixture of
we

ethanol q water when the evaporation starts

obviously ethanol will go quicker than water
so locally the surface of the substrate
there will be a higher conn of water

Also locally there will be an increase of

Conon of the surfactant

The increase of the coma of surfactants will

produce some micelles The more micelles we
make the more we start organizing them
The micelles will organise themselves in
arrays as shown below in the surface of
the substrate

08888
At the same time the coma of water
which means water will start attacking the
tetraethony silane to produce silica

Tetraethony silane is soluble but silica is a

solid so we start polymenising silica around
the micelles

ÉE
The silica will occupy the porous places on
the surface
Ment we can either washoff our
surfactant I burn them by thermolysis

We will be now left with an organized

array of holes and walls of silica around it

In this case surfactants acted as

Porogens
the key idea is that

awe form aninorganic matrix around

organic micelles especially by sol gel reactions

I Burn away the micelles

1 Pores with the dimensions of surfactant

micelles mesohores are left in the
Material

Another example of fabrication of ordered

Mesoporousbilica using Miscelles
The researchers started by preparing
cylindrical micelles and the micelles can then
assemble together as if the micelle itself is the
building block not the surfactant

The cylindrical micelles can help us get a

good degree of order

pretty
The cylindrical micelles are all arranged in
one direction
At the same time silica is formed from the
silica precursor material Gay tetraethony silane

The silica will get deposited in the

space that is free left by the micelle

Silica forms with a sol gel process

So we start from a solution of
Tetraethoxy silanes other precursors that only
contain one Silicon atom more silicon
atoms can make the material a solid
and hence sol gel process wouldn't world
 The solutionspolymerase to form silica that
are able to localise in the tiny region and
condensate together to form a

continious matrix

Upon thermal treatment we can remove the

micelles and farther condense the silica
This process is called sintering

we end up with something that looks like

this
 Cylindrical micelles For ordered Mesoporous
silica

for disordered
Ordinary spherical micelles
mesoperous silica

MelgFTrimethylammoniam
Bromide CTA's is the
commonly used surfactant because it can form a

nice interconnected network

Commonly used silica precursors

tetraethoxy silane TESH
tetramethylorthosilicate Thos

silica particle formation is indicated by

turbidityof solution
 ORDE s4stms

Y
One of the porous system with controlled

More dimensions is inverse opals

Inverse opals are made by assembling polymeric

particles that can then be used
as a template

to cast an inorganic matrix come of the

most common one is silica but we are not
limited to Silica we can use any inorganic
material we want After a thermal treatment
we get a continious silica inorganic matrix

with pores that are templated by the

colloidal particles we used the beginning

As evident the pores are

of homogenous size

baes
Slayer of
The important feature of this system is that the
pores are interconnected The interconnection area
is called neck which allow optimal flow of
substance in the porous structure especially compared
to mesopcrous silica in which
we
might not
have continious pores as they are just inflated
micelles that are not assembled in an ordered
by
way

These matrix can then be easily functionalused with

a Self assembled monolayers say silanes silica

It is also easy to tailor the morphology of

the
what we want to obtain by changing
colloidal charticles we use we can easily change
the fore dia and neck size
 mmonapplicationofIOIals
Co

Catalysis

On the surface of an inverse opal

it is possible to localize metallic particles that
have catalytic properties

Eg we can deposit gold nanoparticles

and this can be done in many different way

An interesting way of doing it is

preassembling particles on top of the templating

particles eg gold HP on PS creating the

opal
Then we can co assemble the inorganic
matrix
After removing the template we will get
a Silica inorganic matrix that is
completely covered in small gold nanoparticles

This material can then be efficiently used

as a catalyst support since we have a very
good flow of gases liquid on the surface
we have a lot of gold nanoparticles on the
surface which are immobilized so we do
not have to worry about them being washed
away

It is also having a
very high surface area

2 Wetting based sensors

Inverse opals with very regular

porous
structure can be made by filling a

with a silica precursor

polymer opal

They can also be used as sensors we

can do so by exploiting their wetting

properties

wetting of Inverse opals are a very interesting

phenomena
Not all nanostructures wet easily depending on

the central geometry

so we can observe that in an inverse opal

when we start from a silica inverse opal
 we wet in some solvents and will
not wet in other solvents

This is because certain liquids cannot infiltrate the

if certain geometrical conditions are
pores
not met

We need to observe that the receding

angle of the liquid in the pose can actually
decide the diffusion
of the liquid inside it

This is done in a
simple way
we can
just measure the contact angle of
the liquid that we are interested in on a
flat substrate Let this be Oc

Now we know the preceding

should
angle of the liquid in the pore Ko
are
remain
 If Oc 40 Non wetting substrate
If Oc C Yo wetting substrate

Honanisacommonneckopeningans

To modify it's
behavior we can again ur
self assembled monolayers to tomctionalize our surface
This will change the interaction b w the solvent
and the silica surface or the inverse opal
surface in general and thus we will be able to
change wettability of the material

A change in contact angle triggers

transition blo wet a non wetted pores

This phenomenon can then be used to create

Common sensors are based on a
sensors
photonic readout Cie it is very easy to
observe ie when an inverse opal is dog it
would be coloured and we can just simplify
it and think about Bras scattering in Lecture 8
such sensors have different layers with
different refractive indents
enough
If there is metractive
difference btw lasers
btw these with one
indents is silica and
other
one lit
say
inden indent
refractive refractive a
a
is
air observecolour
will
we structural

But when we wet it the pores will be

filled with water or a liquid The refractive
usually around 13 1.5
inden of a liquid is
becomes
Hence the contrast b w the two layers
insignificant and light would just travel
through the material q we will not observe
any colour
 Deletion of different liquids based on

wettability

The wetting nature can be applied to

distinguish bio different liquids

The inverse opals are functionalized with

different self assembled monolayers

d
 completigged
areaghvisible
little still
the be
Iigdw areas
had two
acetone area
with three
water
with

so we can use them as a platform to

distinguish btw three different solvent

Determination of Ethanol content

Also the same method has been

used to distinguish ble different alcohol
and this is way more interesting
percentages

for es to see alcoholic beverages are legit