Field induced and controlled heliconical structure of cholesteric liquid crystal
09732277 · 2017-08-15
Assignee
Inventors
- Oleg D. Lavrentovich (Kent, OH, US)
- Jie V. Xiang (Kent, OH, US)
- Sergij V. Shiyanovskii (Stow, OH, US)
- Corrie T. Imrie (Aberdeen, GB)
- Daniel A. Paterson (Aberdeen, GB)
- John M. Storey (Aberdeen, GB)
Cpc classification
G02F1/13718
PHYSICS
G02F1/134363
PHYSICS
International classification
G02F1/137
PHYSICS
Abstract
A liquid crystal cell includes substrates defining a gap and electrodes having one of (i) an in-plane geometry generating an electric field parallel with the substrates and (ii) a top-down geometry generating an electric field across the gap between the two spaced apart substrates. A liquid crystal material disposed in the gap between the substrates comprises a chiral nematic material formed by a mixture of: 1-(4-cyanobiphenyl-4′-yl)-6-(4-cyanobiphenyl-4′-yloxy)hexane (CB6OCB) or α,ω-bis(4,4-cyanobiphenyl)nonane (CB9CB) dimeric liquid crystal material; at least one additional dimeric liquid crystal material; and a chiral dopant. The liquid crystal material within an operational range of electric field applied by the electrodes exhibits a heliconical state with an oblique angle helicoid director whose helicoid axis is oriented parallel with the electric field and whose helicoid pitch is sized to provide diffraction or Bragg reflection of light in a spectral range of interest impinging on one of the substrates of the liquid crystal cell.
Claims
1. An electrooptic device comprising: a liquid crystal cell including spaced apart substrates defining a gap between the substrates and electrodes having one of (i) an in-plane geometry generating an electric field parallel with the substrates and (ii) a top-down geometry generating an electric field across the gap between the two spaced apart substrates; a liquid crystal material disposed in the gap between the substrates and comprising a chiral nematic material formed by a mixture of: 1-(4-cyanobiphenyl-4′-yl)-6-(4-cyanobiphenyl-4′-yloxy)hexane (CB6OCB) dimeric liquid crystal material, at least one additional dimeric liquid crystal material other than CB6OCB, and a chiral dopant; wherein the liquid crystal material within an operational range of electric field applied by the electrodes exhibits an N*.sub.oh state with an oblique angle helicoid director whose helicoid axis is oriented parallel with the electric field and whose helicoid pitch is sized to provide diffraction or Bragg reflection of light in a spectral range of interest impinging on one of the substrates of the liquid crystal cell.
2. The electrooptic device of claim 1 wherein the at least one additional dimeric liquid crystal material other than CB6OCB comprises: 1″,7″-bis(4-cyanobiphenyl-4′-yl)heptane (NC(C6H4)2(CH2)7(C6H4)2CN (CB7CB) dimeric liquid crystal material.
3. The electrooptic device of claim 1 wherein the at least one additional dimeric liquid crystal material other than CB6OCB comprises a dimeric liquid crystal material having bend elastic constant K.sub.3 that is smaller than twist constant K.sub.2.
4. The electrooptic device of claim 1 wherein the mixture further includes at least one liquid crystal material that is not a dimeric liquid crystal material.
5. The electrooptic device of claim 1 wherein the spectral range of interest is the visible spectrum or a portion of the visible spectrum.
6. The electrooptic device of claim 1 wherein: the electrodes have an in-plane geometry generating an electric field parallel with the substrates, and the liquid crystal material within the operational range of electric field applied by the electrodes exhibits the N*.sub.oh state with the oblique angle helicoid director whose helicoid axis is oriented parallel with the substrates and whose helicoid pitch is sized to provide diffraction of light in the spectral range of interest impinging on one of the substrates of the liquid crystal cell.
7. The electrooptic device of claim 1 wherein: the electrodes have a top-down geometry generating an electric field across the gap between the two spaced apart substrates, and the liquid crystal material within the operational range of electric field applied by the electrodes exhibits the N*.sub.oh state with the oblique angle helicoid director whose helicoid axis is oriented transverse to the substrate and whose helicoid pitch is sized to provide Bragg reflection of light in the spectral range of interest impinging on one of the substrates of the liquid crystal cell.
8. The electrooptic device of claim 1 wherein: the liquid crystal material within a lower non-operational range of electric field applied by the electrodes exhibits a chiral nematic (N*) state whose director has a right angle helix with its helical axis oriented transverse to the electric field; wherein the lower non-operational range of electric field is lower than the operational range of electric field.
9. The electrooptic device of claim 8 wherein: the liquid crystal within a higher non-operational range of electric field applied by the electrodes exhibits a homeotropic state whose director is oriented parallel with the electric field; wherein the higher non-operational range of electric field is higher than the operational range of electric field.
10. A liquid crystal device comprising: a liquid crystal (LC) cell including two substrates, a cholesteric liquid crystal material disposed within the liquid crystal cell between the substrates, and two electrodes, the electrodes disposed on the substrates and configured to apply an electric field through the cholesteric liquid crystal material disposed within the liquid crystal cell, wherein the cholesteric liquid crystal material includes a mixture of at least two dimeric liquid crystal materials including at least one of: 1-(4-cyanobiphenyl-4′-yl)-6-(4-cyanobiphenyl-4′-yloxy)hexane (CB6OCB), α,ω-bis(4,4-cyanobiphenyl)nonane (CB9CB), and 1″,7″-bis(4-cyanobiphenyl-4′-yl)heptane (NC(C6H4)2(CH2)7(C6H4)2CN (CB7CB); and a power generator for generating the applied electric field, the power generator configured to vary the strength of the applied electric field to produce diffracted or reflected light from the cholesteric liquid crystal material within the visible spectrum; wherein the applied electric field induces the cholesteric liquid crystal material into a heliconical state including an oblique helicoid director.
11. The liquid crystal device according to claim 10, wherein the cholesteric liquid crystal material further includes between 1 and 5 wt % of chiral dopant.
12. The liquid crystal device according to claim 10, wherein the cholesteric liquid material further includes at least one liquid crystal material that is not a dimeric liquid crystal material.
13. The liquid crystal device according to claim 12, wherein the at least one liquid crystal material that is not a dimeric liquid crystal material comprises pentylcyanobiphenyle (5CB).
14. The liquid crystal device according to claim 10, wherein the cholesteric liquid crystal material includes a eutectic mixture of the at least two dimeric liquid crystal materials.
15. The liquid crystal device according to claim 10, wherein: the electrodes have an in-plane geometry generating an applied electric field in the plane of the substrates, and the applied electric field in the plane of the substrates induces the cholesteric liquid crystal material into the heliconical state including the oblique helicoid director whose helicoid axis is oriented in the plane of the substrates whereby the liquid crystal device diffracts light from the cholesteric liquid crystal material within the visible spectrum.
16. The liquid crystal device according to claim 10, wherein: the electrodes have a vertical geometry generating an applied electric field normal to the plane of the substrates, and the applied electric field normal to the plane of the substrates induces the cholesteric liquid crystal material into the heliconical state including the oblique helicoid director whose helicoid axis is oriented normal to the plane of the substrates whereby the liquid crystal device reflects light from the cholesteric liquid crystal material within the visible spectrum.
17. The liquid crystal device according to claim 10, wherein the applied electric field induces the cholesteric liquid crystal material into the heliconical state including the oblique helicoid director with a helicoid pitch effective to cause the reflected light to have a wavelength between approximately 400 nm and 700 nm.
18. A method of operating an electro-optic cholesteric liquid crystal device, the method comprising: providing cholesteric liquid crystal material comprising a mixture including 1-(4-cyanobiphenyl-4′-yl)-6-(4-cyanobiphenyl-4′-yloxy)hexane (CB6OCB) or α,ω-bis(4,4-cyanobiphenyl)nonane (CB9CB) dimeric liquid crystal material and a second dimeric liquid crystal material; applying an electric field to the cholestric liquid crystal material that is effective to induce a heliconical state in which the director forms an oblique helicoid; while applying the electric field, diffracting or reflecting light of a wavelength selected by the applied electric field from the cholesteric liquid crystal material; and adjusting the electric field to adjust the wavelength of light that is diffracted or reflected from the cholesteric liquid crystal material.
19. The method according to claim 18, wherein the second dimeric liquid crystal material comprises CB7CB dimeric liquid crystal material.
20. The method according to claim 19, wherein the mixture includes one of: (i) a eutectic mixture of CB6OCB and CB7CB dimeric liquid crystal materials or (ii) a eutectic mixture of CB9CB and CB7CB dimeric liquid crystal materials.
21. The method according to claim 18, wherein the mixture further includes at least one liquid crystal material that is not a dimeric liquid crystal material.
22. The method according to claim 19, wherein the mixture further includes a chiral dopant.
23. The method according to claim 19, wherein the applying, diffracting or reflecting, and adjusting operations are performed with the cholesteric liquid crystal material in the temperature range 20° C. to 30° C. inclusive.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(15) The above noted problems can be solved by a very distinct mode of electrically induced deformation of N*. This electrically induced deformation produces a state with the director forming an oblique angle helicoid as opposed to a right angle helicoid. This state of the chiral nematic is denoted herein as N*.sub.oh, where the subscript “oh” derives from the “oblique helicoid” may also be referred to as the “heliconical” state.
(16) The devices and methods disclosed herein provide electrical control of colored reflections within chiral nematic (N*) materials with an oblique helicoid director. Applications of the described approaches include, but are not limited to, diffraction grating and color tuning applications.
(17) In various embodiments, the present disclosure provides methods and devices for electric control of chiral nematics N* with oblique angle helicoid, the state labelled as N*.sub.oh. As disclosed herein, the problems associated with direct coupling of the electric field and the ground state right-helicoid structure of N* can be overcome by electrically induced deformation of N* to produce a state N*.sub.oh with an oblique angle helicoid director and with a pitch and cone angle that both depend on the applied electric field.
(18) The described methods and devices generally allow for electrical tuning of the Bragg reflection from N* within the full visible spectrum with a narrow width of the reflection peak. In the ground field-free (or low field) state, the director is in the conventional chiral nematic N* state. An (increased) applied electric field directed perpendicular to the helix direction of the N* material causes a state change in which the director transforms to the N*.sub.oh state to form an oblique helicoid with its helix direction oriented parallel with the applied electric field, with both the pitch and cone angle of the N*.sub.oh controlled by the field. The color change is a result of the pitch change of the heliconical structure N*.sub.oh with the helix axis oriented along the direction of the electric field. This electrically induced deformation approach can be applied to devices and methods to feature a broad color tunable range, a narrow reflection bandwidth and millisecond switching times. This broad range color switching of heliconical structure in chiral nematics could be used in applications such as reflection displays, color filters, and tunable LC lasers.
(19) The N*.sub.oh state has been theoretically predicted for a material in which the bend elastic constant K.sub.3 is much smaller than the twist constant K.sub.2. See R. B. Meyer, Applied Physics Letters 12, 281 (1968); P. G. de Gennes, Solid State Communications 6, 163 (1968); J. Xiang, S. V. Shiyanovskii, C. Imrie, and O. D. Lavrentovich, Physical Review Letters 112, 217801 (2014). This condition is not satisfied in typical nematics formed by rod-like molecules.
(20) The devices disclosed herein operate in conjunction with N* material formed by molecular dimers in mixture with chiral dopant. Other materials formed by non-dimeric molecules, are also possible for the disclosed devices, as long as their response to the applied external electric field results in formation of the oblique helicoidal state N*.sub.oh. The molecular dimers, in which the flexible aliphatic chain links two rigid rod-like arms, exhibit a nematic state with an anomalously small value of K.sub.3. See K. Adlem et al., Physical Review E 88, 022503 (2013); V. Borshch et al., Nature Communications 4, 2635 (2013); R. Balachandran, V. Panov, J. Vij, A. Kocot, M. Tamba, A. Kohlmeier, and G. Mehl, Liquid Crystals 40, 681 (2013). As disclosed herein, a mixture of molecular dimers with chiral dopant when subjected to appropriate electric field may transform from the conventional chiral nematic N* state with its helix axis perpendicular to the electric field to an N*.sub.oh state in which the director forms an oblique helicoid with its axis oriented parallel with the applied electric field and with a helicoidal period in a useful range, e.g. suitable for performing diffraction or Bragg reflection of light in the visible, infrared, and/or ultraviolet range. This N*.sub.oh material with oblique heliconical director may be used in numerous practical applications, e.g. color tuning and diffraction grating, as the pitch and cone angle of the oblique heliconical director both depend on the applied electric field. Further examples of practical application of the heliconical state with electrically controlled periodicity include (but are not limited to) smart windows with field-controlled transparency in ultraviolet, visible, and infrared parts of spectrum, electrically tunable transreflective displays that can be used as transparent informational panels; lasers with the electrically tunable wavelength of emission, when the heliconical state is doped with dyes, tunable light limiters used in laser countermeasures, tunable filters for spectroscopy, etc.
(21) According to one embodiment, N*.sub.oh material with heliconical director are used in a device 100 to implement a tunable diffraction grating. With reference to
(22) The LC cell 101 may be a flat glass cell with a thickness d (that is, separation between the plates 103) between 10-20 μm. (As just noted,
(23) According to a second embodiment, which provides a tunable Bragg reflector, liquid crystal material with oblique heliconical director in the state N*.sub.oh are used in a device 200 for electrically induced color tuning. With reference to
(24) The shift of the electric field over the range E.sub.1, E.sub.2, E.sub.3 induces a shift in the wavelength of the reflected light 221, 222, 223 within the visible spectrum by using the field-induced heliconical state of N*.sub.oh with the helicoid axis A.sub.H of the director 212 parallel to the applied electric field E.sub.1, E.sub.2, E.sub.3. The wavelength λ of reflected light is given by Bragg's law, which for normal incidence on the substrate 203 is λ=2P/n where P is the period of the helicoid director 212 and n is the effective refractive index. Adjusting the electric field strength within the range for which the LC material 200 is in the N*.sub.oh state adjusts the period of the heliconical director 212 along its vertical axis, and hence tunes the reflection wavelength λ. In one embodiment, E.sub.1 is approximately 3.4 V/μm and reflected light 221 appears blue in color, E.sub.2 is approximately 3.1 V/μm and reflected light 222 appears green in color, and E.sub.3 is approximately 2.8 V/μm and reflected light 223 appears red in color. The wavelength λ.sub.1, λ.sub.2, λ.sub.3 of the reflected light 221, 221, 223 may be tuned within the full visible spectrum, e.g. approximately between 400 nm and 700 nm, with a narrow width of the reflection peak occurring around 30 nm. The response time between switching colors of the reflected light 221, 222, 223 is in the millisecond range.
(25) In general, the disclosed electrooptic devices include LC material 100, 200 comprising chiral nematic material formed by a mixture of molecular dimers and chiral dopant, which within an operational range of applied electric field exhibit an N*.sub.oh state with an oblique angle helicoid director whose helicoid axis A.sub.H is oriented parallel with the electric field and with electric field-dependent helicoid pitch and cone angle. The choice of materials is not limited by the set of molecular dimers, as any other type of chemical structure of the liquid crystal that produces the oblique helicoidal state under the action of the external field can be used in the disclosed devices. The helicoid pitch over the operational range of applied electric field is effective to provide Bragg reflection and/or optical diffraction of light in a spectral range of interest (typically the visible spectrum or a portion thereof, although operational ranges in the infrared, visible, and/or ultraviolet are contemplated. Such materials typically have bend elastic constant K.sub.3 much smaller than twist constant K.sub.2. The LC materials 100, 200 may include the molecular dimer 1″,7″-bis(4-cyanobiphenyl-4′-yl)heptane (NC(C.sub.6H.sub.4).sub.2(CH.sub.2).sub.7(C.sub.6H.sub.4).sub.2CN (CB7CB) (or like materials) doped with an amount of chiral dopant. In one embodiment, the amount of chiral dopant includes between 1 and 5 wt % of chiral (left-handed) dopant S811. As further illustrative examples, the molecular dimers may be α,ω-bis(4,4-cyanobiphenyl)nonane (CB9CB) and/or 1,11-di-(1″-cyanobiphenyl-4-yl)undecane (CB11CB), optionally mixed with monomers such as pentylcyanobiphenyle (5CB), heptylcyanobiphenyle (7CB), 4-Cyano-4-N-Pentyl-P-Terphenyl (5CT), and octulcyanobiphenyle (8CB). The chiral dopant may, for example, include one or more of the commercially available chiral dopants R811, CB15, R1011, S1011, or BDH-1281.
(26) With reference to
(27) At S102, a liquid crystal material is provided which is chiral nematic at low (or zero) electrical bias, and in which the bend elastic constant K.sub.3 is much smaller than the twist constant K.sub.2.
(28) At S104, an electric field is applied to the LC material at a field strength effective to induce a “heliconical” state in which the director forms an oblique helicoid with its axis oriented parallel with the electric field E.sub.NC.
(29) When the applied electric field is very high, the director of the N* is parallel to the applied electric field, {circumflex over (n)}=(1,0,0), because dielectric anisotropy of the N*∈.sub.a>0. Suppose now that the field is reduced, so that the tendency to twist caused by chiral nature of molecules, can compete with the dielectric torque. Below some threshold field,
(30)
the unwound nematic state transforms into a “heliconical” state in which the director follows an oblique helicoid, {circumflex over (n)}=(cos θ, sin θ, cos φ, sin θ sin φ) with the conical angle θ>0 and the angle of homogeneous azimuthal rotation φ(x)=2πx/P, where the heliconical pitch P is inversely proportional to the field:
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and the conical angle θ related to the field:
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where κ=K.sub.3/K.sub.2 and
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and P.sub.0 is the pitch of the N* phase, ∈.sub.a is the dielectric anisotropy and ∈.sub.0 is the vacuum permittivity.
(34) At S106, a light is propagated onto the LC materials and a Bragg reflected light is within the visible light spectrum and has a first wavelength.
(35) The center wavelength for the Bragg reflection reads
λ.sub.p=
with the reflection bandwidth
Δλ=Δn.sub.effP (EQN. 4)
where
(36)
(37) At S108, the electric field applied to the LC materials is decreased, wherein the Bragg reflected light is within the visible spectrum and has a second wavelength that is longer than the first wavelength.
(38) At S110, the electric field applied to the LC materials is increased, wherein the Bragg reflected light is within the visible spectrum and has a third wavelength that is shorter than the second wavelength.
(39) Further disclosure is provided in the form of the following examples. The examples provided are merely representative of the work that contributes to the teaching of the present disclosure.
Example 1: Preparing in-Plane LC Cell for Diffraction Grating Application of Cholesteric LCs with Oblique Heliconical Director
(40) An LC dimer material 1″,7″-bis(4-cyanobiphenyl-4′-yl)heptane (NC(C.sub.6H.sub.4).sub.2(CH.sub.2).sub.7(C.sub.6H.sub.4).sub.2CN, CB7CB) was used which shows a uniaxial N phase with a positive dielectric anisotropy, sandwiched between the isotropic and the twist-bend nematic phase N.sub.tb. See V. Borshch et al., Nature Communications 4, 2635 (2013); D. Chen et al., Proceedings of the National Academy of Sciences of the United States of America 110, 15931 (2013). The dielectric permittivities were measured parallel and perpendicular to the director ∈.sub.∥=7.3 and ∈.sub.⊥=5.9, respectively; the elastic constants were determined by the Frederiks transition technique to be K.sub.1=5.7 pN and K.sub.2=2.6 pN. See P. G. de Gennes and J. Prost, The Physics of Liquid Crystals (Clarendon Press, Oxford, 1993). All data corresponds to 106° C. To prepare the N* phase, CB7CB was doped with a small amount (1 wt %) of chiral (left-handed) dopant S811. The phase diagram is different from the case of an un-doped CB7CB: N* melts into an isotropic fluid at T.sub.N*I=112° C. and transforms into a homochiral version of N.sub.tb at T*=99° C. The pitch P.sub.0 of the N* phase, measured in the Grandjean-Cano wedge, decreases from 8.8 μm at T*+1° C. to 6.2 μm at T.sub.N*I−1° C. The electro-optic experiments were performed at the temperature T*+3° C., at which P.sub.0=(7.5±0.5) μm.
(41) Flat glass cells of thickness d=(11-16) μm were used. The glass substrates were coated with polyimide PI2555 that sets a homeotropic (perpendicular) orientation of the molecules. When the cell is filled with N*, it shows a fingerprint texture with the helicoid axis in the plane (x,y) of the cell. This geometry allows one to clearly visualize the periodic structure of both the heliconical and cholesteric structures, as the wave-vector of director modulations in both cases is confined to the plane (x,y). To assure a uniform alignment of the helicoid, the polyimide coatings were rubbed unidirectionally along the axis x.
(42) For the polarizing optical microscopy (POM) study, two aluminum foil electrodes were placed between the glass plates to apply the electric field parallel to the rubbing direction x. This geometry corresponds to the diffraction grating device geometry described with reference to
(43) To establish the spatial pattern of the electric field, COMSOL Multiphysics finite-element based solver was employed. The simulations show that in the central part of the cell, the field is uniform and horizontal in the middle of the cell. For example, for the ITO case, for the applied voltage U=100 V, the field is 0.7 V/μm with a 5% accuracy in the range −20 μm≦x≦20 μm and across the entire extension of the LC slab along the z-direction. The field acting in the center of the cell can be calculated as E=βU/L, where β is the correction coefficient, determined by numerical simulations to be 0.67 for ITO and 0.75 for aluminum electrodes.
(44)
(45) The described scenario illustrated by
Example 2: Optical Diffraction Method and PolScope—In-Plane LC Cell Diffraction Grating Application of Cholesteric LCs—
(46) An optical diffraction experiment was performed with a He—Ne laser beam (λ=633 nm) directed normally to the cell. Polarization of incident light was varied by a rotating polarizer. The diffraction pattern was projected onto a screen 9.5 cm away from the sample. The heliconical state is a polarization-sensitive phase diffraction grating. For normal incidence, the diffraction condition is given by Bragg's law, mλ=P sin Θ.sub.m, where m is the diffraction order, Θ.sub.m is the corresponding diffraction angle. For small cone angles θ, the first-order diffraction intensity∝ sin.sup.2 2θ is expected to be higher than the second-order diffraction intensity∝ sin.sup.4θ. This is indeed the case, as the values of P calculated from the field dependence of Θ.sub.1, see
(47) With reference to
(48)
the same as measured in the N phase 106° C. With the above data, one deduces a rather small value of the bend elastic constant in N*, K.sub.3=0.3 pN.
(49) PolScope was used to characterize the oblique helicoid when the cone angle θ is small. PolScope maps the optical retardance Γ(x,y) of the sample, Γ=∫Δn.sub.effdz, where Δn.sub.eff is the effective birefringence of the heliconical state. For a small θ, one can use an approximation Δn.sub.eff≈Δn(1−3/2 sin.sup.2θ), where Δn is the birefringence of the unwound {circumflex over (n)}=(1,0,0) state. As a measure of Δn, the experimentally determined birefringence of pure CB7CB was used, Δn=0.15 at 106° C. With reference to
Example 3: Preparing Top-Down LC Cell for Color Tuning Application of Cholesteric LCs with Oblique Heliconical Director
(50) To demonstrate the color tuning application of heliconical structure, a doped LC dimer material CB7CB with a small amount (4.9 wt %) of chiral dopant S811 was used. The phase diagram is different from the case of an undoped CB7CB: N* melts into an isotropic fluid at 101.5° C. and transforms into a homochiral version of N.sub.tb at T*=90 C. The electrooptic experiments were performed at the temperature T*+3 C.
(51) To explore the electrooptic response of N* cell, a flat glass cell of thickness d=50 μm was used. The glass substrates were coated with polyimide PI2555 that sets a homeotropic (perpendicular) orientation of the molecules. When the cell is filled with N*, it shows a fingerprint texture with the helicoid axis in the plane (x,y) of the cell. To assure a uniform alignment of the helicoid, the polyimide coatings were rubbed unidirectionally along the axis x. The AC field of frequency 3 kHz was used to explore the electrooptic properties of heliconical structure of the N* cells. The LC cell geometry corresponds to that described with reference to
(52) Due to the helicoid character of the heliconical structure, it exhibits a Bragg reflection property. The center wavelength for the Bragg reflection reads
λ.sub.p=
with the reflection bandwidth
Δλ=Δn.sub.effP (EQN. 6)
where
(53)
(54) With reference to
(55) With reference to
Example 4: Chromaticity Diagram—Top-Down LC Cell for Color Tuning Application of Cholesteric LCs with Oblique Heliconical Director
(56) The chromatic sensation of human eyes to a specific optical spectrum is usually characterized by a chromaticity diagram. In what follows, we use the CIE1931 2° basis with D65 illuminant to characterized the colorimeters of the heliconical structure of N* samples. Each circle corresponds to the reflection color obtained from heliconical structure under the applied electric field. With reference to
Example 5: Response Time Measurement—Top-Down LC Cell for Color Tuning Application of Cholesteric LCs with Oblique Heliconical Director
(57) With reference to
(58) With reference to
Example 6: Field-Induced Heliconical Structure Employing a Liquid Crystal Mixture with Broad Temperature and Spectral Ranges of Operation
(59) The foregoing examples employ chiral-doped CB7CB liquid crystal dimer material as the active layer that exhibits the heliconical state. The chiral-doped CB7CB exhibits the heliconical state at temperatures in excess of 90° C., which is too high for use as a room-temperature device.
(60) In this example, a cholesteric mixture is employed, which exhibits a broad temperature range of stability that embraces the room temperature, and which has a small bend elastic constant K.sub.3 which is smaller than the twist constant K.sub.2, which as mentioned previously correlates with achievability of the oblique helicoidal state. Using such mixtures, it was demonstrated that selective reflection of light can be obtained, I with the selection wavelength tunable within a wide spectral range from ultraviolet (UV) to near infrared (near IR), by a low driving electric fields, a few V/μm.
(61) The approach exemplified by this example leverages the observation that a mixture of two materials can sometimes exhibit a lower melting temperature than either material individually. Here and in what follows, the melting temperature is defined as a temperature above which the material exhibits the heliconical state. Below that temperature, it might be in any other state, say, crystalline, nematic twist-bend phase, smectic state, columnar phase, amorphous state, etc. Some such materials exhibit a so-called “eutectic composition” at which the mixture exhibits a minimum melting temperature (as a function of mixture composition). This minimum melting temperature is referred to as the “eutectic temperature”. The “eutectic point” is the location on the phase diagram of the mixture defined by the eutectic composition and eutectic temperature. Although the eutectic composition provides the minimum melting temperature, there is generally a range of mixture compositions for which the mixture has a lower melting temperature than either individual constituent. The approach exemplified by this example is premised on the hypothesis that a eutectic mixture (or a mixture close to the eutectic composition having a depressed melting temperature) may exhibit the chiral nematic (N*) state at a lower temperature than either one of the two constituent materials.
(62) The illustrative mixture was formulated by mixing two dimeric liquid crystal materials: (1′,7′-bis(4-cyanobiphenyl-4′-yl)heptane (CB7CB) and 1-(4-cyanobiphenyl-4′-yl)-6-(4-cyanobiphenyl-4′-yloxy)hexane (CB6OCB)), along with the liquid crystal material pentylcyanobiphenyle (5CB) (Merck). The mixture was doped with a left handed chiral additive S811 (Merck) that determines the pitch P.sub.0. Three tested mixture compositions, designated M.sub.1, M.sub.2, and M.sub.3, are summarized in the table below.
(63) TABLE-US-00001 CB7CB:CB60CB:5CB:S811 Mixtures Tested Composition Composition ratio (in weight units) Temperature range of designation CB7CB:CB6OCB:5CB:S811 cholesteric phase M.sub.1 30:20:46:4 20° C.-66.5° C. M.sub.2 30.1:20:45.9:4 22° C.-68° C. M.sub.3 29:20:49:2 21° C.-69.5° C.
All three mixtures M.sub.1, M.sub.2, and M.sub.3 demonstrated electrically tunable light reflection in the cholesteric phase at temperatures up to 45° C.; at higher temperatures, the effect disappears as K.sub.3 in dimeric materials increases with temperature. All data reported herein for the mixtures M.sub.1, M.sub.2, and M.sub.3 were obtained at 25° C. In the experiments, the cholesteric material was sandwiched between two glass plates with transparent indium tin oxide (ITO) electrodes for applying the electrical bias.
(64) A second illustrative mixture was formulated by mixing two dimeric liquid crystal materials: (1′,7′-bis(4-cyanobiphenyl-4′-yl)heptane (CB7CB) and ω-bis(4,4-cyanobiphenyl)nonane (CB9CB)), along with the liquid crystal material pentylcyanobiphenyle (5CB) (Merck). The mixture was doped with a right handed chiral additive CB15 (Merck) that determines the pitch P.sub.0. The mixture composition is CB7CB:CB6OCB:5CB:CB15 (in weight units) being 30:20:44:6. The mixture produces heliconical state in the temperature range 23-50° C.
(65) With reference to
(66) As seen in
(67) With reference to
(68) With reference to
(69) With reference to
(70) In some devices, it is desired to block visible and near-IR light selectively and independently, by varying the applied voltage. Such a task can be performed by multilayered stacks of oblique helicoidal cholesterics with different concentration of chiral additive, since the materials are not absorbing.
(71) With reference to
(72) Experimental results on the field dependence of λ.sub.p (see
(73)
It has been shown that the tilt angle θ decreases as the electric field increases, so that Δn.sub.eff becomes smaller. This is why, for a given material, the reflectivity is typically weaker at high fields; it is also weaker at low fields, as the number of cholesteric layers in the cell of a fixed thickness decreases as the pitch increases, as seen in
(74) When the light beam is not strictly perpendicular to the cell, the oblique helicoid produces reflection not only at λ.sub.p, but also at 2λ.sub.p since the molecules separated by P/2 are tilted in opposite directions. In the presented experiments with normally incident beams of small divergence, the peak at 2λ.sub.p, although observable, was about 10 times weaker than the main peak at λ.sub.p.
(75) To change the color, the pitch adjusts to the electric field, either through slippage at the bounding plates or through nucleation and propagation of dislocations. Indeed, some of these defect lines are observable in
(76) The results for the CB7CB:CB6OCB mixture-based material exhibit an electrically tunable selective reflection of light in UV, visible and IR by the heliconical cholesteric state that exists in a broad temperature range including room temperature. The tunable structural color was achieved in a simple sandwich geometry, in which the cholesteric was confined between two plates with transparent electrodes, thus implying a low cost and easy fabrication process. The color change occurred over the entire electrode area that can be designed as a desired pattern suitable, for example, for “see-through” color displays. The electrically tunable colors can be additionally controlled by the cholesteric composition of the CB7CB:CB6OCB mixture and by employing reflective stacks. The effect can be tuned to practically any spectral regions in UV, visible and IR by chiral additives of different twisting power or concentrations.
(77) The illustrative example employs a mixture of CB7CB and CB6OCB dimeric liquid crystal materials near the eutectic composition. More generally, it is expected that mixtures of other dimeric liquid crystal materials that individually exhibit the heliconical state may be employed, with the impact of the mixture typically being to reduce the melting point and thereby enable lower-temperature heliconical operation. The advantage of low temperature operation is expected to be greatest for the mixture at or near the eutectic point. The experimental results provide a reasonable expectation that such devices will operate in the heliconical state at room temperature, e.g. at 25° C. as tested, or in a typical room temperature range such as 20° C. to 30° C. inclusive. Moreover, it is contemplated for the mixture to include more than two dimeric liquid crystal materials, with the three- or more-component mixture preferably being at or near the eutectic point for the three- or more-component mixture.
(78) Illustrative embodiments including the preferred embodiments have been described. While specific embodiments have been shown and described in detail to illustrate the application and principles of the invention and methods, it will be understood that it is not intended that the present invention be limited thereto and that the invention may be embodied otherwise without departing from such principles. In some embodiments of the invention, certain features of the invention may sometimes be used to advantage without a corresponding use of the other features. Accordingly, all such changes and embodiments properly fall within the scope of the following claims. Obviously, modifications and alterations will occur to others upon reading and understanding the preceding detailed description. It is intended that the present disclosure be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.