Liquid crystals

By,

Dr. Pushpanjali P A
 What are liquid crystals ?
Liquid crystals form from organic compounds and is
thought of as the phase of matter between the solid
and liquid state of a crystal.
Phase change of matter
 Normal matter
 Temp↑
 Single phase change
 crystalline solid  isotropic
liquid
 Some organic
molecules
 Temp↑
 Multiple phase change
 crystalline solid 
mesophase(s) 
isotropic liquid
 In ordered fluid mesophases, matters have properties
between those of a conventional liquid, and those of a
solid crystal. For instance, a liquid crystal can flow
like a liquid, but have the molecules in the liquid
arranged and/or oriented in a crystal-like way.
Mesomorphic Behaviour
 Mesomorphic state of matter is a state of matter intermediate between
liquid and solid.

 It occurs with the solids having greater tendency to an ordered

arrangement.

 It has certain properties of solids like double refraction of light or

interference pattern in polarised light.

 It also has some properties of liquid, like surface tension, flow and
viscosity.
 Liquid crystals are very important in the study of optics,

chemistry and polymer science.

 The discovery of the liquid crystal happened over a century and

since this time the phenomena has been applied to many

products in our society.

 This presentation will cover the properties, different phases and

uses of liquid crystals

Isotropic
Liquids and gases
(uniform properties in all
directions).

vs.
Anisotropic
Liquid Crystals
have orientational order
Anisotropy
 The tendency of the liquid crystal molecules to point
along the director leads to a condition known as
anisotropy
 This term means that the properties of a material
depend on the direction in which they are measured
Requirements for formation of mesophase
( or liquid crystal)

• The requirements for a substance to form mesophase

are
• it should have elongated structure
• it should have a central rigid core with flexible ends.
• it should be polarized or polarizable.
Chemical constitution and liquid crystal
behavior
 Long chain hydrocarbons have an elongated structure
but do not have a rigid core and hence do not form
liquid crystals. E.g. n – alkanes cannot form liquid
crystals
 CH3 – CH2 -– CH2 -– CH2 -– CH2 -– CH2 -– CH2 -– CH2 –
CH3
 Similarly, long chain n- alkanoic acids have elongated
structure but do not form liquid crystals.
CH3 – CH2 -– CH2 -– CH2 -– CH2 -– CH2 -– CH2 -– CH2 –
COOH
• If the alkanoic acids form a dimer, they form a cyclic
ring at the center due to hydrogen bonding, but the
molecule is not rigid enough and hence does not
favour mesophase formation.

• If conjugated double bonds are introduced in the

above, it gives a rigid core with flexible ends and thus,
alkenoic acids can form mesophase
 O

H3CO N=N OCH 3

• Aromatic rings with para substituents have elongated structure

with flexible ends can form liquid crystals.
• Thus a compound with two benzene rings linked through
double bonds and substituents at the other ends ( at p and p’
positions)of the benzene rings can form mesophase.
• E.g., para azoxy anisole can exhibit mesophase because it has an
elongated structure
• It has a rigid core comprising of two benzene nuclei linked
through N=N
• It has alkoxy groups at p and p’ positions as flexible ends.
Classification of Liquid crystals

Liquid crystal

Thermotropic LC Lyotropic LC

Nematic Smectic Cholestric

 Lyotropic liquid crystals
• LC phases formed by dissolving the compound in an appropriate solvent
(under given concentration and temperature conditions) are known as lyotropic.
• Compounds forming lyotropic mesophases usually consist of a flexible
lipophilic chain (the tail) and a polar (ionic or non-ionic) head group.
• Typical example of a lyotropic phase is formed by dissolution of soap in
water.

Tail is an alkyl chain in most cases with 6 to 20 methylene groups;

Lyotropic liquid crystals : SURFACTANTS
Thermotropic liquid crystals
 The mesophases obtained by temperature variation are called
thermotropic.
 Thermodynamically stable mesophases which appear both on
heating and cooling are termed enantiotropic, while the thermotropic
mesophases that appear only on cooling are monotropic.
 Despite the significance of lyotropic LCs, thermotropic LCs have
claimed a relatively greater attention, firstly because they are simple
to realize and handle and secondly they serve as an important medium
in fabricating low-power display devices.
 The temperature at which the crystal transforms into mesophase is
called melting point, while that from the mesophase to isotropic state is
called clearing point.
 Materials displaying thermotropic LC property are mostly organic or
metal containing organic compounds.
 Among the enormous number of organic compounds known, only a
small fraction shows this LC behaviour. Such types of compounds
usually comprise of hard (rigid) and soft (flexible) regions.
 The aromatic cores and some non-aromatic cores account for the
rigidity while paraffinic chains are the soft regions of the molecule.
 However these two distinct parts are combined in a specific way so as
to attain a particular anisotropic shape of the molecule.
The orientational order arises from the parallel alignment of anisometric
molecules and positional order is mainly the consequence of specific
attractive forces and amphiphilicity.

Director:

The distinguishing characteristic of the liquid

crystalline state is the tendency of the molecules
(mesogens) to point along a common axis, called
the director.
Order parameter (S):

 where theta is the angle between the director and the long axis
of each molecule.
 The brackets denote an average over all of the molecules in the
sample.
 In an isotropic liquid, the average of the cosine terms is zero,
and therefore the order parameter is equal to zero.
 For a perfect crystal, the order parameter evaluates to one.
 Typical values for the order parameter of a liquid crystal range
between 0.3 and 0.9, with the exact value a function of
temperature, as a result of kinetic molecular motion.
1. Conventional liquid crystals
Rod-like and disc-shaped mesogens exhibit thermotropic mesomorphism; they
are popularly known as calamitics and discotics respectively.

2. Non conventional liquid crystals

In recent times a great deal of attention has been given to the generation of self-
organized systems with complex mesophase morphologies. This is achieved by
tailoring the shape of rigid segments by increasing the number of incompatible
units in the molecules or by changing the volume fractions of the incompatible
segments. These molecules with anisometric shape that deviates from the
conventional rod or disc shape are collectively termed as ‘non-conventional
liquid crystals’.
Calamitic liquid crystals: phases and structures

In calamitic mesogens, there are three types of mesophases namely the

nematic, cholesteric and smectic originally classified by Friedel based on the
degree of positional and orientational order.

(a)Nematic (N) phase:

The nematic liquid crystal phase is characterized by molecules that have no
positional order but tend to point in the same direction (along the director).
 The simplest LC phase is the nematic and it generally occurs just below the
isotropic phase with a viscosity comparable to those of isotropic liquids.
 Depending on the surface conditions, N phase exhibits schlieren, marble and
pseudoisotropic textures.
 In this phase the constituent molecules have no positional order but are on an
average, oriented about a particular direction called the director, n.
 Even though the preferred direction of molecules varies from point to point in the
medium, a uniformly aligned sample is optically uniaxial.
 The orientational order of the phase is quantified by the order parameter S and the
values increase from, about 0.3 near the clearing temperature to 0.6-0.7 at temperatures
below the clearing point.
 Because of the parallel alignment of the molecules along their long axes they
exhibit anisotropic physical properties.
2. Smectic phases
 In some phases the molecular center of gravity is on an average
arranged in equidistant planes, so that in addition to orientational
order, positional order is also present which leads to a layered
structure: such phases have been called smectics.
 Depending on the molecular arrangements within the layer and
the extent of inter-layer correlations smectic mesophases are
classified into different types according to the chronological order
of their detection the smectic phases have been designated with
code letters A,B,C…etc.
1. The Smectic A phase has layers oriented at 90
degrees to the director.
2. The Smectic C phase has a director tilted with
respect to the layers.
SMECTIC PHASES

Smectic phases have orientational order, and some degree of positional order.
These phases are distinguished by the presence of layers perpendicular to the
director. The Smectic A phase has layers oriented at 90 degrees to the
director. The Smectic C phase has a director tilted with respect to the layers.
Below, schematics for these phases are shown
 a. Smectic A phases
 In the smectic A phase the director lies along the layer normal.
 The molecular packing within the layers is liquid-like and has no long-range
positional correlation.
 Likewise, there is no correlation between the lateral positions of the molecules in
successive layers. Because of the disorder within the layers, the layers are not well
defined and in formal terms the SmA phase can be described as a one-dimensional mass
density wave.
 As a consequence, in the SmA phase , when an electric field is applied orthogonal to
the layer normal direction there will be a coupling of the electroclinic susceptibility to
the field and the long molecular axes of the molecules will tilt with respect to the layer
planes for relatively low applied fields, the tilt angle varies linearly with the field. This
linear electrooptic phenomenon is called electroclinic effect.
 Schematic representation of the SmA phase formed by chiral rod-like
anisometric molecules:
a) orthogonal layered geometry;
b) tilted layered structure (electroclinic effect) obtained by the application of
electric field along the layer planes of geometry (a)
b. Smectic C phases

 The smectic C phase differs from the SmA phase in that the
director of each layer is inclined at an angle to the layer normal
and this angle being identical for all layers.
 While the SmA phase is generally optically uniaxial, the SmC
phase is optically biaxial.
 The tilt angle in this phase has been shown to vary with
temperature and it often increases monotonically with decreasing
temperature. X-ray studies indicate that the layer thickness in this
phase is considerably less than the molecular length.
SMECTIC C*
The chiral analogue of the
Smectic C phase is denoted by a
star (*). In this phase, the tilt
direction of the mesogens
rotates as one progresses
through the layers. In the figure,
the different layers are coloured
differently for convenience. The
diagram to the far right shows
the twisting of the mesogens in a
more idealized way, and
emphasizes the chiral twisting
of the director
 LIQUID CRYSTALLINE BEHAVIOUR
IN HOMOLOGOUS SERIES
 A series of compounds in which the members have the same functional group and the molecular
formulae of adjacent members differ by CH2 is called a homologous series.

 Thermal stability of the members of a homologous series varies with change in the number of
carbon atoms or chain length.

 Similarly, the thermal stability of a liquid crystal compound may be altered by altering the
molecular structure e.g., by increasing its chain length.

 One of the requirements for liquid crystal formation is that the molecular ordering in the
corresponding solid substance should break down in stages on heating

 In a homologous series, the transition temperatures between crystalline state and mesophase
changes with change in the number of carbon atoms in the flexible ends.

 A similar change is observed in the transition temperatures between mesophase and isotropic
liquid state.
 PAA Series
MBBA Series
O

N=N OCH 3
H3CO CH=N C4H9
H3CO

N=N OC 2H5
H5C2O C4H9
H5C2O CH=N

N=N OC 3H7
H7C3O CH=N C4H9
H7C3O

N=N OC 4H9
H9C4O CH=N C4H9
H9C4O

H2n+1CnO N=N OCnH2n+1 C4H9

H2n+1CnO CH=N

p-azoxy anisole N-(4-Methoxybenzylidene)-4-butylaniline

Change in the Liquid crystalline behavior
1. As the no. of C-atom
increases in the side
chain transition
temperature decreases
2. Lower members show
nematic phase upto 8
C-atoms in the side
chain where as higher
homologues show
Smectic phase
1. As the no. of C-atom
increasein the side chain
transition temperature
decreases its lowest for 8
carbon atoms in the chain
2. All members show nematic
phases.
 Homeotropic texture

Homeotropic alignment is the state in which a rod-like liquid crystalline

molecule aligns perpendicularly to the substrate.
Homogeneous or planar texture
In contrast, the state in which the molecule aligns to a substance in
parallel is called homogeneous or planar alignment
Schlieren texture
When viewed between crossed polars, thin films (approximately 10μm
thick) of liquid crystals exhibit schlieren textures, as seen in the
micrograph below, which shows a nematic liquid crystalline polymer.

The black brushes are regions where the director is either parallel or
perpendicular to the plane of polarisation of the incident radiation, and
the points at which the brushes meet are known as disclinations.
Chiral phases
 Special cases of nematic and smectic phases are sometimes formed by molecules
that display chirality— that is, they can exist in either left- or right-handed forms that
cannot be superposed on each other.
 In the resulting chiral phase, successive molecules positioned along the long axis
are rotated around this axis, giving rise to a periodicity that repeats itself at distances
corresponding to a complete rotation.
 These twisted phases are able to rotate the plane of polarized light that passes
along the axis. If the molecules are polar, this twisting can be turned off by imposing
an external electric field at either end of the long axis.
 Besides the very important application of this property (known
as ferroelectricity) to liquid crystal displays, these materials can be used to make
electrooptic shutters which can be switched open and closed in microseconds.
Cholesteric (Chiral nematic or twisted nematic) LC

The cholesteric (or chiral nematic) liquid crystal phase is typically

composed of nematic mesogenic molecules containing a chiral center
which produces intermolecular forces that favor alignment between
molecules at a slight angle to one another
 These form a helix in space with a well-defined pitch that is much longer than the
size of a single molecule.
 Helical twist may be right handed or left handed depending on the molecular
conformation.
 This helical arrangement is responsible for the unique optical properties of the
phase, such as selective reflection.
 When plane-polarised light interacts with this chiral macroscopic structure, its plane
of polarization is rotated along the direction of the helix.
 When the pitch of the helix corresponds to a wavelength in the visible region of the
spectrum (~400-800 nm) the chiral mesophase is colored.
Properties of Liquid Crystals

 Since liquid crystals are anisotropic fluids, various physical

properties measured in different directions will not be the same.
 The anisotropy of liquid crystals causes them to
exhibit birefringence. That is, light that enters the crystal is broken up
into two oppositely-polarized rays that travel at different velocities.
 Observation of a birefringent material between crossed polarizing
filters reveals striking patterns and color effects.

 The colors arise from interference between the ordinary ray and
the extraordinary ray; the latter traverses a slightly longer path through
the material, and thus emerges later (and out-of-phase) with the
former.
Optical anisotropy (Birefringence)

 All crystal types other than cubic are optically anisotropic or birefringent.
 The free rotation in liquids averages out any asymmetry of molecular
shape and the medium becomes optically isotropic.
 Mesogens due to their shape and polarization anisotropy are birefringent,
exhibiting different properties for light traveling with the electric vector
propagating parallel and perpendicular to the director or optic axis.
 The electric vector of incident plane polarized light entering a liquid
crystalline phase is split into two components called ordinary (o) and
extraordinary (e) rays.
 The electric field of the o-ray is always perpendicular to the optic axis, so
its refractive index no is a constant and independent of propagation direction.
 The electric field of e- ray lies in a plane that contains the optic axis, so
its refractive index ne (θ) varies with the ray propagation angle with respect
to the optic axis.
 Thus the birefringence of the medium, Δn (θ), depends on the
propagation direction and is defined as Δn (θ) = ne (θ) - no.
 Most nematic liquid crystals have positive birefringence (Δn > 0),
meaning that the e-ray is delayed with respect to the o-ray on passage
through the LC phase.
 Interference between the e-ray and the o-ray that travel through the
medium with different velocities gives rise to the coloured appearance of
these thin films.
 Applications of liquid crystals
1. Display applications

When an electric field is imposed on the liquid crystal phase, the component
molecules line up in the field and the chirality is lost. Light passing through the cell
does not undergo rotation of its polarization plane, and is therefore stopped by the
right polarizing filter, turning the display off.
 How does the calculator display work?

1. Glass plate with polarizing filter oriented vertically

2. Glass plate with electrodes to form the numbers
3. Liquid crystal material
4. Transparent conductive material
5. Glass plate with polarizing filter oriented horizontally
6. Reflective surface to send light back to the viewer

 When electricity is applied to specific regions of the display (2), the liquid
crystal molecules line up with the electric field. This disrupts the helical
alignment, so the liquid crystal can’t rotate the light.
 When no electricity is applied, light travels through both polarizing filters,
reflects off the mirror (6), and comes back to your eyes.
 When electricity is applied to certain areas of the display, light passes
through one filter but not the other, so that part of the screen is black.
2. Temperature sensors
 Chiral nematic (cholesteric) liquid crystals reflect light with a wavelength proportional
to the magnitude of pitch. Because the pitch is dependent upon temperature, the colour
reflected also is dependent upon temperature.
 Thus, cholesteric LCs make it possible to accurately gauge temperature just by looking
at the colour.
 By mixing different cholesteric LCs, a device for practically any temperature range can
be built. This property has been exploited for practical applications in diverse areas
including medicine, packing industry and electronics.
 Cholesteric liquid crystals as „fever strips‟ are in use as disposable thermometers.
 LC thermal sensors can be attached to skin to show a thermal map.
 This is useful because often physical problems such as tumors have a different
temperature than the surrounding tissue.
 LC temperature sensors can also be used to find bad connections on a circuit board by
detecting the characteristic higher temperature.
Some history
In 1888, Friedrich Reinitzer observed something
strange with the melting behaviour of cholesteryl
benzoate:
Blue-violet colour at melting (145.5oC)cloudy liquid
blue colour around 178.5oC clear liquid

W. Heintz had observed similar behaviour with stearin

38 years before.
• Reinitzer, Otto Lehmann and others: liquid crystal
phase.
•In 1922 Georges Freidel proposed a classification
scheme of liquid crystals: nematic, smectic and
cholesteric.
•In 1958 Wilhelm Maier and Alfred Saupe (diploma
thesis) formulated a theory for the phase behaviour of
liquid crystals.
de Gennes and colleagues revive interest in liquid
crystals in 1960’s ...
(1889)
States of matter
• Solid
– Definite shape
– Particles are packed
closely together to form
crystal structure
– Particles cannot move
freely, only vibration is
possible
PHOSPHOLIPIDS
BANANA LIQUID CRYSTALS
Identification and molecular
ordering in liquid crystals:
 Liquid crystals exhibit optical anisotropy
and hence liquid crystals and their phase
transitions can be identified using optical
polarizing microscopy.
 When thin films of liquid crystals are
placed between two glass plates and are
viewed through a polarizing microscope,
complex patterns, referred to as optical
textures, can be observed.
 From the texture, it is possible to identify
whether the mesophase is nematic, chiral
nematic (or cholesteric), smectic, discotic
and so on.
Molecular ordering in Liquid
crystalline phase

Nematic phase
Cholesteric or twisted nematic
phase[TNLC]
Smectic phase
Discotic or columnar phase
Liquid Crystal Phases
 Nematic Phases
 The nematic liquid crystal phase is characterized by
molecules that have no positional order but tend to point
in the same direction (along the director)
The nematic phase
 Cholesteric Phases

 The cholesteric (or chiral nematic)

liquid crystal phase is typically
composed of nematic mesogenic
molecules containing a chiral center
which produces intermolecular forces
that favor alignment between
molecules at a slight angle to one
another
They exhibit broken fan like texture.
DISCOTIC LIQUID CRYSTALS

Disc-shaped mesogens are called discotic. The structure of a typical discotic is

shown on the top. Disc-shaped molecules have a tendency to lie on top of one
another forming either discotic nematic phases (with discs oriented similarly) or
columnar phases (which, obviously, have column-like structure).
 Electro optic
 Electric effect:
effect
 When a film of liquid crystal Field off Field on

is placed between two glass

plates, the molecules are
oriented in a direction
parallel to the surface of the
glass.
 If an electric field is applied
perpendicular to the plate,
the molecules of the liquid
crystal try to align themselves
parallel to the applied field
Optical effect
 When light passes through two crossed
polarisers, light coming out of one
polariser is absorbed by the other and
hence darkness is observed.
 However, when a film of liquid crystals BRIGHT DARK

placed between specially treated glass

plates is placed in between the crossed
polarisers the director acts as a wave guide,
and light emerges in the orthogonal
direction and brightness is observed.
 Electrooptic effect is utilized in LCDs. 4-6 3v
m
 The conditions necessary are:
 Light should be incident either parallel or
perpendicular to the glass surface. And
Liquid
 The wavelength of the light incident crystal

should be  = P  n where P is the pitch

of the liquid crystal and n is the Light Light

difference in the refractive indices

perpendicular and parallel to the director.

Twisted nematic field effect
 First discovered in 1970
Principle of LCD
 How LCD Projector work

LCD projectors employ a three-panel LCD (Liquid Crystal Display) system, referred to
as 3LCD. LCD projectors crisply reproduce bright, naturally colored images that are
easy on the eyes. LCD projectors are also capable of detailed shadow reproduction that
is ideal for demanding business and home theater applications.
The white light from the projector lamp is split into red, green, and blue components using two
dichroic mirrors, special mirrors that only transmit light of a specified wavelength.
Each red, green and blue beam then passes through a dedicated LCD panel made up of
thousands of miniscule pixels.
An electrical current turns the panel's pixels on or off to create the grayscale equivalent of that
color channel.
The three colors are then recombined in a prism and projected through the projector lens and
onto the screen.
By using a combination of three LCDs to produce a final image, LCD projectors are capable of
billions of colors and smooth grayscale gradations.
The resolution of the image is determined by the number of pixels in the LCD panels used.
Currently LCD panels offer resolutions as high as true HD (1920 x 1080) for home theater
applications. New panels promise resolutions as high as 4K (3840 x 2160).
LCDs are not just found in projectors. They are found in many of the electronics
you use everyday, from a cell phone to an MP3 player to your digital alarm
clock. LCDs are very common because they offer distinct advantages: they are
thinner, lighter, and draw less power than many competing display
technologies.
A reliable, sophisticated technology with universal appeal, 3LCD is the world's
most popular projection technology, delivering high quality images for the most
demanding business and consumer audiences.
 Self-alignment of Inorganic Liquid Crystals: Effect of Magnetic
Field
Martinez-Miranda, Luz J. ; Wilson, Alicia Rose Douglas, Jr.
American Physical Society, Annual APS March Meeting, March 18 - 22, 2002
Indiana Convention Center; Indianapolis, Indiana Meeting ID: MAR02,
abstract #U26.006

The system of Al-FeOOH is one of the inorganic liquid crystal systems. It

responds to surface forces as well as magnetic field. We have studied three
systems, with increasing aspect ratio and how they react to a prepared
surface and the surface with the magnetic field added. For a grated surface,
we find that the smaller and the intermediate particles align following the
contour of the surface, whereas the large particles tend to agglomerate and
sit on the surface with no order at all. We then apply a magnetic field to the
particles on the grated surface. We find that for the smaller particles, there is
a competition between the magnetic field and the surface. The top particles
will align with the magnetic field. The intermediate particles act as though
they are large particles, and tend to agglomerate in the magnetic field, even
when there is a grated surface. The large particles behave the same as in
contact with the surface.