Abstract:
This invention discloses the product of a liquid crystal display (LCD) device and the method of making same, wherein the resultant product is an improved color oriented LCD in which the liquid crystal material and the color dye material are intimately comingled within an enclosure of polymer material and/or encapsulated within the structure of microdroplets. The resulting color displayed by this LCD device is controlled by the selective application of electrical parameters, namely, voltage and frequency, to permit the droplets within a display device to absorb, scatter, or transmit light, and/or color, or mixture of colors, determined by the dye materials and the applied electrical parameters employed.

Description:
This application is a continuation-in-part (C-I-P) application of prior pending application, Ser. No. 07/521,126, filed May 3, 1990, by the present inventors, now abandoned, which prior application was itself a C-I-P of patent application, Ser. No. 07/380,973, filed Jul. 17, 1989, by the inventors of the instant application, and which later application issued on Oct. 15, 1991, as U.S. Pat. No. 5,056,898, for &#34;Reverse Mode Microdroplet Liquid Crystal Light Shutter Displays&#34; to the Inventors of this invention; and the contents of said prior applications and of said patent and the file wrappers thereof, are incorporated herein by reference. Co-inventor B. G. Wu&#39;s prior U.S. Pat. No. 4,671,618, and other U.S. patents cited therein, are also incorporated herein by reference. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to Liquid Crystal Displays (LCD&#39;s), which, in use, utilize unique optical properties of liquid crystals to provide display devices that require lower power to operate, and provide precise control of light intensity, contrast and color, thru the use of the electrical parameters of voltage and frequency. 
     2. Prior Art 
     U.S. Pat. No. 4,671,618, to B. G. Wu, et al; patents and references cited therein, and the following are part of the prior art: 
     1. J. W. Doane, N. A. Vaz, B. G. Wu &amp; S. Zumer, Appl. Phys. Lett. 48, 269 (1986) 
     2. P. Drzaic, J. Appl. Phys. 60, 2142 (1986) 
     3. B. G. Wu, J. L. West &amp; J. W. Doane, J. Appl. Phys. 62, 3925 (1987) 
     4. J. W. Doane, A. Golemme, J. L. West, J. B. Whitehead, Jr., and B. G. Wu, Mol. Cryst. Liquid Crystals 165, 511 (1988) 
     5. B. G. Wu, J. H. Erdmann, J. W. Doane, Liq. Cryst. 5, 511 (1989) 
     6. Y. D. Ma, B. G. Wu &amp; G. Xu, Liquid Crystal Displays, J. W. Doane &amp; Z. Yaniv, eds., SPIE 1257 (1990) 
     7. D. W. Allender &amp; S. Zumer, Liquid Crystal Chemistry, Physics Applns. J. W. Doane &amp; Z. Yaniv, eds., Proc. SPIE 1080, 18 (1989); J. H. Erdmann, S. Zumer &amp; J. W. Doane, Phys. Rev. Lett. 64, 5107 (1990) 
     SUMMARY OF THE INVENTION 
     An object of this invention is to provide a unique liquid crystal display device wherein the output light is absorbed or scattered from droplets that are selectively controlled to show the desired colors. 
     Another object of this invention is to provide a method of making a color output liquid crystal display device, wherein the liquid crystal material and dye material are encapsulated within the same droplet. 
     A further object is to provide an extremely small and yet effective microdroplet containing liquid crystal material and dye material which are encapsulated in a transparent polymer material. When the term &#34;miniature&#34; is used it refers to droplet size or LCD thickness. 
     And another object is to produce a full-color addressable miniature display based on the microencapsulated dye/liquid crystal concept. 
     A still further object is to provide a liquid crystal display device that comprises a plurality of at least three dye materials contained in separate droplets with liquid crystals so that any one of the three colors may be displayed by selective control of the electrical parameters. 
     Another object is to provide a method of making these devices. 
     An additional object is to provide a method of activating the dye containing droplets of liquid crystal display material, selectively to produce a display of a particular color from a full color spectrum. 
     And yet an additional object is to provide a method of activating said droplets for color display that involves the use of electrical parameters, namely voltage and frequency. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     FIG. 1A represents a bipolar structure in the optic &#34;off&#34; state of a microdroplet (referred to as &#34;droplet&#34; hereafter) containing nematic liquid crystals material with a positive dielectric anisotropy; 
     FIG. 1B is a representation of the item of FIG. 1A showing a depiction of the structure in the optic &#34;on&#34; state; 
     FIG. 2A represents an axial structure in the optic &#34;on&#34; state of a droplet containing nematic liquid crystal with a negative dielectric anisotropy; 
     FIG. 2B is a representation of the item of FIG. 2A showing a depiction of the structure in the optic &#34;off&#34; state; 
     FIG. 3A represents a dual frequency axial structure when subjected to a field of high voltage and low frequency, with the director lines parallel to the electric field, and the droplet in the optic &#34;on&#34; state; 
     FIG. 3B is a representation of the item of FIG. 3A when the field is one of low voltage and high frequency, and the droplet is in the optic &#34;off&#34; state; 
     FIG. 4 is a chart showing the values of the dielectric constants in a direction parallel to the longitudinal axis of the liquid crystal and in a direction perpendicular to that axis for different frequencies of the applied field; and showing that the dielectric anisotropy, will change its sign at about 1000 Hz, when the temperature is 22° C. 
     FIG. 5 is a representation of a cross section through a liquid crystal display device having segmentated layers separating groups of polymer dispersed liquid crystals (PDLC) according to their individual structures and the color of the dye contained within the droplet; 
     FIG. 6 is a display configuration with three kinds of droplets with different skins, liquid crystal structures and dyes, but being contained within a common polymer transparent medium; 
     FIG. 6A is a display configuration showing the reaction of the three kinds of droplets in the presence of a zero voltage condition; 
     FIG. 6B is similar to FIG. 6A, but with low voltage and low frequency conditions; 
     FIG. 6C is similar to FIG. 6A, but with low voltage and high frequency conditions; 
     FIG. 6D is similar to FIG. 6A, but with high voltage and low frequency conditions. 
    
    
     DESCRIPTION OF PREFERRED EMBODIMENTS 
     Referring now more particularly to the characters of reference in the drawing, it will be observed in FIG. 1, that the representation shown in that of a single polymer dispersed liquid crystal (PDLC) droplet 1, more fully disclosed in B. G. Wu, et al, U.S. Pat. No. 4,671,618, which is incorporated herein by reference. This droplet 1 comprises a mixture of PDLC having a bipolar orientation, wherein the dielectric anisotropy of the liquid crystal material is greater than zero. This droplet comprises a nematic material liquid crystal. 
     In the instant invention, the liquid crystal material in the droplet is further mixed with one of three liquid crystal dyes taken from a group of primary colors, in this case, read, green and blue, with high dichroic ratios, which are dissolved in the particular host liquid crystal. 
     Droplet 1 contains a blue dye, and is effective to display a blue color in the absence of any applied electric field as shown in FIG. 1A, and to display no color when an electric field is present, as in FIG. 1B. This droplet does not utilize a separate encapsulating skin, and utilizes a &#34;normal mode&#34; function. 
     The droplets shown in FIGS. 2A, 2B &amp; 3B demonstrate the &#34;reverse mode&#34; function, as first described in U.S. Pat. No. 5,056,898, and as here shown to portray &#34;aligned&#34; molecules in FIGS. 2A and 3A, and to portray &#34;non-aligned&#34; molecules (also directors, when under electric influence) in FIGS. 2B and 3B, where the directors are perpendicular to the applied electric field. 
     The droplet 2 of FIG. 2A is a droplet having orientation where the dielectric anisotropy of this nematic liquid crystal is less than zero. Droplet 2 contains a red dye, and is effectivbe to display a red color in the presence of an electric field, as indicated in FIG. 2B. 
     The droplet 3 of FIGS. 3A an d 3B, is a mixture of PDLC having an axial structure whose dielectric anisotropy changes from greater than zero at low frequencies to less than zero at high frequencies. This droplet presents a transparent colorless display both in the presence of an electric field at low frequencies, as seen in FIG. 3A, and in the absence of an electric field, and presents a green color display at low voltage and high frequencies, as shown in FIG. 3B. 
     In FIGS. 2A-3B (and in FIGS. 6A-6D), the reverse mode droplets 2 and 3 are comprised, respectively, of liquid crystal bodies 2b and 3b, that are enclosed in their polymer skin 2a and 3a. 
     The chart of FIG. 4 shows the range wherein the dielectric anisotropy, which is the value of the dielectric constant in the direction parallel to the longitudinal axis of the liquid crystal molecule, less the dielectric constant perpendicular to this axis, changes with the applied frequency. From this chart, it will be observed that the crossover frequency for the dual frequency material of FIG. 3B, would be about 1000 Hertz for the host liquid crystal used, and when the temperature is approximately 22 degrees C. 
     The device shown in FIG. 5, illustrates the employment of three layers within the liquid crystal display housing 10, wherein each layer contains droplets of the same structure, orientation and dye material. The outer layers of this device are relatively thick glass substrates, 11, which are approximately 43 mils thick, and to which layers are deposited on the inner sides, layers 12, which comprise the ITO (indium tin oxide) coatings that form the electrodes, which are separated by a distance of 30 micrometers, which is the space available for the plurality of droplets in the three separated layers 13 of FIG. 5, and for the entire single layer 13A of the space occupied by the droplets of FIG. 6. 
     The Table 1, shown below, lists the electrical parameters necessary to provide the colors red, green and blue respectively, in the droplets of FIG. 6. When a voltage of selected frequency and strength is applied to the device, the display shows colors blue, green, red, or colorless as shown in Table 1. The colors can be mixed by mixtures of momentarily applied voltages and frequencies. Different complementary colors may be obtained by changing the electrical parameters so rapidly that the human eye detects the complementary color rather than the two separate colors that are being combined. The following chart shows the results of selective electric parameters: 
     
                                           TABLE 1__________________________________________________________________________Full Color Function Grid                 GreenApplied       Red     Low Voltage                          BlueVoltage  Frequency         High turn-on V                 Δε &gt; 0 at low f                          Low turn-on VV      f      Small Δε &lt; 0                 Δε &lt; 0 at high f                          Δε &gt; 0__________________________________________________________________________Zero          Colorless                 Colorless                          BlueLow Voltage  Low Values         Colorless                 Colorless                          ColorlessLow Voltage  High Values         Colorless                 Green    ColorlessHigh Voltage  Low Values         Red     Colorless                          Colorless__________________________________________________________________________ 
    
     All of the host liquid crystal materials used have a small delta &#34;n&#34; (&lt;0.07), so that the average refractive index of the droplet is not significantly different for any direction of incident light. The droplets of the first set of FIG. 5 are dispersed in a thin polymer film (10 μm) to make a blue color filter where the refractive index of the polymer is selected to be about (n o  +n e )/2; the film will possess almost no scattering in both the field &#34;ON&#34; and &#34;OFF&#34; states. The polymer film containing the second set of microdroplets is a green color filter only in the case where high frequency and low voltage is applied. The film with the third set of microdroplets is a red color filter when high voltage is applied because of the small delta-epsillon. These materials can be applied to a substrate in the methods shown in FIGS. 5 and 6. 
     FIGS. 6A through 6D of the drawing, depict a representation of the droplets of FIG. 6, when they are subjected to the various operational electrical parameters, namely changes in voltage and/or frequency. The bipolar structured LCD droplets contains a blue dye in its mixture, so in the absence of an electric field, it will display a blue color, whereas the axial structured droplet and the dual frequency axial droplet will remain colorless, as shown in FIG. 6A. Under conditions of low voltage and low frequency, all of the droplets will be colorless, as shown in FIG. 6B. In FIG. 6C, the droplets are subjected to a low voltage and high frequency field, and only the dual frequency droplet will display a color, i.e., green. The droplets of FIG. 6D are in the presence of a high voltage, low frequency field, and the only color displayed will be that of red from the axial droplets. 
     There are at least the following advantages flowing from the use of this full color PDLC device and method shown: 
     1. The color elements can be very small, such as a unit pixel, since the microdroplets are about 1 μm in diameter. 
     2. The film is solid and can be coated or painted on a large area, even one with a curved or flexible surface. 
     3. The color can be changed in the same location by changing the electric field parameters. 
     COMPENDIUM OF THE INVENTION 
     The use of polymer-dispersed liquid crystals (PDLC) for information display has attracted the interest of several researchers, because PDLC&#39;s do not require polarizers and displays can be simply fabricated on large flexible substrates. Dyes may be incorporated in the liquid crystal materials to add color and improve contrast. The display modes achieved so far, however, have been monochromic, allowing the display to switch only between a clear and colored state. 
     A new PDLC display mode with three different dyes dissolved in three different kinds of nematic microdroplets, each of which can be switched independently by changing the strength and frequency of applied electric field allows the achievement of a full color miniature liquid crystal display. 
     Two kinds of nematic droplet structures are used in this multi-colored PDLC display mode: the bipolar structure (FIGS. 1A/1B), and the axial structure (FIGS. 2A/2B). 
     For the bipolar structure, tangential alignment at the boundry is needed, while for axial structure, perpendicular alignment is required. 
     For the bipolar nematic droplet with positive dielectric anisotropy (Δε&gt;0), when an external electric field is applied, the director will align parallel to the direction of the external field, as shown in FIG. 1B; while the axial nematic droplet with a negative dielectric anisotropy (Δε&lt;0), under the applied electric field, the directors will align perpendicular to the external field as shown in FIG. 2B. 
     The axial structure is used by the newly developed &#34;Reverse Mode Microdroplet Liquid Crystal Display&#34; (Prior Art reference #6, and in U.S. Pat. No. 5,056,898 of the instant inventors. 
     For the miniature color display mode, a third kind of liquid crystal material is needed, one of dual-frequency property (Δε&gt;0 at low frequency, and Δε&lt;0 at high frequency), as illustrated in FIGS. 3A and 3B. 
     We add red dye to the axial nematic microdroplets with Δε&lt;0 to form &#34;red cells&#34;; blue dye to the bipolar nematic microdroplets with Δε&gt;0 to form &#34;blue cells&#34;; and green dye to the axial nematic microdroplets with the dual-frequency liquid crystal host to form &#34;green cells&#34;. All three liquid crystal host materials should have small Δn(&lt;0.07), so that the average refraction index of the droplets will not be significantly different for the incident light from any direction. The refractive index of the polymer matrix that hosts the cells is selected to be comparable (n e  +n o )/2, so that the scattering of the incident light is reduced to be insignificant and the film appears to allow almost no scattering in either the field &#34;ON&#34; or the field &#34;OFF&#34; state. 
     A polymer film with only the green cells can be used as a green color filter, switching on with a high frequency voltage. When the high frequency drives Δε negative, the electric field will align the direction of the field. All the light, except the green, entering the film will be absorbed by the dye. 
     Similarly a film with the red cells will be a red filter under high voltage, if we choose a liquid crystal host with small Δε; and a film with blue cells acts as a blue filter, under a lower voltage than the one used for the red filter, with suitable choice for its Δε&gt;0. 
     A three color display film is formed by stacking the three films of color filters together and sandwiching them between a pair of glass substrates with ITO patterns, as shown in FIG. 5. Another way of making the display film is to have the three kinds of cells uniformly dispersed in a polymer film, as shown in FIG. 6. The switching property of the display film is not significantly different in either method. 
     Table 1 lists the four states of display mode, their switching V-f range, color of the transmitted light and director structure for each kind of the colored cell. This is only one of the possible arrangements; there are many other combinations which may be selected. 
     From Table 1, we see that this new PDLC film gives four states: red, green, blue and white (colorless). By mixing the four states temporarily, we obtain any color. To do so, we need to be able to switch among these states fast enough so that our eyes will see only a color which is a mixture of three primary colors. The proportion of each &#34;primary color&#34; is proportional to the time that each color is allowed to stay at its &#34;ON&#34; state. 
     With the refractive index of the polymer matching n e  and n o  of the liquid crystal droplet, also with small Δε (&lt;0.07), all of the states of the display, no matter whether color-on or color-off, will be transparent. This property makes the display useful in applications such as TV projectors. When the refractive indices are mismatched, the color-on states will become opaque, with the colors as listed in Table 1, while the colorless state can still be made transparent, if we choose n o  =n p , where n p  is the refractive index of the polymer. A film made this way can also be used for making display devices. If we use the film reflectively, we can switch it among a black background (transparent state), and three colored, but opaque states, by applying suitable voltage with suitable strength and frequency. For all three kinds of color cells, the ideal situation is to have directors and dye molecules uniformly aligned along the Z-axis in the color-off states, and perpendicular to the Z-axis in the color-on states. The real configuration of directors however, is determined by field, boundry alignment and size and shape of the droplets. The field and size effect has been studied by Zumer and Doane (Prior Art reference No. 7). The shape effect is of particular importance in the reverse mode display (U.S. Pat. No. 5,056,898). 
     To make a display film with a large viewing angle, it is very important to make sure that for each cell in its colorless state, the directors be aligned parallel to the Z-axis as much as possible; in a word, to be more &#34;axial-like&#34;. From the information shown in Table 1, we see that for a blue cell, its colorless state can be helped by applying higher voltage or choosing higher value for Δε, the same is true for a green cell under low frequency voltage. But for a green cell under zero voltage and for a red cell, their colorless states cannot be helped by an applied field. The only way to acheive better alignment is to choose liquid crystal material with higher value of electric constant, and make the cells flatter, or to decrease the size and/or the anchoring energy at the boundary. 
     The full color PDLC display method reported here is the first V-f switchable, miniature (in this specification, &#34;miniature&#34; means miniature thickness only) display, and has the following features: 
     1. The color element, like a unit pixel, can be made very small, since the microdroplets are only about 1 μm in diameter, compared to 100 μm of the lateral dimension for the other methods of LCD&#39;s. 
     2. The V-f switching mode makes color selection as well as gray scale control possible at the same time. 
     The devices and methods shown herein may be accomplished in many ways, within the scope of the appended claims: