KR102481460B1 - TRANSPARENT SUBSTRATE WITH A MULTILAYER THIN FILM coating - Google Patents

Abstract

The present substrate relates to a transparent substrate having a multilayer thin film coating, wherein the multilayer thin film coating includes a metal functional layer having infrared reflective properties and an absorption layer that absorbs electromagnetic waves of a predetermined wavelength range using a localized surface plasmon resonance phenomenon. wherein the absorption layer includes a dielectric medium and metal nanoparticles dispersed in the dielectric medium, the dielectric medium includes silicon nitride having a chemical formula represented by SiN _x (x<1.33), and the metal nanoparticles At least one selected from the group consisting of Ag, Au, Cu, Al, Pt, Pd, Ni, Co, Fe, Mn, Cr, Mo, W, V, Ta, Nb, Sn, Pb, Sb, and Bi do.

Description

Transparent substrate with multilayer thin film coating {TRANSPARENT SUBSTRATE WITH A MULTILAYER THIN FILM coating}

It relates to a transparent substrate provided with a multilayer thin film coating. Specifically, it relates to a transparent substrate provided with a colored multilayer thin film coating having easy property control, simple manufacturing method, and low emission characteristics.

Low-emissivity or low-emissivity glass is glass on which a low-emissivity layer containing a metal having high reflectivity in an infrared region, such as silver (Ag), is deposited as a thin film. This low-emissivity glass is a functional material that reduces energy consumption of buildings by reflecting infrared rays to block solar radiation from entering the room in the summer and conserving heating radiation flowing from the inside to the outside in the winter. In glass, emissivity refers to the degree to which glass reflects infrared energy of long wavelengths (2,500 to 40,000 nm). The lower the emissivity is, the better the reflection is, so more infrared energy is reflected, and accordingly, the movement of heat is reduced and the thermal transmittance value is lowered, so the insulation effect is increased. For example, uncoated general glass has an emissivity of about 0.84, but the more the coating is applied, the lower the emissivity. In the case of glass having a low emissivity coating layer, for example, it may have an emissivity of 0.10. If the emissivity is low, the shielding factor is also low.

In the case of low-emissivity glass, it has an important effect on the appearance of buildings, such as being used as a glazing for buildings, and thus, not only low-emissivity characteristics, but also color and solar heat transmittance are very important characteristics. In general, the thickness of a light absorber such as a metal or metal nitride film is adjusted in order to adjust color (adjust absorption of visible light) and lower solar heat transmittance (correction of infrared ray transmittance). For example, as the thickness of the metal protection layer formed on the metal functional layer having low-emissivity increases, the transmittance decreases and the emissivity increases. In addition, when the thickness of the metal functional layer is increased to obtain low emissivity, the reflectance of visible light also increases. However, when the thickness of the metal protective layer is increased to compensate for this, a contradiction arises in that the emissivity also increases again. Therefore, there is a limit to color control in low-emissivity glass, and most cases have green and yellow transmittance.

In order to overcome this, a method of forming a coating layer on the surface of a transparent substrate such as glass has been studied. A method of expressing color through a coating layer includes a method of coating a light absorbing material and a method of extinguishing a specific wavelength by adjusting the thickness of thin films having different refractive indices and using interference of light. However, in the case of coating a light absorbing material, it is difficult to find a material that selectively absorbs a specific wavelength range, so it is difficult to implement it. In case of using the interference of light by adjusting the thickness of the thin film, it is theoretically possible, but it is possible to use the interference of light by adjusting the thickness of the thin film. Since it can be implemented as a multi-layer film, production cost increases, so it is difficult to implement in reality.

Accordingly, recently, as a method for imparting color to a transparent substrate, a technique of dispersing metallic nanoparticles in a medium and selectively absorbing a specific wavelength using a localized surface plasmon resonance phenomenon has been attempted. That is, when the size of the metal nanoparticle is much smaller than the wavelength of the incident wave, collective oscillation of electrons distributed in the metal nanoparticle is generated by the electric field of the incident wave, unlike in the case of a thin film. The period of the generated vibration varies depending on the size of the metal particles and the distance between the particles, and through this, the absorption wavelength region can be selectively adjusted.

However, the method of forming a metal nanoparticle structure to use the local surface plasmon resonance phenomenon has been mostly wet coating in which nano-metal is dispersed in a dielectric material so far, but when mixing with sputtering coating to form a multilayer film, additional costs and There are difficulties in the process. For example, after the dielectric layer is coated, a thin metal coating is applied, but at this time, a dewetting phenomenon of the metal material is used, or a discontinuous metal layer is artificially formed through laser or flash annealing after both the dielectric layer and the metal layer are laminated. There is a way to make this happen. However, in this case, the nanoparticles are arranged only in plane, that is, in two dimensions, so there is a limit to increasing the degree of light absorption, and the possibility of defects increases when voids or the like occur in the process of forming the upper dielectric layer. Alternatively, there is a method of simultaneously depositing a sputtering target by using a mixture of a metal material and a dielectric material or by installing two targets in one chamber. However, even in this case, the dielectric and metal have different electrical properties, it is difficult to adjust the particle size, and the process is unstable and reproducibility is low, so there is a limit to implementing a layer that selectively absorbs light through this and controlling its characteristics. there is

The present invention is to solve this problem, in implementing a selective light absorption layer using a localized surface plasmon resonance phenomenon for low-emissivity glass, metal nanoparticles are evenly distributed and excellent in light absorption properties, but the properties are easy It is to provide a transparent substrate including a selective light absorption layer that can be controlled.

However, the problems to be solved by the embodiments of the present invention are not limited to the above problems and can be variously extended within the scope of the technical idea included in the present invention.

A transparent substrate according to an embodiment of the present invention is a transparent substrate having a multilayer thin film coating, wherein the multilayer thin film coating uses a metal functional layer having infrared reflection characteristics and a localized surface plasmon resonance phenomenon in a predetermined wavelength range. An absorption layer that absorbs electromagnetic waves, wherein the absorption layer includes a dielectric medium and metal nanoparticles dispersed in the dielectric medium, and the dielectric medium includes silicon nitride having a chemical formula represented by SiN _x (x<1.33) , The metal nanoparticles are from the group consisting of Ag, Au, Cu, Al, Pt, Pd, Ni, Co, Fe, Mn, Cr, Mo, W, V, Ta, Nb, Sn, Pb, Sb, and Bi Including one or more selected species.

The multilayer thin film coating includes a first anti-reflection layer and a second anti-reflection layer disposed with the metal functional layer interposed therebetween, the first anti-reflection layer and the second anti-reflection layer each including at least one dielectric layer, At least one of the first anti-reflection layer and the second anti-reflection layer may include the absorption layer.

The first anti-reflection layer may be disposed between the transparent substrate and the metal functional layer, and the first anti-reflection layer may include a first dielectric layer, an absorption layer, and a second dielectric layer sequentially disposed in a direction away from the transparent substrate. there is.

The second anti-reflection layer may be disposed on the metal functional layer, and the second anti-reflection layer may include a first dielectric layer, an absorption layer, and a second dielectric layer sequentially disposed in a direction away from the metal functional layer.

Each of the first anti-reflection layer and the second anti-reflection layer may include a first dielectric layer, an absorption layer, and a second dielectric layer sequentially disposed in a direction away from the transparent substrate.

The absorption layer may be disposed in direct contact with at least one of the first dielectric layer and the second dielectric layer.

At least one of the first dielectric layer and the second dielectric layer may include silicon nitride represented by a chemical formula of Si ₃ N ₄ .

The absorption layer may have a thickness of 5 nm to 40 nm.

The absorption layer may have an absorption peak in the visible light region.

A metal protective layer disposed on at least one surface of the metal functional layer in contact with the metal functional layer may be further included.

The metal protective layer may include a nickel-chromium alloy.

Depending on the relative positions of the metal functional layer and the absorption layer, the absorption value of the glass surface and the absorption value of the coated surface of the transparent substrate at the same wavelength may vary.

A transparent substrate according to another embodiment of the present invention is a transparent substrate having a multilayer thin film coating, wherein the multilayer thin film coating is laminated apart from a first metal functional layer having infrared reflective properties and the first metal functional layer , a second metal functional layer having infrared reflection characteristics, and at least one absorption layer absorbing electromagnetic waves in a predetermined wavelength range using localized surface plasmon resonance, wherein the absorption layer includes a dielectric medium and a metal dispersed in the dielectric medium. nanoparticles, the dielectric medium includes silicon nitride having a chemical formula represented by SiN _x (x<1.33), and the metal nanoparticles include Ag, Au, Cu, Al, Pt, Pd, Ni, Co, At least one selected from the group consisting of Fe, Mn, Cr, Mo, W, V, Ta, Nb, Sn, Pb, Sb, and Bi may be included.

The multilayer thin film coating includes a first antireflection layer, the first metal functional layer, a second antireflection layer, the second metal functional layer, and a third antireflection layer sequentially disposed in a direction away from the transparent substrate, At least one of the first anti-reflection layer, the second anti-reflection layer, and the third anti-reflection layer may include the absorption layer.

The first anti-reflection layer, the second anti-reflection layer, and the third anti-reflection layer each include at least one dielectric layer, and the first anti-reflection layer, the second anti-reflection layer, and the third anti-reflection layer include the absorption layer. The layers may include a first dielectric layer, the absorption layer, and a second dielectric layer sequentially arranged in a direction away from the transparent substrate.

One of the first anti-reflection layer, the second anti-reflection layer, and the third anti-reflection layer may include an absorption layer.

Two of the first anti-reflection layer, the second anti-reflection layer, and the third anti-reflection layer may include an absorption layer.

All of the first anti-reflection layer, the second anti-reflection layer, and the third anti-reflection layer may each include an absorption layer.

The absorption layer may be disposed in direct contact with at least one of the first dielectric layer and the second dielectric layer.

At least one of the first dielectric layer and the second dielectric layer may include silicon nitride represented by a chemical formula of Si ₃ N ₄ .

The absorption layer may have a thickness of 5 nm to 40 nm.

The absorption layer may have an absorption peak in the visible light region.

A metal protection layer formed on at least one surface of the first metal functional layer and the second metal functional layer may be further included.

The metal protective layer may include a nickel-chromium alloy.

Depending on the relative positions of the first metal functional layer, the second metal functional layer, and the absorption layer, the absorption value of the glass surface and the absorption value of the coated surface of the transparent substrate at the same wavelength may vary.

According to an embodiment of the present invention, in implementing a selective light absorption layer using localized surface plasmon resonance, metal nanoparticles are evenly distributed to have excellent light absorption properties, and the properties can be easily controlled. A transparent substrate having a multilayer thin film coating including an absorption layer and a low-emissivity layer can be obtained.

1 is a cross-sectional view of a first aspect of a transparent substrate provided with a multilayer thin film coating according to an embodiment of the present invention.
2 is a view showing the configuration of an antireflection layer including an absorption layer in a transparent substrate provided with a multilayer thin film coating according to an embodiment of the present invention.
3 is a view showing a method of manufacturing an absorption layer in a transparent substrate provided with a multilayer thin film coating according to an embodiment of the present invention.
4 is a cross-sectional view of a second aspect of a transparent substrate provided with a multilayer thin film coating according to an embodiment of the present invention.
5 is a cross-sectional view of a third aspect of a transparent substrate provided with a multilayer thin film coating according to an embodiment of the present invention.
6 is a cross-sectional view of a first aspect of a transparent substrate provided with a multilayer thin film coating according to another embodiment of the present invention.
7 is a cross-sectional view of a second aspect of a transparent substrate provided with a multilayer thin film coating according to another embodiment of the present invention.
8 is a cross-sectional view of a third aspect of a transparent substrate provided with a multilayer thin film coating according to another embodiment of the present invention.
9 is a cross-sectional view of a fourth aspect of a transparent substrate provided with a multilayer thin film coating according to another embodiment of the present invention.
10 is a cross-sectional view of a fifth aspect of a transparent substrate provided with a multilayer thin film coating according to another embodiment of the present invention.
11 is a cross-sectional view of a sixth aspect of a transparent substrate provided with a multilayer thin film coating according to another embodiment of the present invention.
12 is a cross-sectional view of a seventh aspect of a transparent substrate provided with a multilayer thin film coating according to another embodiment of the present invention.
13a and 13b are graphs showing absorption values in the transparent substrate provided with a multilayer thin film coating obtained in Experimental Example 1.
14a and 14b are graphs showing absorption values in the transparent substrate provided with a multilayer thin film coating obtained in Experimental Example 2.

Hereinafter, various embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. This invention may be embodied in many different forms and is not limited to the embodiments set forth herein.

In order to clearly describe the present invention, parts irrelevant to the description are omitted, and the same reference numerals are assigned to the same or similar components throughout the specification.

In addition, since the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of explanation, the present invention is not necessarily limited to the shown bar. In the drawings, the thickness is shown enlarged to clearly express the various layers and regions. And in the drawings, for convenience of explanation, the thicknesses of some layers and regions are exaggerated.

Terms such as first, second and third are used to describe, but are not limited to, various parts, components, regions, layers and/or sections. These terms are only used to distinguish one part, component, region, layer or section from another part, component, region, layer or section. Accordingly, a first part, component, region, layer or section described below may be referred to as a second part, component, region, layer or section without departing from the scope of the present invention.

The terminology used herein is only for referring to specific embodiments and is not intended to limit the present invention. As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite. The meaning of "comprising" as used herein specifies particular characteristics, regions, integers, steps, operations, elements and/or components, and the presence or absence of other characteristics, regions, integers, steps, operations, elements and/or components. Additions are not excluded.

When a part is referred to as being "above" or "above", or is referred to as being "below" or "below" another part, it may be directly above or below the other part, or with another part in between. It can be. In contrast, when a part is referred to as being “directly on” or “directly below” another part, there is no intervening part between them.

Although not defined differently, all terms including technical terms and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs. Terms defined in commonly used dictionaries are additionally interpreted as having meanings consistent with related technical literature and currently disclosed content, and are not interpreted in ideal or very formal meanings unless defined.

In the present invention, the terms "emissivity" and "transmittance" are used as commonly known in the art. "Emissivity" is a measure of how much light at a given wavelength is absorbed and reflected. In general, the following expression is satisfied.

(Emissivity) = 1 - (Reflectivity)

In this specification, the term "transmittance" means visible light transmittance.

Although not defined differently, all terms including technical terms and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs. Terms defined in commonly used dictionaries are additionally interpreted as having meanings consistent with related technical literature and currently disclosed content, and are not interpreted in ideal or very formal meanings unless defined.

Hereinafter, referring to FIGS. 1 and 2 , a transparent substrate 100 provided with a multilayer thin film coating according to an embodiment of the present invention will be described.

1 is a cross-sectional view of a first aspect of a transparent substrate provided with a multilayer thin film coating according to an embodiment of the present invention.

Referring to FIG. 1 , a transparent substrate 100 provided with a multilayer thin film coating according to an embodiment of the present invention includes a transparent substrate 110 and a multilayer thin film coating 120 formed on the transparent substrate 110. .

The transparent substrate 110 is not particularly limited, but is preferably made of a hard inorganic material such as glass or a polymer-based organic material.

The multi-layer thin film coating 120 is sequentially formed from the transparent substrate 110, the antireflection layer 11 including the absorbing layer 113, the metal functional layer 20 having an infrared reflective function, and the reflective layer not including the absorbing layer 113. It includes an anti-blocking layer 12, and an overcoat 40. At this time, both surfaces of the metal functional layer 20 include a first metal protective layer 31 and a second metal protective layer 32 . In addition, in addition to the layers described in this embodiment, the multilayer thin film coating 120 may further include various optional layers.

The metal functional layer 20 has infrared (IR) reflective properties. The metal functional layer 20 may include one or more of gold (Au), copper (Cu), palladium (Pd), aluminum (Al), and silver (Ag). Specifically, silver or a silver alloy may be included. The silver alloy may include a silver-gold alloy and a silver-palladium alloy. Among these, silver having a low specific resistance may be particularly preferably included. The thickness of the metal functional layer 20 may be 7 nm to 30 nm. If the thickness is too thin, the solar heat gain coefficient (SHGC) may increase. If the thickness is too thick, the color coordinates of the transmitted color may move away from blue.

A first metal protective layer 31 and a second metal protective layer 32 may be respectively included on the lower and upper surfaces of the metal functional layer 20 . The metal protective layers 31 and 32 are layers formed to prevent the metal functional layer 20 from being oxidized and corroded. The metal protective layers 31 and 32 may include one or more of titanium, nickel, chromium, and niobium. More specifically, it may include a nickel-chromium alloy. In this embodiment, it is illustrated that the metal protective layers 31 and 32 are formed on both the upper and lower surfaces of the metal functional layer 20, but it is not limited thereto, and the possibility of damage to the metal functional layer 20 and the multilayer thin film coating 120 ) may be formed on only one of the upper and lower surfaces of the metal functional layer 20 in consideration of the structure of the transparent substrate 100 and the optical characteristics of the transparent substrate 100, and is not limited to the illustrated configuration.

An upper surface of the second metal protective layer 32 may include an overcoat 40 . That is, the overcoat 40 is formed on the outermost surface of the multilayer thin film coating 120 . The overcoat 40 is made from zirconium-titanium oxide (TiZrO), zirconium-titanium nitride (TiZrN), zirconium-titanium oxynitride (TiZrON), zirconium oxide (ZrO), zirconium nitride (ZrN), and zirconium oxynitride (ZrON). It may contain one or more selected ones. Preferably, the overcoat 40 may include TiZrO. By including such an overcoat 40, it is possible to prevent damage to the layers included in the multilayer thin film coating 120. The thickness of the overcoat 40 may be 2 nm to 5 nm.

The anti-reflection layers 11 and 12 may be positioned above and below the metal functional layer 20, respectively, and include at least one dielectric layer. In addition, at least one of them may include an absorption layer 113 . In this embodiment, the layer disposed between the metal functional layer 20 and the transparent substrate 110 is composed of the antireflection layer 11 including the absorption layer 113 .

The dielectric layer included in the anti-reflection layers 11 and 12 may include metal oxide, metal nitride, or metal oxynitride. The metal may include at least one of aluminum (Al), titanium (Ti), hafnium (Hf), zirconium (Zr), zinc (Zn), indium (In), tin (Sn), and silicon (Si). can Here, not only the anti-reflection layer 11 including the absorption layer 113, but also the anti-reflection layer 12 not including the absorption layer 113 is not limited to the illustrated configuration, and may be composed of multi-layer dielectric layers, especially It is not limited.

With reference to FIGS. 2 and 3 , the configuration of the antireflection layer 11 including the absorption layer 113 will be described in more detail.

FIG. 2 is a view showing the configuration of an antireflection layer including an absorption layer 113 in a transparent substrate having a multilayer thin film coating according to an embodiment of the present invention, and FIG. 3 is a multilayer according to an embodiment of the present invention. It is a drawing showing a manufacturing method of the absorption layer 113 in the transparent substrate provided with a thin film coating.

Referring to FIG. 2 , the antireflection layer 11 including the absorption layer 113 may include a first dielectric layer 111, an absorption layer 113, and a second dielectric layer 112 in a direction away from the transparent substrate 110. can

The first dielectric layer 111 and the second dielectric layer 112 include aluminum (Al), titanium (Ti), hafnium (Hf), zirconium (Zr), zinc (Zn), indium (In), tin (Sn) and One or more types of silicon (Si) may be included. At least one of these is placed in direct contact with the absorption layer 113 and includes silicon nitride represented by the chemical formula Si ₃ N ₄ . Additionally, aluminum, zirconium, and the like may be doped. By doping aluminum, the dielectric layer can be smoothly formed in the manufacturing process. In addition, optical properties such as refractive index can be adjusted by doping with zirconium. In addition, although this embodiment has been described as including the first and second dielectric layers 111 and 112, only one of these layers may be included or an additional dielectric layer may be included, and is not particularly limited.

The absorption layer 113 includes a dielectric medium and metal nanoparticles 1131 dispersed in the dielectric medium. The dielectric medium includes silicon nitride (SiN _x , x<1.33). The metal nanoparticle is selected from the group consisting of Ag, Au, Cu, Al, Pt, Pd, Ni, Co, Fe, Mn, Cr, Mo, W, V, Ta, Nb, Sn, Pb, Sb, and Bi. One or more may be included. The absorption layer 113 may have a thickness of 5 nm to 40 nm.

The metal nanoparticles 1131 dispersed in the absorption layer 113 may absorb electromagnetic waves of a predetermined wavelength range using a localized surface plasmon resonance phenomenon. That is, when the size of the metal nanoparticles 1131 is much smaller than the wavelength of the incident wave, collective oscillation of electrons distributed in the metal nanoparticles 1131 occurs due to the electric field of the incident wave. The period of the vibration generated in this way varies according to the size of the metal nanoparticles 1131 and the distance between the metal nanoparticles 1131, and through this, the absorption wavelength region can be selectively adjusted. In particular, by adjusting the absorption peak of the absorption layer 113 in which the metal nanoparticles 1131 are dispersed to be in the visible light region, the multilayer thin film coating 120 including the absorption layer 113 may have a specific color.

In one embodiment of the present invention, the configuration of the metal nanoparticles 1131 dispersed in the dielectric medium is to form a metal layer on a dielectric layer made of the dielectric medium and heat-treat the metal of the metal layer to the dielectric medium in the form of metal nanoparticles 1131. It can be obtained by dispersing in This will be described in more detail with reference to FIG. 3 .

First, as shown in FIG. 3(a), a dielectric medium 2 is laminated, and a metal layer 3 is formed thereon.

The dielectric medium 2 may be formed at a location where the absorption layer 113 is to be formed, and may be formed on the first dielectric layer 111 in the present embodiment, for example.

At this time, the dielectric medium 2 includes silicon nitride represented by the chemical formula of SiN _x (x<1.33). Silicon nitride constituting the dielectric medium 2 is stoichiometrically in a silicon excess (or nitrogen deficiency) state, where x in SiN _x is less than 1.33. Preferably it may be less than 1.25. The dielectric medium 2 may be formed by a sputtering process, and at this time, by adjusting the nitrogen concentration during the sputtering process, an absorption wavelength band of the absorption layer 113 formed thereafter may be adjusted. A detailed description of this will be given later.

The metal layer 3 may be deposited thinly on the surface of the dielectric medium 2 to have an effective thickness of 0.2 nm to 1 nm. Here, "effective thickness" is, It is a theoretical thickness derived from a value obtained by detecting the amount of individual nanoparticles coated and assuming a uniform layer. In this embodiment, the measured thickness of an arbitrary deposition layer and the detected amount of a metal component detected by an X-ray fluorescence analyzer (XRF) were measured, and the relationship between them was defined. Thereafter, the effective thickness was derived by measuring the detection amount of the metal component by XRF for the sample whose effective thickness is to be measured and converting it into thickness by substituting it into the relationship between the detection amount and the actual thickness.

At this time, the metal layer 3 is formed in the form of a thin layer, and the sheet resistance of the metal layer 3 may be 50 Ω/sq to 500 Ω/sq. The metal layer 3 may be formed by a sputtering process, and the light absorption amount of the absorption layer 113 formed thereafter may be adjusted by adjusting the power applied to the metal target during the sputtering process. A detailed description of this will be given later.

Next, as shown in FIG. 3(b), a second dielectric layer 112 is deposited on the metal layer 3.

The second dielectric layer 112 has a composition different from that of the dielectric medium 2, including silicon nitride of the Si ₃ N ₄ composition. At this time, the second dielectric layer 112 may be formed to a thickness of 20 nm to 50 nm, and may be doped with one or more selected from aluminum and zirconium.

In addition, in this embodiment, it is shown that the dielectric medium 2, the metal layer 3, and the second dielectric layer 112 are sequentially stacked, but it is not limited thereto, and the metal layer 3 is the dielectric medium 20 and the second dielectric layer 112. As long as the two dielectric layers 112 are interposed in direct contact with each other, the order may be changed.

Next, heat treatment is performed on the multilayer thin film coating in which the dielectric medium 2, the metal layer 3, and the second dielectric layer 112 are laminated, as shown in FIG. 3(c).

Heat treatment includes thermal strengthening, bending, and the like. In this description, it has been described that heat treatment is performed after laminating the second dielectric layer 112, but it is not limited thereto, and heat treatment is performed in a state in which all of the multilayer thin film coatings 120 as shown in FIG. 1 are laminated to form an absorption layer 113 ) may be obtained. The heat treatment in this embodiment is performed as a thermal strengthening treatment at a temperature of 500°C or more and 750°C or less for a time of 5 minutes or more and 20 minutes or less. Due to the applied heat, the metal contained in the metal layer 3 is dissolved by Si contained in the dielectric medium 2, and at the same time, as shown in FIG. 3(c), compression occurring in the second dielectric layer 112 pressed by stress. As a result, the metal contained in the metal layer 3 is dispersed into the dielectric medium 2 .

More specifically, the metal included in the metal layer 3 has a property of dissolving at a high temperature in Si present in excess in the dielectric medium 2 . In addition, the metal included in the metal layer 3 has a property of dewetting the surface of Si ₃ N ₄ included in the second dielectric layer 112 . For this reason, in the high-temperature environment of the heat treatment, the metal contained in the metal layer 3 is not diffused from the surface of the second dielectric layer 112 to the second dielectric layer 112 side by a dewetting phenomenon, and the dielectric medium 2 dissolved and dispersed into it. At this time, since compressive stress is generated in the second dielectric layer 112, as shown in FIG. be able to stimulate

As a result, as shown in FIG. 3(d), the absorption layer 113 in which the metal nanoparticles 1131 are evenly dispersed in the dielectric medium 2 is completed.

That is, all of the metal included in the metal layer 3 is dispersed into the dielectric medium 2 and has the form of metal nanoparticles 1131 uniformly dispersed in the silicon nitride of the dielectric medium 2 . According to this, instead of the metal layer 3 formed in the form of a thin film having a sheet resistance of 50 Ω / sq to 500 Ω / sq before heat treatment, it is converted into a state of metal nanoparticles 1131 discontinuously dispersed in the absorption layer 113, Most of the conductivity that it had before heat treatment disappears. Therefore, in the case of the absorption layer 113 obtained as shown in FIG. 3(d), its sheet resistance becomes 1000 Ω/sq or more.

In addition, in the case of the absorption layer 113 obtained by this embodiment, since the metal nanoparticles 1131 do not exist in the absorption layer 113 in a planar shape, but are evenly dispersed in the layer and distributed in a three-dimensional space, the absorption intensity can be made higher, and the degree of absorption can be more easily adjusted.

Meanwhile, in the present embodiment, a case in which one metal layer 3 is interposed between the dielectric medium 2 and the second dielectric layer 112 and dispersed into the dielectric medium 2 has been described as an example, but is not limited thereto. Alternatively, it is also possible to form two metal layers 3 respectively disposed on both sides of the dielectric medium 2 so that the metal can be diffused from both sides of the dielectric medium 2 . That is, it is also possible to form an absorption layer by heat treatment by stacking dielectric layer/metal layer (Ag)/dielectric medium/metal layer (Ag)/dielectric layer in this order. In this case, a form in which a metal layer is interposed between the dielectric medium and the dielectric layer may be stacked so as to be positioned on both sides of the dielectric medium. When heat treatment is applied to such a laminated structure, diffusion of metal as described above may be performed toward the dielectric medium from both the top and bottom of the dielectric medium.

By adjusting the composition of the dielectric medium 2 in the process of forming the absorption layer 113 by the above heat treatment, an absorption wavelength absorbed by the transparent substrate 100 including the multilayer thin film coating can be selected. That is, in the silicon nitride of SiN _x (x<1.33) constituting the dielectric medium 2, as the value of x increases, the peak wavelength of the wavelength band absorbed by the absorption layer 113 decreases. Such an x value can be adjusted by varying the concentration of nitrogen (N ₂ ) gas supplied during the sputtering process of the dielectric medium 2, for example. Therefore, according to one embodiment of the present invention, the absorption wavelength region of the absorption layer 113 can be selectively implemented by a sputtering process.

In addition, the degree of light absorbed by the absorption layer 113 can be adjusted by adjusting the thickness of the metal layer 3 in the process of forming the absorption layer 113 by heat treatment. That is, the amount of light absorption can be increased by increasing the concentration of the metal nanoparticles 1131 dispersed in the dielectric medium in the absorption layer 113 . The concentration of the metal nanoparticles 1131 dispersed in the dielectric medium can be adjusted by adjusting the thickness of the metal layer 3 formed during sputtering. Therefore, the amount of light absorbed by the absorption layer 113 can also be easily adjusted by the sputtering process.

In addition, the inclusion of a plurality of absorbing layers in the multi-layer thin-film coating allows further adjustment of color and, in particular, reflective properties. For example, if two or more absorbing layers are included, the reflectance can be further reduced without affecting the emissive properties of the multilayer thin film coating. In this case, since the composition of each absorption layer (eg, thickness of the absorption layer, absorption peak wavelength, concentration of metal nanoparticles, etc.) may be the same or different from each other, various absorption patterns may be formed as needed. A multi-layer thin film coating can be configured to have. A plurality of absorption layers may be included in the same antireflection layer, or may be included in different antireflection layers as will be described later.

As described above, according to the present embodiment, in the transparent substrate 100 having the multilayer thin film coating 120 having low-emission characteristics, the absorption layer 113, which can be easily controlled only by sputtering and heat treatment during the manufacturing process, can be obtained. there is. In particular, since a layer in which metal nanoparticles are uniformly dispersed is used as the absorption layer 113, a transparent substrate having a multilayer thin film coating capable of efficiently lowering transmittance and reflectance and adjusting color without affecting emissivity. can be obtained.

Hereinafter, with reference to FIGS. 4 and 5 , other aspects of a transparent substrate provided with a multilayer thin film coating according to an embodiment of the present invention will be described.

4 is a cross-sectional view of a second aspect of a transparent substrate provided with a multilayer thin film coating according to an embodiment of the present invention, and FIG. 5 is a transparent substrate provided with a multilayer thin film coating according to an embodiment of the present invention. It is a drawing showing a cross section of the third aspect of.

Other aspects of one embodiment of the present invention, compared to the first aspect described above, are different only in one or more characteristics of the location and number of the antireflection layer 11 including the absorption layer 113, in other configurations other than the difference. Since it is the same as the first aspect, detailed description is omitted.

Referring to FIG. 4 , in the transparent substrate 101 provided with the multilayer thin film coating 121 according to the second aspect of an embodiment of the present invention, the upper portion of the multilayer thin film coating 121, that is, the metal functional layer 20 is formed. An antireflection layer 11 including an absorption layer 113 is disposed at a position away from the transparent substrate 110 as a reference. That is, on the upper side of the metal functional layer 20, the antireflection layer 11 including the first dielectric layer 111, the absorption layer 113, and the second dielectric layer 112 is sequentially disposed.

According to this configuration, compared to the first aspect in which the absorption layer 113 is formed adjacent to the transparent substrate 110 rather than the metal functional layer 20, the light absorption efficiency on the side where the multilayer thin film coating 121 is formed is higher. . That is, in a transparent substrate provided with a multilayer thin film coating, if it is desired to improve the light absorption efficiency on the non-coated surface, that is, the glass surface (one surface of the transparent substrate 110 on which no coating is formed on the drawing), the first aspect and Likewise, if the position of the absorption layer 113 is disposed closer to the transparent substrate 110 than the metal functional layer 20, and the light absorption efficiency of the coated surface is to be increased, as in the second aspect, the absorption layer 113 What is necessary is just to arrange it so that the position may be farther away from the transparent base material 110 than the metal functional layer 20. In this way, by changing only the formation position of the absorption layer 113, it is possible to easily control the light absorption characteristics of the transparent substrate provided with the multilayer thin film coating.

Next, referring to FIG. 5 , in the transparent substrate 102 provided with the multilayer thin film coating 122 according to the third aspect of an embodiment of the present invention, the metal functional layer 20 based on the metal functional layer 20 An antireflection layer 11 including an absorption layer 113 is disposed on both upper and lower portions of the upper and lower sides.

According to this configuration, since the absorption layer 113 is disposed on both sides of the metal functional layer 20, light absorption efficiency can be increased on both sides of the transparent substrate 102 provided with the multilayer thin film coating 122. In addition, since the amount of light absorbed by the absorption layer 113 increases, the degree of coloring of the transparent substrate 102 can be increased. On the other hand, as described above, the absorber layer 113 of the present invention is a state in which the isolated metal nanoparticles 1131 are dispersed in a dielectric medium, so as in the third aspect of an embodiment, two or more absorber layers ( 113), the low emission characteristics and the like are not affected by the absorption layer 113, and the infrared reflection characteristics by the metal functional layer 20 can be well maintained.

In the above, various embodiments of the transparent substrate having a multilayer thin film coating according to an embodiment of the present invention have been described, but are not limited thereto, and include more than two absorber layers 113, or absorber layer 113 Various modifications by changing the position of are possible. In particular, as described above, since various optical properties can be easily controlled according to the location, number, deposition conditions, etc. of the absorption layer 113, the composition of the multilayer thin film coating including the absorption layer 113 according to the desired optical properties. You can choose from a variety of

Hereinafter, aspects of a transparent substrate provided with a multilayer thin film coating according to another embodiment of the present invention will be described with reference to FIGS. 6 to 12 .

6 is a cross-sectional view of a first aspect of a transparent substrate provided with a multilayer thin film coating according to another embodiment of the present invention, and FIG. 7 is a transparent substrate provided with a multilayer thin film coating according to another embodiment of the present invention. Figure 8 is a view showing a cross section of the second aspect of the transparent substrate provided with a multi-layer thin film coating according to another embodiment of the present invention, Figure 9 is a view showing the cross section of the third aspect of the present invention It is a view showing a cross section of a fourth aspect of a transparent substrate provided with a multilayer thin film coating according to an embodiment, and FIG. 10 is a cross section of a fifth aspect of a transparent substrate provided with a multilayer thin film coating according to another embodiment of the present invention. 11 is a cross-section of a sixth aspect of a transparent substrate equipped with a multi-layer thin film coating according to another embodiment of the present invention, and FIG. 12 is a multi-layer thin film coating according to another embodiment of the present invention. It is a figure showing the cross section of the 7th aspect of the transparent base material provided with this.

In the embodiments of another embodiment of the present invention, compared to the embodiment described above, the difference is only in the location or number of the antireflection layer 11 including the two metal functional layers 20 and the absorption layer 113. There is, since the configuration other than the corresponding difference is the same as in one embodiment, a detailed description thereof will be omitted.

Referring to FIG. 6 , in the transparent substrate 200 provided with the multilayer thin film coating 220 according to the first aspect of another embodiment of the present invention, the multilayer thin film coating 220 includes two metal functional layers 20 It includes a multi-layer thin film coating 220 that does. That is, sequentially from the transparent substrate 110, the antireflection layer 11 including the absorbing layer 113, the first metal functional layer 21 having an infrared reflecting function, and the antireflection layer 12 not including the absorbing layer 113 ), a second metal functional layer 22 having an infrared reflective function, an antireflection layer 12 not including an absorption layer 113, and an overcoat 40. At this time, the first metal protective layer 31 and the second metal protective layer 32 are included on both surfaces of each of the metal functional layers 21 and 22 .

Here, the two metal functional layers 21 and 22 have infrared (IR) reflection characteristics. The two metal functional layers 21 and 22 may each contain one or more of gold (Ag), copper (Cu), palladium (Pd), aluminum (Al), and silver (Ag). Specifically, silver or a silver alloy may be included. The silver alloy may include a silver-gold alloy and a silver-palladium alloy. In addition, the sum of the thicknesses of the two metal functional layers 21 and 22 may be 20 to 35 nm. If the thickness is too thin, the solar heat gain coefficient (SHGC) may increase. If the thickness is too thick, the color coordinates of the transmitted color may move away from blue. In addition, each of the two metal functional layers 21 and 22 may have a thickness of 7 nm to 20 nm.

A first metal protective layer 31 and a second metal protective layer 32 may be included on the lower and upper surfaces of each of the metal functional layers 21 and 22 , respectively. The configuration of each of the transparent substrate 110, the metal protective layers 31 and 32, the antireflection layers 11 and 12, and the overcoat 40 is the same as the corresponding configuration of the above-described embodiment.

According to this configuration, it is possible to easily implement light absorption performance even in the multilayer thin film coating 220 having the two metal functional layers 21 and 22 . In particular, in the first aspect of this other embodiment, since the antireflection layer 11 including the absorption layer 113 is arranged closer to the transparent substrate 110 than the two metal functional layers 21 and 22, It is suitable for increasing light absorption efficiency on the non-coated surface of the transparent substrate 110 .

Referring next to FIG. 7 , in the transparent substrate 201 provided with the multilayer thin film coating 221 according to the second aspect of another embodiment of the present invention, the absorption layer 113 between the two metal functional layers 21 and 22 An antireflection layer 11 including ) is disposed. That is, an antireflection layer 11 including a first dielectric layer 111, an absorption layer 113, and a second dielectric layer 112 is sequentially disposed on the upper side of the first metal functional layer 21, and such an antireflection layer ( 11) A second metal functional layer 22 is disposed thereon.

According to this configuration, since the absorption layer 113 is disposed between the metal functional layers 21 and 22, the light absorption effect of the absorption layer 113 is amplified due to the multiple reflection effect between the metal functional layers 21 and 22. Thus, both the light absorption rate on the coated and non-coated surfaces of the transparent substrate 110 can be improved.

Referring next to FIG. 8 , in the transparent substrate 202 provided with the multilayer thin film coating 222 according to the third aspect of another embodiment of the present invention, the antireflection layer 11 including the absorption layer 113 includes two It is disposed farthest from the transparent substrate 110 than the metal functional layers 21 and 22 . That is, the antireflection layer 11 including the first dielectric layer 111, the absorption layer 113, and the second dielectric layer 112 is sequentially disposed on the upper side of the second metal functional layer 22.

According to this configuration, since the absorption layer 113 is located farther from the transparent substrate 202 than the two metal functional layers 21 and 22, the light absorption efficiency on the coating surface on which the multilayer thin film coating 222 is formed increases. .

Therefore, in the first to third aspects of other embodiments of the present invention, since the absorption efficiency on each surface varies depending on the position of the absorption layer 113, utilizing this, a laminated structure in a multilayer thin film coating can be obtained. Desired optical properties can be obtained by different methods. That is, in a transparent substrate equipped with a multilayer thin film coating, when it is desired to increase the absorption efficiency on the non-coated surface, the absorption layer 113 is positioned closer to the transparent substrate than the two metal functional layers 21 and 22, and the non-coated surface When it is desired to increase the absorption efficiency and lower the reflectivity on both the surface and the coated surface, the absorption layer 113 is placed between the two functional metal layers 21 and 22. In addition, in order to increase the absorption efficiency on the coated surface, the absorption layer 113 is located farther from the transparent substrate than the two functional metal layers 21 and 22.

Furthermore, by properly combining and arranging two or more absorption layers 113 together with two metal functional layers 21 and 22, the wavelength range of selectively absorbed light can be set within the visible and infrared ranges. it is possible to adjust

Additional embodiments according to such other embodiments are further illustrated in FIGS. 9 to 12 .

Referring to FIG. 9 , in the transparent substrate 203 provided with the multilayer thin film coating 223 according to the fourth aspect of another embodiment of the present invention, two antireflection layers 11 including an absorption layer 113 are included, , in a direction away from the transparent substrate 110, the antireflection layer 11, the first functional metal layer 21, the antireflection layer 11, and the second functional metal layer 22 are sequentially disposed. That is, the first functional metal layer 21 may be interposed between the two absorption layers 113 .

Referring to FIG. 10, in the transparent substrate 204 provided with the multilayer thin film coating 224 according to the fifth aspect of another embodiment of the present invention, two antireflection layers 11 including an absorption layer 113 are included, , in a direction away from the transparent substrate 110, the first functional metal layer 21, the antireflection layer 11, the second functional metal layer 22, and the antireflection layer 11 are sequentially disposed. That is, the second functional metal layer 22 may be interposed between the two absorption layers 113 .

Referring to FIG. 11, in the transparent substrate 205 provided with the multilayer thin film coating 225 according to the sixth aspect of another embodiment of the present invention, two anti-reflection layers 11 including an absorption layer 113 are included, , the antireflection layer 11, the first metal functional layer 21, the second metal functional layer 22, and the antireflection layer 11 are sequentially disposed in a direction away from the transparent substrate 110. That is, the first metal functional layer 21 and the second metal metal layer 22 may be interposed between the two absorption layers 113 .

Referring to FIG. 12, in the transparent substrate 206 provided with the multilayer thin film coating 226 according to the seventh aspect of another embodiment of the present invention, three antireflection layers 11 including an absorption layer 113 are included, , In a direction away from the transparent substrate 110, the antireflection layer 11, the first functional metal layer 21, the antireflection layer 11, the second functional metal layer 22, and the antireflection layer 11 are sequentially disposed. . That is, the three absorption layers 113 and the two metal functional layers 21 and 22 may be alternately disposed.

Although various laminated structures have been exemplified above, the present invention is not limited thereto, and as described above, various laminated structures may be applied based on the metal functional layer and the absorption layer in order to obtain desired optical properties.

In this way, desired optical properties can be obtained in a transparent substrate equipped with a multilayer thin film coating by various laminated structures. As a result, the absorption layer 113 can be easily formed. In addition, since the use of such an absorption layer 113 does not affect the low-emissivity characteristics of the metal functional layer, light in a specific wavelength region is absorbed using the absorption layer 113 without impairing the original characteristics required as low-emissivity glass. By doing so, it is possible to easily realize glass having an aesthetic color, and thus it can be used in various industrial fields. For example, as a transparent substrate having a color on the coated surface, it can be used for cover glass of electronic products, interior glass, and glazing of buildings or automobiles.

Hereinafter, the action and effect according to the embodiment of the present invention will be described with reference to experimental examples.

Experimental Example 1: (Evaluation of multilayer thin film coating having one metal functional layer)

As a transparent substrate, an antireflection layer (= first dielectric layer/absorption layer/second dielectric layer) sequentially including an absorption layer on a glass substrate/first metal protective layer/metal functional layer/second metal protective layer/not including an absorption layer An antireflection layer/overcoat was formed to fabricate a transparent substrate equipped with a multilayer thin film coating as shown in FIG. 1 (Example 1).

In Example 1, a transparent substrate having a multilayer thin film coating as shown in FIG. 4 was manufactured by changing the location of the antireflection layer including the absorption layer (Example 2).

In Examples 1 and 2, the absorber layer is a dielectric medium, and when SiN _x is deposited, the concentration of N ₂ injection gas (=N ₂ /(N ₂ +Ar)) is set to 30%, and an Ag layer is used as a metal layer. It was obtained by forming a thickness of 1 nm on the top and bottom of the dielectric medium and heat-treating at 650 ° C. for 7 minutes.

As a comparative example, a transparent substrate provided with a multilayer thin film coating having a laminated structure of a transparent substrate/an antireflection layer without an absorption layer/a first metal protective layer/a metal functional layer/an antireflection layer without an absorption layer/overcoat was manufactured. (Comparative Examples 1 and 2). In particular, in Comparative Example 1, the thickness of the remaining layers except for the absorption layer was the same as in Examples 1 and 2, and in Comparative Example 2, the thickness of the metal protective layer was adjusted to have a transmittance similar to that in Examples 1 and 2.

In Examples 1 and 2 and Comparative Examples 1 and 2, the composition of the antireflection layer is shown in Table 1 below.

(Lower) Antireflection Layer
(nm) (Upper) antireflection layer
(nm) 1st dielectric layer absorption layer 2nd dielectric layer 1st dielectric layer absorption layer 2nd dielectric layer Example 1 16 7 16 49 - - Example 2 37 - - 22 7 22 Comparative Example 1 37 - - - - - Comparative Example 2 37 - - - - -

For each of Examples and Comparative Examples, transmittance, uncoated surface (glass surface) reflectance, coated surface reflectance, glass surface absorbance and coated surface absorbance for light of 550 nm wavelength, solar heat gain coefficient (SHGC) and corrected emissivity were measured. The results are shown in Table 2 and Table 3 below.

permeation non-coated surface reflection coating surface reflection % a* b* % a* b* % a* b* Example 1 34.9 -4.6 2.8 25.2 -2.0 -0.4 18.0 9.6 -20.7 Example 2 34.0 -5.7 -1.0 29.3 1.6 0.6 8.0 15.8 -29.5 Comparative Example 1 42.1 -5.1 4.2 28.0 -0.4 -3.0 15.5 10.7 -22.0 Comparative Example 2 34.8 -5.2 4.3 28.9 -0.9 -0.2 18.2 10.7 -22.2

Absorption on uncoated side @550nm absorption of coated surface
@550nm SHGC
(uncoated side) Crystalized emissivity (%) Example 1 40.4 48.2 0.293 3.3 Example 2 36.1 58.4 0.268 3.4 Comparative Example 1 29.2 43.1 0.299 3.4 Comparative Example 2 35.5 48.1 0.267 5.6

As shown in Table 2, in the case of Examples 1 and 2 including the absorption layer, it was confirmed that the transmittance of visible light was reduced compared to Comparative Examples 1 and 2. In addition, from Examples 1 and 2, it was confirmed that the difference in absorption rate on the non-coated surface and the coated surface according to the position of the absorption layer was confirmed. In this regard, the △ absorption value was measured in Examples 1, 2 and Comparative Example 2 with respect to the absorption value of Comparative Example 1 (a structure that does not include an absorption layer and does not change the thickness of the metal protective layer) of Comparative Example 1, which is the standard. This is shown in Figures 13a and 13b. Here, Δ absorption is a value obtained by subtracting the absorption value in Comparative Example 1 from the absorption value in Examples 1 and 2 and Comparative Example 2.

As shown in Table 2, Table 3, and FIGS. 13A and 13B, in the case of Example 1 in which the absorber layer is disposed adjacent to the transparent substrate (that is, disposed between the metal functional layer and the transparent substrate), compared to Comparative Examples, The coating surface reflectance decreased, and in the case of Example 2, in which the absorption layer was disposed away from the transparent substrate (ie, disposed between the metal functional layer and the overcoat), the coating surface reflectance decreased compared to the comparative examples.

Therefore, when light absorption on the non-coated surface is required, the efficiency can be increased by disposing the absorption layer below the metal functional layer as in Example 1, and when light absorption on the coated surface is required, Example 2 As described above, the efficiency can be increased by arranging the absorption layer below the metal functional layer.

On the other hand, in the case of transmittance, in Comparative Example 2 in which the thicknesses of the first and second metal protective layers were adjusted to have transmittance similar to Examples 1 and 2, it was confirmed that the transmitted color was almost unchanged compared to Comparative Example 1. That is, it can be seen that light absorption in visible light is hardly achieved. On the other hand, in Examples 1 and 2 including the absorber layer, permeation b* decreased compared to Comparative Example 1, and in Example 1, a* increased by about 0.5. This indicates that light absorption of some green and yellow areas was increased by the absorption layer. Therefore, it was confirmed that light absorption in the visible ray region was also more efficient than when the thickness of the metal protective layer was increased.

In addition, in the case of Comparative Example 2 in which the thickness of the metal protective layer was increased to reduce transmittance and increase light absorption, the corrected emissivity increased significantly compared to Comparative Example 1 (emissivity compared to Comparative Example 1 increased by about 65%), and in Examples 1 and 2, it was confirmed that almost no change in emissivity appeared. This means that even if light absorption is achieved using the absorber layer of the present invention, the emissivity performance achieved by the metal functional layer is not affected. Therefore, it can be appropriately applied as a light absorption layer in low-emissivity glass or the like.

Experimental Example 2: (Evaluation of multilayer thin film coating with two layers of metal functional layer)

A transparent substrate, including an antireflection layer (= first dielectric layer/absorption layer/second dielectric layer)/first metal protective layer/first metal functional layer/second metal protective layer/absorbent layer sequentially including an absorber layer on a glass substrate Transparent antireflection layer/first metal protective layer/second metal functional layer/second metal protective layer/antireflective layer without absorption layer/overcoat provided with a multilayer thin film coating as shown in FIG. 6 A substrate was prepared (Example 3).

In Example 3, the location of the antireflection layer including the absorption layer was changed to prepare a transparent substrate having a multilayer thin film coating as shown in FIG. 7 (Example 4).

In Example 3, a transparent substrate having a multi-layer thin film coating as shown in FIG. 8 was manufactured by changing the position of the antireflection layer including the absorption layer (Example 5).

As the dielectric medium in Examples 3 to 5, when depositing SiN _x , the concentration of the N ₂ injection gas (=N ₂ /(N ₂ +Ar)) was set to 30%, and the Ag layer as the metal layer was used as the dielectric medium. It was obtained by forming a thickness of 1 nm on the upper and lower portions of the antireflection layer and heat-treating it at 650° C. for 7 minutes. Absorption In addition, the antireflection layer including each absorption layer in Examples 3 to 5 is an antireflection layer corresponding to Comparative Example 3 and optical The thickness was adjusted to be the same.

As Comparative Example 3, a commercially available Double Roy product from Korea Glass Industries Co., Ltd., which does not contain an absorbent layer, was used.

In Examples 3 to 5 and Comparative Example 3, the composition of each layer is shown in Table 4 below.

Comparative Example 3
(nm) Example 3
(nm) Example 4
(nm) Example 5
(nm) (Upper) antireflection layer
(nm) 2nd dielectric layer - - - 13.6 absorption layer - - - 7 1st dielectric layer 30 30 30 13.5 3 3 3 3 (middle) antireflection layer
(nm) 2nd dielectric layer 3 3 3 3 - - 38 - absorption layer - - 7 - 1st dielectric layer 82 82 39 82 5 5 5 5 (Lower) antireflection layer
(nm) 2nd dielectric layer 5 5 5 5 - 13.5 - - absorption layer - 7 - - 1st dielectric layer 32 13.5 32 32

For each of Examples and Comparative Examples, transmittance, uncoated surface (glass surface) reflectance, coated surface reflectance, glass surface absorbance and coated surface absorbance for light with a wavelength of 550 nm, solar heat gain coefficient (SHGC) and corrected emissivity were measured. The results are shown in Table 5 and Table 6 below.

permeation non-coated surface reflection coating surface reflection % a* b* % a* b* a*60° b*60° % a* b* Comparative Example 3 57.1 -10 -1.6 16 -1.2 -9.7 0 -8 17.8 15 6.5 Example 3 51.5 -10.3 0.4 17.1 -9.9 -5.1 -9.8 -8.6 16.1 13.3 -3.1 Example 4 44.3 -11.0 -9.6 8.5 1.5 -15.2 5.3 -12.4 21.2 18.0 20.8 Example 5 44.9 -9.8 -4.2 19.6 -4.8 -9.4 -1.5 -8.4 15.8 7.6 12.0

Absorption on uncoated side @550nm absorption of coated surface
@550nm SHGC
(uncoated side) Crystalized emissivity (%) Comparative Example 3 23.9 24.6 0.307 0.201 Example 3 27.1 31.6 0.292 0.199 Example 4 44.5 34.7 0.280 0.200 Example 5 32.5 37.8 0.268 0.200

As shown in Table 5, in the case of Examples 3-5 including the absorption layer, it was confirmed that the transmittance of visible light was reduced compared to Comparative Example 3. In addition, from Examples 3 to 5, it was confirmed that the difference in absorption rate on the non-coated and coated surfaces according to the position of the absorption layer was confirmed. In this regard, the measurement of the Δ absorption value in Examples 3-5 with respect to the absorption value of Comparative Example 3 (a structure not including an absorption layer) as a reference is shown in FIGS. 14A and 14B. Here, Δ absorption is a value obtained by subtracting the absorption value in Comparative Example 3 from the absorption value in each Example 3-5.

As shown in Tables 5 and 6, and FIGS. 14A and 14B, in the case of Example 3 in which the absorber layer is disposed adjacent to the transparent substrate (that is, disposed between the first metal functional layer and the transparent substrate), the non-coated surface and Absorption on the coated surface was evenly exhibited, and infrared absorption on the uncoated surface was particularly large compared to other examples and comparative examples. In addition, in the case of Example 4, where the absorption layer was located between the first metal functional layer and the second metal functional layer, the highest absorption rate was exhibited on the uncoated and coated surfaces, and in particular, the highest visible light absorption rate was exhibited on the uncoated surface. was This is thought to be due to the amplification of the effect due to the multi-reflection effect between the first metal functional layer and the second metal functional layer, which was also confirmed from the fact that the non-coated surface reflection was reduced by about 8%. Finally, in the case of Example 5 in which the absorption layer was located on the second metal functional layer, it was confirmed that the coating surface absorption increased significantly, and thus the solar heat gain coefficient significantly decreased.

In addition, in the case of emissivity, it was confirmed that all of Examples 3-5 maintained almost the same value as compared to Comparative Example 3 not including an absorption layer. This means that even if light absorption is achieved using the absorber layer of the present invention, the emissivity performance achieved by the metal functional layer is not affected. Therefore, it can be appropriately applied as a light absorption layer in low-emissivity glass or the like.

The present invention is not limited to the above embodiments, but can be manufactured in a variety of different forms, and those skilled in the art to which the present invention pertains may take other specific forms without changing the technical spirit or essential features of the present invention. It will be understood that it can be implemented as. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

100, 101, 102, 200, 201 to 206: transparent substrate provided with multilayer thin film coating
110: transparent substrate
120, 121, 122, 220, 221 to 226: multilayer thin film coating
11: antireflection layer comprising an absorption layer
12: antireflection layer not containing an absorption layer
20: metal layer
21: first metal functional layer
22: second metal functional layer
113: absorption layer
1131: metal nanoparticles

Claims (25)

As a transparent substrate with a multilayer thin film coating,
The multilayer thin film coating,
A metal functional layer having infrared reflective properties, and
An absorption layer that absorbs electromagnetic waves in a predetermined wavelength range using localized surface plasmon resonance,
The absorption layer includes a dielectric medium and metal nanoparticles dispersed in the dielectric medium,
the dielectric medium comprises silicon nitride having the formula SiN _x (x<1.33);
The metal nanoparticle is selected from the group consisting of Ag, Au, Cu, Al, Pt, Pd, Ni, Co, Fe, Mn, Cr, Mo, W, V, Ta, Nb, Sn, Pb, Sb, and Bi. Including one or more species,
The multilayer thin film coating includes a first anti-reflection layer and a second anti-reflection layer disposed with the metal functional layer interposed therebetween, the first anti-reflection layer and the second anti-reflection layer each including at least one dielectric layer,
At least one of the first anti-reflection layer and the second anti-reflection layer includes the absorption layer;
the absorber layer is in direct contact with the at least one dielectric layer;
The dielectric layer in contact with the absorber layer includes silicon nitride represented by a chemical formula of Si ₃ N ₄ . delete According to claim 1,
The first anti-reflection layer is disposed between the transparent substrate and the metal functional layer;
The first anti-reflection layer includes a first dielectric layer, the absorption layer, and a second dielectric layer sequentially disposed in a direction away from the transparent substrate. According to claim 1,
the second anti-reflection layer is disposed on the metal functional layer;
The second anti-reflection layer includes a first dielectric layer, the absorption layer, and a second dielectric layer sequentially disposed in a direction away from the metal functional layer. According to claim 1,
Each of the first anti-reflection layer and the second anti-reflection layer includes a first dielectric layer, an absorption layer, and a second dielectric layer sequentially disposed in a direction away from the transparent substrate. According to any one of claims 3 to 5,
Wherein the absorption layer is disposed in direct contact with at least one of the first dielectric layer and the second dielectric layer. delete According to any one of claims 1, 3 to 5,
A transparent substrate having a thickness of the absorption layer of 5 nm to 40 nm. According to any one of claims 1, 3 to 5,
The absorption layer is a transparent substrate having an absorption peak in the visible light region. According to claim 1,
The transparent substrate further comprises a metal protective layer disposed on at least one surface of the metal functional layer in contact with the metal functional layer. According to claim 10,
The metal protective layer is a transparent substrate comprising a nickel-chromium alloy. According to claim 1,
A transparent substrate in which an absorption value of an uncoated surface and an absorption value of a coated surface at the same wavelength of the transparent substrate are different depending on the relative positions of the metal functional layer and the absorption layer. As a transparent substrate with a multilayer thin film coating,
The multilayer thin film coating,
A first metal functional layer having infrared reflective properties;
A second metal functional layer laminated apart from the first metal functional layer and having an infrared reflective characteristic, and
At least one absorption layer absorbing electromagnetic waves of a predetermined wavelength range using a localized surface plasmon resonance;
The absorption layer includes a dielectric medium and metal nanoparticles dispersed in the dielectric medium,
the dielectric medium comprises silicon nitride having the formula SiN _x (x<1.33);
The metal nanoparticle is selected from the group consisting of Ag, Au, Cu, Al, Pt, Pd, Ni, Co, Fe, Mn, Cr, Mo, W, V, Ta, Nb, Sn, Pb, Sb, and Bi. Including one or more species,
The multilayer thin film coating,
a first antireflection layer, the first metal functional layer, the second antireflection layer, the second metal functional layer, and a third antireflection layer sequentially disposed in a direction away from the transparent substrate;
At least one of the first anti-reflection layer, the second anti-reflection layer, and the third anti-reflection layer includes the absorption layer;
The first anti-reflection layer, the second anti-reflection layer, and the third anti-reflection layer each include at least one dielectric layer,
Among the first anti-reflection layer, the second anti-reflection layer, and the third anti-reflection layer, the layer including the absorption layer includes a first dielectric layer, the absorption layer, and a second dielectric layer sequentially disposed in a direction away from the transparent substrate,
The absorption layer is disposed in direct contact with at least one of the first dielectric layer and the second dielectric layer,
Among the first dielectric layer and the second dielectric layer, a layer disposed in direct contact with the absorption layer includes silicon nitride represented by a chemical formula of Si ₃ N ₄ . delete delete According to claim 13,
A transparent substrate in which one of the first anti-reflection layer, the second anti-reflection layer, and the third anti-reflection layer includes an absorption layer. According to claim 13,
Two of the first anti-reflection layer, the second anti-reflection layer, and the third anti-reflection layer include an absorption layer. According to claim 13,
The transparent substrate of claim 1 , wherein all of the first antireflection layer, the second antireflection layer, and the third antireflection layer each include an absorption layer. delete delete The method of any one of claims 13 and 16 to 18,
A transparent substrate having a thickness of the absorption layer of 5 nm to 40 nm. The method of any one of claims 13 and 16 to 18,
The absorption layer is a transparent substrate having an absorption peak in the visible light region. According to claim 13,
The transparent substrate further comprising a metal protective layer formed on one surface of at least one of the first metal functional layer and the second metal functional layer. According to claim 23,
The metal protective layer is a transparent substrate comprising a nickel-chromium alloy. According to claim 13,
The transparent substrate wherein the absorption value of the non-coated surface and the absorption value of the coated surface at the same wavelength of the transparent substrate are different depending on the relative positions of the first metal functional layer, the second metal functional layer, and the absorption layer.

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