U.S. patent application number 11/331357 was filed with the patent office on 2006-10-19 for photo-induced dichroic polarizers and fabrication methods thereof.
This patent application is currently assigned to The Hong Kong University of Science and Technology. Invention is credited to Vladimir Grigorievich Chigrinov, Vladimir Markovich Kozenkov, Hoi Sing Kwok, Elena Karlovna Prudnikova, Wing Chiu Yip.
Application Number | 20060232860 11/331357 |
Document ID | / |
Family ID | 25316566 |
Filed Date | 2006-10-19 |
United States Patent
Application |
20060232860 |
Kind Code |
A1 |
Kozenkov; Vladimir Markovich ;
et al. |
October 19, 2006 |
Photo-induced dichroic polarizers and fabrication methods
thereof
Abstract
The present invention provides a method of forming a polarizing
material comprising exposing a layer of dichroic material to
activating light illumination to provide an ordered structure with
a distinguished absorption axis and thus photo-induce polarization,
and fixing the induced polarization by polymerisation of the
dichroic layer. The present invention also provides novel
polarizing formed thereby. By selectively exposing regions of the
dichroic material to differing activating radiation, different
regions with different polarization axes can be created. The
polarizing material can also be provided with a coating or coatings
to alter the spectral response, and a stack formed of a plurality
if dichroic layers may be provided.
Inventors: |
Kozenkov; Vladimir Markovich;
(Kowloon, HK) ; Yip; Wing Chiu; (Kowloon, HK)
; Chigrinov; Vladimir Grigorievich; (Kowloon, HK)
; Prudnikova; Elena Karlovna; (Kowloon, HK) ;
Kwok; Hoi Sing; (Kowloon, HK) |
Correspondence
Address: |
BUCHANAN, INGERSOLL & ROONEY PC
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Assignee: |
The Hong Kong University of Science
and Technology
|
Family ID: |
25316566 |
Appl. No.: |
11/331357 |
Filed: |
January 13, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09853648 |
May 14, 2001 |
7070913 |
|
|
11331357 |
Jan 13, 2006 |
|
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|
Current U.S.
Class: |
359/487.02 ;
359/487.05; 359/487.06 |
Current CPC
Class: |
G02B 5/3033
20130101 |
Class at
Publication: |
359/491 |
International
Class: |
G02B 5/30 20060101
G02B005/30 |
Claims
1.-12. (canceled)
13. A polarizing material comprising a layer of photochemically
stable dichroic molecules exhibiting photo-induced anisotrophy upon
the absorption of light.
14. (canceled)
15. A polarizing material as claimed in claim 13 wherein said
dichroic absorber is selected from the group consisting of: mono-,
bis-, tris-, and poly-azo dyes, quinone dyes, mono- and
poly-oxyanthraquinone dyes, sulfur-substituted
hydroxythio-anthraquinone dyes, aminohydroxy-anthraquinone dyes,
anthrapyrimidinone dyes, merocyane dyes, azomethine dyes,
polycyclic compounds, benzoquinones, napthoquinones, tolanes,
diphenyls, p-nitroanilines, p-nitrosodialkylanilines,
dialkylaminostyroles.
16. (canceled)
17. A polarizing material as claimed in claim 13 wherein the
polarizing material is provided with a coating of a material
selected to alter the spectral response of said material.
18. A polarizing material as claimed in claim 17 wherein the
selected material is iodine.
19. A polarizing material according to claim 13, wherein said
dichroic molecules are formed within a polymer matrix.
20. A polarizing material according to claim 19, wherein the
polymer matrix is formed of polymeric materials selected from the
group consisting of: polyimide, polyethylene, cellulose acetate,
polystyrene, polycarbonate, polyester, polyacrylonitrile,
polyacetal, polyacrylamide, polybutadiene, polyvinylalcohol,
polymethylmethacrylate, and polyvinylcinnamate
Description
FIELD OF THE INVENTION
[0001] This invention relates to methods of fabricating polarizers
from dichroic materials, and to polarizers fabricated by such
methods. In particular, the invention relates to photochemically
stable dichroic molecules and the device structures, which are
suitable for the fabrication of thin light polarizers.
PRIOR ART
[0002] Light-polarization films or polarizes are major components
liquid crystal displays (LCDs) and other liquid crystal (LC)
devices. Commercial polarizers are usually based on
polyvinyl-alcohol-iodine (PVA) films of 150-400 .mu.m thick. These
polarizers are generally placed on the external glass surfaces of
the LC cell and require protective films (e.g. cellulose triacetate
or cellulose acetate butyrate). The fabrication of such known
commercial polarizers is rather complicated and expensive.
Recently, to improve the cost-effectiveness, there are have been
proposals to fabricate the light polarizers by printing or
photo-alignment technologies.
[0003] In U.S. Pat. Nos. 5,739,296 and 6,049,428, polarizing films
are formed from dyestuffs, which have stable lyotropic liquid
crystalline phases in a wide range of concentrations, temperatures
and pH-values. In a sheared flow, the lyotropic liquid crystal
molecules are self-assembled and oriented preferentially in
connection with the flow direction. When the proper preparation
conditions are met, a well ordered solid phase of the lyotropic
liquid crystal is formed. In certain cases, the order parameter as
a measure of this alignment effect is high, so that this material
is suitable for the fabrication of polarizers. To create this
sheared flow, rollers and blades have been suggested.
[0004] To minimize any defects due to the shear flow alignment, a
photo-alignment technology to prepare the thin photo-patterned
polarizer has bon proposed [V. Kozenkov et al, SID'00 DIGEST, p.
1099]. Since this is a non-contact method, the particulates and
static charges generated can be in principle eliminated. In
addition, the cross contamination problems can be minimized. With a
birefringent mask, this technique makes the fabrication of
multi-domain structures more cost-effective for the wide
viewing-angle LCD applications
SUMMARY OF THE INVENTION
[0005] According to the present invention there is provided a
method of forming a polarizing material comprising the steps of:
(a) forming a layer of a dichroic material on a substrate, and (b)
exposing said layer to activating light illumination to provide an
ordered structure with a distinguished absorption axis. Preferably
the layer may be polymerised.
[0006] Preferably different regions of the polarizing material are
polarized by activating radiation with different polarization axes
so as to produce regions of said polarizing material with differing
axes of polarization. This may be achieved by regions of the layer
being exposed independently by the use of masks to isolate selected
regions for exposure. Alternatively a birefringence mask may be
used to create activating radiation with a selected spatial
distribution of polarization vectors.
[0007] In preferred embodiments the layer may be provided with a
coating (eg iodine) to change its spectral response. If different
regions of the layer are formed with different coatings a
multi-color polarizing material may be produced.
[0008] A stack of layers may be formed on a substrate with the lays
being separated by isolation layers.
[0009] The activating radiation is polarized or non-polarized, but
directed and may be a continuous waveform or may be pulsed. The
polarization of the dichroic layer may be controlled by varying
parameters selected from the group consisting of the incident angle
of the activating radiation, the exposure energy density and the
process temperature.
[0010] According to the present invention there is also provided a
polarizing material comprising a layer of a photochemically stable
dichroic absorber. Preferably the absorber is formed within a
polymer matrix.
[0011] The dichroic absorber may be selected from the group
consisting of: mono-, bis-, tris-, and poly-azo dyes, quinone dyes,
mono- and poly-oxyanthraquinone dyes, sulfur-substituted
hydroxythio-anthraquinone dyes, aminohydroxy-anthraquinone dyes,
anthrapyrimidinone dyes, merocyane dyes, azomethine dyes,
polycyclic compounds, benzoquinones, napthoquinones, tolanes,
diphenyls, p-nitroanilines, p-nitrosodialkylanilines,
dialkylaminostyroles.
[0012] The polymeric materials may be selected from the group
consisting of: polyimide, polyethylene, cellulose acetate,
polystyrene, polycarbonate, polyester, polyacrylonitrile,
polyacetal, polyacrylamide, polybutadiene, polyvinylalcohol,
polymethylmethacrylate, and polyvinylcinnamate.
[0013] The polarizing material may be provided with a coating of a
material (eg iodine) selected to alter the spectral response of
said material.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Some examples of the invention will now be described by way
of example and with reference to the accompanying drawings, in
which:--
[0015] FIG. 1 shows the transmittance of an azodye film during the
pumping (a) and the dark relaxation (b), the molecular
transformation is pumped by a laser beam of about 100 mW/cm.sup.2
at 488 nm or 514 nm, whereas the signal is probed by a 0.2 mW-633
nm laser source,
[0016] FIG. 2 shows the absorption spectra of the exposed azodye
film, A.sub.0 represents the absorbance before the illumination,
and p and s are the suffixes of p- and s-waves,
[0017] FIG. 3 shows the transmission spectra of the exposed azodye
film before (a) and after (b) treatment with iodine,
[0018] FIG. 4 shows an embodiment of the invention in the form of a
multi-layer structure,
[0019] FIG. 5 shows an embodiment of the invention with a polarizer
having areas of different polarization axes,
[0020] FIG. 6 shows another embodiment of a multi-axes
photo-induced polarizer,
[0021] FIG. 7 shows embodiments of the invention with multi-colour
structures, and
[0022] FIG. 8 is an illustration of induced optical anisotropy when
an azodye layer is illuminated obliquely by a polarized or
non-polarized but directed light.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0023] Before describing a number of embodiments and examples of
the present invention, it would be useful to define a number of
terms to be used in this specification.
[0024] By "anisotropically absorbing molecules", reference is made
to compounds with anisotropic geometry, such as rod-shaped or
disc-shaped, which exhibit absorption properties with different
values along different axes. For example, dichroic compounds and
lyotropic liquid crystal compounds are anisotropic absorbers.
[0025] By "linear polarized light" is meant light that is polarized
mostly along one axis (the major axis) of a plane orthogonal to the
propagation direction.
[0026] The term "photochemically active molecules" refers to
molecules that are involved in irreversible or reversible
photochemical reactions. In the solid phase, the quantum efficiency
associated with the photochemical reaction is about 0.1-1.
[0027] The term "photochemically stable molecules" refers to
molecules that are no longer involved in the irreversible or
reversible photochemical reaction. In the solid phase, in such
cases the quantum efficiency associated with the photochemical
reaction is about 10.sup.-8-0.1.
[0028] The term "photostable molecules" refers to cases where the
quantum efficiency associated with the photochemical reaction is
less than 10.sup.-8.
[0029] By the term "photo-anisotropic medium" (PAM) is meant that
the isotropic solid phases of photochemically active,
photochemically stable and photostable molecules exhibit
photo-induced anisotropy (absorption dichroism and birefringence),
upon the absorption of polarized or non-polarized photons. The
induced anisotropy is associated with the direction of polarization
vector, the incident angle and exposure energy of the light
illumination.
[0030] The term "substrate" refers to any medium able to support
the formation of thin surface layers of PAM for example. A
substrate can be any solid combination of layered materials. The
materials can be any combination of glass, silicon, oxides,
plastics and metals. In particular, silver, gold, aluminum,
polyimide, silicon monoxide, indium-tin-oxide, silicon dioxide, and
color filter layers are common examples.
[0031] As will be seen from the following description of preferred
embodiments and examples, the present invention provides
photo-induced polarizers formed of dichroic materials. In
particular, as can be seen from FIG. 1(a), when the dichroic
molecules are exposed to a low power actinic radiation,
long-lasting optical anisotropy and dichroism are
photo-induced.
[0032] There are two major types of physical mechanisms, which give
rise to the photo-induced phenomena. The first is based on
irreversible photo-chemical reactions, such as photo-induced
cross-linking and photo-decomposition. The anisotropic layers
formed in this way are characterized by a small value of the order
parameter (<0.4) and the corresponding low value of the induced
optical anisotropy and dichroism. The order parameter is very
sensitive to the exposure time and chemical content of the
substance and has to be accurately controlled. Moreover the
contamination of the initial substance by the by-products of the
photo-degradation is possible in certain cases. The dichroic
spectra of these substances considerably change its form during the
exposure. All these disadvantages prevent the application of the
absorbing layers, formed by photo-chemical mechanism as dichroic
polarizers.
[0033] The second mechanism is based on the reversible cis-trans
isomerization and Weigert effect, i.e. Brownian motion in a
potential field of the actinic light. The probability .epsilon. of
photo-absorption is proportional to the square of cosine angle
between the polarization vector of actinic light E.sub.hv and the
vectorial absorption dipole .mu..sub.gc, i.e.
.epsilon..about.|.mu..sub.gc.cndot.E.sub.hv|.sup.2. In other words,
the molecules that have their transition dipole moments parallel to
the direction of the polarized light will probably undergo the
conformational molecular changes. Consequently, these will lead to
a non-uniform distribution of molecules. However, with this
mechanism when the pumping light source is removed, the molecules
and domains relax slowly (FIG. 1b). The order parameter as a
measure of these photo-induced effects can be very high in some
dichroic materials, but since these are reversible processes,
blending with a polymer matrix or polymerization to form a network
is preferable so as to fix the alignment against any thermal or
photo perturbation. Therefore, a polarizer can be produced by this
clean and non-contact method. In addition, the fabrication methods
for multi-layers, -axes and -colour photo-induced polarizers based
on the same dichroic materials are described in the following. The
polarizers and the polarizer fabrication techniques described in
this specification are all compatible with current LCD
manufacturing techniques.
[0034] The photo-induced optical anisotropy of PAM takes place due
to the orientational molecular ordering. The major axis of induced
anisotropy is perpendicular to the direction of polarized
activating radiation. It will however be parallel to the plane of
incidence for the non-polarized actinic radiation. Some of the
photochemically stable substances give rise to the high molecular
order parameter S>0.8 and are thermally stable up to the melting
temperature of the substances. In some cases, the corresponding
temperature is 140.degree. C.-180.degree. C. In addition, the
spectral absorption changes of these substances are not
noticeable.
[0035] The PAMs materials can be based on photostable organic
compounds and dichroic dyes with an anisotropic absorption either
in UV-, visible or IR-spectral region in the range between 200 and
2000 nm and, in particular, in the visible region between 400 and
800 nm.
[0036] These substances belong to the following dye groups: mono-,
bis-, tris- and poly-azo dyes, metal-complex azo dyes; quinone
dyes; mono- and poly-oxyanthraquinone dyes, sulphur-substituted
hydroxythio-anthraquinone dyes, aminohydroxy-anthraquinone dyes;
anthrapyrimidinone dyes; merocyane dyes; azomethine dyes;
polycyclic compounds; benzoquinones and naphthoquinones; tolanes;
diphenyls; p-nitroanilines, p-nitrosodialkylanilines;
dialkylaminostyroles etc. Besides, these substances can have
bi-functional reactive groups, which polymerize by thermal or photo
treatment to form a polymer network. Alternatively, these
substances can be introduced as the chromophores in the polymer
matrix. Some examples of the polymer matrix are polyimide;
polyethylene, cellulose acetate; polystyrene; polycarbonate;
polyester; polyacrylonitrile; polyacetal, polyacrylamide;
polybutadiene; polyvinylalcohol; polymethyl-methacrylate;
polyvinylcinnamate. In both cases, the thermal, optical, electrical
and mechanical properties can be improved. Usually the
concentration of the substances in the polymer matrix does not
exceed 5-15 wt/wt % so that the final thickness cannot be too thin
however. The additives, which promote good adhesion, suitable
viscosity and low curing temperature, can also be introduced.
[0037] Various methods can be used to put the PAM layer to the
substrate, including spin-coating, dipping, spraying, brushing,
printing, Langmuir-Blodgett technique and thermal evaporation in
vacuum.
[0038] The following examples demonstrate the device structures,
fabrications and applications of the photo-induced polarizers using
the PAM materials. The PAM layers, obtained in the following
examples, can be deposited on rigid or flexible substrates.
EXAMPLE. 1
[0039] A thin film of the following azodye (1) ##STR1## is prepared
by the method of vacuum sublimation at pressure of about 210.sup.-5
mm Mercury. The deposition temperature onto two glass plates is
20.degree. C. The melting temperature of the azodye is 146.degree.
C. The deposition rate is 0.93 nm/sec and the total deposition time
is 4.5 minutes. The final thickness of the azodye layer is 0.25
microns. During the deposition process, one of the glass plates is
in-situ exposed to a linearly polarized light. The light is
generated by a 250-Watt Mercury lamp with peak wavelength at 546 nm
and the power density is 22.3 mW/cm.sup.2. The same polarized light
exposes the second glass plate after the azodye layer has been
formed. It is found that the photo-induced optical retardation of
the azodye, which is measured at wavelength 632.8 nm, is equal to
.lamda./12. This is significant for many display applications. The
energy densities for the first and second glass plates are about
4.1 J/cm.sup.2 and 12.7 J/cm.sup.2 respectively.
EXAMPLE. 2
[0040] Another useful azodye (2) is shown below. ##STR2##
[0041] To prepare the PAM layer, 1-10 wt % solution of the azodye
in chlorobenzene is spin-coated on a glass substrate at room
temperature. This solid dye film is then irradiated at normal
incidence by a polarized UV light. The light source is a 1000 W
Oriel Xenon arc lamp. The UV sheet polarizer is purchased from
Oriel Instruments. The intensity of polarized UV light at 365 nm is
about 6 mW/cm.sup.2. The energy density is about 10.8 J/cm.sup.2.
In FIG. 2, the absorption spectra of azodye (2) are shown, and the
order parameter calculated in this case is 0.86. FIG. 2 shows the
absorption spectra prior to exposure to polarized light (Ao) and of
the p (Ap) and s (As) waves respectively after exposure to
polarized light. The high absorption of the p wave in contrast to
the s wave shows that the azodye layer is effectively
polarized.
EXAMPLE. 3
[0042] The azodye layer can have a top coating of iodine or alcohol
molecules. Such a coating may change the spectra of the dye making
it more useful for applications in the visible light range. FIG. 3
shows the transmission spectra of the azodye (2) before (a) and
after (b) the treatment with iodine. The exposed PAM layer is
prepared in accordance with Example 2, and then the iodine
molecules are evaporated at room temperature and atmospheric
pressure. The film thickness of iodine molecules has been measured
in a control experiment. In the present example, a thin film of
about 20 nm is deposited on top of the exposed PAM layer. The
coated layer is stable against the ambient light and low power
laboratory lasers.
EXAMPLE 4
[0043] To optimise the extinction ratio and optical transmittance,
a multi-layers structure may be formed as shown in FIG. 4. The
exposed PAM layer, which has a top coating of iodine, is prepared
in accordance with Example 3. However, the thickness of the PAM
layer and the top coating are reduced accordingly. To isolate this
coated layer from each other, a thin layer about 10 nm of polymer
such as polyvinyl-alcohol is thermally evaporated onto the iodine
layer. This embodiment of the invention improves both the optical
and mechanical properties of the resultant polarizer.
EXAMPLE 5
[0044] The preferred orientation of the dye molecules and
consequently the direction of the polarization axis can be
independently varied in different surface regions. The sizes of
these regions may vary from several microns to tenths of
centimeters. FIG. 5 shows an embodiment of the invention in the
form of a multi-axis photo-induced polarizer, which has different
local polarization axes in different regions. A dichroic layer 2 is
formed on a substrate 2 and is divided into a plurality of regions
3. Each region 3 is exposed selectively by polarized light in order
to induce the polarization shown by the polarization axes 4. The
different regions may be formed by masking the remainder of the
azodye layer and subjecting a selected region to a particular form
of polarized light. Each region may thus be polarized in turn. FIG.
6 provides another possible realization of the multi-axes
polarizers. FIG. 6 shows the result of illuminating a plate bearing
a dichroic layer with axially polarized light and allowing the
plate to rotate. This creates the polarization distribution shown
in FIG. 6. Because the dichroic layer will be polarized in a
direction perpendicular to the axis of the polarizing light, the
rotational movement of the plate results in circumferential
polarization. The photographs in crossed polarizers illustrate the
corresponding distribution of the intensity variations.
EXAMPLE 6
[0045] The absorption bands of the dye molecules and consequently
the colour can be independently varied in different surface
regions. The sizes of these regions vary from several microns to
tenths of centimeters. FIG. 7 (a) and (b) show the multi-colour
photo-induced polarizers, which have different local absorption
spectra in different regions. In the figures the letters R, G, B
and D stand for red, green, blue and dark respectively am examples.
This can be achieved by applying different coatings to different
regions in order to provide different spectral responses in the
various regions.
EXAMPLE 7
[0046] The direction of polarization axis can be induced using the
obliquely incident polarized or non-polarized light (FIG. 8). The
optical anisotropy and dichroism depend on the exposure energy,
incident angle and process temperature. This makes possible the
uniform polarization direction on the curved surface (e.g. lens) or
micro-objects with a surface relief profile (e.g. diffraction
gratings).
[0047] It will thus be seen that, at least in its preferred forms,
the present invention provides novel device structures and
fabrication technologies for photo-induced polarizing materials.
When the dichroic molecules are optically pumped by a polarized
light beam, the probability of their transformation is proportional
to the square of the cosine .theta., the angle between the
transition dipole moments of the molecules and the direction of the
polarized light. In other words, the molecules that have their
transition dipole moments parallel to the direction of the
polarized light will probably undergo the transformation. To
minimize the dipolar absorption at the low power density regime,
cis-trans isomerization and/or thermal diffusion in a potential
field of the actinic light occurs and both lead to a non-uniform
distribution of the molecules. In certain dichroic materials, these
give rise to long-lasting optical anisotropy and dichroism that are
able to polarize the light wave selectively. In a polymer matrix,
this induced optical anisotropy and dichroism can be even higher
and kept for a long time. This can also be accomplished if the
dichroic molecules can be polymerized by thermal or photo
treatment. Therefore, a permanent polarizer can be fabricated by a
non-contact technique that basically require an actinic radiation
source. In preferred forms of the invention, multi-layers, -axes
and -colour polarizers using these dichroic materials are also
possible and which may have applications, for example, for the wide
viewing-angle LCD applications.
* * * * *