WO2013054962A1 - 배향막, 배향막 형성 방법, 액정 배향 조절 방법, 그리고 액정 표시 장치 - Google Patents
배향막, 배향막 형성 방법, 액정 배향 조절 방법, 그리고 액정 표시 장치 Download PDFInfo
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- WO2013054962A1 WO2013054962A1 PCT/KR2011/007672 KR2011007672W WO2013054962A1 WO 2013054962 A1 WO2013054962 A1 WO 2013054962A1 KR 2011007672 W KR2011007672 W KR 2011007672W WO 2013054962 A1 WO2013054962 A1 WO 2013054962A1
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/29—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the position or the direction of light beams, i.e. deflection
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133773—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers the alignment material or treatment being different for the two opposite substrates
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133776—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers having structures locally influencing the alignment, e.g. unevenness
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/2457—Parallel ribs and/or grooves
- Y10T428/24587—Oblique to longitudinal axis of web or sheet
Definitions
- An embodiment of the present invention relates to a display device, and more particularly, to an alignment film, an alignment film forming method, and a liquid crystal alignment control method used in the display device.
- LCDs liquid crystal displays
- the liquid crystal display uses an electric signal to change an optical transmittance by electro-optic modulation in a state where a liquid crystal, which is an intermediate state material between a liquid and a crystal, is placed between a pair of polarizers according to an applied voltage. It transfers the image by changing the visual information. That is, a conventional liquid crystal display device is composed of two substrates provided with electrodes and liquid crystals injected between the substrates, and an electric field is applied to the liquid crystals by applying a voltage to the two substrates. The light transmittance between the pairs changes.
- the arrangement of the liquid crystal changes depending on the electric field due to the dielectric anisotropy of the liquid crystal. That is, the liquid crystal molecules have different physical properties in the long axis direction and the short axis direction, and thus, when an electric field is applied, the electric forces acting in the long axis direction and the short axis direction of the liquid crystal molecules are different. It becomes a drive source to rotate.
- the liquid crystal has positive dielectric anisotropy or negative dielectric anisotropy depending on the type. That is, based on the long axis direction of the liquid crystal, the former is arranged in parallel to the direction of the electric field when the electric field is applied, the latter is arranged perpendicular to the direction of the electric field.
- Liquid crystals also have refractive index anisotropy, which causes the transmittance of light to vary depending on the arrangement of the liquid crystals.
- the refractive anisotropy of the liquid crystal causes a problem that the viewing angle is narrow in the liquid crystal display device.
- the viewing angle refers to a direction in which the viewer views the display screen, and the image of the liquid crystal display is distorted toward the side rather than the front, so that the viewing angle is narrower than that of other display devices.
- a single pixel is divided into regions so that the liquid crystals may be inclined in different directions in each region. That is, multiple domains are formed according to the arrangement direction of the liquid crystal for each region of each pixel. For example, when the liquid crystals of the first region are arranged to be inclined in the first direction and the liquid crystals of the second region are arranged to be inclined in the second direction, even when light is not transmitted through the liquid crystal of the first region when viewed from one side, Since light may pass through the liquid crystal, the viewing angle of the liquid crystal display may be increased.
- a multi-milt-stable liquid crystal display device in which multiple patterns of submicro size are formed in an alignment layer has been proposed.
- This multi-stable liquid crystal display device has two stable states due to the submicro-sized parallel multi-array layer, which has the advantage of preserving contents without electric reproduction even when the power is turned off.
- the sub-microphone size pattern is formed by a method such as multi-rubbing, multiple photo arrays, nanoimprints, and the like.
- the method of forming such a submicro size pattern has a poor yield, is difficult to apply to a large area panel, and does not adjust the arrangement of the liquid crystal directors well.
- An embodiment of the inventive concept provides an alignment layer and a method of forming the same.
- An embodiment of the inventive concept provides a mold for imprinting an alignment layer and a method of forming the same.
- An embodiment of the inventive concept provides a liquid crystal display device.
- An embodiment of the inventive concept provides a liquid crystal alignment control method.
- a method of forming an alignment layer may include a plurality of first grooves extending in a first direction and spaced apart from each other, and a plurality of first spaced apart from each other crossing the first grooves in a second direction It includes forming two grooves in the alignment film.
- the first groove and the second groove are formed to have different width and depth dimensions.
- a plurality of first protrusions extending in a first direction and spaced apart from each other are formed on an elastic film, and the first protrusions extend in a second direction.
- the forming of the second protrusions may include expanding the elastic membrane on which the first protrusions are formed, performing a shrinkage control process for adjusting the contraction of the expanded elastic membrane, and shrinking the expanded elastic membrane.
- a method of forming an alignment layer includes printing a plurality of first grooves and the plurality of first grooves corresponding to the first protrusions and spaced apart from each other by imprinting an elastic layer formed by the mold forming method for alignment layer imprint. Forming a plurality of second grooves corresponding to the two protrusions and spaced apart from each other.
- An alignment layer may include a plurality of first grooves extending in a first direction and spaced apart from each other, and a plurality of second spaced apart from each other crossing the first grooves in a second direction Includes a groove.
- the liquid crystal display according to the exemplary embodiment of the inventive concept may include a first alignment layer and a second substrate facing each other, and a first alignment layer and a first alignment layer formed on opposite surfaces of the first substrate and the second substrate. 2 alignment films.
- Each of the first alignment layer and the second alignment layer may include a plurality of first grooves extending in a first direction and spaced apart from each other, and a plurality of second grooves spaced apart from each other to extend in a second direction and cross the first grooves.
- a multi-stable liquid crystal display device includes a first alignment layer and a second substrate facing each other, and a first alignment layer formed on opposite surfaces of the first substrate and the second substrate. And a second alignment layer.
- Each of the first alignment layer and the second alignment layer may include a plurality of first grooves extending in a first direction and spaced apart from each other, and a plurality of second grooves extending in a second direction and intersecting with the first grooves. And wherein the ratio of the azimuthal orientation energy by the first grooves and the azimuthal orientation energy by the second grooves is about one.
- a multi-domain liquid crystal display device may include a first substrate and a second substrate disposed to face each other, a first alignment layer formed on a surface of the first substrate and the second substrate to face each other, and A second alignment layer is included.
- Each of the first alignment layer and the second alignment layer may include a plurality of first grooves extending in a first direction and spaced apart from each other, and a plurality of second grooves extending in a second direction and intersecting with the first grooves. Wherein the ratio of the azimuthal orientation energy by the first grooves to the azimuthal orientation energy by the second grooves is about zero.
- the liquid crystal alignment adjusting method applied to the liquid crystal display according to the exemplary embodiment of the inventive concept may include a plurality of first grooves extending in a first direction and spaced apart from each other in the alignment layer, and extending in the second direction. Forming a plurality of second grooves spaced apart from each other, the aspect ratio of the first grooves and the aspect ratio of the second grooves are selectively adjusted to enable multi-stable liquid crystal alignment or multi-domain liquid crystal alignment.
- the alignment layer imprint mold may include a plurality of first protrusions extending in a first direction and spaced apart from each other, and a plurality of spaced apart from each other crossing the first protrusions in a second direction. And a second protrusion of the.
- the height and width dimensions of the first protrusion are formed differently from the height and width dimensions of the second protrusion.
- an alignment layer may be formed without a conventional rubbing process.
- the alignment layer may be simply and economically formed by an imprint method by using an elastic layer having a double pattern engraved therein.
- a large area multistable liquid crystal display device may be easily manufactured.
- the azimuth orientation energy may be easily adjusted.
- a multi-domain bistable liquid crystal display device may be easily manufactured.
- FIG. 1 schematically illustrates an alignment layer having a double uneven structure according to an embodiment of the inventive concept.
- FIG. 2 schematically illustrates an alignment layer having a double uneven structure according to still another embodiment of the inventive concept.
- FIG 3 is a view for explaining a multi-stable liquid crystal array according to an embodiment of the present invention.
- FIG. 4 is a diagram for describing a multi-domain liquid crystal array according to an exemplary embodiment of the present invention.
- FIG. 5 is a view schematically illustrating formation of an alignment layer according to an embodiment of the present invention.
- FIG. 6 schematically illustrates a structure of an imprint mold according to an embodiment of the present invention.
- FIG. 8 to 12 illustrate a method of forming the imprint mold of FIG. 6 according to an embodiment of the inventive concept.
- FIG. 13 to 15 illustrate a method of forming an imprint mold of FIG. 7 according to an embodiment of the inventive concept.
- 16 is a view for explaining a method of forming a micro protrusion according to an embodiment of the inventive concept.
- 17 to 19 illustrate a method of forming an alignment film using an imprint mold described with reference to FIGS. 8 to 12.
- Figure 21 shows the correlation between the oxygen plasma treatment time and the bending period of the micro uneven structure.
- FIG. 22 is a graph showing the amplitude and the bending period of the macro uneven structure and the micro uneven structure.
- FIG. 23 is a graph showing the surface free energy density with respect to the azimuth angle function according to the variation of the alignment determination factor G in relation to FIG.
- Fig. 24 is a graph showing an easy azimuth axis according to the alignment determining factor G, showing a simulation (expressed in triangle) and Experimental Example 2 (indicated in a circle) based on Equation (4).
- 25 is a polarization microscope image of a liquid crystal according to a bending period of a macroconcave-convex structure according to an embodiment of the present invention.
- a film when it is mentioned that a film is on another film or substrate, it means that it may be formed directly on another film or substrate or a third film may be interposed therebetween.
- An embodiment of the inventive concept relates to a method of controlling liquid crystal alignment, an alignment layer according to the same, and a liquid crystal display device.
- the alignment layer according to the embodiment has a double uneven structure.
- the two kinds of irregularities forming the double uneven structure show different dimensions. For example, they have grooves of different depths and widths (widths). Or projections of different heights and widths (widths).
- the arrangement direction of the liquid crystals can be controlled, and a multi-stable liquid crystal display device or a multi-domain liquid crystal display device can be selectively implemented.
- FIG. 1 schematically illustrates an alignment layer having a double uneven structure according to an embodiment of the inventive concept.
- the alignment layer 100 extends in a first direction (y-axis direction in the drawing) and extends in a plurality of first grooves 121 and a second direction (x-axis direction in the drawing) spaced apart from each other.
- the first groove 121 includes a plurality of second grooves 141 spaced apart from each other.
- the first groove 121 and the second groove 142 may be perpendicular to each other, for example. That is, the first groove 121 is periodically arranged along the second direction, and the second groove 141 is periodically disposed along the first direction while being perpendicular to the first groove 121. From the periodic arrangement of the grooves, protrusions can be defined between adjacent grooves.
- a first protrusion 123 may be defined between adjacent first grooves
- a second protrusion 143 may be defined between adjacent second grooves. That is, the first groove 121 and the first protrusion 123 are alternately disposed along the second direction (x axis), and the second groove 141 and the second protrusion 143 are in the first direction (y axis). Are placed alternately along.
- the depth of the grooves corresponds to the height of the protrusions and the distance between adjacent grooves corresponds to the width of the protrusions, and likewise the distance between adjacent protrusions corresponds to the width of the grooves.
- the first groove 121 and the second groove 141 may be formed in different dimensions.
- the depth of the first groove (121) (M A) and a width (L M) may be formed to a larger dimension than the depth (A m) and a width (L m) of the second groove 141.
- the height and width of the first protrusion 123 may be formed to have a size larger than the height and width of the second protrusion 143.
- the relatively large first groove 121 is referred to as a macro groove
- the relatively small second groove 141 is referred to as a micro groove for convenience of explanation and a better understanding in the description regarding the alignment layer. It may be called a micro-groove.
- the relatively large first protrusion 123 between the macro grooves may be referred to as a macro protrusion
- the relatively small second protrusion 143 between the micro grooves may be referred to as a micro protrusion.
- the depth and width of the grooves or the height and width of the protrusions are not limited by the title.
- a structure in which the macro grooves 121 and the macro protrusions 123 are alternately arranged is called a macro uneven structure 120
- a structure in which the micro grooves 141 and the micro protrusions 143 are alternately arranged is referred to as a micro uneven structure ( 140).
- the aspect ratio of the groove is defined as (depth of the groove) / (width of the groove).
- the aspect ratio of the protrusions is defined as (height of protrusions) / (width of protrusions).
- the arrangement of the liquid crystals in the alignment layer may be easily controlled by adjusting the aspect ratios of the macro grooves 121 and the micro grooves 141.
- FIG. 2 schematically illustrates an alignment layer having a double uneven structure according to still another embodiment of the inventive concept.
- the alignment film of FIG. 2 differs from the groove of FIG. 1, which is formed somewhat flat in that the bottom and sidewalls of the groove (the upper surface and the sidewall of the protrusion) are smoothly formed.
- the arrangement of the liquid crystals in the alignment layer may be easily controlled by adjusting the aspect ratios of the first and second grooves.
- the alignment of the liquid crystal is influenced by the surface topology of the alignment film on which the liquid crystal is placed.
- the anisotropic interaction force that the liquid crystal receives by the alignment layer is represented by azimuthal anchoring energy between the liquid crystal and the surface of the alignment layer.
- the arrangement of the liquid crystals can be determined by the azimuthal orientation energy.
- the azimuthal orientation energy is related to the aspect ratio of the groove.
- FIG 3 is a view for explaining a multi-stable liquid crystal array according to an embodiment of the present invention.
- the alignment layer 100 includes a macro recessed and projected structure 120 and a micro recessed and projected structure 140 formed in the macro recessed and projected structure 120. That is, micro grooves 141 and micro protrusions 143 are formed in each of the macro grooves 121, and micro grooves 141 and micro protrusions 143 are formed in each of the micro protrusions 143.
- Equation 1 A M is an amplitude of the macro uneven structure 120, and ⁇ M is a bending period of the macro uneven structure 120.
- Equation 2 A m is the amplitude of the micro uneven structure 140, ⁇ m is the bending period of the micro uneven structure 140.
- the amplitude of the uneven structure corresponds to the height of the groove or the depth of the protrusion
- the bending period of the uneven structure corresponds to the overall width of the groove and the protrusion. Therefore, since the bending period ⁇ is related to the groove or protrusion width, the azimuthal orientation energy of the uneven structure is related to the aspect ratio of the groove.
- Equation 1 the ratio of W and W ⁇ M from ⁇ m ( ⁇ M W / W ⁇ m) arranged to be defined by the determinant (G) can be obtained as shown in the following equation 3.
- the alignment of the liquid crystal may be controlled in the alignment layer of the double uneven structure according to the exemplary embodiment of the inventive concept.
- the factor G value depends on the ratio of the aspect ratio of the microgroove 141 to the aspect ratio of the macrogroove 121.
- Azimuth orientation energy W of macro uneven structure 120 ⁇ M Orthogonal Orientation Energy W of the Micro-Concave-Convex Structure 140 ⁇ m If similar to (W ⁇ M ⁇ W ⁇ m ), The value of the factor G is close to 1 (G (A M 2 / ⁇ M 3 ) x ( ⁇ m 3 / A m 2 ⁇ 1), thus the liquid crystal 200 is arranged in a bistable state.
- FIG. 4 is a diagram for describing a multi-domain liquid crystal array according to an exemplary embodiment of the inventive concept.
- the liquid crystal 200 has a pretilt direction determined according to the geometry of the macro groove 121, and the micro groove 141.
- the liquid crystals are arranged in a multi-domain state because they are arranged along the azimuthal orientation energy of.
- a multi-domain liquid crystal alignment or a multi-stable liquid crystal alignment may be realized by forming an alignment layer having a double uneven structure and appropriately adjusting a ratio of aspect ratios of macro grooves and micro grooves.
- the alignment layer may be formed in an imprint manner.
- 5 is a view schematically illustrating formation of an alignment layer according to an embodiment of the present invention. Referring to FIG. 5, the alignment layer first includes forming an imprint mold 300 having a double uneven structure, and imprinting the imprint mold 300 on the alignment layer 100 formed on the substrate 400. .
- the imprint mold may have a double uneven structure so that the alignment film has a double uneven structure.
- 6 schematically illustrates a structure of an imprint mold according to an embodiment of the present invention.
- the imprint mold 300 includes a first protrusion 323 corresponding to the first groove 121 of the alignment layer of FIG. 1, and a second protrusion 321 corresponding to the second groove 123 of the alignment layer. .
- a plurality of first protrusions 323 extending in a first direction (y-axis direction in the drawing) and spaced apart from each other, and a plurality of spaced apart mutually intersecting first protrusions in a second direction (x-axis direction in the drawing) And a second protrusion 343.
- the first protrusion 323 and the second protrusion 343 may be orthogonal to each other, for example. That is, the first protrusion 323 is periodically arranged along the second direction, and the second protrusion 343 is periodically disposed along the first direction while being perpendicular to the first protrusion 323.
- grooves defining the protrusions of the alignment layer can be defined between adjacent protrusions.
- a first groove 321 may be defined between the adjacent first protrusions 323, and a second groove 341 may be defined between the adjacent second protrusions 343.
- the height of the protrusions of the imprint mold 300 defines the depth of the grooves of the alignment layer, and the distance between adjacent protrusions of the imprint mold defines the width of the grooves of the alignment layer.
- the first protrusion 323 and the second protrusion 343 of the imprint mold 300 may have different dimensions.
- the height of the first projection (323) (M A) and a width (L M) may be formed to a larger dimension than the height (A m) and a width (L m) of the second projection (343).
- the relatively large protrusions 323 and the grooves 321 are macro protrusions and grooves, respectively, and the relatively small protrusions 343 and grooves 341 are described in the following description of the alignment layer.
- the structures of the macro protrusions 323 and the macro grooves 321 arranged alternately in the mold 300 are converted into the macro protrusions and protrusions 320 to the micro protrusions 343 and the micro grooves 341 arranged alternately.
- the structure by this can be called the micro uneven structure 340.
- the aspect ratio of the protrusions or of the imprint mold 300 may be adjusted, and thus the arrangement of the liquid crystals in the alignment layer may be adjusted.
- FIG. 7 schematically illustrates an imprint mold according to another embodiment of the inventive concept.
- the imprint mold according to the present embodiment is for manufacturing the alignment film of FIG. 2, which is the same in terms of showing a double uneven structure compared to the imprint mold of FIG. 6, but the shape of the protrusion or groove is somewhat different from that of FIG. 6. .
- the upper surface and the sidewall of the protrusion are smoothly formed, which is different from the protrusion of FIG.
- FIG. 8 to 12 illustrate a method of forming the imprint mold of FIG. 6 according to an embodiment of the inventive concept. It can be broadly divided into a step of forming a macro protrusion (Figs. 8 to 9) and a step of forming a micro protrusion (Figs. 10 to 12).
- a method of forming a macro protrusion (which defines a macro groove of an alignment layer) will be described with reference to FIGS. 8 to 9.
- a plurality of protrusions 610 are formed on the substrate 500 through a photolithography process.
- a groove 620 is defined between the protrusions 610.
- the protrusion 610 may be formed by spin-coating a photoresist on the substrate 500 and then performing an exposure and ashing process.
- the protrusion 610 may be formed by etching a substrate or by patterning an insulating film or a conductive film.
- the macro groove 321 and the groove corresponding to the protrusion 610 may be contacted by contacting the mold 300 with the substrate 500 on which the protrusion 610 and the groove 620 are formed.
- a macro protrusion 323 corresponding to 620 is formed in the mold 300.
- the mold 300 may be formed of, for example, an elastic and adhesive material.
- the mold 300 may be formed of PDMS, polyurethane, silicone-containing polyurethane, poly (tetramethyloxide), poly (ethylene oxide), poly (oxetane), polyisoprene, polybutadiene, or a combination thereof. .
- the mold in which the macro recessed and projecting structure is formed is expanded and then contracted anisotropically so that the micro recessed and projecting structure is spontaneously formed in the macro recessed and projected structure.
- the mold 300 in which the macro recessed and projected structure 320 is formed is heat-treated.
- the heat treatment is for expanding the mold.
- the mold 300 having the macro recessed and projected structure 320 may be heated in an oven within about 45 minutes at 50 degrees to 250 degrees Celsius. This heating furnace mold 300 thermally expands.
- an oxygen plasma process is performed on the expanded mold 300.
- the oxygen plasma is for controlling the contraction of the mold 300.
- the mold 300 is exposed to oxygen plasma at intervals of about 10-30 minutes.
- the non-shrinkable oxide layer 700 is formed on the mold surface by the oxygen plasma treatment.
- the oxide layer 700 on the surface of the mold may have a lower coefficient of thermal expansion than a mold that is not oxidized to act as a layer that suppresses shrinkage of the mold on the surface of the mold.
- the mold heated by the heat treatment is expanded. Cooling is for shrinking the expanded mold. Plasma treated mold is left at room temperature for cooling.
- the mold contracts anisotropically due to the macro recessed and projected structure due to the macro grooves and the macro protrusions arranged alternately with each other, and protrudes into the marks of the mold 300 due to the difference in the thermal expansion coefficient of the surface oxide layer 700 and the mold.
- Micro-projection structure 420 is formed in structure 320.
- anisotropic shrinkage of the mold means that there is a lot of shrinkage in one direction (the direction in which the protrusion extends) and very little or almost no contraction in the other direction (the vertical direction of the direction in which the protrusion extends). Low shrinkage).
- FIG. 13 to 15 illustrate a method of forming an imprint mold of FIG. 7 according to an embodiment of the inventive concept.
- This embodiment differs from the embodiment described with reference to FIGS. 8 through 12 in that a reflow process for a photoresist is performed. Therefore, in order to repeat the same description, description of overlapping contents will be omitted.
- a photolithography process is performed on the substrate 100 to form a plurality of protrusions 610 formed of photoresist.
- a groove 620 is defined between the protrusions.
- a reflow process for the substrate is performed so that the edges of the photoresist protrusions become curved profiles.
- the mold 300 is brought into contact with the substrate 400 on which the photoresist protrusion 610 and the groove 620 are formed.
- the macro protrusion 323 corresponding to the photoresist groove 620 and the macro groove 321 corresponding to the photoresist protrusion 610 are formed in the mold 300.
- the mold in which the macro protrusions and the grooves are formed, is heated to expand, to form a shrinkage control layer on the surface thereof, and to shrink the mold.
- the mold 300 is formed of PDMS as an example.
- ⁇ L in Fig. 16 One ⁇ L is the change rate in the direction orthogonal to the direction in which the macro protrusions 323 extend (that is, the direction in which the macro protrusions are arranged, in the x-axis direction in the drawing). 2 Denotes the rate of change in the direction in which the macro protrusion 323 extends (in the figure, the y-axis direction).
- the PDMS 300 having the macro recessed and projected structure 320 is heat treated. The heat treatment expands the PDMS 300.
- the heat treatment may apply anisotropic stress to the PDMS 300 due to the macro recessed and projected structure 320.
- Heat Treatment L PDMS 300 One L than in the direction 2 Direction can be expanded relatively much ( ⁇ L One ⁇ L 2 ).
- oxygen plasma treatment After the PDMS 300 is expanded, its surface is subjected to oxygen plasma treatment.
- the molecular structure of the PDMS surface changes to a structure similar to a non-shrinkable stiff SiOx (shrinkage suppression layer is formed).
- the PDMS 300 When the PDMS 300 is then left to cool to room temperature, the PDMS 300 is, for example, anisotropically contracted due to the macro recessed and projected structure 320 due to the macro grooves 321 and the macro protrusions 323 arranged alternately with each other. Do it.
- the micro-concave-convex structure 420 is formed in the macro-concave-convex structure 320 due to the difference in the thermal expansion coefficient between the oxide layer, which is a shrinkage inhibiting layer, and the PDMS.
- the oxygen plasma treatment may change the surface structure of the PDMS to form a surface oxide layer.
- the surface oxide layer may function to control shrinkage of the PDMS due to the difference in coefficient of thermal expansion with the PDMS.
- the surface oxide layer is for example the lower L 2 It is relatively L by macro uneven structure extending in the direction 2 L rather than direction One The shrinkage in the direction can be much more suppressed.
- the PDMS when the PDMS cools, the PDMS is L One Look in the direction L 2 Can shrink much more in the direction ( ⁇ L One ⁇ ⁇ L 2 ).
- L 2 L perpendicular to the projections extending in the direction One Micro protrusions extending in the direction are spontaneously formed.
- the rate of change in expansion due to heat treatment is ⁇ L One ⁇ L 2
- the change rate relationship in shrinkage due to cooling after oxygen plasma treatment is ⁇ L
- One ⁇ ⁇ L 2 L 2 Micro protrusions are formed along the direction, that is, the direction in which the macro protrusions extend.
- L due to expansion and contraction One L than the rate of change in the direction (x axis direction) 2 Since the rate of change in the direction (y-axis direction) is much larger, L 2 Micro protrusions are formed along the direction (y-axis direction).
- any layer may be used as the layer for inhibiting shrinkage of the PDMS as long as the thermal expansion coefficient is lower than that of the PDMS instead of the oxide layer.
- a metal layer may be formed on the PDMS surface to be used as a layer to suppress shrinkage.
- a gold layer by electron beam deposition can be used as the metal layer.
- the coefficient of thermal expansion of PDMS is more than 20 times greater than that of gold.
- the oxygen plasma treatment or the metal layer may be performed or formed during the heat treatment.
- FIG. 17 to 19 illustrate a method of forming an alignment film using an imprint mold described with reference to FIGS. 8 to 12.
- an alignment layer 100 is formed on a substrate 400.
- a polyimide polymer resin may be used as the alignment layer 300.
- the imprint mold 300 having a double uneven structure is imprinted on the alignment film 100, and a curing process of the alignment film is performed.
- the hardening process can apply photocuring using an ultraviolet-ray, for example.
- the double uneven structures 320 and 340 provided in the mold are transferred to the alignment layer 100 by imprint. As a result, the alignment layer 100 has double uneven structures 120 and 140.
- FIG. 20 illustrates a correlation between annealing temperature and an amplitude of a micro uneven structure according to an embodiment of the inventive concept
- FIG. 21 illustrates a correlation between an oxygen plasma treatment time and a bending period of a micro uneven structure. do.
- the bending period and amplitude of the micro-concave-convex structure can be controlled.
- the amplitude the height of the protrusion or the depth of the micro grooves
- the bending period the distance between adjacent micro protrusions or distance between adjacent micro grooves
- Oxygen plasma treatment is related to the thickness of the oxide layer formed on the PDMS surface, and the heat treatment temperature is related to the amount of anisotropic stress.
- the amplitude and the bending period of the macroconcave-convex structure can be easily controlled by appropriately controlling the photolithography process, for example, by appropriately adjusting the deposition thickness of the photoresist and the distance between adjacent photoresist patterns.
- a multi-domain liquid crystal device and a bistable liquid crystal device can be formed.
- the alignment film was formed by setting the amplitude of the macroconcave-convex structure to 1.6 ⁇ m, the bending period to 40 ⁇ m, the amplitude of the micro-concave-convex structure to 0.2 ⁇ m, and the bending period to 3 ⁇ m.
- the alignment factor G (A M 2 / ⁇ M 3 ) x ( ⁇ m 3 / A m 2 ) ⁇ 0.027, and a multidomain liquid crystal device can be formed.
- the amplitude of the macro recessed and projected structure was fixed at 0.81 ⁇ m, and the bending periods were variously set to 5 ⁇ m, 6 ⁇ m, and 7 ⁇ m to form the macro recessed and projected structure.
- Macro irregularities were formed on the substrate through a photolithography process and then transferred to the PDMS substrate.
- PDMS was heated to 180 ° C. within 1 hour and then subjected to oxygen plasma treatment (50 W, 30 sccm, 30 seconds). Then PDMS was left at room temperature. Thereafter, the double uneven structure formed in the PDMS was transferred to the alignment layer by imprint method.
- FIG. 22 is a graph thereof.
- the alignment determination factor G value can be easily controlled by adjusting the bending period of the macroconcave-convex structure, that is, by controlling the photolithography process.
- FIG. 23 is a graph showing the surface free energy density with respect to the azimuth angle function according to the variation of the alignment determination factor G in relation to FIG.
- the surface free energy density is given by the following equation.
- the alignment determining factors G are 0.732, 1.036, and 2.080.
- FIG. 24 is a graph showing an axis of easy azimuth according to the alignment determining factor G, which shows a simulation (shown with a triangle) and Experimental Example 2 (shown with a circle) based on Equation 4 above. Referring to Fig. 23, it can be seen that the experimental results and the simulation are almost identical.
- the axis of easy azimuth of the liquid crystal changes accordingly.
- the micro-concave-convex structure changes (amplitude and bending period change)
- the azimuth-like easy axis fluctuation occurs.
- the azimuthal easy axis of the liquid crystal director can be easily adjusted by changing the azimuthal fixing force of the double uneven structure.
- FIG. 25 is a polarization microscope image of a liquid crystal according to a bending period of a macroconcavo-convex structure according to an embodiment of the present invention.
- the easy axis of the azimuth angle of the liquid crystal director changed with the bending period of the macroconcave-convex structure.
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Abstract
Description
λM | 5 3㎛ | 6㎛ | 7㎛ |
λm | 1.07㎛ | 0.91㎛ | 1.052㎛ |
Am | 0.0556㎛ | 0.0470㎛ | 0.0555㎛ |
AM 2/λm 3 | 0.00252㎛ | 0.00242㎛ | 0.00264㎛ |
Claims (31)
- 액정 배향을 위한 배향막 형성 방법으로,상기 방법은:제1 방향으로 신장하고 서로 이격된 복수의 제1 홈 및 제2 방향으로 신장하여 상기 제1 홈들과 교차하는 서로 이격된 복수의 제2 홈을 배향막에 형성하는 것을 포함하고,상기 제1 홈과 상기 제2 홈은 폭과 깊이의 치수가 다른 것을 특징으로 하는 배향막 형성 방법.
- 제1 항에 있어서,상기 제1 홈의 폭과 깊이의 치수는 각각 상기 제2 홈의 폭과 깊이의 치수보다 큰 것을 특징으로 하는 배향막 형성 방법.
- 제2 항에 있어서,상기 제1 방향과 상기 제2 방향은 직교하는 것을 특징으로 하는 배향막 형성 방법.
- 제2 항에 있어서,상기 제1 홈의 종횡비와 상기 제2 홈의 종횡비를 조절하여 액정의 방위각상 배향 에너지를 조절하는 것을 특징으로 하는 배향막 형성 방법.
- 제4 항에 있어서,상기 제1 홈들에 의한 방위각상 배향 에너지가 상기 제2 홈들에 의한 방위각상 배향 에너지 보다 더 작도록 상기 제1 홈들 및 상기 제2 홈들이 형성되는 것을 특징으로 하는 배향막 형성 방법.
- 제5 항에 있어서,상기 제1 홈들에 의한 방위각상 배향 에너지와 상기 제2 홈들에 의한 방위각상 배향 에너지의 비가 약 0이 되도록 상기 제1 홈들 및 상기 제2 홈들이 형성되는 것을 특징으로 하는 배향막 형성 방법.
- 제4 항에 있어서,상기 제1 홈들에 의한 방위각상 배향 에너지와 상기 제2 홈들에 의한 방위각상 배향 에너지가 거의 동일하도록 상기 제1 홈들 및 상기 제2 홈들이 형성되는 것을 특징으로 하는 배향막 형성 방법.
- 제7 항에 있어서,상기 제1 홈들에 의한 방위각상 배향 에너지와 상기 제2 홈들에 의한 방위각상 배향 에너지의 비가 약 1이 되도록 상기 제1 홈들 및 상기 제2 홈들이 형성되는 것을 특징으로 하는 배향막 형성 방법.
- 제2 항에 있어서,상기 제1 홈과 상기 제2 홈은:상기 제1 홈들 및 상기 제2 홈들에 각각 대응되는 제1 돌출부들 및 제2 돌출부들이 구비된 몰드를 형성하고;상기 제1 돌출부들 및 상기 제2 돌출부들이 형성된 몰드를 배향막에 임프린트하는 것을 포함하는 배향막 형성 방법.
- 제9 항에 있어서,상기 제1 돌출부들은 기재에 형성된 패턴을 몰드로 전사하여 형성되고;상기 제2 돌출부들은 상기 제1 돌출부들이 형성된 몰드를 가열하여 팽창시키고 상기 팽창된 몰드 표면에 수축 제어층을 형성하고 상기 수축 제어층이 형성된 몰드를 냉각하여 수축시켜 형성되는 것을 특징으로 하는 배향막 형성 방법.
- 제10 항에 있어서,상기 수축 제어층은 산화층 또는 금속층인 것을 특징으로 하는 배향막 형성 방법.
- 배향막 임프린트용 몰드 형성 방법으로,탄성막에 제1 방향으로 신장하고 서로 이격된 복수의 제1 돌출부를 형성하고; 그리고,제2 방향으로 신장하여 상기 제1 돌출부들과 교차하는 서로 이격된 복수의 제2 돌출부를 형성하는 것을 포함하고,상기 제2 돌출부들을 형성하는 것은:상기 제1 돌출부들이 형성된 몰드를 팽창시키고,상기 팽창한 몰드의 수축을 조절하기 위한 수축조절처리를 수행하고,상기 팽창된 몰드를 수축시키는 것을 포함하는 배향막 임프린트용 몰드 형성 방법.
- 제12 항에 있어서,상기 몰드의 팽창은 상기 몰드를 열처리하는 것을 포함하고,상기 팽창한 몰드의 수축을 조절하기 위한 수축조절처리는 상기 팽창한 몰드 표면에 수축 제어층을 형성하는 것을 포함하고,상기 팽창된 몰드의 축소는 냉각처리하는 것을 포함하는 배향막 임프린트용 몰드 형성 방법.
- 제13 항에 있어서,상기 수축 제어층을 형성하는 것은 팽창한 몰드 표면을 산소 플라즈마 처리하는 것을 포함하는 배향막 임프린트용 몰드 형성 방법.
- 제13 항에 있어서,상기 수축 제어층을 형성하는 것은 팽창한 몰드 표면 상에 금속 박막을 형성하는 것을 포함하는 배향막 임프린트용 몰드 형성 방법.
- 제12 항 내지 제15 항 중 어느 한 항에 있어서,상기 제1 돌출부와 상기 제2 돌출부는 높이 및 폭의 치수가 서로 다르게 형성되는 것을 특징으로 하는 배향막 임프린트용 몰드 형성 방법.
- 제16 항에 있어서,상기 제1 돌출부의 높이 및 폭의 치수는 각각 상기 제2 돌출부의 높이 및 폭의 치수보다 크게 형성되는 것을 특징으로 하는 배향막 임프린트용 몰드 형성 방법.
- 제16 항의 배향막 임프린트용 몰드 형성 방법에 의해서 형성된 탄성막을 배향막에 임프린트하여 상기 제1 돌출부들에 대응하고 서로 이격된 복수의 제1 홈 및 상기 제2 돌출부들에 대응하고 서로 이격된 복수의 제2 홈을 형성하는 배향막 형성 방법.
- 액정 표시 장치의 액정을 배향하기 위한 배향막으로,상기 배향막은:제1 방향으로 신장하고 서로 이격된 복수의 제1 홈; 그리고,제2 방향으로 신장하여 상기 제1 홈들과 교차하는 서로 이격된 복수의 제2 홈을 포함하는 배향막.
- 제19 항에 있어서,상기 제1 홈의 폭과 깊이의 치수는 각각 상기 제2 홈의 폭과 깊이의 치수보다 큰 것을 특징으로 하는 배향막.
- 제20 항에 있어서,상기 제1 홈들에 의한 방위각상 배향 에너지가 상기 제2 홈들에 의한 방위각상 배향 에너지 보다 작은 특징으로 하는 배향막.
- 제21 항에 있어서,다중 도메인 액정 소자를 위해 상기 제1 홈들에 의한 방위각상 배향 에너지와 상기 제2 홈들에 의한 방위각상 배향 에너지의 비가 약 0인 것을 특징으로 하는 배향막.
- 제20 항에 있어서,상기 제1 홈들에 의한 방위각상 배향 에너지와 상기 제2 홈들에 의한 방위각상 배향 에너지가 거의 동일한 것을 특징으로 하는 배향막.
- 제23 항에 있어서,다중안정 액정 소자를 위해 상기 제1 홈들에 의한 방위각상 배향 에너지와 상기 제2 홈들에 의한 방위각상 배향 에너지의 비가 약 1인 것을 특징으로 하는 배향막.
- 마주하여 배치된 제1 기판 및 제2 기판; 그리고,상기 제1 기판 및 상기 제2 기판의 마주하는 면에 형성된 제1 배향막 및 제2 배향막을 포함하고,상기 제1 배향막 및 상기 제2 배향막은 각각:제1 방향으로 신장하고 서로 이격된 복수의 제1 홈; 그리고,제2 방향으로 신장하여 상기 제1 홈들과 교차하는 서로 이격된 복수의 제2 홈을 포함하는 것을 특징으로 하는 액정 표시 장치.
- 마주하여 배치된 제1 기판 및 제2 기판; 그리고,상기 제1 기판 및 상기 제2 기판의 마주하는 면에 형성된 제1 배향막 및 제2 배향막을 포함하고,상기 제1 배향막 및 상기 제2 배향막은 각각:제1 방향으로 신장하고 서로 이격된 복수의 제1 홈; 그리고,제2 방향으로 신장하여 상기 제1 홈들과 교차하는 서로 이격된 복수의 제2 홈을 포함하며,상기 제1 홈들에 의한 방위각상 배향 에너지와 상기 제2 홈들에 의한 방위각상 배향 에너지의 비가 약 1인 것을 특징으로 하는 다중안정 액정 표시 장치.
- 마주하여 배치된 제1 기판 및 제2 기판; 그리고,상기 제1 기판 및 상기 제2 기판의 마주하는 면에 형성된 제1 배향막 및 제2 배향막을 포함하고,상기 제1 배향막 및 상기 제2 배향막은 각각:제1 방향으로 신장하고 서로 이격된 복수의 제1 홈; 그리고,제2 방향으로 신장하여 상기 제1 홈들과 교차하는 서로 이격된 복수의 제2 홈을 포함하며,상기 제1 홈들에 의한 방위각상 배향 에너지와 상기 제2 홈들에 의한 방위각상 배향 에너지의 비가 약 0인 것을 특징으로 하는 다중 도메인 액정 표시 장치.
- 액정 표시 장치에 적용되는 액정 배향 제어 방법으로,상기 액정 배향 제어 방법은:배향막에 제1 방향으로 신장되고 서로 이격된 복수의 제1 홈과 제2 방향으로 신장하여 상기 제1 홈들과 교차하는 서로 이격된 복수의 제2 홈을 형성하되, 상기 제1 홈의 종횡비 및 상기 제2 홈의 종횡비를 조절하여 다중안정 액정 배향 또는 다중 도메인 액정 배향을 선택적으로 가능하게 하는 액정 배향 제어 방법.
- 제28 항에 있어서,다중안정 액정 배향을 위해서 상기 제1 홈의 방위각상 배향 에너지와 상기 제2 홈의 방위각상 배향 에너지의 비가 약 1이 되도록 상기 제1 홈의 종횡비 및 상기 제2 홈의 종횡비를 조절하는 것을 특징으로 하는 액정 배향 제어 방법.
- 제28 항에 있어서,다중 도메인 액정 배향을 위해서 상기 제1 홈들에 의한 방위각상 배향 에너지와 상기 제2 홈들에 의한 방위각상 배향 에너지의 비가 약 0이 되도록 상기 제1 홈의 종횡비 및 상기 제2 홈의 종횡비를 조절하는 것을 특징으로 하는 액정 배향 제어 방법.
- 배향막 임프린트용 몰드로서,상기 탄성막은:제1 방향으로 신장하고 서로 이격된 복수의 제1 돌출부; 그리고,제2 방향으로 신장하여 상기 제1 돌출부들과 교차하는 서로 이격된 복수의 제2 돌출부를 포함하고,상기 제1 돌출부의 높이와 폭의 치수는 상기 제2 돌출부의 높이와 폭의 치수와 다른 것을 특징으로 하는 배향막 임프린트용 몰드.
Priority Applications (3)
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PCT/KR2011/007672 WO2013054962A1 (ko) | 2011-10-14 | 2011-10-14 | 배향막, 배향막 형성 방법, 액정 배향 조절 방법, 그리고 액정 표시 장치 |
KR1020147009862A KR101675017B1 (ko) | 2011-10-14 | 2011-10-14 | 배향막, 배향막 형성 방법, 액정 배향 조절 방법, 그리고 액정 표시 장치 |
US14/351,634 US9791741B2 (en) | 2011-10-14 | 2011-10-14 | Alignment film, method for forming alignment film, method for adjusting liquid crystal alignment, and liquid crystal display device |
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PCT/KR2011/007672 WO2013054962A1 (ko) | 2011-10-14 | 2011-10-14 | 배향막, 배향막 형성 방법, 액정 배향 조절 방법, 그리고 액정 표시 장치 |
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CN110262134A (zh) * | 2019-05-31 | 2019-09-20 | 昆山龙腾光电有限公司 | 配向膜的制造方法及显示装置 |
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KR20060134759A (ko) * | 2005-06-23 | 2006-12-28 | 엘지.필립스 엘시디 주식회사 | 배향막 제조장치 및 이를 이용한 액정표시패널의 제조방법 |
KR20070119624A (ko) * | 2005-02-03 | 2007-12-20 | 유니버시티 오브 노스캐롤라이나 앳 채플 힐 | 액정 디스플레이에서 사용되는 낮은 표면 에너지 고분자물질 |
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- 2011-10-14 WO PCT/KR2011/007672 patent/WO2013054962A1/ko active Application Filing
- 2011-10-14 US US14/351,634 patent/US9791741B2/en not_active Expired - Fee Related
- 2011-10-14 KR KR1020147009862A patent/KR101675017B1/ko active IP Right Grant
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Also Published As
Publication number | Publication date |
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KR20140066229A (ko) | 2014-05-30 |
US20140247417A1 (en) | 2014-09-04 |
US9791741B2 (en) | 2017-10-17 |
KR101675017B1 (ko) | 2016-11-23 |
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