Liquid Crystals

for Active Matrix

Displays
Michael Heckmeier, Georg Lüssem,
Kazuaki Tarumi and Werner Becker
Overview
The meaning of displays in modern communi-
cation and information society is permanently
growing. Almost everywhere, displays provide
an interface between humans and technology.
Living without displays has become inconceiv-
able.
Due to their compactness, flat displays are
preferred for many applications. Mobile
telephones, portable notebook computers or flat
desktop monitors are indispensable in business;
an increasing number of flat displays is used
for private applications.
Liquid Crystal Displays (LCDs) play a major
role for the applications described above and
dominate the market of various display sizes
from mobile tools up to desktop monitors. The
majority of liquid crystal displays contains
nematic liquid crystals. In this paper, we want
to give an overview about liquid crystal
displays with nematic liquid crystals. Our focus
is put on liquid crystal material development
and its relation with new liquid crystal display
technologies. These technologies fulfil all
requirements needed for modern displays like
small viewing angle dependency and fast
switching times. For an integral presentation,
toxicological and eco-toxicological aspects of
liquid crystals will be elucidated.
Introduction
The extraordinary optical, elastic and viscous properties of liquid
crystals paved the way to a huge research program in physics
and chemistry of liquid crystals.

Introduction

The liquid crystal phase was discovered by the "Deformation of aligned phases”, "Ferroelectrics”,
botanist Friedrich Reinitzer in 1888. The extra- "Guest-Host” and "PDLC (Polymer Dispersed
ordinary optical, elastic and viscous properties Liquid Crystals)” is only a short list of technolo-
of liquid crystals paved the way to a huge gies which finally turned out to be not successful
research program in the physics and chemistry for commercial display applications.
of liquid crystals. We give a brief overview about
Currently, almost all liquid crystal displays use
liquid crystals in appendix 1. The unique phase
nematic liquid crystal mixtures. It is necessary to
properties, already reflected in the term "Liquid
use mixtures of liquid crystals, since, so far,
Crystal”, led to a stormy development in the
there is no single liquid crystal material, which
research of these materials.
would fulfil the specifications of even the
In parallel to this basic scientific interest, the past simplest display. The material properties required
40 years have seen a lot of research and develop- for display applications, for example a large
ment of liquid crystals for display applications. operating temperature range, can only be
The driving forces for this development, achieved by solving a complex optimization
particularly during the past years, have been the problem and typically mixing 10 to 20 liquid
following key advantages of liquid crystal crystal singles together.
displays compared to the standard cathode ray
Basically, two types of commercially available
tube: the flatness and compactness leading to
liquid crystal displays exist: In active matrix
lighter weight and significant reduction in
displays each matrix point (pixel) is driven by a
power consumption. From the beginning phase
one to one related electronic switching device.
of this development of liquid crystal displays,
Additionally, there is the possibility, to drive all
Merck has played a major role in the material
pixels only column- and row- wise, not using This article was
development which has led to a profitable liquid
electronic switching devices associated directly published already
crystal business.
to one pixel. This so called passive matrix slightly modified in
In the time frame mentioned, several possibilities driving exhibits cost advantages for smallsize German in Bunsen-
for the application of liquid crystals in displays displays. However, with regard to their optical Magazin, 4. Jahrgang,
have been discussed. "Dynamic scattering”, performance and picture quality, particularly for 5/2002, p. 106-116

3
Introduction
larger size displays, passive matrix liquid crystal
displays cannot compete with active matrix
liquid crystal displays. Therefore, research and
development for liquid crystal materials for
active matrix displays is most important. We
only refer to Merck’s research activities for
passive matrix display applications [1]. In this
paper we will not cover these activities for
passive matrix display applications.

We will give an overview about the current

development situation for active matrix liquid
crystal displays and about the related research
for liquid crystal materials. The link between
basic physical effects and display parameters
and the overall performance of liquid crystal
displays will be outlined. The quality of liquid
crystal displays is related with the microscopic
structure of liquid crystals.
 Basics about
active matrix liquid crystal displays

The combination of fluid behaviour, optical and

dielectric anisotropy of liquid crystals is very
important for their use in LCDs. A pre-requisite for
the functionality of an LCD is the existence of a
uniformly oriented range of the liquid crystal
(mono-domain cp. appendix 3).

TN–Cell
The transmissive type TN-cell (Twisted Nematic) [2]
currently is mostly used for active matrix LCDs. A
typical setup is shown in figure 1.

Figure 1:
Setup and function of an LCD- pixel (TN- cell).
Typical liquid crystal layer thickness is between 4µm and 5µm. The glass thickness is around 0.7mm.

5
 The outer surfaces of the glass substrates are laminated
with polarizers with their transmission direction parallel
to the respective rubbing direction of the polyimide film
on the same glass substrate (normally white mode). The
case of two polarizers with parallel orientation is called
normally black mode.

In such a helically oriented birefringent medium,

propagating light can be described by two elliptically
polarized optical modes (Eigen modes). In the Mauguin
limit d·∆n>>Φλ/π (∆n birefringence of the liquid crystal,
d thickness of the liquid crystal layer, Φ twist angle of the
liquid crystal layer, λ wavelength of the light) these Eigen
modes become linearly polarized and linearly polarized
light follows the helix structure during the transmission
(so called wave-guiding).

The cell consists of two glass substrates, being coated (π )

with transparent, electrically conductive ITO (Indium Tin
Oxide) on their inner surfaces. The two glass substrates are Equation 1
kept at a constant distance of some microns by using
"Spacers”. The ITO- electrodes are coated with a thin In the case that the Mauguin limit is not fulfilled, after
polyimide film (some 10 nm thickness), serving as an transmission of the cell, the light generally is elliptically
orientation layer. The liquid crystal mixture is sandwiched polarized. Equation 1 shows the transmission of a TN 90°
between the two polyimide layers and without applied cell as a function of a normalized retardation parameter u.
electric field, the local director (see appendix 1) is almost This equation has been derived by Gooch and Tarry [3],
parallel to the glass surfaces (homogeneous orientation, cp. assuming parallel orientations of both polarizers and a
appendix 3). parallel orientation of the polarizer transmission axis and
In a TN- cell, the two polyimide rubbing directions, are the rubbing direction at the point of light entrance into
twisted against each other. The special case where these the cell.
rubbing directions are perpendicular leads to a TN 90°-
cell (often called TN-cell). In such a perpendicularly
rubbed environment, the liquid crystal shows a helical
configuration.

6
 Basics
Figure 2 shows the Gooch-Tarry-curve. The curve exhibits given by the following equation and is independent
a series of minima and maxima and converges for large of the cell gap of the liquid crystal cell.
values of the parameter u to the Mauguin limit. For display
applications T=0 is required (normally black mode), which
provides for a typical optical wavelength (ca. 550 nm,
where human’s eye is most sensitive) an optimum value of
Equation 2
d ·∆n.
The contrast ratio is defined as the ratio of maximum and
minimum light transmission of the cell. In the TN- case,
this contrast ratio strongly depends on the observation
viewing angle and has its maximum value for perpendicu-
lar viewing angle. Generally, a picture is perceived at a
contrast ratio of 2:1 and for a contrast ratio of 5:1 or
higher, the human perception assigns clear contrast to a
picture. Commercially available active matrix liquid crystal
displays typically provide contrast ratios in the range of
250:1 or higher (assuming perpendicular observation). A
common mean to visualize the viewing angle dependency
of the contrast is the iso-contrast curve, using the polar
angle (angle between observation direction and the normal
of the cell) and the azimuth angle (angle between the
Figure 2: Gooch–Tarry–curve: Transmission of a TN–cell as a function of projection of the observation direction onto the cell and the
the optical retardation u=2d∆n/λ. transmission axis of the first polarizer), cp. figure 4.

The display is then used in this minimum of the Gooch-

Tarry-curve.
In a TN-cell, liquid crystals with positive dielectric
anisotropy are used, which orient parallel to an applied
electric field (figure 1). Usually, the conditions for a simple
wave-guiding are not fulfilled. In the case of crossed
polarizers (normally white mode) the state with applied
electric field corresponds to minimum transmission while
for parallel polarizers (normally black mode) maximum
transmission occurs.
DC- voltage would induce electro-chemical processes in
liquid crystals, therefore, as standard, liquid crystal
displays are driven with AC- voltage. The electro- optical
curve of a TN-cell is shown in figure 3. Only, if the applied
voltage exceeds a threshold voltage Vth (RMS–value) a
Figure 3:
change in the optical transmission is observed. For pre-tilt Electro- optical curve of a TN- cell. RMS– value of the applied voltage
angle zero (cp. appendix 3) the threshold voltage Vth is (typically 1kHz frequency) against normalized light transmission.

7
Figure 4: Iso contrast plot of a TN- cell for crossed polarizers in the 1. Gooch–Tarry–Minimum.

A good dark state

is essential for
good contrast
performance. Therefore,
TN-cells are based on the
first ( ) or second ( )
minimum of the Gooch-Tarry-curve
(fig. 2). For an average wavelength of
550 nm this corresponds to an optical
path length of d·∆n=0.48µm (1st
minimum) or d·∆n=1.07µm (2nd
minimum).
Due to the faster switching time (cp.
appendix 1) and less viewing angle
dependency, the first minimum is
preferred. Cell gaps in commercially
available displays are typically
around 4 µm, needing liquid crystal
mixtures with ∆n (birefringence)
between 0.090 and 0.1050.
 Basic setup
and working
principle

Basic setup and working principle

of an active matrix display
An active matrix display is built of a matrix- type arrangement of rectangular sub-millimeter sized elements (pixel).
Each of these pixels can be addressed individually by an active electric switching element. The active element is a diode
(MIM: Metal–Insulator–Metal) or a transistor (TFT: Thin Film Transistor) and is located at the periphery of each pixel
(cp. figure 1). In this paper, only TFT- matrix displays are discussed due to their dominance in AMDs.

On the upper glass substrate (upper means close to the pixel contains another capacitor (Storage Capacitance,
backlight, cp. figure 1), the TFTs are controlling the Cst) in order to minimize the voltage decrease during the
voltage applied to each pixel; the lower glass substrate is non- select time TF–TS≈TF. The voltage decay is
coated with an ITO-layer, acting as a counter electrode. governed by leakage currents through the liquid crystal,
Usually, the colour filter layer is also placed onto this caused by mobile ions in the liquid crystal and inside the
lower glass substrate, consisting of a two dimensional, polyimide layer [4].
periodic array of colour absorbing surfaces of the basic
colours red, green and blue. Sometimes, this is called
sub-pixel for each basic colour, which is addressed
independently by a TFT.

During the select time TS (TS=TF/N, N: number of rows C st C 1c

of the display matrix, e.g. N=768 for a display with
SXGA resolution), the transistor charges the pixel, acting
electrically as a capacitor. During the frame time TF S D
(typically 16.7 ms, corresponding to an image frequency R 1c
of 60 Hz) all other rows of the matrix are addressed and G
within this time, the voltage decrease at the pixel of
reference must be as small as possible, to avoid optical
contrast degradation. Line by line of the display matrix is
selected via the TFT gate line and the source line is
providing the signal information.

Figure 5 shows a scheme of the electric circuit of a TFT- Capacitor

matrix. The liquid crystal is characterized by its Resistor

resistance Rlc and its capacitance Clc . Additionally, each Figure 5: Equivalent circuit of a TFT–LCD.

9
Stability of a liquid crystal mixture and
picture quality of the display
The liquid crystals used in a display must be stable to ultra violet
light due to the display manufacturing process (which uses UV
sealant), the backlight system and use in sunlight. The liquid
crystal mixture must also be thermally stable. This is necessary
due to the operational temperature and environmental temperature
at which the display works.

For the quality of a display, parameters such as brightness,

contrast, colour authenticity, colour homogeneity, gray scale
capability etc. are important. These parameters are directly
influenced by so called reliability parameters of the complete
system of liquid crystal and display peripheral materials like
orientation layer, glass, ITO, color filter, sealant etc. The reliability
parameters determine the functionality, the optical performance
and the life time of an active matrix LCD. We dedicate appendix 2
for an introduction of these reliability parameters.
Current research and
development activities Research
activities

Current liquid crystal research and development

for displays can be separated into two topics.
One part comprises the synthesis of new liquid
crystals in order to improve the physical
parameters of liquid crystal mixtures. We will
only briefly discuss some basic principles of the
design of new liquid crystal materials.

The second part is the physical assessment of

liquid crystal materials and the development of
new, improved liquid crystal mixtures. In
addition to the "traditional” requirements of
electro-optical, thermodynamic, and dynamic
performance, special display requirements are of
increasing importance (appendix 2). Based on
recent developments of LCDs, the relationship
between tailored liquid crystals and display
properties is outlined.

Focus for current displays and the corresponding

liquid crystal research is on the following areas:

1.) Notebook–PCs
2.) Organizer, PDA (Personal Digital Assistant)
and mobile phones
3.) Desktop monitors and TV–sets
4.) Multimedia–LCD–front projectors,
LCD–rear projection–TVs, View Finder for
digital cameras /Camcorders and portable
mini computers (headset/head mounted
displays).

11
 Chemical structure of some mesogenic materials being used in LCDs.

Figure 6 a: Figure 6 b:
Molecule (Ester linked Molecule with small optical
three ring structure anisotropy (∆n=0.059,
with polar, OCF3– extrapolated) and medium
endgroup) for low dielectric anisotropy
Vth–applications (∆ε=6.8, extrapolated).
(∆ε=15.4, ∆n=0.127,
extrapolated).

1. Liquid crystal mixtures

with low threshold voltage for notebook applications
Liquid crystal mixtures with low threshold voltage (in the following: ’low Vth’) are advantageous for
displays. The possibility of addressing the pixels with lower voltages enables the simplification of the
complete environment- and driving electronics, e.g. smaller driving circuits can be used. The resulting
saving in space and weight is a key issue for notebooks. Additionally, the use of lower voltages reduces
the power consumption of the device.

Drivers with 3.3 V are currently used as standard, and corresponding liquid crystal mixtures have
threshold voltages in the range of 1.3 V and a dielectric anisotropy ∆ε≈10. Some display applications
with 2.5 V drivers are already commercialized. This is also important for low Vth–mixture develop-
ment, targeting mixtures with Vth of about 1.0 V and good reliability properties.

Equation 2 contains two possibilities for influencing Vth, either by changing elastic constants or by
changing dielectric anisotropy. The reduction of the threshold voltage via the elastic constant K11 is not
playing a major role. Nevertheless such effects of elastic constants can be used to optimize the threshold
voltage of liquid crystal mixtures.

12
Figure 6 c: Figure 6 d:
Molecule with ∆ε<0 Molecule with ∆n<0 for reflective type
for VALCDs; applications. The lateral triple bond causes
(∆ε=–5.5, ∆n=0.086, large polarizability perpendicular to the
extrapolated). molecule’s long axis and induces the negative
value of the birefringence
(∆ε≈0, ∆n=–0.005, extrapolated).

A systematic material development stakes on the relationship between the threshold voltage and the
dielectric anisotropy ∆ε.

The dielectric anisotropy of a liquid crystal mixture is obtained in good approximation by linearly
averaging the dielectric anisotropies of the single components in the mixture, weighted with their mass
percentage. Association effects, which induce a preferred parallel or anti-parallel alignment of
molecules, can be described by the Kirkwood factor. In liquid crystal mixtures for display applications,
association effects lead to deviations of ∆ε from the described linear behavior by about <10%. In the
following we will not consider further such non- linearities and assume, that an increase of ∆ε of a
liquid crystal mixture can be achieved by an increase of ∆ε of the liquid crystal singles in the mixture.
This directly implies the search for liquid crystal materials with high ∆ε.

Figure 6a shows a typical liquid crystal material being used in low Vth–mixtures. The material exhibits
liquid crystalline properties with the following phases: K 65 SmA 105 N 154 I. Based on the trifluoro
endgroup, the molecule has a large dipole moment resulting in high value of ∆ε=15. Generally,
molecules with polar endgroups have a big impact in low Vth–mixture development.

13
Using liquid crystals with endgroups of increasing polarity seems to be an appropriate mean for the
development of low Vth–liquid crystal mixtures. The limits of this approach are illustrated in figures 7a
and 7b. So called reliability parameters (e.g. Voltage Holding Ratio ; VHR, cp. appendix 2) are affected
negatively by strongly polar materials, conversely an increase in the dielectric anisotropy of a mixture
tends to increase the rotational viscosity (cp. appendix 1) and hence the resulting switching time. The
value of the Voltage Holding Ratio decreases with increasing ∆ε. Additionally, for TFT- mixtures, only
liquid crystals with fluorinated endgroups can be used. Stronger polar materials, like cyano- endgroups
decrease VHR significantly and must not be used in TFT.

Figure 7b is showing the empirical correlation between the rotational viscosity γ1 and the dielectric
anisotropy ∆ε of a liquid crystal mixture. Strong polar endgroups, like (–O–CF3, –O–CF2, –CF3)
extend the molecule’s long axis, which directly results in an increase of γ1. The corresponding increase
in switching times is acceptable only in a very limited amount.

Basic challenge of the low Vth–mixture development is the development of polar liquid crystal mixtures
with good reliability parameters and small rotational viscosities. For this purpose, Merck uses quantum-
mechanical calculations to predict the interaction of liquid crystals with freely moving ions and
performs experiments, elucidating the interaction of liquid crystals with peripheral materials like
orientation layers.

Figure7 a: Figure 7 b:
Voltage Holding Ratio as a function of the dielectric anisotropy of liquid Rotational viscosity as a function of the dielectric anisotropy of liquid
crystal mixtures. crystal mixtures.

14
2. 2. Liquid crystal mixtures
with small birefringence for reflective
and transflective displays
Reflective and
transflective
The described liquid crystal mixtures for low is parallel to the direction of orientation of the
displays
Vth–applications are almost exclusively used in molecules close to the upper substrate. The
displays based on the TN- principle. The use of a combination of a polarizer and a λ/4–foil
backlight system is typical for TN- cells, converts the entering non-polarized light into
accounting for most of the power consumption circularly polarized light. In the on-state, the
of a liquid crystal display. light is not influenced by the liquid crystal layer
(effective retardation d⋅∆n=0, if the molecules
For mobile and stand- alone applications, the
power consumption has to be reduced. This can
be achieved by using reflective type displays
which use the environmental light and therefore
require no backlight system. Various techniques
for reflective displays have been proposed based
on one of the following principles: Phase-
retardation, rotation of the plane of polarization,
absorption, scattering or Bragg- reflection. So
far, the only commercial success, is the so called
r-TN type, using a polarizer in combination with
a optical retardation film (λ/4–foil). This has
become the dominant technology due to colour
and video- capability in combination with
acceptable contrast ratio.

Like the transmissive TN- display, which requires

a defined value for the product of the liquid
crystal cell gap d and the birefringence ∆n (1st
Gooch-Tarry-Extremum), also for r-TN, the value
of d · ∆n has to be optimized. Depending on the
actual twist angle and the retardation film used,
maximum contrast has to be provided.
Generally, this leads to optical path lengths of
d·∆n≈0.20–0.35µm. The preferred range for the
retardation is one half of the value used for a
TN- cell. Simplifying, this can be explained by
the fact, that in a reflective type display, the light
has to propagate twice through the liquid crystal
layer. Figure 8 is illustrating the generation of
"bright” and "dark” state under the assumptions,
that 1) the cell has a twist angle of 90°; 2) there
is a λ/4 film with its fast axis oriented 45° with
respect to the polarizer axis and 3) the polarizer

15
 are aligned parallel to the electric field), is polarized, and is not blocked by the combina-
reflected by the mirror which changes the tion of the polarizer and the λ/4–foil:
handedness of the circularity, and is blocked by This leads to a bright state.
the combination of polarizer and λ/4–foil:
From a display manufacturing point of view, it is
This leads to a dark state.
very difficult to reduce the cell gap of a display
In the off-state, the circularly polarized light is in order to match the lower value of
converted into elliptically polarized light by the d⋅∆n≈0.20–0.35µm, being required for reflective
liquid crystal layer. After being reflected by the applications. Typically, liquid crystal mixtures
mirror, the light is still elliptically polarized with with lower ∆n–values between 0.060 and 0.080
altered handedness. After penetrating the liquid are used to cope with reflective display optical
crystal layer again, the light is still elliptically requirements. The challenge for the liquid crystal
mixture development are materials with
extremely low ∆n and sufficiently high values of
the dielectric anisotropy in order to ensure, that
Bright (Off) Dark (On) the liquid crystal mixtures can be driven with
realistic driving voltages. Figure 6b is showing a
representative liquid crystal molecule, being
used in current liquid crystal mixtures and
providing only a small contribution to the
Polarizer birefringence of the liquid crystal mixture [5].

λ/4 Foil Typical applications for r-TN displays are PDAs,

hand-geld games, view- finders for digital
Liquid cameras or high- resolution displays for mobile
Crystal phones. This is also the main application field for
layer
so called transflective types of liquid crystal
displays. In this type of display, each pixel is
divided into a reflective and a transmissive sub-
pixel, with an area ratio of about 1:2. The
reflective part exploits the environmental light
(d∆n) refl =0.5(d∆n) trans d∆n= 0 and consists of a reflective substrate layer (e.g.
aluminium), which also acts as electrode. The
transmissive part is acting as a TN- cell. Using
Reflector an optional backlight, the device provides
sufficient contrast in poor environmental light
Figure 8: conditions. For most mobile applications, the
Setup and functionality of a reflective display (skew).
transflective type display has superior optical
performance and is the preferred choice
compared to reflective type displays.

16
 3. New LCD- technologies
for monitor and TV- applications: IPS and VA
For the discussed mobile display applications, power consumption and reduction of weight are most
important. The focus of the LCD- development for monitor- and TV- applications is on the picture
quality (contrast and brightness), the viewing angle dependency and the switching times. Due to the Monitor
increasing number of moving picture internet applications, and the resulting overlap of monitor-, and TV-
video- and TV- technology, the reduction of switching times is the key issue of the liquid crystal applications
material development.

Presently, there are three commercially successful LCD- technologies, matching the difficult requirements
for monitor applications. Apart from TN- displays, already described, which for monitor applications
are equipped with a special optical compensation film (wide view film) for improving their viewing
angle dependency, the so called IPS (In Plane Switching) technology and the VA (Vertically Aligned)
technology are of major importance. These technologies are suitable for monitor- and TV- applications.
Because of their different optical switching behavior they induce various possibilities for the liquid
crystal mixture development.

In Plane Switching (IPS) LCDs

In contrast to the TN- cell, in IPS cells, the electrodes are placed only on one glass substrate [6]. The
resulting electric field is inhomogeneous, and in a first order approximation parallel to the surface of
the substrate (equi-potential lines are perpendicular to the surface of the glass substrate, cp. figure 9).
The molecules are switched in the plane of the substrate (accounting for name "in-plane”), leading to
significantly reduced viewing angle dependency of the transmitted light intensity, compared to a TN-
display. This improved viewing angle dependency, which can be achieved without an additional optical
compensating film is a major benefit for the IPS- technology which makes IPS very attractive for
monitor applications.

IPS Cell
Figure 9:
Liquid Numerical simulation of the
Crystal director distribution and of
Molecules
equi–potential lines in an IPS
cell with applied voltage. Two
outer electrodes (black) and
Equipotential
Lines one inner electrode (red) are
shown on one substrate
(green). The liquid crystal
molecules (lightblue) orient
perpendicularly to the equi-
potential lines (yellow),
darkened parts of the
molecules indicate an
orientation out of the paper
Electrode Electrode Electrode
plane.

17
 TN
IPS
Another particularity of the IPS- cell results of the unique arrangement of electrodes and
orientation layer. While in the TN- case, the equivalent electric circuit of orientation layer
and liquid crystal is a series connection, the IPS- structure provides coupling in parallel of
the orientation layer and the liquid crystal (cp. figure 10). According to Ohm’s law, the
relevant total resistance of an IPS- cell is less dependent of the resistance of the liquid
crystal than in the TN- case. The specific resistance of the liquid crystal mixture in IPS can
be smaller than in TN, still providing sufficient VHR of the pixel. This enables the use of
highly polar cyano- materials in IPS, which cannot be used for TFT-TN liquid crystal
mixtures.
These enhanced possibilities of using liquid crystal materials for the development of liquid
crystal mixtures for IPS pave the way to materials with improved viscous and electro-
optical properties. For example, a typical liquid crystal mixture concept for IPS provides a
rotational viscosity of about 80 mPas, while the value of the rotational viscosity is around
100 mPas for comparable low Vth– mixtures for 3.3 V driving. The slower switching times
in IPS, based on the elastic constant K22, governing the in plane switching effect, are
compensated by the superior material properties of IPS- mixtures and hence the switching
times of IPS and TN are in a similar range. IPS- displays are especially well suited for
displaying optical gray levels and therefore are determined for video- type applications.

Figure 10: Equivalent electric circuit of TN vs. IPS.

TN IPS
Orientation Orientation
layer LC layer

Orientation
layer

LC

Orientation
layer
Orientation
layer

Pixel- Capacitor Pixel-

voltage Resistor voltage
Vertically Aligned (VA) LCDs
For VA- LCDs, homeotropically oriented liquid shifted against each other so that the electric field is
crystals are switched parallel to the glass substrates not purely perpendicular to the glass substrates, but
by applying an electric field. This switching is containing an oblique field component. This
behaviour requires liquid crystal mixtures with induces, as in MVA, a defined switching behaviour.
negative dielectric anisotropy (∆ε<0), which orient In addition to the contrast advantage, already
perpendicular to an electric field. This can be mentioned, VA- technology provides excellent
achieved by introducing lateral polar groups into switching times, almost no viewing angle
mesogenic molecules (cp. figure 6c). The dependency and fulfils all requirements for
homeotropic orientation of the liquid crystals leads successful applications in the field of monitors and
to an almost perfect black state between crossed television [9].
polarizers. VA- monitors provide excellent optical
contrast and usually are driven in the normally
black mode.

As for planar orientation in a TN- display,

homeotropic orientation also requires a preferred
direction for switching the liquid crystals in order
to avoid orientation defects (e.g. reverse tilt
domains, cp. appendix 3). In contrast to planar
orientation, for homeotropic oriented liquid crystals
this defined switching cannot be achieved by the
orientation material and induction of a pre- tilt
angle alone.

In commercially available VA- displays, various

possibilities exist for a defined switching without
reverse tilt domains. In MVA-LCDs (Multidomain
Vertically Aligned [7]) the substrates used are not
flat, but are structured by small protrusions. These
protrusions determine a defined switching direction
for each area (domain). Each pixel is divided into
two or four sub- pixels with different setting of the
switching direction (modulo 180° or 90°, respec-
tively). This improves the viewing angle dependen-
cy. Disclination lines, appearing close to the peaks
of the protrusions, are covered by a light absorbing
layer (so called "black matrix”) and do not
contribute to the active display.

A defined switching characteristic of the liquid

crystal molecules in a VA- display can also be
achieved, without protrusions. In PVA- displays
(Patterned Vertically Aligned [8]), the electrodes are

19
4. 4. Liquid crystal mixtures
with large birefringence for microdisplays

Recently the so called ‘microdisplays' were switching times for moving picture applica-
invented. These are small displays (typically tions. The fast switching times additionally are
smaller than 5 cm) with high resolution, being supported by the high operating temperature
always combined with some kind of optical which is in the range of about 50°C caused by
system. The optical system enables the strong light sources enabling sufficient light
visibility of an image, generated by the display. density for projection.
A common distinction is made between
Special liquid crystal mixture properties can be
personal viewer systems, generating a virtual
deduced directly from the described LCoS-
image on the observer’s retina (e.g. head set
display features: The mixtures need a high
systems) and projection systems, providing an
clearing point (typically ≥90°C) and a large
enlarged picture on a screen which can be
birefringence (typ. ∆n=0.20) due to the low cell
viewed by several people simultaneously (e.g.
gap of LCoS- displays. Since the liquid crystal
rear projection TV- sets with image sizes up to
is exposed to high light intensities, it has to
60 inches). There is an additional distinction
guarantee sufficient stability against visible
between transmissive, reflective and emissive
and UV- light.
systems. The advantage of microdisplays is
their small size and corresponding low costs. In
the following we only briefly introduce liquid
crystal microdisplays, accounting for the major
part of this technology segment.

Most of current projection systems are based

on transmissive TN- cells with poly – silicon
technology (p-Si). This means, that the TFT-
elements are made of poly- crystalline silicon,
instead of amorphous silicon (α-Si). Polysili-
con technology provides higher electron
mobility which leads to a larger integrating
density and better display resolution.

For rear projection TV- sets, LCoS– technology

(Liquid Crystal on Silicon) is of fundamental
importance. LCoS often works with reflective,
TN- like cell configurations, where the light
reflective layer is formed by a silicon substrate.
The liquid crystal cell gap is very small
(typically d ≤ 2 µm), which provides fast

20
Outlook Outlook
Acting as interface between humans
and technology, flat displays are key
compounds in our information
society. In our natural environment,
the importance of toxicological and
ecotoxicological effects is continuous-
ly increasing [14].
The world market for flat panel application. However, in this segment,
displays is booming. Leading market there is also room for optimizing the
research institutes forecast annual existing TFT- technology. For
growth rates of about 20 %. The share example, the main part of TFT-
of LCDs in the flat panel display world displays is based on amorphous
market is currently almost 90 %. silicon technology. The transition to
Presently, the turnover of actively poly crystalline silicon, (p-Si), leads to
driven LCDs is about twice as large as higher charge carrier mobility and to
the turnover of passively driven LCDs. improvement in picture quality
The dominance of high resolution conducted by finer micro structuring
active matrix LCDs will continuously of the pixels.
increase, driven by the following These technology developments are
important trends: The increasing flanked by the permanent develop-
importance of LCDs for desktop ment of new liquid crystal mixtures
monitors, the possibilities of using for display manufacturers by Merck.
LCDs as flat TV- sets, the increase of
Merck is the only non-Asian liquid
sub note-PC and handheld applica-
crystal manufacturer. Merck will
tions (e.g. PDAs, mobile phones,
continuously expand its position as
digital cameras etc.) and a steady
world market leader and will also
development of note- PC applications.
intensively support the liquid crystal
Based on the transfer of voice- display market in the future.
orientation to data- orientation
(Internet, mobile commerce), display
requirements for mobile phones We thank CapCom AG, Darmstadt, and
become more and more severe. In this "Fraunhofer Anwendungszentrum
segment of relative small displays Computergrafik in Chemie und
with high resolution, displays based Pharmazie, Frankfurt” for making
on organic light emitting diodes figure 1.
(OLEDs) show a certain potential for We also thank Dr. Farrand,
Merck NB-C, UK for proof reading.
Appendix 1
“Liquid Crystals“
Liquid crystals combine flow properties of liquids with optical properties of crystals.
They consist of molecules of anisotropic shape (mostly rod-, filament- or disc- like),
interacting with each other and exhibiting self- organizing effects. Between the
crystalline (K) and the isotropic (I) phase, one or several additional phases exist. These
phases are called liquid crystalline phases or mesophases and if a material exhibits
such phases, this is called the mesogenic property of the material.
The transition from the liquid crystalline to the isotropic phase takes place at the
clearing point (the name is based on the drastic reduction of light scattering at this
temperature), a typical phase sequence is named as K 31 N 55 I, which means that the
liquid crystalline phase (in this case: the nematic phase), is located between 31°C and
55°C. The nematic phase is most important for AMLCDs. This phase is characterized by
molecules, that exhibit a statistically preferred angular orientation but do not show
positional long range order.
Nematic phases can be approximately described by two parameters: The director n(r)
describes the macroscopic preferred direction of molecules in a volume, which is small
compared to the total liquid crystal system, but which is large compared to one liquid
crystal molecule. The order parameter
S=<3cos2 θ–1>/2, which describes the
distribution of molecules around the director
direction (θ polar angle) within the volume. The
brackets <..> indicate an ensemble average.
The majority of liquid crystals used in LCD-
applications have an elongated molecular
structure, consisting of two, three or four ring-
type core molecules (e.g. aromatic rings,
cyclohexyl rings etc.), which are either attached
directly or via linking groups. In the terminal
para- position of the core structure further
groups like alkyl-, alkoxy-, fluoro- or carboxyl
may be added. Representative examples of
liquid crystal molecules which are used in
current Merck liquid crystal mixtures are shown
in figures 6a-d.
The anisotropic shape of liquid crystal
molecules leads to anisotropic physical
properties on a macroscopic scale. Describing
an ordered, cylinder- symmetric, nematic liquid
crystal by use of a macroscopic coordinate
system (e.g z- axis in parallel to n), the tensor of
dielectric anisotropy becomes an ellipsoid.

22
Applying an electric field in z- direction provides a
measurement of εz = εll (parallel to the director),
applying the field in x- or y- direction provides a
Physics
measure of ε. This provides the dielectric anisotropy
∆ε = εll – ε⊥. The Maier–Meier theory [10] gives a
Liquid Crystals
simplified relation between ∆ε and the displacement
polarization, orientation polarization (existence of
permanent dipole moments), absolute temperature and
degree of order.

For a uniformly oriented, uni- axial liquid crystal

and induce reaction forces. Location and orientation
(mono- domain), two indices of refraction ne and no
of molecules of a liquid crystal ensemble are
can be observed (ordinary and extra- ordinary index
described by the vector field n(r). There are three
of refraction), which are caused by the molecular
types of deformations: twist, bend and splay. The
anisotropy of polarisability (Lorenz-Lorentz-
elastic energy density of a (non- compressible) liquid
equation). With regard to the director (optical axis) it
crystal for an arbitrary deformation is described in
is ne = nll and no = n⊥ and the value for the optical
the following equation:
anisotropy is ∆n = nll – n⊥.

εj and nj depend on the molecular structure, the order

→→ →→ → → → →
parameter S, the temperature, the frequency of applied f= 21 (K11(∇⋅ n)2 +K22(n⋅ ∇x n)2+K33(n x∇x n)2)
field and the wavelength of the light source. Typical
values for ∆ε of technical relevant liquid crystals are Equation 3
between –10 and +60 (at 20°C and 1kHz frequency of
the applied electric field), typical values for ∆n are Kii are elastic constants of the liquid crystal. Their
between 0 and 0.45 (at 20°C and 589nm light dimension is energy/ length and elastic constants
wavelength). Recently, Merck was successful in the typically are in the range of several pN.
synthesis of nematic liquid crystals with negative
The anisotropic viscous properties of liquid crystals
optical anisotropy (cp. figure 6d), which can be used in
are also of importance for their display behaviour.
liquid crystal mixtures [11]. All single values of ∆ε
The tensor of shear viscosity has five independent
and ∆n are extrapolated (10%-20% single in a liquid
components. From these five components, the
crystalline host mixture), since not every liquid crystal
rotational viscosity γ1, an important parameter for
exhibits a mesophase at room temperature and some
the switching of liquid crystals in displays can be
materials without nematic or even a mesogenic phase
deduced. γ1 basically describes the rotation of the
are used in mixtures. For the extrapolation of liquid
molecule around an axis which is perpendicular to
crystal single values, both the influence of thermal
the local director. The rotational viscosity is of
fluctuations and the influence of the order parameter
major importance, if the director reorients in an
is taken into account.
applied electric field. The switching time in a
For display applications, elastic properties of liquid display is proportional to γ1 · d2 (d thickness of the
crystals are also of importance. Elastic properties are liquid crystal layer) and therefore is temperature
caused by local variations of the director orientation dependent.

23
Appendix 2
“Reliability–Parameter"
Voltage Holding Ratio (VHR)
AMLCDs use the so called frame memory technique, storing charges for pixel driving
until the pixel is addressed in the next driving frame. If the capability of keeping the
charge at a pixel is not sufficient, contrast decrease, non- uniformity of the brightness
or even image flickering can occur.

The capability of keeping charges is called Voltage Holding Ratio (VHR) and is defined
as the ratio of the RMS- voltage at a pixel within one frame- period and the initial
voltage value:

[ ∫ (Voe -t/RC )2dt]

Tf

VHR = 1 1
1/2

Vo Tf O Equation 4

V0 is the voltage applied of the addressing and RC is the time constant of the pixel.
VHR depends on the chemical structure and polarity of the liquid crystal mixture, the
orientation layer, preparation of the test cell and further factors (water content,
impurities, glass etc.). Therefore, VHR comparisons are only helpful if exactly the
same production and experimental conditions of the prepared test cell are used.
Consequently, VHR must be considered as a system parameter (test cell and liquid
crystal) and not as a liquid crystal parameter alone. Empirically, it is found that
increasing ∆ε leads to decreasing VHR (cp. figure 7a).

With increasing concentrations of organic or inorganic impurities, VHR is reduced.

For sufficiently large VHR, both the specific resistance of the liquid crystal and the
use of an ultra-pure polyimide is required. To minimize contamination, optimized
polyimide rubbing is used.
 Image Sticking
The apparent "burning-in” of pictures ( image sticking) of LCDs is undesirable but can occur if
the display is addressed over long time periods.

In all AMLCs, there is a small dc- part of the driving voltage, which leads to the adsorption of
ions at the polyimide orientation layer surface. The underlying physical process is a space
charging polarization process [12].

The surface of the orientation layer cannot leak away adsorbed ions. This forms a constant
electric field and a polarization of the liquid crystal layer. The magnitude of this effect depends
on the number of ions, the ion mobility and the characteristic time constants of the involved
adsorption- and desorption processes [13]. To reduce the image sticking effect, the liquid crystal
Physics
must contain the lowest possible concentration of residual ions.
Liquid Crystals

Appendix 3
“Orientation of liquid crystal molecules –
generating mono- domains"
The generation of a uniformly oriented liquid crystal within the electrode configuration is
crucial for the operation of a display. The molecules have to form a mono- domain.
Some years after the discovery of liquid crystals, their unique orientation behaviour was
realised. A systematic development of surface treatments for the orientation of liquid crystals
was made in the 1970s. One decade later, experimental methods such as AFM (Atomic Force
Microscopy), STM (Scanning Tunneling Microscopy), SHG (Second Harmonics Generation) and
NEXAFS (Near Edge X–Ray Absorption Fine Spectroscopy) were used to investigate the
orientation of liquid crystals on surfaces. This orientation is based on processes like hydrogen
bonding, van der Waals interactions and dipole-dipole interactions between the surface and the
molecules. The orientation is further dependent on interactions induced by the surface topology
and the anisotropic elasticity of the liquid crystal.

Without an external field, two basic types of orientation of the director with regard to the
surface exist: homeotropic (perpendicular) and homogeneous (parallel) orientation. These
two extreme cases are not required for LCDs, since without a certain angle between the
molecules and the substrate surface, orientation defects (so called reveres tilt domains) occur
under an applied electric field. The generation of the required orientation on the surface is
made by special surface treatment methods. The method, mostly used by the LCD- industry,
is the coating of the surface with a some 10 nm thick polyimide film and the rubbing of this
film with a velvet roller.

The rubbing orients the polymer chains, which then can orient the liquid crystal. With this
rubbing technique, pre- tilt angles between 0° and 20° can be adjusted. The combination of the
polyimide, the rubbing parameters and the chemical structure of the liquid crystal determines
the magnitude of the tilt- angle. For AMLCDs pre- imidized polyimides are used, releasing less
water during the tempering process (which increases the pixel resistance) and requiring lower
temperature (only the solvent has to be vapourized). This hampers a diffusion of contaminating
ions from the glass substrate into the inner parts of the display.

25
 Appendix 4
“Toxicological and Ecotoxicological
Investigations of Liquid Crystals"

Toxicological testing strategy for Toxicological and ecotoxicological

liquid crystals at Merck teamwork
Toxicity is the capacity of a chemical to cause The LC division of Merck agreed together with other
adverse effects i.e. functional or structural changes LC producers (together covering well over 90% of the
to a living organism. Toxicity is dependent on the liquid crystal world market), to market no acutely
dose administered, as already Paracelsus (1493- toxic or mutagenic liquid crystals. For more than 250
1541) found: ‘All substances are poison, only the Merck LCs, investigations confirmed that they have
dose makes that a substance is not a poison’. very low toxicological and eco-toxicological
Toxicological studies are designed to reveal such potential (data presented in [14]). This may be
hazardous properties and to provide data for risk summarized as follows:
assessment purposes.
To find possible hazardous properties of these 1. Liquid crystals are not acutely toxic.
compounds, acute toxicity studies, skin and eye 2. A few can be irritant, corrosive, or sensitizing, but
irritation studies and bacterial mutagenicity tests these effects can be avoided by limiting the
have been performed with many liquid crystals. concentration of these substances in mixtures.
Additionally, information on skin sensitization, 3. Liquid crystals are not mutagenic in bacteria
aquatic toxicity and biodegradability is available (Ames test) and in mammalian cells (MLA
for a few LCs. Data from these studies are used in screening; test with mouse lymphoma cells).
human health hazard evaluation and may also 4. Liquid crystals are not suspected of being
serve as basis for classification and labelling of the carcinogenic.
substances. All toxicological studies were 5. They are not harmful to aquatic organisms
performed according to recent International (bacteria, algae, daphnia, or fish).
Guidelines (OECD, EU), and followed the national 6. Some are not readily biodegradable.
regulations for animal welfare as well as the
principles of ‘Good Laboratory Practice’ (GLP).

26
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Merck-brochure "Toxicological and Ecotoxico-
logical Investigations of Liquid Crystals and
Disposal of LCDs", February 2003
Merck KGaA · Germany
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