Optimization of

Liquid Crystals for Television

Detlef Pauluth and Kazuaki Tarumi
Optimization of liquid crystals for television

Detlef Pauluth Abstract — LCD TVs have dramatically improved in performance during the last 2 years. At the same
Kazuaki Tarumi time, the sale prices decreased by more than 50%. Together with the introduction of digital terrestrial
broadcasting, this resulted in increasing sales of LCD TVs. This paper gives an overview of the main
liquid-crystal display (LCD) technologies used for TVs. We discuss key materials, synthesis, structural
property relationships, and the optimization of LC mixture properties. For all technologies, we have
achieved fast-switching LC mixtures (16 msec). Novel materials for LC mixtures for the next generation
of superior performance LCD TVs with 8-msec switching times are shown.

Keywords — Nematic liquid crystals, super fluorinated materials, rotational viscosity, lateral fluori-
nated compounds, stability.

tor of the nematic phase.1 Depending on the molecular

1 Introduction
The first LCD TVs appeared in the Japanese market in the
late 80s. These TVs where based on passive-matrix technol-
ogy and, due to screen diameters of about 5 in. and narrow
viewing angles, were suitable only for personal use. About
10 years later, the first 15-in. TFT-LCD TVs became com-
mercially available. These TVs also suffered from narrow
viewing angles. Low switching speed and very high prices
prevented broader acceptance. The main research target at
that time had been displays for desktop monitors. This
changed after the realization of 15-in. TFT-LCD monitors
for multimedia applications in 1998. Now, large-screen
wide-viewing-angle fast-switching LCD TVs have become
the most important research target of the LCD industry.
Technically, the display of full moving pictures has been the
most challenging point. Therefore, a switching time under
the so-called frame time (see below) of 16 msec was
required. This one-frame switching time can be achieved
together with high brightness, high contrast and good color
quality. For this ambitious goal, the displays, electronics,
and materials had to be improved. In this article, we begin
with an overview of the basic requirements of TV applica-
tion and the essential physical properties of liquid crystals.
We then concentrate on the LC-material development.
2 Basic requirements and physical properties
LCs for commercial application must have a broad nematic
phase range from –40 to 100°C in order to guarantee the
so-called operating temperature range of the display. The
clearing point of a liquid crystal is the temperature at which
the liquid-crystal phase vanishes. It has to be at least 10°C
higher than the operating temperature of the device. To be
able to respond to an applied electric field, LCs must exhibit
a dielectric anisotropy (∆ε), defined as the difference of the
dielectric constants parallel and perpendicular to the direc-
structure, the dielectric anisotropy can be positive (molecu-
lar dipole parallel to the long axis of the molecule) or nega-
tive (molecular dipole perpendicular to the long axis of the
molecule). Elastic constants Ki are the proportional con-
stants between the force (the electric field in case of LCDs)
and the deformation of director fields. The three elastic
constants Ki (i = 1,2,3) are dependent on the deformation of
the director (splay, twist, bend).1 The operating voltage is
proportional to the square root of the ratio between the elas-
tic constants and the dielectric anisotropy. The reorientation
of the LCs during switching depends on the configuration
of the display and the switching mode. The basis of the vis-
ible electro-optical effect is the birefringence (∆n), which is
defined as the difference between the extraordinary refrac-
tive index (light polarized parallel to the director) and the
ordinary refractive index (light polarized perpendicular to
the director). Upon switching, the reorientation of the LC
molecules leads to an effective change in the optical path
which is defined as d∆n (d is the cell gap). This results in a
change in the transmission of the display between 0 and
100%. The switching time of an LCD is proportional to the
rotational viscosity (γ1) of the liquid crystal.2 Recent results
demonstrate, in addition, the importance of the flow effect.3
Low viscosity is the key material parameter for TV applica-
tion. Each pixel in a display is driven by a TFT charging the
pixels by signal pulses. The voltage has to be sustained until
the next refresh signal pulse arrives. This time span is called
one frame time. The voltage drop during this time is char-
acterized by the voltage holding ratio (VHR), which is
defined as the ratio of the voltages at a pixel at the end and
the beginning of the frame time.5 A high VHR is prereq-
uisite for a flicker-free picture.
All structural elements (side chain, rings, linking
groups, and terminal group) of a liquid-crystal molecule
contribute to the physical properties (Table 1). For example,

Received 04/7/05; accepted 6/15/05.

The authors are with Merck KGaA, Research Liquid Crystals Division, Frankfurter Landstrasse 250, 64293 Darmstadt, Germany;
telephone +49-(0)-615-72-6164, fax -2593, e-mail: detlef.pauluth@merck.de.
© Copyright 2005 Society for Information Display 1071-0922/05/1308-0693$1.00

Journal of the SID 13/8, 2005 693

TABLE 1 — Characteristic ∆n, ∆ε, and γ1 ranges4 for different core
structures with polar substituents. R is an alkyl or alkenyl group. Z can
be a COO group, a CH2CH2 group, or a single bond.
benzene rings with polar substituents significantly contrib-
ute to the dielectric anisotropy.
In addition, the aromatic ring contributes to higher
values of the optical anisotropy compared to a cyclohexane
ring. As a consequence, we empirically found limitations for
highly polar liquid crystals with low ∆n values. Other con-
tradictory requirements are the coexistence of a high clear-
ing point and low viscosity and the coexistence of high
polarity and low viscosity. Thus, it is very difficult to obtain
LCs with a high clearing point (broad operating tempera-
ture range) and low viscosity (fast switching) or LCs with
high polarity (low operating voltage) and low viscosity. How-
ever, these are the decisive LC properties for LCD products
(Table 2). Recent breakthroughs to overcome these pheno-
menological limitations have been achieved by the introduc-
tion of the CF2O linking group in dielectrically positive
compounds and by dielectrically negative indane deriva-
tives.
In Table 1, characteristic property combinations for
the most important LC parameters (∆n, ∆ε, and γ1) for dif-
ferent core structures are shown. Additional properties such
as solubility, etc., play a decisive role for practical use. More-
over, liquid crystals must be chemically, photochemically,
and electrochemically stable. Empirically, VHR values
decrease with increasing dielectric anisotropy of the LCs.
The combination of high polarity with high VHR is there-
fore another usually contradictory material requirement.
Only a few super fluorinated materials (SFM) have suitable
property combinations.6
The main material research target is synthesis and
identification of compounds with lower viscosity while
maintaining or even improving the other properties. Com-
puter simulations for the calculation of ∆ε and ∆n based on
694 Pauluth and Tarumi / Optimization of liquid crystals for television
TABLE 2 — Overview material requirements for the most important
active-matrix-addressed LCDs used in LCD TVs.
molecular properties, such as dipole moments and polariza-
tion are often in good agreement with measured values of
LCs.7 Calculated electrostatic potentials give useful hints
for the so-called reliability parameters.8 Computer simula-
tion of bulk properties such as elastic constants, viscosities,
and melting points, on the other hand, are still in an early
stage.9
Single liquid-crystal compounds cannot fulfill the
complex requirements of displays. The wide operating
temperature range in combination with other properties
requires mixtures of typically 10–20 compounds. Neverthe-
less, melting points of LC mixtures are not thermodynami-
cally defined phase transitions but metastable states with a
very long lifetime.
3 LCD technologies for TV application and
their material requirements
3.1 Vertically aligned mode
The vertically aligned (VA) mode LCDs (Fig. 1) was com-
mercially introduced in 199810 in a monitor display. This
mode requires LCs with negative dielectric anisotropy. The
average molecular orientation (director orientation) without
an electric field is perpendicular to the substrate of the dis-
play. With this homeotropic orientation and crossed polariz-
ers, the VA mode works in the so-called normally black
mode. For incident light the liquid crystal in the off-state
behaves like an isotropic medium (the light “sees” only the
ordinary refractive index). As a consequence, very good
black states can be achieved independent of the wavelength
of the light and the operating temperature. Pixel and elec-
trode designs of VA displays allow for a high aperture ratio
(the fraction of transparent pixel area) resulting in high
brightness. These two points are the main reason for the
good contrast of VA LCDs. The first generation already
achieved fast switching times of about 25 msec. Thus, the
VA mode was from the beginning a very promising technol-
ogy because of the combination of intrinsically good con-
trast values and fast-switching times. Challenging points are

FIGURE 1 — Setup and basic principle of the VA switching mode in the
off (left) and on (right) state.
the controlled switching-on mechanism and gray-scale
switching. Because the directors are oriented homeotropi-
cally in the off-state, they can be tilted randomly in any
direction by an electric field. This leads to disclination lines
between domains of equal orientation, thus deteriorating
the optical performance. Several ideas have been developed
to overcome this problem. Additionally, these different
techniques allow the realization of multiple domains, which
lead to excellent viewing angles.11 The gray-scale switching
of VA LCDs is relatively slow compared to other LCD
modes such as TN or IPS because of the low rate of change
of transmission with voltage, especially near the black state.
Recently, this has been significantly improved by the
so-called over-driving technique.12
Regarding material properties, the following basic
requirements must be fulfilled. The standard TFT driver
requires an operating voltage under 6 V. As a consequence,
the dielectric anisotropy of the LC mixture has to be at least
around –3, taking the corresponding elastic constants into
consideration. The switching time from black to white of
25 msec is not sufficient to realize full moving pictures. The
slower gray-scale switching (about 50 msec especially near
black states) made the development of LCs with lower vis-
cosity necessary. The required optical path d∆n is slightly
less than 0.3. For currently used cell gaps, this results in ∆n
values for VA mixtures of around 0.08. Because the viscosity
of LC mixtures in this ∆n range could not be sufficiently
reduced, smaller cell gaps were introduced; 3 µm or even
lower values for the cell gap require higher ∆n values for the
liquid crystals.
The common feature of dielectrically negative liquid
crystals is that lateral polar substituents induce a dipole moment
perpendicular to the long axis of the molecule. Commercial
dielectrically negative liquid crystals are based on the 1,2-
difluoro-benzene building block.13 Difluorinated alkoxy
compounds like 1 and 2 in Table 3 with extrapolated ∆ε
values of about –6 are polar workhorses. But for fast-switch-
ing TV mixtures, the viscosity of phenylbicyclohexyl deriva-
tives like 2 is too high. In the alkyl derivative 3, the viscosity
is in the desired range, but ∆ε is too small. The rings in
phenylbicyclohexyl structures can freely rotate. Neverthe-
TABLE 3 — Liquid Crystals with negative ∆ε and medium ∆n.
less, calculations predicted an increase of ∆ε values for com-
pounds with additional lateral fluorine atoms at the cyclo-
hexane ring like that in 4. This was confirmed by the
experimental values given in Table 3. But γ1 of compound 4
is even higher than that of compound 2. Obviously, lateral
fluorination of the cyclohexane ring has a stronger impact on
γ1 than on ∆ε.
A significant improvement, but with higher ∆n, is cy-
clohexylbiphenyl derivative 5. Whereas ∆ε and the clearing
point are comparable to 2, γ1 is reduced by almost 50%.
The comparison of 5 and 6 demonstrates the influence
of different polar substituents. Substitution of one lateral
fluorine atom by the stronger electron-withdrawing CF3
group results in a desired ∆ε increase of 24%, but at the
expense of a γ1 increase of 174%. As a conclusion, low γ1
values cannot be found for compounds with bulky lateral
substituents. It should also be noted that 6 no longer exhibit
a liquid-crystalline phase.14
A further reduction in viscosity for compounds with
high ∆n is possible when using the terphenyl structure.13,15
9 in Table 4 combines a moderate negative dielectric aniso-
tropy with a high clearing point and a viscosity of only 90 mPas.
As described above, additional lateral fluorination
results in an increase in the negative ∆ε. From 9 to 12, ∆ε
goes from –2.5 to –7.2. On the other hand, the clearing point
goes down from 9 to 12 by more than 130°C. The liquid-
crystalline phase gets lost in hexafluoroterphenyl 12. Even
Journal of the SID 13/8, 2005 695
SCHEME 1 — Synthesis of an indane derivative with negative ∆ε.
though narrow cell gaps had been introduced in the produc-
tion of VA displays, there is a need for fast switching in LC
mixtures with lower ∆n values. Because it was not possible
to make a significant step forward for cyclohexane-based
compounds, it was necessary to identify a novel core struc-
ture. Indane derivatives such as 7 and 816 combine high
negative ∆ε values with low viscosity and low ∆n. Compared
to 1 especially 8 has a significantly higher clearing point, ∆ε
is more negative and γ1 is only slightly increased. The syn-
thesis of 8 is shown in Scheme 1.
A disadvantage of the 2,3-difluoroethoxybenzene
building block is related to the relatively good ion complex-
ing ability resulting in moderate VHR values. Empirically,
VHR values are correlated to electrostatic potentials. Figure
2 shows space filling models of compounds 5 and 10. Elec-
trostatic potentials are visualized using a color code. Com-
pound 5 has two red centers with a strong negative
electrostatic potential allowing strong interactions with cat-
ions. Compound 10 with a similar negative ∆ε shows only
yellow color with a moderate negative electrostatic potential
distributed over the π system.
Higher VHR values for 10 were experimentally con-
firmed. Dielectrically negative terphenyl derivatives are
TABLE 4 — Liquid Crystals with negative ∆ε and high ∆n.
696 Pauluth and Tarumi / Optimization of liquid crystals for television
FIGURE 2 — Space-filling models of compounds 5 and 10. The color is
visualizing electrostatic potentials. Blue represents a positive
electrostatic potential (ESP) and red represents a negative electrostatic
potential. In the oxygen-containing compound 5, the ESP is more
concentrated compared to tetrafluoroterphenyl 10.
promising candidates to improve both γ1 and VHR of VA
mixtures with ∆n values of 0.09 or higher.17 In 8 the nega-
tive charge is distributed over the indane ring system. This
indicates a potential for good VHR values despite a very
negative ∆ε (Fig. 3).
Figure 4 is a typical comparative diagram between the
first generation of LC mixtures for monitor application and
the recently developed LC mixtures for TV application. The
switching times, which are proportional to γ1/∆n2 have been
significantly improved for all important threshold voltages
V0. The compounds of type 1, 2, and 3 are used for LC
mixtures for monitor application mainly in order to meet the
specified ∆n (about 0.08) and ∆ε. In addition to these types
of compounds, cyclohexylbiphenyl derivatives of type 5 and
terphenyl derivatives such as 9 are very effective in improv-
ing γ1 for LCD TV mixtures, maintaining the operating volt-
age of mixtures with higher ∆n values. Fast switching
mixtures with low ∆ values contain indane derivatives such
as 8.
FIGURE 3 — The ESP of the oxygen-containing compound 1 with a ∆ε
of –6.2 has a more negative center compared to the indane derivative 8
with a ∆ε of –8.6.
 SCHEME 2 — Synthesis of a highly fluorinated compound with positive
FIGURE 4 — Dependence of switching-time parameter γ1/∆n2 on the ∆ε.
threshold-voltage V0 of reference (䊏) and new (䊉) VA-mixtures with TNI
= 80–85°C.
uid crystals with an improved relation of ∆ε to γ1. Since the
required d∆n for IPS is a slightly above 0.3, the necessary
3.2 In-plane-switching mode ∆n of LC mixtures is in the range of 0.08–0.09 for standard
In the IPS display the reorientation upon switching takes cell gaps. Up to now, only IPS displays using dielectrically
place in a plane parallel to the substrates18 (Fig. 5). This positive LCs have been commercialized.
requires both electrodes to be constructed on the same side ∆ε values of more than ten combined with ∆n values
of one substrate (referred to as inter-digital electrodes). As of 0.08 to 0.09 can practically not be realized by the use only
a consequence, the viewing-angle dependency of d∆n is of fluorinated benzene ring building blocks. An enhance-
homogeneous. For TV, this intrinsic advantage of good view- ment of ∆ε by polar linking groups or by other polar building
ing angles for IPS displays is very important to minimize the blocks is required (Table 5). The comparison of compounds
color shift that was of lower priority in monitor applications. 11 and 18 shows the effect of the ester group and the com-
Another advantage of IPS displays is the homogeneous gray- parison of compounds 12 and 18, the effect of a dioxane
scale switching behavior, which is the result of a flatter volt- ring.14 If the ester linking group is placed between two aro-
age versus transmission curve compared to VA and TN.
A disadvantage of the inter-digital electrodes is the
limitation of the aperture ratio resulting in lower brightness. TABLE 5 — Liquid Crystals with medium-to-high positive ∆ε.
Thus, one of the most challenging points is to achieve high
brightness in combination with good contrast. A feasible
method to increase the aperture ratio is to increase the dis-
tance between the inter-digital electrodes. But this gives
rise to an increase of the driving voltage. The compensation
requires higher ∆ε LC materials, which normally leads to
higher rotational viscosities, which in turn might deteriorate
the switching times. Consequently, this mode requires liq-

FIGURE 5 — Setup and basic principle of the IPS switching mode in the
off (left) and on (right) state.

Journal of the SID 13/8, 2005 697

 FIGURE 7 — Setup and basic principle of the TN switching mode in the
off (left) and on (right) state.
FIGURE 6 — Dependence of the switching time parameter γ1/∆n2 on
the threshold-voltage parameter V0 ∆n of reference (䊏) and new (䊉) IPS
mixtures with TNI = 70–75°C.
3.3 Twisted-nematic mode
matic rings, the effect is even more pronounced. An addi- The conventional twisted-nematic (TN) mode is the most
tional benefit is the high clearing point of aromatic esters mature LCD mode.25 The first calculator utilizing this
like 13. A disadvantage for application in IPS mixtures is mode was in the marketplace before 1980. The reorienta-
that ∆n is almost doubled.19 tion of the LCs in the TN display upon switching is complex.
Liquid crystals with a CF2O linking group were first Whereas the molecules, without an applied electrical field,
described in 1990.20 At that time, only certain compounds lie in the plane of the display and form a chiral helical
with the CF2O group between two aromatic rings where structure,1,24 they are oriented perpendicular (the helix
accessible via laborious methods. A systematic investigation unwinds) when an electrical field is applied (Fig. 7).25
was not possible. But as the first examples already indicated, This leads to an effective change of the optical path
the potential for compounds with low viscosity existed and (d∆n ~ 0.5) of the LC material. The TN-LCD is driven in
therefore a systematic search for new synthesis methods was
started. In the late 1990s a broad structural variety of CF2O-
linked compounds had been made21 based on new proto- TABLE 6 — Liquid crystals with low-to-medium ∆n.
cols.22 Besides low viscosity another unexpected feature of
some CF2O-linked LCs is the good solubility of highly fluor-
inated compounds. Heptafluoro compound 16 (Table 5) is
well soluble and provides a ∆ε of 25 combined with low γ1
of 96 mPas. The analogous pentafluroro compound 17 with-
out the CF2O linking group has a melting point above 100°C
and poor solubility. By adding two more fluorine atoms to
16 an d in troducing an alkoxy side chain, the ∆ε o f
nonafluoro compound 18 reaches 35. However, compared
to 16, γ1 is more than doubled.
Another approach is the combination of a dioxane ring
with fluorinated benzene rings and the CF2O-linking group
resulting in 19. This four-ring compound combines a ∆ε of
almost 30 with a clearing point about 180°C higher than 16
with relatively low ∆n and acceptable γ1. Compounds based
on these structural features could be important in the
improvement of materials for fast-switching IPS TV dis-
plays.
Figure 6 is a typical comparative diagram between the
first generation of LC mixtures for monitor application and
the recently developed LC mixtures for TV application.
The standard-monitor LC mixtures consist of com-
pounds of type 13, 14, and 15. The combination of these
compounds with CF2O compound 16 and super low viscous
compound 2723 is very effective in achieving higher ∆ε and
lower γ1 for IPS TV mixtures.

698 Pauluth and Tarumi / Optimization of liquid crystals for television


FIGURE 8 — Dependence of the switching time parameter γ1/∆n2 on
the threshold-voltage Vo of reference (䊏) and new (䊉) TN-mixtures with
TNI = 80°C.
the normally white mode (the switching-off state is white).
As already explained in the previous chapters, the quality of
the black state is decisive for the contrast. The first problem
with the TN mode is that in principle infinitely large oper-
ating voltages are needed in order to orient the molecules
homeotropically. And even in this case, the perfect black
state cannot be achieved because the molecules at the align-
ment layers are still oriented homogeneously as a conse-
quence of the strong anchoring between alignment layers
and liquid crystals. Another disadvantage is the limited
viewing angle due to the complex re-orientations between
the switching off- and on-states. This can be improved only
to a certain extent by compensation films,26 finally resulting
in the need for LCs with low-to-medium ∆n values com-
bined with high ∆ε and very low γ1 (Table 6).
Intensive research for materials for TN TFT applica-
tion has been performed since the late 1980s. A huge port-
folio of compounds is available. Polar workhorses for all low
∆n TFT applications are 1,2,3-trifluorobenzene derivatives
such as 13, 14, and 20. Based on new protocols, compounds
with a CF2O-linking group between a cyclohexane ring and
a benzene ring became easily accessible.22 The correspond-
ing compound 21 has almost the same polarity as the ester
compound 13 but a significantly lower γ1 and better reliabil-
ity. Computer simulations predicted an increase in ∆ε for
the combination of a dioxane building block with a 1,2,3-tri-
fluorobenzene building block and a CF2O-linking group. 22
practically turned out not to be an improved “derivative” of
14 because the clearing point dropped by 24°C.
∆n values below 0.06 can only be achieved by com-
pounds with a core made up of saturated building blocks
such as in 23 (Table 6). The obvious disadvantage of this
compound is a clearing point of –20.5°C. Substitution of the
terminal CF3 group by the difluorovinyloxy function results
in 24 with a comparable ∆ε but with a clearing point
increased by 35°C and at the same time γ1 is reduced by
about 30%.14 Compounds containing three cyclohexane
rings like 25 combine a very high clearing point with
FIGURE 9 — Setup and basic principle of the OCB switching mode in
the off (left) and on (right) state.
medium ∆ε and acceptable γ1. But the broad smectic phase
limits the practical use. On the other hand, for the develop-
ment of TFT mixtures for one-frame switching, even the
viscosity of polar single compounds with a CF2O linking
group is still too high. Neutral compounds with very low γ1
such as 27 are essential in reducing the viscosity of mixtures.
Because it was very difficult to make further improvements
with the concept of mixing highly polar compounds with
dielectrically neutral low viscous compounds, recently
medium polar compounds have also become of interest
again. The combination of structural elements from the
most-efficient neutral compounds with the highly polar
OCF3 terminal group (super fluorine) results in compound
26 with an excellent ratio of γ1 to clearing point.27 Figure 8
shows the recent LC material development for TN applica-
tion.
3.4 High ∆n technology
In 1993, the optically compensated bend (OCB)28 mode
was proposed for fast switching TFT-LCDs (Fig. 9). There
have been two challenging points for this technology, to
assure the transition from splay to bend orientation and to
achieve the optical film compensation to the same level as
for IPS and VA. Because it was difficult to find practical
solutions, it took until 2004 for the first OCB displays to
appear in a commercial 23-in. LCD TV.29 This mode
requires liquid crystals with high positive ∆ε values and
large ∆n values.
The increase of the display size is one of the biggest
challenges for the display makers. The largest direct-view
LCD-TV prototype exhibited at conferences in 2004 had a
diagonal of 65 in.30 Even larger sizes are possible with pro-
jection technology. Microdisplays of only 1–2-in. diameter,
driven in the TN mode are the heart of LCD projectors. To
achieve short switching times the cell gap must be small,
typically <2 µm. The operating temperature must be about
50° higher than that of direct-view LCD TVs, and high-
power lamps are used to obtain sufficient brightness. As a
consequence, liquid crystals with high ∆n values, high clear-
ing points, and high thermal and light stability are required.
Journal of the SID 13/8, 2005 699
∆n values of about 0.2 combined with high stability is a fea- TABLE 7 — Liquid crystals with positive ∆ε and high ∆n.
ture of terphenyl derivatives. The fluorinated terphenyl 28
combines a ∆n of 0.218 with a clearing point of almost 80°C,
medium ∆ε, and moderate viscosity. Compared to fluorine,
the polarizability of chlorine is higher. As a consequence,
the ∆n value of the chloroterphenyl 29 is increased to
0.248.31 On the other hand, γ1 of chloroterphenyls such as
29 is relatively high. Dielectrically neutral terphenyls could
be one possibility to reduce the viscosity. But their practical
use is limited by their smectic phases. This can be overcome
by using lateral fluorine as in 30.31 This compound is purely
nematic and combines a high clearing point with low viscos-
ity. High ∆ε compounds require more lateral fluorine sub-
stituents pointing in the direction of the fluorine in the
terminal position such as in 31.14 To compensate for the low
clearing point, polar quaterphenyls are attractive (Table 7).
An additional advantage of quaterphenyl derivatives is the
potential to improve the light stability of LC mixtures.32
Tetrafluoroquaterphenyl 32 offers quite well balanced
properties, a clearingpoint of almost 250°C, a ∆ε of 18, a ∆n
of almost 0.3, and an acceptable viscosity. Unfortunately, the
solubility is limited as a consequence of the high melting
point. So far it was not possible to overcome this problem.
Additional fluorination such as in 33 results in an even
higher melting point. The search for low-melting-point
emissive-display principle, there is almost no viewing-angle
derivatives is ongoing. Quaterphenyls are an ideal target
dependency and the switching time is very fast. One of the
for automated parallel synthesis. The recently developed
convergent synthesis strategy based on a sequence of Suzuki most serious drawbacks, lifetime problems, seems to have
couplings will speed up synthesis and the identification of been significantly improved. Small OLEDs are already used
compounds with better solubility.33 in cellular phones and digital cameras.39 In the second half
of 2004, a medium-sized PDA, which is mainly intended for
entertainment, was released in the Japanese market. The
question of whether OLEDs can also compete with large-
4 Outlook screen LCD-TV technologies already in the market will
LCDs and CRTs have different advantages and disadvan- become clear in the next years.
tages. But the overall picture is that LCD TVs have achieved
the same level of picture quality as CRTs. In the case of
high-definition TV (HDTV), LCD TVs are said to have bet- Acknowledgment
ter picture quality due to the capability of higher resolution. A part of the work reviewed in this article was supported by
To improve the weak points specially for LCD TVs larger
the German Bundesministerium für Bildung und For-
than 30 in., a further reduction of the response time is re-
quired combined with higher contrast of the display.34 The schung (01 B 621/1). We thank our colleagues M. Bremer,
most promising LCD technologies at the moment are VA P. Kirsch, M. Klasen-Memmer, L. Lietzau, A. Manabe,
and IPS due to their unique combination of very good con- E. Poetsch, V. Reiffenrath and A. Taugerbeck for their con-
trast, wide viewing angle, and fast switching times. These tributions and our collaborators in LC R&D for their tech-
technologies will dominate larger TV screens over 30 in. on nical assistance.
the diagonal. A significant growth for LCD TVs is fore-
casted, resulting in a share of about 20% of the total TV
market in 2007.37 References
A competing flat-panel TV technology in the plus-37- 1 G Vertogen and W H de Jeu, Thermotropic Liquid Crystals Funda-
in. size is the plasma-display panel (PDP). Whereas the con- mentals (Springer, Berlin, 1988).
troversial discussion about advantages and disadvantages of 2 K Tarumi, U Finkenzeller and B Schuler, “Dynamic behaviour of
PDPs compared to LCDs is ongoing,34,35 big players in the twisted nematic liquid crystals,” Jpn J Appl Phys 31, 2829–2836
(1992).
TV market have announced to discontinue PDP-TV produc-
3 Y Iwata, H Naito, M Inoue, H Ichinose, M Klasen-Memmer, and K
tion.36 Tarumi, “Transient current of nematic liquid crystals with negative
One of the promising emerging technologies could be dielectric anisotropy induced by step-voltage excitation,” Jpn J Appl
organic light-emitting-diode displays (OLED).38 Due to the Phys 43, 1588, 12B (2004).

700 Pauluth and Tarumi / Optimization of liquid crystals for television

 4 The phase-transition temperatures are given in °C, the γ1 values in
mPas. Phase abbreviations are C = crystalline, Sx = smectic X, N =
nematic, I = isotropic Usually, TNI,extr, ∆ε, ∆n, and γl were determined
by linear extrapolation from a 10% w/w solution in the commercially
available Merck mixture ZLI-4792 (TNI = 928°C, ∆ε = 53, ∆n =
00964). The extrapolated values are corrected empirically for differ-
ences in the order parameter. In some marked cases the mixture
ZLI-2857 (TNI = 823°C, ∆ε = –14, ∆n = 00776) was used for extrapo-
lation. For the pure substances, the mesophases were identified by
optical microscopy and the phase transition temperatures by differen-
tial scanning calorimetry.
5 A Sasaki, T Uchida, and S Miyagami, “Active addressing for flat panel
display,” Proc Jpn Display, 62 (1986).
6 (a) H J Plach, G Weber, and B Rieger, “Liquid crystal mixtures for
active matrix displays using new terminally fluorinated compounds,”
SID Symposium Digest Tech Papers 21, 91–94 (1990); (b) Fluoroben-
zene derivatives and liquid-crystalline medium, EP 0441932 (1989);
(c) Trifluorobenzene derivatives and liquid-crystal compositions con-
taining the same, EP 0387032 (1989); (d) K Tarumi, M Bremer, and
B Schuler, “Development of new liquid crystal materials for TFT
LCDs,” IEICE Trans Electron E79-C, No. 8, 1035–1039 (1996).
7 (a) M Bremer and K Tarumi, “Gas phase molecular modeling of liquid
crystals: Electro-optical anisotropies,” Adv Mater 5, 842–848 (1993);
(b) M Klasen, M Bremer, A Götz, A Manabe, S Naemura, and K
Tarumi, “Calculation of optical and dielectric anisotropy of nematic
LCs,” Jpn J Appl Phys 37, L945–L948 (1998).
8 The calculations were carried out at the B3LYP/6-31G(d)//B3LYP/6-
31G(d) level of theory using the Gaussian series of quantum-chemistry
programs: Gaussian 98, Revision A7 M J Frisch et al, Gaussian, Inc,
Pittsburgh, PA, 1998; Electrostatic potentials are mapped on the
electron density isosurfaces and were visualized using the SPARTAN
program package: SPARTAN ‘02, Wavefunction, Inc, 18401 Von Kar-
man Avenue, Suite 370, Irvine, CA 92612.
9 S Kuwajima and A Manabe, “Computing the rotational viscosity of
nematic liquid crystals by an atomistic molecular dynamics simula-
tion,” Chem Phys Lett 332, 105–109 (2000).
10 K Ohmuro, S Kataoka, T Sasaki, and Y Koike, “Development of super
high-image-quality vertical-aligned mode LCD,” SID Symposium Di-
gest Tech Papers 28, 845 (1997).
11 (a) A Takeda, S Kataoka, T Sasaki, H Chida, H Tsuda, K Ohmuro, Y
Koike, Tsasabayashi, and K Okamoto, “A super-high-image-quality
multi domain vertical alignment LCD by new rubbing-less technol-
ogy,” SID Symposium Digest Tech Papers 28, 1077–1080 (1998); K H
Kim, S-B Park, J-U Schim, and J-H Souk, “New LCD modes for
wide-viewing-angle applications,” SID Symposium Digest Tech Papers
28, 1085–1088 (1998); (c) Y Ishii, S Mizushima, and M Hijikigawa,
“High performance TFT LCDs for AVC applications,” SID Sympo-
sium Digest Tech Papers 32, 1090–1093 (2001).
12 K Sekiya and H Nakamura, “Overdrive method for TN-mode LCDs,”
SID Symposium Digest Tech Papers 32, 114–117 (2001).
13 (a) Difluorobenzene derivatives, EP 0364538 (1988); (b) V Reiffen-
rath, J Krause, H J Plach, and G Weber, “New liquid-crystalline
compounds with negative dielectric anisotropy,” Liquid Crystals 5,
159–170 (1989); (c) M Klasen, M Bremer, and K Tarumi, “New LC
materials for active matrix displays with negative dielectric anisotropy
and low rotational viscosity,” Jpn J Appl Phys 39, L1180–1182 (2000).
14 P Kirsch and M Bremer, “Nematic liquid crystals for active matrix
displays: molecular design and synthesis,” Angew Chem Int Ed 39,
4216–4235 (2000).
15 Fluorinated oligophenyls and their use in liquid crystals materials, EP
87/00515, WO 89/02425 (1987).
16 M Bremer and L Lietzau, “1,1,6,7- Tetrafluoroindanes: improved
liquid crystals for LCD-TV application,” New J Chem 29, 72–74
(2005).
17 Liquid crystalline medium and electro-optical display element, EP-A
1352943 (2002).
18 (a) R Kiefer, B Weber, F Winscheid, and G Baur, “In-plane switching
of nematic liquid crystals,” Proc Jpn Display, 547 (1992); (b) M Oh-e,
M Ohta, S Aratani, and K Kondo, “Principles and characteristics of
electro-optical behaviour with in-plane switching mode,” Proc Asia
Display, 577 (1995); (c) M Oh-e and K Kondo, “The in-plane switch-
ing of homogeneously aligned nematic liquid crystals,” Liquid Crys-
tals 22, 379–390 (1997).
19 K Tarumi, M Heckmeier, and M Klasen-Memmer, “Advanced LC
materials for TFT monitors and TV applications,” J Soc Info Display
10, 127–132 (2002).
20 Difluoromethylene compounds, DE-A 4006921 (1989).
21 (a) Liquid-crystal composition and liquid-crystal display containing
same, JP-A H5-112778, 1991; (b) Difluoroxymethane derivative and
liquid crystal composition, EP 0786445 (1994); (c) S Matsui, T Kondo,
and K Sago, “Synthesis and properties of novel liquid crystalline
compounds having a difluoromethyleneoxy moiety as a linkage group,”
Abstracts of the 19th International Liquid Crystal Conference (2000).
22 (a) Benzene derivative and its production method, U.S. Patent
6231785 (1998); (b) Producing liquid crystals with CF2O bond, US
Patent 6787062 (2000); (c) P Kirsch, M Bremer, A Taugerbeck, and T
Wallmichrath, “Difluoro-oxymethylene-bridged liquid crystals: A
novel synthesis based on the oxidative alkoxydifluorodesulfuration of
dithianylium salts,” Angew Chem Int Ed 40, 1480–1484 (2001).
23 (a) M Schadt, R Buchecker, and A Villiger, “Synergisms, structure-ma-
terial relations and display performance of novel fluorinated alkenyl
liquid crystals,” Liq Cryst 7, 519–536 (1990); (b) M Schadt, “Linear
and non-linear liquid crystal materials and electro-optical effects,
present and future applications,” Liq Cryst 14, No. 1, 73–104 (1993).
24 D Pauluth and A E F Wächtler, Chirality in Industry II, ed. A N
Collins, G N Sheldrake, and I Crosby (Wiley, Chichester, 1997), pp.
263–286.
25 M Schadt and W Helfrich, “Voltage-dependent optical activity of a
twisted nematic liquid crystal,” Appl Phys Lett 18, 127 (1971).
26 E Lueder, Liquid Crystal Displays, ed. A C Lowe (Wiley, Chichester,
2001), pp. 105–114.
27 E Poetsch, V Reiffenrath, and B Rieger, “12-Di-(4-alkenylcyclohexyl)-
ethenes, a new LC material for application in STN displays,” Abstracts
of the 24th Freiburger Arbeitstagung Flüssigkristalle, P01 (1995).
28 T Miyashita, P Vetter, M Suzuki, Y Yamaguchi, and T Uchida, “Wide
viewing angle display mode for active matrix LCD using bend align-
ment liquid crystal cell,” Proc Eurodisplay, 149–152 (1993).
29 Nanao 26-inch commercially available in Japan in 2004, wwwforistv.
30 65-in. Aquos at FPD international at Yokohama, Japan.
31 M J Goulding, S Greenfield, D Coates, and R Clemitson, Liquid
Crystals 14, 1397–1408 (1993).
32 Photostable liquid crystalline medium, WO 2004/035710 (2002).
33 O Deeg, P Kirsch, D Pauluth, and P Bäuerle, “Combinatorial parallel
synthesis and automated screening of a novel class of liquid crystalline
materials,” Chem Commun, 2762–2763 (2002).
34 W Kim, “How to improve large-sized TFT-LCDs for television,” In-
formation Display 20, No. 8, 20–23 (August 2004).
35 L F Weber, “Do LCD TVs really last longer than PDP TVs?,” Infor-
mation Display 20, No. 8, 12–17 (August 2004).
36 Asia Times Online, 23 December 2004, wwwatimescom.
37 DisplaySearch, Quarterly LCD TV Shipment and Forecast Report Q2
‘03, wwwdisplaysearchcom.
38 K M Vaeth, “OLED-display technology,” Information Display 19, No.
6, 12–18 (June 2003).
39 K Allen, “Emerging Displays,” Proc 21st Annual Flat Information
Display Conference (2004).
Detlef Pauluth received his Diploma in chemistry
in 1981 and his Ph.D. in 1984 both from the Uni-
versity of Hannover, Germany. In the same year,
he joined the Central Research and Development
Department of Merck in Darmstadt where he
worked on the development of specialty chemi-
cals and pharmaceuticals. In 1990, he moved, as a
group leader, to the liquid-crystal division. Since
1991, he has been head of the chemical research
department. He has authored about 20 papers
and more than 100 patents.
Journal of the SID 13/8, 2005 701
 Kazuaki Tarumi received his M.S. degree from
Waseda University, Japan. After a scholarship
(Deutscher Akademischer Austausch Dienst), he
worked in a research group in Germany from
1981 to 1987. During this time, he received his
Ph.D. degree in the field of theoretical physics in
1985. From 1987 to 1990, Dr. Tarumi was engaged
at Gunma University, General Study, Department
of Physics in Japan as an assistant professor. He
joined Merck KGaA in 1991 and has been work-
ing in the Physical Liquid Crystal Research department. Since 1998, he
has been head of the physics department. He has published 70 research
papers and more than 100 patents. Dr. Tarumi has obtained several
awards (SID 1996, German Future Prize, 2003).

702 Pauluth and Tarumi / Optimization of liquid crystals for television

Merck KGaA
Liquid Crystals Division
Liquid Crystal Research
Frankfurter Straße 250
64293 Darmstadt
Germany
www.merck.de