Liquid crystals and liquid crystalline polymers

The study of liquid crystals began in 1888 when an Austrian botanist named
Friedrich Reinitzer observed that a material known as cholesteryl benzoate had two
distinct melting points. In his experiments, Reinitzer increased the temperature of a solid
sample and watched the crystal change into a hazy liquid. As he increased the temperature
further, the material changed again into a clear, transparent liquid. Because of this early
work, Reinitzer is often credited with discovering a new phase of matter - the liquid crystal
phase.

In the solid state, molecules are highly ordered and have little translational freedom.
The characteristic orientational order of the liquid crystal state is between the traditional
solid and liquid phases and this is the origin of the term mesogenic state.

The distinguishing characteristic of the liquid crystalline state is the tendency of the
molecules (mesogens) to point along a common axis, called the director. 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. The anisotropic nature of liquid crystals is responsible for the
unique optical properties exploited by scientists and engineers in a variety of applications.

The following parameters describe the liquid crystalline structure:

1. Positional Order

2. Orientational Order

3. Bond Orientational Order

 Positional order refers to the extent to which an average molecule or group of
molecules shows translational symmetry. Orientational order, represents a measure of the
tendency of the molecules to align along the director on a long-range basis. Bond
Orientational Order describes a line joining the centers of nearest-neighbor molecules
without requiring a regular spacing along that line.

Requirements of a molecule to exhibit liquid crystal nature:

i) Long, thin structure

ii) Rod shaped molecule
iii) Should contain a rigid part and a flexible end

Liquid crystal molecules are further classified into thermotropic and lyotropic
crystals. Thermotropic liquid crystals which change proportionally with respect to the
changes in pressure and temperature are discussed here. They can exist in nematic, smectic
and cholesteric (chiral nematic) liquid crystal phases, which are explained in the following
paragraphs.

A representation of the molecular arrangement of liquid crystalline phase

transitions by rod-like thermotropic liquid crystals is shown below.

Nematic Phases

Nematic phase is the simplest mesophase known; there is long range orientational
order between the mesogens but with no positional order. Mesogens are able to freely
translate and rotate along the director field (n) but are randomly distributed in space.
“Nematic” comes from the Ancient Greek word νεμα (“nema” meaning thread) as when
observed through a microscope thread-like structures are observed. The greatest
advantage of a nematic phase liquid crystal substance is that it can bring about predictable
controlled changes according to the electric current passed through them. Twisted
Nematics, a particular nematic substance is twisted naturally. When a known voltage is
applied to the substance, it gets untwisted in varying degrees according to our
requirement. This in turn is useful in controlling the passage of light.

Smectic Phases

Liquid crystals with smectic mesophases were originally discovered from

amphiphilic molecules, the phase type coming from the Ancient Greek word σμεκτοσ
(“smektos” meaning soap-like). Today, the word smectic is used for liquid crystals in which
the molecules occupy orientational order, but are also organised in layers (no long range
positional order). These organised layers can slide relative to each other, which contributes
to the liquid character of the liquid crystal phase. Many smectic phases have been
discovered, each smectic phase differs in the orientation and position of the mesogens.
Smectic phases are distinguished by letters; SmA, SmB, SmC etc. with SmA and SmC being
the most common. Smectic phases are distinguished via the molecular orientation within
the layers. Smectic A (SmA) mesophases have molecules aligned along a director field (n)
and are parallel to the layer normal and in smectic C (SmC) mesophases the molecules are
tilted at a certain angle away from the layer normal.

Cholesteric Phases

The cholesteric phase is a special type of nematic phase where the mesogens change
orientation in a helical manner with respect to the director field (n). The director field in
the cholesteric phase changes direction and is perpendicular to the direction of the helix.
The chirality comes from the molecules orienting themselves into a helix; each layer is non-
superimposable. Within the cholesteric mesophase is the pitch, which is defined as the
distance between one mesogenic layer and another, which has rotated 360 ° to the director
field.
 Representation of the cholesteric mesophase with the cholesteric pitch.
The first observed liquid crystals based on cholesterol derivatives showed this
mesophase type, which is where the mesophase name “cholesteric” originates.

Basic structure of an LCD

A liquid crystal cell consists of a thin layer of a liquid crystal sandwiched between
two glass sheets with transparent electrodes deposited on their inside faces. The LCD does
not produce any illumination of its own. It, in fact, depends entirely on illumination falling
on it from an external source for its visual effect.
 LCD assembly

Polarizing filters in an isotropic medium (such as air). The system's optical

throughput depends on the relative orientation of the polarizer and analyzer.
 Working of LC during voltage on and off conditions

Twisted Nematic Liquid Crystal Cells

A Twisted Nematic (TN) cell is made up of

 two bounding plates (usually glass slides), each with a transparent conductive
coating (such as indium tin oxide) that acts as an electrode;

 spacers to control the cell gap precisely;

 two crossed polarizers (the polarizer and the analyzer);

 the nematic liquid crystal material.

The surfaces of the transparent electrodes in contact with the LC are coated with a
thin layer of polymer, which has been rubbed or brushed in one direction. The nematic LC
molecules tend to orient with their long axes parallel to this direction. The glass plates are
arranged so the molecules adjacent to the top electrode are oriented at a right angle to
those at the bottom. Each polarizer is oriented with its easy axis parallel to the rubbing
direction of the adjacent electrode (so the polarizer and analyzer are crossed).
 In the absence of an electric field, the nematic director undergoes a smooth 90
degree twist within the cell (hence the name "twisted" nematic liquid crystal). Unpolarized
light enters the first polarizing filter and emerges polarized in the same plane as the local
orientation of the LC molecules. The twisted arrangement of the LC molecules within the
cell then acts as an optical wave guide and rotates the plane of polarization by a quarter
turn (90 degrees) so that the light which reaches the second polarizer can pass through it.
In this state the LC cell is transparent.

When a voltage is applied to the electrodes, the liquid crystal molecules tend to align
with the resulting electric field E (Fig.) and the optical wave guiding property of the cell is
lost. The cell is now dark, as it would be without the LC present (as in Fig.). When the
electric field is turned off, the molecules relax back to their twisted state and the cell
becomes transparent again.

For applications such as digital watches and calculators, a mirror is used under the
bottom polarizer. With no voltage applied, ambient light passes through the cell, reflects off
the mirror, reverses its path, and re-emerges from the top of the cell, giving it a silvery
appearance. When the electric field is on, the aligned LC molecules do not affect the
polarization of the light. The analyzer prevents the incident light from reaching the mirror
and no light is reflected, causing the cell to be dark. When the electrodes are shaped in the
form of segments of numbers and letters they can be turned on and off to form an alpha-
numeric display. Passive displays such as these can function solely using ambient lighting,
which makes them ideal for battery-operated devices.

Advantages of LCDs

 LCD consumes less amount of power compared to CRT and LED.

 LCDs consist of some microwatts for display in comparison to some milliwatts for
LEDs.

 LCDs are of low cost.

 Provides excellent contrast.

 LCDs are thinner and lighter when compared to cathode-ray tube and LED.
Disadvantages of LCDs

 Require additional light sources.

 Range of temperature is limited for operation.

 Low reliability.

 Speed is very low.

 LCDs need an AC drive.

Applications of LCDs

Liquid crystal technology has major applications in the field of science and
engineering as well on electronic devices.

 Optical imaging

 The liquid crystal display technology is also applicable in the visualization of the
radio frequency waves in the waveguide

 Used in the medical applications

 Mixtures of various types of these liquid crystals are often used to create sensors
with a wide variety of responses to temperature change. Such sensors are used for
thermometers often in the form of heat sensitive films to detect flaws in circuit board
connections, condition of batteries and presence of radiation.