# Patent

## Title
Method of fabricating electro-optical devices with polymer-stabilized liquid crystal molecules

## Abstract

In a preparation method, a chiral or cholesteric liquid crystal, a photoreactive monomer, and a photoinitiator are disposed in a liquid crystal cell. A principal surface of the liquid crystal cell is illuminated with ultraviolet light selected to have a non-uniform ultraviolet light intensity profile in the liquid crystal cell. The illuminating cooperates with the photoinitiator to polymerize at least a portion of the photoreactive monomer near the principal surface to generate a polymer network having a density corresponding to the non-uniform ultraviolet light intensity profile. The polymer network biases the liquid crystal toward a selected helical alignment direction. In some embodiments, the illuminating includes illuminating with first and second ultraviolet light intensity profiles to produce surface and volume polymer network components.

## Background
This application is a continuation-in-part of application Ser. No. 10/766,273 filed Jan. 28, 2004, which has since issued as U.S. Pat. No. 7,038,743 (issued May 2, 2006). Application Ser. No. 10/766,273 filed Jan. 28, 2004 is incorporated herein by reference in its entirety.


BACKGROUND
The present invention relates to the liquid crystal arts. It particularly relates to liquid crystal modulators for applications such as optical waveguides, optical beam scanners, computer-generated holograms, adaptive optics, flat-panel liquid crystal displays, and the like. However, the invention will also find application in conjunction with other electro-optical devices employing liquid crystals.
Liquid crystal materials include anisotropic molecules that can be electrically or magnetically aligned, tilted, rotated, or otherwise manipulated. For example, in nematic liquid crystal phases, the long axis of the anisotropic molecules are generally aligned, but there is substantially no translational ordering. In smectic liquid crystal phases, the long axis of the anisotropic molecules are generally aligned, and additionally some translational ordering is present.
In chiral or cholesteric liquid crystal phases, a mesoscopic helical ordering is also present. The long axis alignment of molecules is relatively rotated between successive layers of molecules, creating a helical rotation along a helix direction that is generally transverse to said layers. A helical pitch is defined as the average distance along the helix direction over which the relative rotation of successive layers corresponds to a complete 360° helical rotation of the anisotropic molecules. For short helical pitches of around 0.2-0.5 micron, the helical characteristic optically manifests as uniaxial birefringence with an optic axis along the helix direction.
In one typical electro-optic device, liquid crystal material is disposed between spaced apart confining surfaces, such as glass surfaces, at least one of which is light transmissive. For light transmission applications, both spaced apart confining surfaces are light transmissive. To induce lateral ordering of the anisotropic liquid crystal molecules, one or both confining surfaces are preferably anisotropic surfaces. For example, a thin polymer coating such as a polymide can be spread on the exemplary glass substrate and rubbed in a selected direction to provide a suitable anisotropic surface for inducing substantial lateral ordering of the liquid crystal molecules.
In the case of short-pitch chiral or cholesteric liquid crystal devices, the helix direction can be aligned perpendicular to the confining surfaces (called a Gradjean texture) or can be aligned parallel to the confining surfaces (called a fingerprint texture). Typically, the fingerprint texture has the helix axes randomly distributed with no long-range ordering in the plane of the confining surface. However, in electro-optic devices the rubbed or otherwise anisotropic surface preferably induces a uniformly lying helix texture in which the helix axis lies parallel to the confining surfaces along a selected helix alignment direction.
The uniformly lying helix texture is optically uniaxially birefringent with an optic axis along the helix alignment direction. In some liquid crystal materials arranged in a uniformly lying helix texture, application of a relatively small electric field directed perpendicular to the confining surfaces induces a flexoelectric in-plane deviation of the optical axis. For higher electric fields, dielectric coupling is present and the helix begins to unwind. At sufficiently high electric field, the helix is substantially completely unwound, producing a homeotropic texture.
For electro-optic device applications, a problem arises in that the unwinding of the helix is generally not completely reversible, and can produce degradation of alignment by the confining surfaces since either the planar or homeotropic surface condition supports the unwound helical structure in the uniformly lying helix texture, and the like. As a result, the electro-optic device does not fully return to the uniformly lying helix texture after the applied electric field is removed.
To address such problems, polymer stabilization of the uniform lying helix texture has been employed. In one configuration described in P. Rudquist, L. Komitov, and S.T. Lagerwall, Liquid Crystals volume 24, page 329 (1988), 10 wt % of a photoreactive monomer dissolved into a cholesteric liquid crystal was optically polymerized to produce a stabilizing polymer network which provided effective stabilization of the uniformly lying helix texture. However, the polymer network produced substantial residual birefringence that decreased cell contrast in the unwound state. This residual birefringence substantially decreased contrast and modulation efficiency and degraded switching time of electro-optic switching devices.
The present invention contemplates an improved apparatus and method which overcomes the aforementioned limitations and others.
SUMMARY
According to one aspect, a preparation method is disclosed. A chiral or cholesteric liquid crystal, a photoreactive monomer, and a photoinitiator are disposed in a liquid crystal cell. A principal surface of the liquid crystal cell is illuminated with ultraviolet light selected to have a non-uniform ultraviolet light intensity profile in the liquid crystal cell. The illuminating cooperates with the photoinitiator to polymerize at is least a portion of the photoreactive monomer near the principal surface to generate a polymer network having a density corresponding to the non-uniform ultraviolet light intensity profile. The polymer network biases the liquid crystal toward a selected helical alignment direction.
According to another aspect, a method is disclosed for fabricating an electo-optic device. A liquid crystal and a photoreactive monomer are disposed in a liquid crystal cell. The disposed photoreactive monomer is less than 5 weight percent of the disposed liquid crystal. The liquid crystal is arranged in a uniformly lying helix texture. The photoreactive monomer is optically polymerized to form a stabilizing polymer network.
According to another aspect, a preparation method is provided. A chiral or cholesteric liquid crystal and a photoreactive prepolymer are disposed in a gap of a liquid crystal cell. A first principal surface of the liquid crystal cell is illuminated with a first ultraviolet light selected to have a non-uniform light intensity profile in the gap of the liquid crystal cell. The illuminating causes polymerization of a portion of the photoreactive prepolymer near the first principal surface to generate a surface polymer network component having a density corresponding to the first light intensity profile. A second principal surface of the liquid crystal cell is illuminated with a second ultraviolet light selected to have a substantially uniform light intensity profile in the gap of the liquid crystal cell. The illuminating causes polymerization of a portion of the photoreactive prepolymer to generate a volume polymer network component that is substantially uniform across the gap of the liquid crystal cell. The surface and volume polymer network components define a polymer network that biases the liquid crystal toward a selected helical alignment direction.
Numerous advantages and benefits of the present invention will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiment.



BRIEF DESCRIPTION OF THE DRAWINGS
The invention may take form in various components and arrangements of components, and in various process operations and arrangements of process operations. The drawings are only for the purpose of illustrating preferred embodiments and are not to be construed as limiting the invention.
FIG. 1 shows a cross-sectional view of an electro-optic device employing a stabilizing single-surface polymer network.
FIG. 2 shows a cross-sectional view of an electro-optic device employing a stabilizing double-surface polymer network.
FIG. 3 shows a cross-sectional view of an electro-optic device employing a stabilizing volume polymer network.
FIG. 4 shows switching behavior of a volume-stabilized electro-optic device responsive to a square wave voltage input.
FIG. 5 shows switching behavior of a volume-stabilized electro-optic device responsive to a triangle wave voltage input.
FIG. 6 shows switching behavior of a double-surface-stabilized electro-optic device responsive to a square wave voltage input.
FIG. 7 shows switching behavior of a double-surface-stabilized electro-optic device responsive to a triangle wave voltage input.
FIG. 8 shows a cross-sectional view of an electro-optic device employing a stabilizing polymer network including both surface and volumetric components.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to FIGS. 1-3, three example electro-optic devices are described. The example devices of FIGS. 1 and 2 are known in the art as surface-stabilized devices in which a stabilizing polymer network is substantially restricted to a surface sub-region. The example device of FIG. 3 is known in the art as a volume-stabilized device in which the stabilizing polymer network is substantially uniform throughout the liquid crystal. It will be appreciated that the polymer networks of FIGS. 1 and 2 are not drawn to scale, and typically reside close to the confining surfaces, that is, within a thin surface sub-region. However, it is also to be appreciated that a continuum of polymer network distributions can exist ranging from a network confined very close to the confining surfaces to the spatially uniform volume-stabilized device of FIG. 3. Thus, the term “surface-stabilized sub-region” does not define any particular thickness of the region containing the polymer network.
With reference to FIG. 1, a surface-stabilized electro-optic device includes a liquid crystal cell 10 having two spaced apart principal confining substrates 12, 14, at least one of which is light-transmissive, and confining side surfaces 16, 18. For light transmission applications, both confining substrates 12, 14 should be light-transmissive. In one suitable embodiment, the confining surfaces 12, 14 are glass plates. Electrodes 20, 22 are disposed on facing surfaces of the confining substrates 12, 14. In one embodiment the electrodes 20, 22 are substantially light-transmissive metal oxide films. At least one of the two spaced apart principal confining substrates 12, 14, specifically the substrate 14 in FIG. 1, includes an anisotropic alignment surface 24 with an anisotropic surface morphology produced by rubbing, anisotropic chemical etching, or the like. In one embodiment the anisotropic alignment surface 24 is provided by spreading a thin polymer coating such as a polymide on the electrode 22 and glass substrate 14, and rubbing the polymer coating in a selected rubbing direction to induce surface anisotropy. A gap G is defined between facing confining surfaces of the two spaced apart principal confining substrates 12, 14.
Within the gap G a liquid crystal material 30 is disposed. The liquid crystal 30 is preferably a chiral liquid crystal such as a cholerestic liquid crystal material, a smectic C* phase liquid crystal material, or the like, which possess a helical molecular order. The liquid crystal 30 is further preferably a short-pitch chiral or cholesteric liquid crystal. The short pitch preferably is less than about 0.5 microns, and more preferably is between about 0.2 microns and about 0.5 microns. However, longer-pitch chiral or cholesteric liquid crystal materials can be used. The liquid crystal material 30 preferably exhibits birefringence for visible light when in the chiral or cholesteric liquid crystal phase, but preferably does not exhibit substantial birefringence when electrically biased into an unwound or homeotropic texture phase.
The liquid crystal material 30 preferably has a uniformly lying helical texture in which the helix axis of the chiral or cholesteric liquid crystal 30 lies parallel to the principal confining substrates 12, 14 along a selected helical alignment direction. Depending upon the pitch of the chiral or cholesteric liquid crystal 30 and the size of the gap G, the selected helical alignment direction can be oriented parallel or perpendicular to the rubbing direction or other anisotropic direction defined by the anisotropic alignment surface 24.
A stabilizing polymer network 32, indicated diagrammatically in FIG. 1, is disposed adjacent the anisotropic alignment surface 24 and extends partway into the gap G. Although FIG. 1 shows a disordered stabilizing polymer network 32, it is also contemplated to use a partially or fully ordered stabilizing polymer network in which, for example, the polymer chains are aligned generally perpendicularly to the confining surfaces 12, 14. The stabilizing polymer network 32 preferably is less than about 5 weight percent (5 wt %) of the liquid crystal material 30, and more preferably is less than about 3 weight percent (3 wt %) of the liquid crystal material 30.
At least one electrode is provided to electrically bias the gap G. Preferably, the pair of electrodes 20, 22 selectively produce an electric field within the gap G directed generally transverse to the facing confining surfaces of the substrates 12, 14. If during electro-optic operation light passes through the confining surface on or in which an electrode is disposed, then the electrode should be substantially light transmissive. For example, a substantially transparent indium tin oxide film can be used, the electrode can be a substantially light transmissive thin metal film, or the electrode can be a gridded electrode having openings for light to pass through.
In one embodiment, the stabilizing polymer network 32 is formed as follows. Initially, a photoreactive monomer is dissolved in the liquid crystal material 30. The uniformly lying helical texture is produced by heating, electrical biasing using electrodes 20, 22, or a combination thereof. The stabilizing polymer network 32 is formed by optically polymerizing the photoreactive monomer using ultraviolet light 46 (indicated diagrammatically by dashed arrows in FIG. 1). To promote the optical polymerizing, a photoinitiator is preferably dissolved into the liquid crystal material 30. In a typical chemical reaction leading to optical polymerization, the monomer includes photoreactive ends that bind with the photoinitiator.
A photon energy or free-space wavelength of the ultraviolet light 46 is selected to have a non-uniform ultraviolet light intensity profile 50 in the liquid crystal material 30. The non-uniform ultraviolet light intensity profile 50 is graphically indicated in FIG. 1 at the left-side of the liquid crystal cell 10, and has a generally exponentially decaying shape according to:

I(x)=Io·e−αx  (1),

where Io is an initial intensity of the ultraviolet light 46 just inside the anisotropic alignment surface 24, the “x” is a distance measured from just inside the anisotropic alignment surface 24, I(x) is the ultraviolet light intensity profile, and α is an absorption coefficient of the ultraviolet light 46 in the liquid crystal material 30.

The ultraviolet light 46 is preferably produced by an ultraviolet fluorescent tube, although an ultraviolet laser or other ultraviolet source can be used. Because the absorption coefficient α is generally wavelength dependent, in the case of a polychromatic ultraviolet source a wavelength-selective filter is preferably inserted between the ultraviolet source and the liquid crystal cell 10 to provide monochromatic ultraviolet light 46.
In exemplary FIG. 1, the exponential intensity decay of the ultraviolet light 46 in the liquid crystal material 30 results in a density profile of the stabilizing polymer network 32 that generally corresponds with the non-uniform ultraviolet light intensity profile 50 of the ultraviolet light 46. This causes the stabilizing polymer network 32 to generally lie within a distance dpoly of the anisotropic alignment surface 24. As diagrammatically indicated in FIG. 1, some polymer chains may reside or extend beyond the distance dpoly. By employing a non-uniform density of the stabilizing polymer network 32 with a highest density near the anisotropic alignment surface 24, the stabilizing polymer network 32 effectively stabilizes the uniformly lying helix texture without producing substantial residual birefringence, optical scattering, or other deleterious effects. The overall mass of the stabilizing polymer network 32 is reduced, enabling a reduction in the amount of source material. The monomer concentration dissolved into the liquid crystal material 30 before optical polymerization preferably is less than about 5 weight percent (5 wt %) of the liquid crystal material 30, and more preferably is less than about 3 weight percent (3 wt %) of the liquid crystal material 30.
FIG. 1 shows a surface-stabilized electro-optic device, in which the anisotropic alignment surface 24 serves as an alignment surface and the stabilizing polymer network 32 is substantially confined to within the distance dpoly of the anisotropic alignment surface 24. In other words, the electro-optic device includes a liquid crystal bulk layer and a surface sub-region containing the stabilizing polymer network 32. This device is suitably referred to as a surface-stabilized chiral or cholesteric electro-optic device.
With reference to FIGS. 2 and 3, other suitable electro-optic devices are shown. In FIGS. 2 and 3, components corresponding to components of FIG. 1 are labeled with similar primed and double-primed reference numbers, respectively. Thus, the exemplary electro-optic device of FIG. 2 includes a liquid crystal cell 10′ with two spaced apart principal confining substrates 12′, 14′ having facing confining surfaces defining a gap G′, confining side surfaces 16′, 18′, electrodes 20′, 22′, and a liquid crystal material 30′ disposed within the gap G′. Similarly, the exemplary electro-optic device of FIG. 3 includes a liquid crystal cell 10′′ with two spaced apart principal confining substrates 12′′, 14′′ having facing confining surfaces defining a gap G′′, confining side surfaces 16′′, 18′′, electrodes 20′′, 22′′, and a liquid crystal material 30′′ disposed within the gap G′′.
The surface-stabilized electro-optic device of FIG. 2 differs from the electro-optic device of FIG. 1 primarily in that both principal confining substrates 12′, 14′ have alignment surfaces. The confining substrate 14′ has an anisotropic alignment surface 24′ formed by rubbing or another process, while the confining surface 12′ has an anisotropic alignment surface 64. During the optical polymerization, first ultraviolet light 46′ illuminates the gap G′ through the principal confining substrate 14′ with ultraviolet light intensity profile 50′, and produces a first stabilizing polymer network portion 32′ generally extending a distance dpoly′ into the gap G′. A second ultraviolet light 66 illuminates the gap G′ through the principal confining substrate 12′ with ultraviolet light intensity profile 70, and produces a second stabilizing polymer network portion 72 generally extending a distance dpoly,2 into the gap G′. Thus, the stabilizing polymer network 32′, 72 has a higher density near each alignment surface 24′, 64′ and a lower density near a center of the gap G′. It will be appreciated that the ultraviolet light intensity profiles 50′, 70 and corresponding distances dpoly′, dpoly,2 may be different, although for simplicity they are drawn to be substantially similar in exemplary FIG. 2. The electro-optic device shown in FIG. 2 is suitably referred to as a double-surface-stabilized chiral or cholesteric electro-optic device.
In contrast to the surface-stabilized devices of FIGS. 1 and 2, the electro-optic device shown in FIG. 3 is a volume-stabilized device in which the polymer network extends throughout the liquid crystal layer and is substantially uniform throughout the liquid crystal layer.
The electro-optic device of FIG. 3 differs from the electro-optic device of FIG. 1 primarily in that ultraviolet light 46′′ used in the optical polymerizing process has a photon energy or free-space wavelength selected to substantially reduce absorption in the liquid crystal material 30′′. Hence, a substantially spatially uniform ultraviolet light intensity profile 50′′ produces a stabilizing polymer network 32′′ that is substantially uniform across the gap G′′. This arrangement is suitably referred to as a volume-stabilized chiral or cholesteric electro-optic device. In the electro-optic device of FIG. 3, each principal confining substrate 12′′, 14′′ has an anisotropic alignment surface 24′′,84 for aligning the liquid crystal 30′′. However, it is also contemplated to have only one of the confining substrates include an anisotropic alignment surface for aligning the liquid crystal.
For typical liquid crystal materials, spatially non-uniform polymer networks such as the networks 32, 32′, 72 of FIGS. 1 and 2 are produced using ultraviolet light having a photon energy that is preferably greater than about 3.55 eV, and that is more preferably greater than about 3.8 eV. For lower photon energies, the ultraviolet light is typically less strongly absorbed by the liquid crystal, producing a substantially spatially uniform polymer network such as the stabilizing polymer network 32′′ of FIG. 3. Based on Equation (1), it will also be appreciated that the extent dpoly, of the stabilizing polymer network 32 or the extent dpoly′, dpoly2 of the stabilizing polymer network portions 32′, 72 depends upon the initial intensity Io of the ultraviolet illumination.
Those skilled in the art can select a suitable wavelength and initial illumination intensity to produce a selected polymer network configuration in a gap of a specific size filled with a specific liquid crystal based on the absorption coefficient versus wavelength or photon energy characteristic of the liquid crystal material. Because the concentration of the monomer is typically low (for example, less than about 5 wt % of the liquid crystal material), the absorption coefficient of the liquid crystal material is typically not changed significantly by the dissolving of the monomer therein. In cases where the monomer incorporation significantly alters the absorption coefficient, or where scattering centers in the liquid crystal create additional scattering optical losses, or so forth, those skilled in the art can readily measure the absorption coefficient change and adjust the ultraviolet light intensity or wavelength, or both, accordingly.
The liquid crystal material 30, 30′, 30′′ is preferably a chiral or cholesteric liquid crystal that exhibits a flexoelectric response to a relatively small electric field applied by the electrodes 20, 22, 20′, 22′, 20′′, 22′′. That is, starting with the electrically unbiased uniformly lying helix texture, application of a small electric field flexoelectrically produces a field-induced deviation of the optic axis. This deviation is typically approximately linear for relatively small applied fields, and is typically governed by:




  
    
      
        
          φ
          ≅
          
            eEp
            K
          
        
        ,
      
    
    
      
        (
        2
        )
      
    
  




where φ is the field-induced angular deviation of the optic axis, Ε is the magnitude of the electric field applied perpendicular to the principle confining substrates 12, 14, 12′, 14′, 12′′, 14′′, p is the pitch of the chiral or cholesteric liquid crystal 30, 30′, 30′′, the parameter e is given by:





  
    
      
        
          e
          =
          
            
              1
              2
            
            ⁢
            
              (
              
                
                  e
                  s
                
                +
                
                  e
                  b
                
              
              )
            
          
        
        ,
      
    
    
      
        (
        3
        )
      
    
  




where es and eb are average values of the splay and bend flexoelectric coefficients, respectively, and the parameter K is given by:





  
    
      
        
          K
          =
          
            
              1
              2
            
            ⁢
            
              (
              
                
                  K
                  11
                
                +
                
                  K
                  33
                
              
              )
            
          
        
        ,
      
    
    
      
        (
        4
        )
      
    
  




where K11 and K33 are the splay and bend elastic constants, respectively.

At higher electric fields, a quadratic effect is produced by dielectric coupling. At these higher electric fields, the helix begins to deform while the pitch increases. When the applied electric field exceeds a certain critical value, the helix is substantially completely unwound, producing a homeotropic texture when the liquid crystal has positive dielectric anisotropy.
Advantageously, because of the stabilizing polymer network 32,32′, 72, 32′′ the liquid crystal 30, 30′, 30′′ returns to the initial uniformly lying helix texture after the applied electric field is removed. In some preferred electro-optic devices the gap G, G′ is about 5 microns, and a thickness of the stabilizing polymer network 32 or of the combined stabilizing polymer network portions 32′, 72 is less than or about 1 micron. Typically, a thickness or combined thickness of the stabilizing polymer network is suitably about 10% of the total gap to provide stabilization of the uniformly lying helix texture. Those skilled in the art can readily adjust these exemplary dimensions for particular density profiles of the stabilizing polymer network, for ordered stabilizing polymer networks in which the polymer chains are partially or substantially aligned or otherwise ordered, or the like.
Typically, surface-stabilized or double-surface-stabilized chiral or cholesteric electro-optic devices such as the exemplary devices of FIGS. 1 and 2 are particularly suitable for operation in polar mode, in which flexoelectric coupling with the applied electric field is of dominant. Volume-stabilized chiral or cholesteric electro-optic devices such as the exemplary device of FIG. 3 are particularly suitable for operation in quadratic mode, in which the dielectric coupling is dominant.
For electro-optic devices operating in the visible range, the liquid crystal material preferably exhibits a chiral or cholesteric phase with a short helix pitch preferably less than about 0.5 microns, and more preferably between about 0.2 microns and about 0.5 microns. The liquid crystal preferably exhibits a pronounced flexoelectric response, and preferably has a positive dielectric anisotropy in a range of about 0.1-10. The liquid crystal material in the chiral or cholesteric phase is preferably a highly. birefringent material, having a large An in a range of about 0.1-0.5. Optionally, the liquid crystal material exhibits a sign reversal of the dielectric anisotropy with frequency of the applied electric field.
In one example of a volume-stabilized chiral or cholesteric electro-optic device, electro-optical liquid crystal cells each having a 2 micron gap were obtained from EHC Co. Ltd. (Tokyo, Japan). Inner surfaces of the liquid crystal cells wee treated for anti-parallel alignment by forming uniaxially rubbed polymide layers assembled at 180° with respect to the rubbing directions. A short-pitched cholesteric liquid crystal material mixture was formed with the following composition:

    
    
        69.75 wt % MLC6080 eutectic nematic;
        25 wt % chiral dopants, including a 3:3:1 ratio of CE1, CB15, and R1011;
        5 wt % RM257 photoreactive monomer; and
        0.25 wt % Irgacure 651 photoinitiator.

These components are all available from Merck & Co., Inc. (Whitehouse Station, N.J.), except for the Irgacure 651 photoinitiator which is available from Ciba Specialty Chemicals (Basel, Switzerland). The liquid crystal cells were filled with the short-pitched cholesteric liquid crystal material mixture by a capillary action, and heated to isotropic temperature of the cholesteric. During cool down to room temperature, a 6.26V, 26 Hz square wave electrical voltage bias was applied across the liquid crystal cell to achieve a uniformly lying helix texture. The optical polymerizing was performed using 365 nm ultraviolet illumination at 0.04 mW/cm2 for thirty minutes at room temperature. The selected ultraviolet illumination provided substantially uniform illumination across the 2 micron gap to produce a volume polymer network, similarly to the optical polymerizing process illustrated in FIG. 3.

    
    


To test for residual birefringence due to the volume polymer network, the electro-optic device was biased at 0 volts, 10 volts, and 25 volts to completely unwind the cholesteric liquid crystal to produce a homeotropic texture. Advantageously, the relatively loose polymeric network produced by the low 5 wt % monomer exhibited no residual birefringence from the polymer network at 25 volts when viewed using crossed polarizers.
With reference to FIG. 4, electro-optic switching properties of the volume-stabilized chiral or cholesteric electro-optic device in the in-plane flexoelectric switching mode were characterized using a digital oscilloscope. A turn-on or rise time of 60 microseconds and a turn-off or decay time of 120 microseconds was observed for a 2 volt/micron, 110 Hz square wave electrical input.
With reference to FIG. 5, a 1 volt/micron, 110 Hz triangle wave was applied to a 2 micron volume-stabilized liquid crystal cell to characterize homogeneous in-plane switching characteristics. FIG. 5 shows a digital oscilloscope plot of the triangle wave input and the transmitted light intensity versus time. The transmitted light measurement indicates symmetric in-plane switching due to moderate positive dielectric anisotropy of the cholesteric liquid crystal material. Preferably, the cholesteric liquid crystal should have a dielectric anisotropy near zero.
In one example of a double-surface-stabilized chiral or cholesteric electro-optic device, electro-optical liquid crystal cells were prepared and filled with a short-pitched cholesteric liquid crystal material mixture in the same way as for the volume-stabilized electro-optic device fabrication, and were heated to isotropic temperature of the cholesteric. During cool down to room temperature, a 9.5V, 22 Hz square wave electrical voltage bias was applied across the liquid crystal cell to achieve a uniformly lying helix texture. The optical polymerizing was performed using 322 nm ultraviolet illumination at 0.08 mW/cm2 applied from both principal surfaces, similarly to the optical polymerizing process shown in FIG. 2, for five minutes at room temperature. The selected ultraviolet illumination provides formation of the polymer network adjacent the illuminated principal surfaces. Compared with the 365 nm ultraviolet light used in the optical polymerizing to produce a volume polymer network, a higher absorption of the shorter wavelength 322 nm ultraviolet light resulted in substantially no optical polymerization near the center of the liquid crystal cell gap. Thus, the shorter wavelength 322 nm ultraviolet light provided a double-surface stabilization polymer network as illustrated in FIG. 2, rather than a volume stabilization polymer network as illustrated in FIG. 3.
To test for residual birefringence due to the surface polymer network portions, the electro-optic device was biased at 0 volts, 10 volts, and 25 volts to completely unwind the cholesteric liquid crystal to produce a homeotropic texture. Advantageously, the polymeric network portions disposed adjacent the confining surfaces exhibited no residual birefringence from the polymer network at 25 volts when viewed using crossed polarizers.
With reference to FIG. 6, electro-optic switching properties of the double-surface-stabilized chiral or cholesteric electro-optic device in the in-plane flexoelectric switching mode were characterized using a digital oscilloscope. A turn-on or rise time of 70 microseconds and a turn-off or decay time of 100 microseconds was observed for a 3.5 volt/micron, 110 Hz square wave electrical input.
With reference to FIG. 7, a 3.5 volt/micron, 110 Hz triangle wave was applied to characterize homogeneous in-plane switching characteristics. FIG. 7 shows a digital oscilloscope plot of the transmitted light intensity versus time. The transmitted light measurement indicates symmetric in-plane switching due to moderate positive dielectric anisotropy of the cholesteric liquid crystal material. Preferably, the cholesteric liquid crystal should have a dielectric anisotropy near zero, in which case the linearity of the polar flexoelectro-optic response substantially improves.
With reference to FIG. 8, an electro-optic device 10′′′ employing a combination of surface-stabilization and volume-stabilization is described. In FIG. 8, components corresponding to components of FIG. 1 are labeled with similar triple primed reference numbers. Thus, the exemplary electro-optic device of FIG. 8 includes a liquid crystal cell 10′′′ with two spaced apart principal confining substrates 12′′′, 14′′′ having facing confining surfaces defining a gap G′′′, confining side surfaces 16′′′, 18′′′, electrodes 20′′′, 22′′′, and a liquid crystal material 30′′′ disposed within the gap G′′′. The principal confining surface 14′′′ has an anisotropic alignment surface 24′′′ formed by rubbing or another process.
Polymerization is performed using two light components applied sequentially or simultaneously. The first light component is ultraviolet light 46a is a short-wavelength light that illuminates the gap G′′′ through the principal confining substrate 14′ to produce a rapidly decaying ultraviolet light intensity profile 50a in the gap G′′′. The rapidly decaying profile 50a produced by ultraviolet light 46a generates a surface-stabilizing polymer network portion 32a generally extending a distance dpoly′′′ into the gap G′′′. A second ultraviolet light 46b illuminates the gap G′′′ through the principal confining substrate 14′′′, as shown, or alternatively through the principal confining substrate 12′′′, to produce a substantially uniform ultraviolet light intensity profile 50b. The substantially uniform profile 50b produced by the ultraviolet light 46b generates a volume stabilizing polymer network portion 32b substantially uniformly filling the gap G′′′.
The two-component polymerization approach used in fabricating the electro-optic device 10′′′ advantageously allows tailoring of the spatial density of the polymer network across the gap G′′′. The density of the volume network 32b is preferably kept low to reduce light scattering. However, the addition of some volume polymer density to the surface stabilization network 32a is expected to be more effective at stabilizing the chiral smectic C, choleteric, or other liquid crystal material in the uniform lying texture versus a purely surface stabilized configuration.
In some embodiments, the short wavelength illumination 46a is applied first, followed by the longer wavelength illumination 46b. Thus, in these embodiments the surface polymer network 32a is formed first, followed by the volume polymer network 32b. In other embodiments, the longer wavelength illumination 46b is applied first, followed by the short wavelength illumination 46a. In these embodiments, the volume polymer network 32b is formed first, followed by the surface polymer network 32a. In yet other embodiments, the illuminations 46a, 46b are applied simultaneously to generate a composite illumination profile 50′′′ that forms the surface and volume polymer networks 32a, 32b simultaneously.
Moreover, it will be appreciated that the illuminations 46a, 46b and corresponding illumination profiles 50a, 50b, or simultaneously applied profile 50′′′, are examples. Additional illumination components can be applied sequentially or simultaneously to tailor the polymer network distribution across the gap G′′′. For example, a double-surface stabilization can be combined with a volumetric polymer network by applying short wavelength light through both principal confining surfaces 12′′′, 14′′′, along with a longer wavelength light that produces the volume polymer network applied through one or both principal confining surfaces 12′′′, 14′′′.
The invention has been described with reference to the preferred embodiments. Obviously, modifications and alterations will occur to others upon reading and understanding the preceding detailed description. It is intended that the invention be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

## Claims

1. A preparation method comprising:
disposing a chiral or cholesteric liquid crystal, a photoreactive monomer, and a photoinitiator in a liquid crystal cell; and
illuminating a principal surface of the liquid crystal cell with ultraviolet light selected to have a non-uniform ultraviolet light intensity profile in the liquid crystal cell, the illuminating cooperating with the photoinitiator to polymerize at least a portion of the photoreactive monomer near the principal surface to generate a polymer network having a density corresponding to the non-uniform ultraviolet light intensity profile, the polymer network biasing the liquid crystal toward a selected helical alignment direction.

2. The method as set forth in claim 1, further comprising:
selectively impressing an electric field on the liquid crystal cell to flexoelectrically bias the liquid crystal away from the selected helical alignment direction.

3. The method as set forth in claim 1, further comprising:
selectively impressing an electric field on the liquid crystal cell to substantially unwind the chiral liquid crystal; and
removing the electric field, the liquid crystal returning to the selected helical alignment direction responsive to the removing.

4. The method as set forth in claim 1, further comprising:
selectively impressing a first electric field on the liquid crystal cell to flexoelectrically bias the chiral liquid crystal away from the selected helical alignment direction; and
selectively impressing a second electric field larger than the first electric field on the liquid crystal cell to substantially unwind the chiral liquid crystal;
wherein removal of the first or second electric field causes the chiral liquid crystal to return to the selected helical alignment direction.

5. The method as set forth in claim 1, further comprising:
converting the liquid crystal to a uniformly lying helical texture having the selected helical alignment direction prior to the illuminating.

6. The method as set forth in claim 5, wherein the converting comprises:
providing an anisotropic inner surface at least at the principal surface; and
applying at least one of heating and electrical biasing to align the liquid crystal into the uniformly lying helical texture, the uniformly lying helical texture having the selected helical alignment direction aligned one of parallel to and perpendicular to an anisotropic direction of the anisotropic inner surface.

7. The preparation method as set forth in claim 1, wherein the polymeric network is less than or about 3 weight percent of the liquid crystal material.

8. The preparation method as set forth in claim 1, wherein the chiral or cholesteric liquid crystal has a helix pitch less than about 0.5 micron.

9. A method for fabricating an electo-optic device, the method comprising:
disposing a liquid crystal and a photoreactive monomer in a liquid crystal cell, the disposed photoreactive monomer being less than 5 weight percent of the disposed liquid crystal;
arranging the liquid crystal in a uniformly lying helix texture; and
optically polymerizing the photoreactive monomer to form a stabilizing polymer network.

10. The method as set forth in claim 9, wherein the optical polymerizing comprises:
illuminating a principal surface of the liquid crystal cell with ultraviolet light selected to have a non-uniform ultraviolet light intensity profile in the liquid crystal cell, the polymer network having a density corresponding to the non-uniform ultraviolet light intensity profile.

11. The method as set forth in claim 10, wherein the disposing further comprises:
disposing a photoinitiator in the liquid crystal cell, the photoinitiator cooperating with the ultraviolet light to effect the optical polymerizing.

12. The method as set forth in claim 10, wherein the non-uniform ultraviolet light intensity profile includes at least one of (i) a uniform intensity component generating a volume polymer network component that is substantially uniform across the gap of the liquid crystal cell and (ii) a non-uniform intensity component that is substantially absorbed inside the liquid crystal cell within one micron of the principal surface to generate a surface polymer network component.

13. The method as set forth in claim 9, wherein the optical polymerizing comprises:
illuminating a principal surface of the liquid crystal cell with ultraviolet light that is substantially absorbed inside the liquid crystal cell within one micron of the principal surface.

14. The method as set forth in claim 9, wherein the optical polymerizing comprises:
illuminating a principal surface of the liquid crystal cell with ultraviolet light having a photon energy greater than about 3.55 eV.

15. The method as set forth in claim 9, wherein the optical polymerizing comprises:
illuminating a principal surface of the liquid crystal cell with ultraviolet light having a photon energy greater than about 3.8 eV.

16. A preparation method comprising:
disposing a chiral or cholesteric liquid crystal and a photoreactive prepolymer in a gap of a liquid crystal cell;
illuminating a first principal surface of the liquid crystal cell with a first ultraviolet light selected to have a first non-uniform light intensity profile in the gap of the liquid crystal cell, the illuminating with the first ultraviolet light causing polymerization of a portion of the photoreactive prepolymer near the first principal surface to generate a first surface polymer network component having a density corresponding to the first non-uniform light intensity profile;
illuminating a second principal surface of the liquid crystal cell different from the first principal surface with a second ultraviolet light selected to have a second non-uniform light intensity profile in the gap of the liquid crystal cell, the illuminating with the second ultraviolet light causing polymerization of a portion of the photoreactive prepolymer near the second principal surface to generate a second surface polymer network component having a density corresponding to the second non-uniform light intensity profile; and
wherein the first and second polymer network components define a polymer network that biases the liquid crystal toward a selected helical alignment direction.

17. The method as set forth in claim 16, further comprising:
converting the liquid crystal to a uniformly lying helical texture having the selected helical alignment direction prior to the illuminating with the first ultraviolet light and prior to the illuminating with the second ultraviolet light.

18. The method as set forth in claim 16, wherein a temporal sequence of the illuminating with the first ultraviolet light and the illuminating with the second ultraviolet light is selected from a group consisting of:
illuminating with the first ultraviolet light before illuminating with the second ultraviolet light,
illuminating with the second ultraviolet light before illuminating with the first ultraviolet light, and
illuminating with the first and second ultraviolet light simultaneously.