KR102562621B1 - Chiroptical substrate and the preparation method for the same - Google Patents

Abstract

resin layer; And a metal layer disposed on one surface of the resin layer, including a concave-convex pattern on the surface of the metal layer, including a curved portion in which the entire substrate is curved, and an angle formed by a tangential direction of the curved portion and a patterning direction of the concave-convex pattern ( θ) is an angle of either 0° < θ < 90° or 90° < θ < 180°, and the substrate exhibits structural chirality, exhibits optical properties in terms of light transmission and light absorption, and is flexible at the same time. As a substrate in the form of a film having a chiro-optical substrate capable of functioning as a two-dimensional optical material applicable to various technical fields such as optoelectronics, sensors, and thin films, and a manufacturing method thereof are provided.

Description

Chirooptic substrate and its manufacturing method {CHIROPTICAL SUBSTRATE AND THE PREPARATION METHOD FOR THE SAME}

It relates to a substrate that has chirality and can be used for optical purposes.

Chirality is a term widely used to indicate asymmetry in various scientific fields such as mathematics, chemistry, physics, and biology. This refers to the relationship between two objects when an object is not congruent with the shape reflected in the mirror. Most substances in nature have chirality. For example, amino acids are mostly composed of L-amino acids, and sugars are mainly composed of D-sugars. Since most of these biological organic substances have one-chirality (homo-chirality), when they react with a material that filters them, they can cause fatal damage to the organism. Recently, as part of an effort to reveal the origin of such chirality, research on introducing chirality into a three-dimensional structure is being actively conducted. A three-dimensional structure having such chirality has been manufactured through, for example, a self-assembly method using a template material or induced by light or a magnetic field. However, compared to research introducing chirality into a three-dimensional structure, research on introducing chirality into a two-dimensional structure is relatively incomplete.

One embodiment of the present invention provides a chiro-optical substrate applicable to optoelectronics, sensors, thin films, etc. as a two-dimensional optical material having structural chirality, exhibiting optical properties in terms of light transmission and light absorption, and having flexibility. do.

Another embodiment of the present invention is a means for manufacturing a substrate applicable to optoelectronics, sensors, thin films, etc. as a two-dimensional optical material having structural chirality, exhibiting optical properties in terms of light transmission and light absorption, and having flexibility. As such, it provides a method for manufacturing a chiro-optical substrate.

In one embodiment of the invention, the resin layer; And a metal layer disposed on one surface of the resin layer, including a concave-convex pattern on the surface of the metal layer, including a curved portion in which the entire substrate is curved, and an angle formed by a tangential direction of the curved portion and a patterning direction of the concave-convex pattern ( θ) is an angle of any one of 0°<θ<90° or 90°<θ<180°, providing a chiro-optical substrate.

The chiro-optic substrate may have a chirality indicator index of more than 0 and less than 10.0 according to Equation 1 below.

[Equation 1]

In Equation 1, Pmax is the absolute value of the maximum peak value of the circular dichroism spectroscopy (CD) of the chiro-optical substrate, and θ is the tangential direction of the curved portion and the patterning direction of the concave-convex pattern is an angle formed by , d is a distance (μm) between concave parts of the concavo-convex pattern, and r is a value of a radius of curvature (cm) of the bent part.

A chirality indicator index according to Equation 1 may be 0.5 to 10.0.

The resin layer may include one selected from the group consisting of polydimethylsiloxane (PDMS), polyimide, polyamide, polyurethane acrylate (PUA), and combinations thereof.

The metal layer may include one selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), and combinations thereof.

The thickness of the resin layer may be about 0.1 mm to about 2.0 mm, and the thickness of the metal layer may be greater than 0 nm and less than about 20 nm.

The bent portion may be a concave portion based on a surface of the metal layer.

The curved portion may be a convex portion based on a surface of the metal layer.

In another embodiment of the present invention, providing a mold (mold) including a reverse pattern of concavo-convex patterns; preparing a resin layer having the concavo-convex pattern by applying and curing a resin composition on the mold and then detaching it; manufacturing a metal layer by depositing a metal on the surface of the resin layer on which the concavo-convex pattern is disposed; And forming a bent portion having a tangential direction forming an angle of any one of 0 ° < θ < 90 ° or 90 ° < θ < 180 ° with the pattern direction of the concavo-convex pattern. Provides a manufacturing method of.

In the step of preparing the resin layer, the resin composition is a group consisting of polydimethylsiloxane (PDMS), polyimide, polyamide, polyurethane acrylate (PUA), and combinations thereof. Including one selected from, the resin composition may be cured for 4 hours to 8 hours at a temperature of 50 ℃ to 100 ℃.

The chiro-optical substrate exhibits structural chirality, exhibits optical properties in terms of light transmission and light absorption, and is a film-type substrate having flexibility, and is a two-dimensional substrate applicable to various technical fields such as optoelectronics, sensors, and thin films. It can function as an optical material.

The manufacturing method of the chiro-optical board is an effective means for manufacturing the chiro-optical board, and the above-described technical advantages of the chiro-optical board manufactured through the method can be maximized.

1 is a perspective view schematically illustrating the resin layer and the metal layer according to an embodiment.
2 is a front view schematically illustrating the chiro-optical substrate according to an embodiment.
3 is a perspective view schematically illustrating the chiro-optical substrate according to an embodiment.
4(a) to (c) show atomic force microscopy (AFM) photographs and height profile graphs of cross-sections of the concave-convex pattern, respectively, according to an embodiment.
5(a) and (b) respectively schematically illustrate cross-sections in the thickness direction of the chiro-optical substrate according to an embodiment.
6 schematically illustrates the sequence of the manufacturing method of the chiro-optical substrate.
7 is a graph showing CD spectra measured for each substrate manufactured in Examples 1-1 to 1-6 and each substrate manufactured in Comparative Examples 1-1 to 1-3.
8 is a graph showing ultraviolet-visible light absorption spectra measured for each substrate prepared in Examples 1-1 to 1-6 and each substrate prepared in Comparative Examples 1-1 to 1-3.

Advantages and features of the present invention, and methods of achieving them, will become apparent with reference to the following implementations or examples. However, the present invention is not limited to the embodiments or examples disclosed below and may be implemented in various different forms. The embodiments or examples specified below make the disclosure of the present invention complete, and are provided only to inform those skilled in the art of the scope of the invention to which the present invention belongs, and the scope of the present invention is claimed Defined by the scope of the scope.

In the drawings, if necessary, the thickness of some components is shown enlarged to clearly express the layer or region. Also, in the drawings, for convenience of description, the thicknesses of some layers and regions are exaggerated. Like reference numbers designate like elements throughout the specification.

In addition, in this specification, when a part such as a layer, film, region, plate, etc. is said to be “on” or “on top” of another part, this is not only when it is “directly on” the other part, but also when there is another part in the middle. It is also interpreted to include When a part is said to be "directly on" another part, it is interpreted to mean that there are no intervening parts. Also, when a part such as a layer, film, region, plate, etc. is said to be "below" or "below" another part, this is not only the case where it is "directly below" the other part, but also the case where there is another part in between. be interpreted as including When a part is said to be "directly below" another part, it is interpreted as having no intervening parts.

Hereinafter, embodiments according to the present invention will be described in detail.

In one embodiment according to the present invention, the resin layer; And a metal layer disposed on one surface of the resin layer, including a concave-convex pattern on the surface of the metal layer, including a curved portion in which the entire substrate is curved, and an angle formed by a tangential direction of the curved portion and a patterning direction of the concave-convex pattern ( θ) is an angle of either 0°<θ<90° or 90°<θ<180°.

In the present specification, a 'chiro-optical' substrate refers to a substrate that exhibits optical properties in terms of light transmission and light absorption while the entire structure exhibits structural chirality. The 'substrate' is a term for referring to a board-shaped structure including a laminate of the resin layer and the metal layer, and the form may be in the form of a normal film or thin film. It may also be a form having a thicker thickness.

1 is a perspective view schematically illustrating the resin layer 10 and the metal layer 20 according to an embodiment. Referring to FIG. 1 , the metal layer 20 is disposed on one surface of the resin layer 10 , and a concavo-convex pattern 40 is included on the surface of the metal layer 20 .

2 is a front view schematically illustrating the chiro-optical substrate 100 according to an embodiment. Referring to FIG. 2, the chiro-optical substrate 100 includes a laminate of the resin layer 10 and the metal layer 20 as shown in FIG. 1, and the entire substrate 100 is Z It may include a bent portion curved in the axial direction. In addition, the angle θ between the tangential direction (T) of the curved portion and the patterning direction (P) of the concavo-convex pattern on the surface of the metal layer 20 is in the range of 0°<θ<90° or 90°<θ<180°. It may be any one angle. 2(a) shows the case where the angle θ is 45° as an example, and FIG. 2(b) shows the case where the angle θ is 135° as an example.

3 includes a laminate of the resin layer 10 and the metal layer 20, and the angle formed by the tangential direction (T) of the bent portion and the patterning direction (P) of the concavo-convex pattern on the surface of the metal layer 20 ( It is a perspective view of the chiro-optical substrate from another side when θ) is 45°.

The chiro-optical substrate 100 includes a concavo-convex pattern 40 on the metal layer 20; a bent portion in which the entirety of the substrate 100 is curved; And as a result of a combination of characteristics in which the patterning direction (P) of the concavo-convex pattern and the tangential direction (T) of the bent part form a predetermined angle, it exhibits chirality and has flexibility and is applied to optoelectronics, sensors, thin films, etc. As a possible two-dimensional optical material, it has the advantage of being able to function in various ways.

4 (a) to (c) show an atomic force microscope (AFM) photograph of a cross section of the concavo-convex pattern 40 and respective height profile graphs according to an embodiment.

Referring to (a) of FIG. 4 , in one embodiment, the uneven pattern 40 may include a directional pattern. That the concavo-convex pattern 40 is a directional pattern may mean that both slopes have different inclinations based on concave portions of the concave-convex pattern 40 . Here, the direction of the directional pattern may be a direction from a steep side to a gentle side. Referring to (c) of FIG. 4 , in another embodiment, the uneven pattern 40 may include a non-directional pattern. That the concavo-convex pattern 40 is a non-directional pattern may mean that there is no substantial difference in the inclination of both slopes based on the concave portion of the concavo-convex pattern 40 .

2 and 3, in the chiro-optical substrate 100, the patterning direction P of the concave-convex pattern 40 means a direction in which concave and convex portions of the concavo-convex pattern repeatedly extend. In all cases where the concave-convex pattern 40 includes a directional pattern or a non-directional pattern, the patterning direction P exists.

Referring to (a) of FIG. 4 , in the concavo-convex pattern 40, the gap between concave parts, that is, the concave part separation distance d is about 1 μm to about 10 μm, for example, about 1 μm to about 9 μm, such as about 1 μm to about 8 μm, such as about 1 μm to about 7 μm, such as about 1 μm to about 6.5 μm, such as 1 μm to about 7 μm About 6.0 μm, such as about 1 μm to about 5.5 μm, such as about 1 μm to about 4.5 μm, such as about 1 μm to about 3.5 μm, such as about 1 μm to about 3 μm μm, for example from about 1 μm to about 2.5 μm.

The curved portion refers to a structure in which the entire substrate 100 is curved in a predetermined direction, and imparts structural asymmetry to the chiro-optical substrate 100 to exhibit chirality. 5 (a) and (b) respectively schematically illustrate cross sections in the thickness direction of the chiro-optical substrate 100 according to an embodiment. Referring to FIG. 5 , the bent portion may have a predetermined curvature radius r. In one embodiment, the curved part may have a concave structure based on the surface of the metal layer 20 as shown in (a) of FIG. 5 . In another embodiment, the curved part may have a convex structure based on the surface of the metal layer 20 as shown in (b) of FIG. 5 . When the curved portion is a convex portion with respect to the surface of the metal layer 20, it is more advantageous to express chiral characteristics because it has a greater influence on the structural change of the concavo-convex pattern than when the curved portion is a concave portion.

In one embodiment, the radius of curvature (r) is from about 1 cm to about 10 cm, such as from about 1 cm to about 9.5 cm, such as from about 1 cm to about 9 cm, such as from about 1 cm to about 8.5 cm, For example, from about 1 cm to about 8 cm, such as from about 1 cm to about 7.5 cm, such as from about 1 cm to about 6 cm, such as from about 1 cm to about 5.5 cm, such as from about 1 cm to about 5 cm, such as about 1 cm to about 4.5 cm, such as about 1 cm to about 3.5 cm, such as about 1 cm to about 4 cm, such as about 1.5 cm to about 3.5 cm, such as It may be about 1.5 cm to about 3 cm.

Referring to FIG. 5 , the tangential direction T of the bent part may mean a direction corresponding to a tangential line of an arc shape of the bent part based on a cross section in the thickness direction of the substrate 100 . As described above, the tangential direction (T) of the curved portion forms a predetermined angle with the patterning direction (P) of the concavo-convex pattern 40, thereby imparting asymmetry to the chiro-optical substrate 100, thereby providing chirality. can be made to show.

In one embodiment, the angle θ formed by the tangential direction (T) of the curved portion and the patterning direction (P) of the concavo-convex pattern 40 is 0°<θ<90°, for example, 5°≤θ< 90°, for example 10°≤ θ < 90°, for example 15°≤ θ < 90°, for example 20°≤ θ < 90°, for example 25°≤ θ < 90° , for example 30°≤ θ < 90°, for example 0°< θ ≤ 85°, for example 0°< θ ≤ 80°, for example 0°< θ ≤ 75°, for example For example, 0°< θ ≤ 70°, for example 0°< θ ≤ 65°, for example 0°< θ ≤ 60°, for example 5°≤ θ ≤ 85°, for example , 10° ≤ θ ≤ 70°, for example 15° ≤ θ ≤ 65°, for example 20° ≤ θ ≤ 65°, for example 25° ≤ θ ≤ 65°, for example 30 It may be an angle of any one of °≤ θ ≤ 60°.

Alternatively, the angle θ between the tangential direction T of the bent portion and the patterning direction P of the concave-convex pattern 40 is 90 ° < θ < 180 °, for example, 95 ° ≤ θ < 180 °, For example, 100°≤ θ < 180°, for example 105°≤ θ < 180°, for example 110°≤ θ < 180°, for example 115°≤ θ < 180°, for example For example, 120° ≤ θ < 180°, for example 90° < θ ≤ 175°, for example 90° < θ ≤ 170°, for example 90° < θ ≤ 165°, for example 90°< θ ≤ 160°, eg 90°< θ ≤ 155°, eg 90°< θ ≤ 150°, eg 95° ≤ θ ≤ 175°, eg 100° ≤ θ ≤ 170°, eg 105° ≤ θ ≤ 165°, eg 110° ≤ θ ≤ 160°, eg 115° ≤ θ ≤ 155°, eg 120° ≤ θ It may be any one angle of ≤ 150°.

Tangential direction T of the chiro-optical substrate and the bent part when the angle θ between the tangential direction T of the bent part and the patterning direction P of the concavo-convex pattern 40 is greater than 0° and less than 90° The chiro-optical substrate may exhibit mutually opposite chirality when an angle θ formed between the angle θ and the patterning direction P of the concavo-convex pattern 40 is greater than 90° and less than 180°. For example, when the angle θ between the tangential direction (T) of the curved portion and the patterning direction (P) of the concavo-convex pattern 40 is greater than 0° and less than 90°, the chirooptic substrate has right chirality. , when the angle θ formed by the tangential direction (T) of the curved portion and the patterning direction (P) of the concave-convex pattern 40 is greater than 90° and less than 180°, the chiro-optical substrate exhibits left chirality. can

The chiro-optical substrate 100 has structural chirality. This means that the chiro-optical substrate 100 structurally satisfies perfect asymmetry and does not have a mirror plane in the structure. The chiro-optical substrate 100 is an index representing its chirality, and a chirality indicator index according to Equation 1 below may be greater than 0 and less than 10.0.

[Equation 1]

In Equation 1, Pmax is the absolute value of the maximum peak value of the circular dichroism spectroscopy (CD) of the chiro-optical substrate, and θ is the tangential direction of the curved portion and the patterning direction of the concave-convex pattern is an angle formed by , d is a distance (μm) between concave parts of the concavo-convex pattern, and r is a value of a radius of curvature (cm) of the bent part.

In one embodiment, the chirality indicator index according to Equation 1 is from about 0.1 to about 10.0, such as from about 0.2 to about 10.0, such as from about 0.3 to about 10.0, such as from about 0.4 to about 10.0, such as from about 0.5 to about 10.0, such as greater than about 0.5 and less than or equal to about 10.0.

The value of Equation 1 is a value derived through calculation of the numerical value of the specified unit for each element, and is expressed as an index without a unit. When the chirality index satisfies the above range, the chiro-optical substrate can obtain an advantage applicable to research in optoelectronics, sensors, thin films, metasurfaces, and 2D nanomaterials based on the corresponding chirality.

The chiro-optical substrate 100 may have an absorbance of about 0.1 to about 1.0, for example, about 0.2 to about 0.9, for any one wavelength in the wavelength range of about 400 nm to about 800 nm. , from about 0.5 to about 0.8. Since the chiro-optical substrate has such optical characteristics, it may be more advantageous to be applied to various applications such as optoelectronics, sensors, and thin films.

In one embodiment, the resin layer 10 is from the group consisting of polydimethylsiloxane (PDMS), polyimide, polyamide, polyurethaneacrylate (PUA), and combinations thereof. Can contain selected one. Since the resin layer 10 includes a resin of such a material, it is advantageous to precisely express a surface concavo-convex pattern, and the chiro-optical substrate secures excellent flexibility and can be applied in various designs.

For example, the resin layer 10 may include polydimethylsiloxane (PDMS), and the polydimethylsiloxane (PDMS) has a mass ratio of base to crosslinking agent, for example, about 5:1 to about 15:1. , such as from about 7:1 to about 13:1, such as from about 8:1 to about 12:1, such as from about 9:1 to about 11:1.

In one embodiment, the thickness of the resin layer 10 is about 0.1 mm to about 2.0 mm, for example, about 0.2 mm to about 1.8 mm, for example, about 0.3 mm to about 1.7 mm, for example, About 0.4 mm to about 1.6 mm, such as about 0.5 mm to about 1.5 mm, such as about 0.6 mm to about 1.4 mm, such as about 0.6 mm to about 1.3 mm, such as about 0.6 mm mm to about 1.2 mm, such as from about 0.6 mm to about 1.1 mm, such as from about 0.6 mm to about 1.0 mm. By applying the resin layer in this thickness range, the chiro-optical substrate can be applied to various uses by simultaneously securing a desired level of chirality and physical flexibility.

In one embodiment, the metal layer 20 may include one selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), and combinations thereof. Since the metal layer includes a metal of such a material, it is advantageous to accurately express the surface concavo-convex pattern of the resin layer without damaging it, and the chiro-optical substrate secures excellent flexibility and can be applied in various designs.

For example, the metal layer may include gold (Au). When the metal layer includes gold (Au), enhanced mineral-material interactions induced by surface plasmons may be provided. In addition, since the metal layer is formed on the concavo-convex pattern of the resin layer, it may be advantageous to excellently maintain the concavo-convex pattern without voids.

In one embodiment, the thickness of the metal layer may be greater than about 0 nm and less than or equal to about 20 nm, such as from about 1 nm to about 20 nm, such as from about 5 nm to about 20 nm, such as from about 10 nm to about 20 nm. can By applying the metal layer in this thickness range, the chiro-optical substrate can be applied to various uses by simultaneously securing a desired level of chirality and physical flexibility.

In another embodiment according to the present invention, a method for manufacturing a chiro-optical substrate is provided. The method of manufacturing the chiro-optical substrate may include providing a mold including a reverse pattern of concavo-convex patterns; preparing a resin layer having the concavo-convex pattern by applying and curing a resin composition on the mold and then detaching it; forming a metal layer by depositing a metal on the surface of the resin layer on which the concavo-convex pattern is disposed; and forming a curved portion having a tangential direction forming an angle of one of 0°<θ<90° or 90°<θ<180° with the pattern direction of the concave-convex pattern.

The manufacturing method presents a method of manufacturing a chiro-optical substrate simultaneously having a concavo-convex pattern on the metal layer, a bent portion in which the entire substrate is curved, and a patterning direction of the concavo-convex pattern and a tangential direction of the bent portion forming a predetermined angle. It is possible to provide a substrate that can function in various ways as a two-dimensional optical material applicable to optoelectronics, sensors, thin films, etc. while exhibiting chirality and flexibility at the same time.

The chiro-optical substrate according to the foregoing may be manufactured through the manufacturing method of the chiro-optical substrate. All the features described above with reference to FIGS. 1 to 5 with respect to the chiro-optical substrate can be interpreted as integratedly applied to the manufacturing method even when not repeatedly described later, or even when not repeatedly described later.

6 schematically illustrates the sequence of the method of manufacturing the chiro-optical substrate. Referring to FIG. 6(a) , the method of manufacturing the chiro-optical substrate may include providing a mold 101 including an inverse concave-convex pattern.

In one embodiment, the mold may include polyester. By applying a mold made of such a material, it may be more advantageous to accurately and precisely transfer the concavo-convex pattern on the resin layer 10, and it may be more advantageous to detach the resin layer and the mold than to detach the mold without residue, It may be more advantageous in terms of realizing long-term durability without structural change.

The mold may include a concave-convex pattern 102 to be formed on the resin layer 10 . By transferring the reverse pattern 102 to the resin layer 10 , a desired concavo-convex pattern may be formed on the resin layer 10 .

Referring to (a) of FIG. 4 , in one embodiment, the uneven pattern 40 may include a directional pattern. That the concavo-convex pattern 40 is a directional pattern may mean that both slopes have different inclinations based on concave portions of the concave-convex pattern 40 . Here, the direction of the directional pattern may be a direction from a steep side to a gentle side. Referring to (c) of FIG. 4 , in another embodiment, the uneven pattern 40 may include a non-directional pattern. That the concavo-convex pattern 40 is a non-directional pattern may mean that there is no substantial difference in the inclination of both slopes based on the concave portion of the concavo-convex pattern 40 .

2 and 3, in the chiro-optical substrate 100, the patterning direction P of the concave-convex pattern 40 means a direction in which concave and convex portions of the concavo-convex pattern repeatedly extend. In all cases where the concave-convex pattern 40 includes a directional pattern or a non-directional pattern, the patterning direction P exists.

Referring to (b) and (c) of FIG. 6 , in the method of manufacturing the chiro-optical substrate, a resin composition 103 is applied and cured on the mold, and then detached to form a resin layer having the concavo-convex pattern 40. (10) may be included.

The resin composition 103 may include one selected from the group consisting of polydimethylsiloxane (PDMS), polyimide, polyamide, polyurethane acrylate (PUA), and combinations thereof. can Since the resin composition includes the resin of such a material, it is advantageous to accurately express the concave-convex pattern on the surface of the resin layer, and the chiro-optical substrate secures excellent flexibility and can be applied in various designs.

The resin composition 103 has a viscosity of about 1,000cps to about 5,000cps, for example, about 1,500cps to about 5,000cps, for example, about 2,000cps to about 5,000cps, for example, about 2,500cps at 25°C. cps to about 5,000 cps, such as about 3,000 cps to about 5,000 cps, such as about 3,500 cps to about 4,500 cps. When the viscosity of the resin composition 103 satisfies this range, it may be uniformly applied on the mold without voids, and it may be more advantageous to cure and detach without damage.

For example, the resin composition 103 may include polydimethylsiloxane (PDMS), and the polydimethylsiloxane (PDMS) has a mass ratio of base to crosslinking agent, for example, about 5:1 to about 15:1. , such as from about 7:1 to about 13:1, such as from about 8:1 to about 12:1, such as from about 9:1 to about 11:1.

In one embodiment, the resin composition may be cured for 4 hours to 8 hours at a temperature of about 50 ° C to about 100 ° C. The curing temperature of the resin composition is, for example, about 50 ° C to about 95 ° C, such as about 50 ° C to about 90 ° C, such as about 50 ° C to about 85 ° C, such as about 55 ° C to about 80°C, such as about 55°C to about 75°C. The curing time of the resin composition may be about 4 hours to about 7 hours, for example, about 5 hours to about 7 hours. When the curing temperature and time of the resin composition satisfy these ranges, the resin layer formed therefrom may secure sufficient flexibility and exhibit excellent optical properties.

In one embodiment, the thickness of the resin layer 10 is about 0.1 mm to about 2.0 mm, for example, about 0.2 mm to about 1.8 mm, for example, about 0.3 mm to about 1.7 mm, for example, About 0.4 mm to about 1.6 mm, such as about 0.5 mm to about 1.5 mm, such as about 0.6 mm to about 1.4 mm, such as about 0.6 mm to about 1.3 mm, such as about 0.6 mm mm to about 1.2 mm, such as from about 0.6 mm to about 1.1 mm, such as from about 0.6 mm to about 1.0 mm. By applying the resin layer in this thickness range, the chiro-optical substrate can be applied to various uses by simultaneously securing a desired level of chirality and physical flexibility.

Referring to (c) and (d) of FIG. 6 , in the method of manufacturing the chiro-optical substrate, metal is deposited on the surface of the resin layer 10 on which the concavo-convex pattern 40 is disposed, thereby forming the metal layer 20. It may include the step of preparing.

As a method of depositing the metal, a sputtering method may be applied. In one embodiment, the metal is about 1 mA to about 10 mA, such as about 1 mA to about 9 mA, such as about 2 mA to about 8 mA, such as about 3 mA to about 7 mA, such as about 3 mA to about 7 mA under room temperature conditions, for example , It may be sputter-deposited for about 50 seconds to about 350 seconds, for example, about 100 seconds to about 300 seconds, for example, about 150 seconds to about 250 seconds under a condition of about 4 mA to about 6 mA.

In one embodiment, the metal may include one selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), and combinations thereof. Since the metal layer includes a metal of such a material, it is advantageous to accurately express the surface concavo-convex pattern of the resin layer without damaging it, and the chiro-optical substrate secures excellent flexibility and can be applied in various designs.

For example, the metal layer may include gold (Au). When the metal layer includes gold (Au), enhanced mineral-material interactions induced by surface plasmons may be provided. In addition, since the metal layer is formed on the concavo-convex pattern of the resin layer, it may be advantageous to excellently maintain the concavo-convex pattern without voids.

In one embodiment, the thickness of the metal layer may be greater than about 0 nm and less than or equal to about 20 nm, such as about 1 nm to about 20 nm, such as about 5 nm to about 20 nm. By applying the metal layer in this thickness range, the chiro-optical substrate can be applied to various uses by simultaneously securing a desired level of chirality and physical flexibility.

In the step of manufacturing the metal layer 20 , the concavo-convex pattern 40 on the surface of the resin layer 10 may appear on the surface of the metal layer 20 . That is, in the process of forming the metal layer 20 on the surface of the resin layer 10 , the concave-convex pattern 40 does not disappear and may appear on the surface of the metal layer 20 in a substantially unchanged form. The metal layer 20 is formed to a thickness that satisfies this and includes a metal of an appropriate material, so that the concavo-convex pattern 40 exposed on the surface of the metal layer 20 is formed by the mineral interaction induced by the surface plasmon of the metal. It can contribute to imparting chirality.

In the concavo-convex pattern 40, the distance between concave portions, that is, the concave portion separation distance d is about 1 μm to about 10 μm, for example, about 1 μm to about 9 μm, for example, About 1 μm to about 8 μm, such as about 1 μm to about 7 μm, such as about 1 μm to about 6.5 μm, such as 1 μm to about 6.0 μm, such as about 1 μm to about 5.5 μm, such as about 1 μm to about 4.5 μm, such as about 1 μm to about 3.5 μm, such as about 1 μm to about 3 μm, such as about 1 μm to about It may be 2.5 μm.

Referring to (d) and (e) of FIG. 6 , in the method of manufacturing the chiro-optical substrate, the pattern direction P of the concavo-convex pattern 40 and 0°<θ<90° or 90°<θ<180 It may include forming a bent portion having a tangential direction (T) forming an angle of any one degree.

The substrate manufactured through the chiro-optical substrate manufacturing method includes a concave-convex pattern 40 on the metal layer 20; a bent portion in which the entire substrate is bent; And as a result of a combination of characteristics in which the patterning direction (P) of the concavo-convex pattern (40) and the tangential direction (T) of the curved portion form a predetermined angle, exhibiting chirality and flexibility while optoelectronics, sensors, As a two-dimensional optical material applicable to thin films, etc., it has the advantage of functioning in various ways.

The curved portion refers to a structure in which the entire substrate is curved in a predetermined direction, and imparts structural asymmetry to the substrate manufactured through the method of manufacturing the chiro-optical substrate to exhibit chirality. In the step of forming the bent part, the bent part may be formed to have a concave structure with respect to the surface of the metal layer 20 as shown in (a) of FIG. 5, or as shown in (b) of FIG. As shown, it may be formed to have a convex structure based on the surface of the metal layer 20 side. 6(e) shows an example in which a bent portion is formed to have a convex structure based on the surface of the metal layer 20 side. When the curved portion is a convex portion with respect to the surface of the metal layer 20, it is more advantageous to express chiral characteristics because it has a greater influence on the structural change of the concavo-convex pattern than when the curved portion is a concave portion.

In one embodiment, the angle θ formed by the tangential direction (T) of the curved portion and the patterning direction (P) of the concavo-convex pattern 40 is 0°<θ<90°, for example, 5°≤θ< 90°, for example 10°≤ θ < 90°, for example 15°≤ θ < 90°, for example 20°≤ θ < 90°, for example 25°≤ θ < 90° , for example 30°≤ θ < 90°, for example 0°< θ ≤ 85°, for example 0°< θ ≤ 80°, for example 0°< θ ≤ 75°, for example For example, 0°< θ ≤ 70°, for example 0°< θ ≤ 65°, for example 0°< θ ≤ 60°, for example 5°≤ θ ≤ 85°, for example , 10° ≤ θ ≤ 70°, for example 15° ≤ θ ≤ 65°, for example 20° ≤ θ ≤ 65°, for example 25° ≤ θ ≤ 65°, for example 30 It may be °≤ θ ≤ 60°.

Alternatively, the angle θ between the tangential direction T of the bent portion and the patterning direction P of the concave-convex pattern 40 is 90 ° < θ < 180 °, for example, 95 ° ≤ θ < 180 °, For example, 100°≤ θ < 180°, for example 105°≤ θ < 180°, for example 110°≤ θ < 180°, for example 115°≤ θ < 180°, for example For example, 120° ≤ θ < 180°, for example 90° < θ ≤ 175°, for example 90° < θ ≤ 170°, for example 90° < θ ≤ 165°, for example 90°< θ ≤ 160°, eg 90°< θ ≤ 155°, eg 90°< θ ≤ 150°, eg 95° ≤ θ ≤ 175°, eg 100° ≤ θ ≤ 170°, eg 105° ≤ θ ≤ 165°, eg 110° ≤ θ ≤ 160°, eg 115° ≤ θ ≤ 155°, eg 120° ≤ θ ≤ 150°. FIG. 6(e) illustrates a case in which an angle θ formed between a tangential direction T of the curved portion and a patterning direction P of the concave-convex pattern 40 is 45° as an example.

Tangential direction T of the chiro-optical substrate and the bent part when the angle θ between the tangential direction T of the bent part and the patterning direction P of the concavo-convex pattern 40 is greater than 0° and less than 90° The chiro-optical substrate may exhibit mutually opposite chirality when an angle θ formed between the angle θ and the patterning direction P of the concavo-convex pattern 40 is greater than 90° and less than 180°. For example, when the angle θ between the tangential direction (T) of the curved portion and the patterning direction (P) of the concavo-convex pattern 40 is greater than 0° and less than 90°, the chirooptic substrate has right chirality. , when the angle θ formed by the tangential direction (T) of the curved portion and the patterning direction (P) of the concave-convex pattern 40 is greater than 90° and less than 180°, the chiro-optical substrate exhibits left chirality. can

The method of forming the curved portion is not particularly limited, but, for example, a method of attaching a laminate of the resin layer and the metal layer to the surface of a half-cylinder or cylinder having a predetermined curvature. can be performed with A bent portion having a radius of curvature corresponding to the curvature of the half-cylinder or cylinder may be formed by attaching the laminated body of the resin layer and the metal layer to a surface of a half-cylinder or cylinder having a predetermined curvature.

The curved portion may be maintained in a state where the laminate of the resin layer and the metal layer is attached to the surface of the half-cylinder or cylinder, or may be maintained in a state where the half-cylinder or cylinder is detached.

Referring to FIG. 5 , the radius of curvature r of the bent portion is about 1 cm to about 10 cm, for example, about 1 cm to about 9.5 cm, for example, about 1 cm to about 9 cm, for example, about 1 cm to about 9.5 cm. About 8.5 cm, such as about 1 cm to about 8 cm, such as about 1 cm to about 7.5 cm, such as about 1 cm to about 6 cm, such as about 1 cm to about 5.5 cm, such as about 1 cm to about 5 cm, such as about 1 cm to about 4.5 cm, such as about 1 cm to about 3.5 cm, such as about 1 cm to about 4 cm, such as about 1.5 cm to about 3.5 cm; For example, it may be about 1.5 cm to about 3 cm.

The chiro-optical substrate manufactured through the manufacturing method has structural chirality. This means that the chiro-optical substrate structurally satisfies perfect asymmetry and has no mirror plane in the structure. The chiro-optical substrate manufactured through the above manufacturing method is an index representing its chirality, and a chirality indicator index according to Equation 1 below may be greater than 0 and less than 10.0.

[Equation 1]

In Equation 1, Pmax is the absolute value of the maximum peak value of the circular dichroism spectroscopy (CD) of the chiro-optical substrate, and θ is the tangential direction of the curved portion and the patterning direction of the concave-convex pattern is an angle formed by , d is a distance (μm) between concave parts of the concavo-convex pattern, and r is a value of a radius of curvature (cm) of the bent part.

In one embodiment, the chirality indicator index according to Equation 1 is from about 0.1 to about 10.0, such as from about 0.2 to about 10.0, such as from about 0.3 to about 10.0, such as from about 0.4 to about 10.0, such as from about 0.5 to about 10.0, such as greater than about 0.5 and less than or equal to about 10.0.

The value of Equation 1 is a value derived through calculation of the numerical value of the specified unit for each element, and is expressed as an index without a unit. When the chirality index satisfies the above range, the chiro-optical substrate can obtain an advantage applicable to research in optoelectronics, sensors, thin films, metasurfaces, and 2D nanomaterials based on the corresponding chirality.

The chiro-optical substrate manufactured through the manufacturing method may have an absorbance of about 0.1 to about 1.0, for example, about 0.2 to about 0.9, for any one wavelength in the wavelength range of about 400 nm to about 800 nm. , for example from about 0.5 to about 0.8. Since the chiro-optical substrate has such optical characteristics, it may be more advantageous to be applied to various applications such as optoelectronics, sensors, and thin films.

Hereinafter, specific embodiments of the present invention are presented. However, the examples described below are only intended to specifically illustrate or explain the present invention, and thus the scope of the present invention is not limited and interpreted, and the scope of the present invention is determined by the claims.

<Examples and Comparative Examples>

Example 1

Install a mold including a concave-convex pattern in a Petri dish with a diameter of 90 mm and a depth of 15 mm, and install a mold with a concave-convex pattern such that the separation distance between concave parts of the inverse pattern manufactured therefrom satisfies 1.5 μm. did A polydimethylsiloxane (PDMS) resin composition having a mass ratio of base (Sylgard 184A) to crosslinking agent (Sylgard 184B) of 10:1 was poured onto the mold, mixed, and cured at 70° C. for 6 hours. . A resin layer having a distance of 1.5 μm and a final thickness of 0.8 mm was prepared by cutting along the edge of the mold. A metal layer having a thickness of 15 nm was prepared by depositing gold (Au) on the concavo-convex pattern of the resin layer by sputtering under conditions of 5 mA and 200 seconds at room temperature. A half-cylinder that satisfies the radius of curvature (r) as shown in Table 1 below and has a hole for an optical path in the center was manufactured by a 3D printing method, and the curvature of the half-cylinder The laminated body of the resin layer and the metal layer is formed in the center hole of the half-cylinder so that the angle between the tangential direction and the patterning direction of the concavo-convex pattern on the resin layer satisfies the angle θ as shown in Table 1 below. attached to cover. At this time, the metal layer was attached to form a convex portion based on the surface of the layer. As a result, a chiro-optical substrate in which the entire substrate includes a curved bent portion and an angle θ formed between a tangential direction of the bent portion and a patterning direction of the concavo-convex pattern satisfies the conditions shown in Table 1 below.

Example 2

Install a mold including concavo-convex patterns in a Petri dish with a diameter of 90 mm and a depth of 15 mm, and install a mold with concave-convex patterns such that the separation distance between concave parts of the inverse pattern manufactured therefrom satisfies 3.0 μm. did Through this, a chiro-optical substrate was manufactured in the same manner as in Example 1, except that a resin layer having a separation distance of 3.0 μm and a final thickness of 0.8 mm was manufactured.

Example 3

Install a mold including a concave-convex pattern in a Petri dish with a diameter of 90 mm and a depth of 15 mm, and install the mold with the concave-convex pattern such that the separation distance between concave parts of the inverse pattern manufactured therefrom satisfies 6.0 μm. did Through this, a chiro-optical board was manufactured in the same manner as in Example 1 except that a resin layer having a distance of 6.0 μm and a final thickness of 0.8 mm was manufactured.

Comparative Example 1

The laminated body of the resin layer and the metal layer was formed in the half-cylinder such that the angle formed by the bending tangential direction of the half-cylinder and the patterning direction of the concavo-convex pattern on the resin layer satisfies the angle θ as shown in Table 1 below. A substrate was prepared in the same manner as in Example 1, except that it was attached to cover the central hole of the substrate.

Comparative Example 2

The laminated body of the resin layer and the metal layer was formed in the half-cylinder such that the angle formed by the bending tangential direction of the half-cylinder and the patterning direction of the concavo-convex pattern on the resin layer satisfies the angle θ as shown in Table 1 below. A substrate was prepared in the same manner as in Example 2, except that it was attached to cover the central hole of the substrate.

Comparative Example 3

The laminated body of the resin layer and the metal layer was formed in the half-cylinder such that the angle formed by the bending tangential direction of the half-cylinder and the patterning direction of the concavo-convex pattern on the resin layer satisfies the angle θ as shown in Table 1 below. A substrate was prepared in the same manner as in Example 3, except that it was attached to cover the central hole of the substrate.

θ(°) d(μm) r(cm) CD Spectroscopy CII Wavelength (nm) Pmax Example 1-1 22.5 1.50 1.50 Around 720 nm 13.469 4.23 Example 1-2 45 1.50 1.50 17.880 7.95 Example 1-3 67.5 1.50 1.50 9.954 3.13 Example 1-4 112.5 1.50 1.50 15.433 4.85 Example 1-5 135 1.50 1.50 18.007 8.00 Example 1-6 157.5 1.50 1.50 6.829 2.15 Examples 1-7 45 1.50 2.25 Around 695 nm 4.799 1.42 Examples 1-8 135 1.50 2.25 7.013 2.08 Examples 1-9 45 1.50 3.00 Around 602 nm 3.169 0.70 Examples 1-10 135 1.50 3.00 3.922 0.87 Example 2-1 45 3.00 1.50 Around 597 nm 10.312 2.29 Example 2-2 135 3.00 1.50 14.242 3.16 Example 2-3 45 3.00 2.25 Around 710 nm 4.329 0.64 Example 2-4 135 3.00 2.25 3.350 0.50 Example 2-5 45 3.00 3.00 Around 597 nm 2.160 0.24 Example 2-6 135 3.00 3.00 2.408 0.27 Example 3-1 45 6.00 1.50 Around 489 nm 4.044 0.45 Example 3-2 135 6.00 1.50 3.107 0.35 Example 3-3 45 6.00 2.25 Around 535 nm 4.233 0.31 Example 3-4 135 6.00 2.25 5.409 0.40 Example 3-5 45 6.00 3.00 Around 500 nm 1.943 0.11 Example 3-6 135 6.00 3.00 3.213 0.18 Comparative Example 1-1 0 1.50 1.50 Around 720 nm 1.120 0.00 Comparative Example 1-2 90 1.50 1.50 0.329 0.00 Comparative Example 1-3 180 1.50 1.50 0.395 0.00 Comparative Example 1-4 0 1.50 2.25 Around 695 nm 0.600 0.00 Comparative Example 1-5 0 1.50 3.00 Around 602 nm 1.211 0.00 Comparative Example 2-1 0 3.00 1.50 Around 597 nm 1.301 0.00 Comparative Example 2-2 0 3.00 2.25 Around 710 nm 3.131 0.00 Comparative Example 2-3 0 3.00 3.00 Around 597 nm 0.711 0.00 Comparative Example 3-1 0 6.00 1.50 Around 489 nm 1.440 0.00 Comparative Example 3-2 0 6.00 2.25 around 535 nm 0.606 0.00 Comparative Example 3-3 0 6.00 3.00 around 500 nm 1.151 0.00

<evaluation>

Measurement Example 1: Circular Dichroism Spectroscopy

For each of the substrates prepared in Examples 1 to 3 and Comparative Examples 1 to 3, a scan rate of 500 nm/min, a data interval of 0.5 nm, and a spectrum was obtained under the condition of a wavelength range of 300 nm to 900 nm. Table 1 shows the wavelength range and the absolute value (Pmax) of the peak showing the maximum value on each of the CD spectra of Examples 1 to 3. In addition, as an example, CD spectra measured for each substrate manufactured in Examples 1-1 to 1-6 and each substrate manufactured in Comparative Examples 1-1 to 1-3 are shown in FIG. It's like a graph.

Measurement Example 2: Derivation of chirality indicator index (CII)

For each of the substrates manufactured in Examples 1 to 3 and Comparative Examples 1 to 3, the angle formed by the Pmax value derived in Measurement Example 1, the tangential direction of the curved portion of each substrate, and the patterning direction of the concavo-convex pattern (θ ) by deriving the chirality index according to Equation 1 below, which uses the absolute value of sin (2θ), the separation distance (μm) of the concavo-convex pattern, and the radius of curvature (cm) of the bent portion as elements It is listed in Table 1.

[Equation 1]

Measurement Example 3: Measurement of optical properties

For each substrate prepared in Examples 1-1 to 1-6 and each substrate prepared in Comparative Examples 1-1 to 1-3, using an ultraviolet-visible ray spectrometer (Scinco, Mega Array), An absorption spectrum with a wavelength of 300 nm to 900 nm was derived. The results are as shown in the graph of FIG. 8 .

100: chiro optical substrate
10: resin layer
20: metal layer
30: bend
40: concavo-convex pattern
101: mold
102: reverse phase pattern
103: resin composition
P: patterning direction of the concavo-convex pattern
T: Tangential direction of the bend
d: lumbar separation distance
r: radius of curvature of the bend

Claims (10)

resin layer; And a metal layer disposed on one surface of the resin layer,
Includes a concavo-convex pattern on the surface of the metal layer,
The entire substrate includes a curved bent portion,
The angle θ formed by the tangential direction of the bent portion and the patterning direction of the concavo-convex pattern is 0 ° < θ < 90 ° or 90 ° < θ < 180 °.
Chirooptical substrate. According to claim 1,
The chirality indicator index according to Equation 1 below is greater than 0 and less than 10.0,
Chirooptic substrate:
[Equation 1]

In Equation 1 above,
The Pmax is the absolute value of the maximum peak value of the circular dichroism spectroscopy (CD) of the chiro-optical substrate,
The θ is an angle between the tangential direction of the curved portion and the patterning direction of the concavo-convex pattern,
Wherein d is the value of the separation distance (μm) of the recessed part of the concave-convex pattern,
The r is a value of the radius of curvature (cm) of the bent portion. According to claim 2,
The chirality indicator index according to Equation 1 is 0.5 to 10.0,
Chirooptic substrate. According to claim 1,
The resin layer includes one selected from the group consisting of polydimethylsiloxane (PDMS), polyimide, polyamide, polyurethane acrylate (PUA), and combinations thereof,
Chirooptic substrate. According to claim 1,
The metal layer includes one selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), and combinations thereof.
Chirooptic substrate. According to claim 1,
The thickness of the resin layer is 0.1 mm to 2.0 mm,
The thickness of the metal layer is greater than 0 nm and less than 20 nm,
Chirooptic substrate. According to claim 1,
The bent portion is a concave portion based on the surface of the metal layer side,
Chirooptic substrate. According to claim 1,
The bent portion is a convex portion relative to the surface of the metal layer side,
Chirooptic substrate. providing a mold including an inverse pattern of concavo-convex patterns;
preparing a resin layer having the concavo-convex pattern by applying and curing a resin composition on the mold and then detaching it;
forming a metal layer by depositing a metal on the surface of the resin layer on which the concavo-convex pattern is disposed; and
Forming a bent portion having a tangential direction forming an angle of any one of 0 ° < θ < 90 ° or 90 ° < θ < 180 ° with the pattern direction of the concavo-convex pattern; Including,
Manufacturing method of chiro optical (Chiroptical) substrate. According to claim 9,
In the step of preparing the resin layer,
The resin composition includes one selected from the group consisting of polydimethylsiloxane (PDMS), polyimide, polyamide, polyurethane acrylate (PUA), and combinations thereof,
The resin composition is cured for 4 hours to 8 hours at a temperature of 50 ° C to 100 ° C,
Manufacturing method of chiro-optical substrate.