KR20140013376A - Thermochromic window - Google Patents

Thermochromic window Download PDF

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Publication number
KR20140013376A
KR20140013376A KR1020120080159A KR20120080159A KR20140013376A KR 20140013376 A KR20140013376 A KR 20140013376A KR 1020120080159 A KR1020120080159 A KR 1020120080159A KR 20120080159 A KR20120080159 A KR 20120080159A KR 20140013376 A KR20140013376 A KR 20140013376A
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KR
South Korea
Prior art keywords
thermochromic
thin film
seed layer
window
oxide
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Application number
KR1020120080159A
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Korean (ko)
Inventor
차지윤
문동건
김현빈
Original Assignee
삼성코닝정밀소재 주식회사
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Priority to KR1020120080159A priority Critical patent/KR20140013376A/en
Publication of KR20140013376A publication Critical patent/KR20140013376A/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/225—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/366—Low-emissivity or solar control coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The present invention relates to a thermochromic window, and more specifically, to a thermochromic window which controls solar light transmittance according to temperatures. For this, the present invention provides the thermochromic window which includes a substrate, a seed layer formed on the substrate, and a thermochromic film formed on the seed layer, wherein the seed layer is crystallized and the difference between the refractive index of the seed layer and the refractive index of the thermochromic film is 0.3 or less.

Description

Thermochromic window {THERMOCHROMIC WINDOW}

The present invention relates to a thermochromic window, and more particularly, to a thermochromic window in which the transmittance of sunlight is controlled according to temperature.

Recently, as the prices of chemical energy sources such as petroleum have skyrocketed, the need to develop new energy sources is growing. In addition, the importance of energy-saving technologies is increasing as well. In fact, more than 60% of household energy consumption is used for heating and cooling. In particular, 24% of the energy consumed by windows in general houses and buildings is consumed.

Accordingly, a variety of efforts have been made to reduce the energy consumed through the windows by increasing the airtightness and insulation properties of the windows while maintaining the aesthetic and visual characteristics of the building, which is the basic function of the windows. Typically, And a method of installing an insulating window.

Types of high-thermal-insulating windows include an argon gas-injected multi-layered window for injecting argon (Ar) gas into the multi-layered glass to prevent heat exchange, a vacuum window made of vacuum between the multi-layered glasses, and a low-E window . In addition, glasses that control the energy inflow through the sun by coating layers with thermal properties on windows are being studied.

In particular, Royglas is coated with a thin metal or metal oxide on the surface of glass, so that most of the visible rays coming through the window penetrate most of it to keep the room bright and effectively block the radiation of infrared rays. In summer, it blocks the heat outside the building, which reduces cooling and heating costs. However, due to the nature of reflection at wavelengths other than visible light, infrared rays emitted from the sun can not be introduced into the room, especially in winter, and the transmittance of sunlight can not be controlled according to the season (temperature).

Thus, when a material having a thermochromic effect is coated on a glass, visible light is emitted when the glass is above a certain temperature, but near infrared rays and infrared rays are blocked to prevent the room temperature from rising, thereby improving the cooling / heating energy efficiency A technique for thermochromic windows is being developed.

Particularly, in the case of the thermochromic window coated with vanadium dioxide (VO 2 ), which has a phase transition temperature close to a practically feasible temperature at 68 ° C. and has a large variation in optical constant (n, k) Research is underway.

FIG. 1 is a graph showing changes in transmittance of sunlight according to temperature before and after phase transition of a thermochromic window coated with a thermochromic thin film made of vanadium dioxide on one surface of a glass substrate.

As shown in Figure 1, by coating the thermochromic material on the glass, it can be seen that the transmittance of the sunlight, in particular in the near infrared region, changes before the phase transition (30 ℃) and after the phase transition (90 ℃), thereby The energy efficiency of cooling and heating in buildings and the like can be improved.

However, the thermochromic window of the single-layer structure in which only the vanadium dioxide thin film is coated on the substrate has a disadvantage in that the conversion efficiency in the near infrared region is only about 5%. Here, the conversion efficiency refers to the transmittance difference before and after the phase transition, and was calculated by giving different weights to each wavelength in the near infrared region.

Meanwhile, the thermochromic window may be designed as a multilayer to improve conversion efficiency and optical characteristics.

Conventionally, in order to improve crystallinity of vanadium dioxide coated on a substrate, a dielectric material such as TiO 2 or SiO 2 is coated to form a seed layer, and then vanadium dioxide is deposited on the seed layer. The coating produced a thermocomic window. However, in this case, the crystallinity of the coated vanadium dioxide thin film is improved, but there arises a problem that the difference in transmittance before and after phase transition in the near infrared region (800 to 1600 nm) becomes small.

In addition, a multi-layered film may be formed by using a material such as a-Si as a lower layer of the vanadium dioxide thin film. In this case, the difference in transmittance before and after phase transition in the near infrared region may be improved, but the crystallinity of the vanadium dioxide thin film is improved. It has the disadvantage of not being able to.

The present invention has been made to solve the problems of the prior art as described above, an object of the present invention is to provide a thermochromic window improved in the difference between the crystallinity of the thermochromic thin film and the transmittance difference before and after the phase transition of the thermochromic window To provide.

To this end, the invention comprises a substrate; A seed layer formed on the substrate; And a thermochromic thin film formed on the seed layer, wherein the seed layer has crystallinity, and the refractive index of the seed layer is within 0.3 with a difference from the refractive index of the thermochromic thin film. Provide a Mick window.

In addition, the thermochromic window may further include an oxide or nitride thin film formed on the thermochromic thin film, and the oxide or nitride thin film may be AlOx, SiOx, Nb 2 O 5 , TiO 2 , and Si 3. It may comprise a material of any one of N 4 .

The seed layer may further include a dopant.

In addition, the thermochromic thin film may be formed of a thermochromic material doped with a dopant, and the dopant may be at least one of Mo, W, Nb, Ti, Sn, and Ni.

The thermochromic thin film may include any one of vanadium dioxide (VO 2 ), titanium (III) oxide (Ti 2 O 3 ), niobium oxide (NbO 2 ), or nickel sulfide (NiS). Can be.

In addition, when the thermochromic thin film includes vanadium dioxide (VO 2 ), the seed layer may include any one of p-Si, CuO, Cu 2 O, AlAs, InGaAs, GaSb, and AlSb. Can be done.

In addition, when the seed layer includes p-Si, B or P may be doped into the seed layer.

In addition, in the thermochromic window according to the present invention, the seed layer includes p-Si, but has a thickness of 100 nm, and the thermochromic thin film includes vanadium dioxide (VO 2 ). It has a thickness of ㎚, the oxide or nitride thin film made of AlOx, but may have a thickness of 50nm.

According to the present invention, it is possible to improve the difference between the crystallinity of the thermochromic thin film and the phase change of the phase change of the thermochromic window.

In addition, the visible light transmittance of the thermochromic window can be improved.

1 is a graph showing the change in transmittance of sunlight according to the temperature before and after the phase transition of the thermochromic window coated with a thermochromic thin film of vanadium dioxide on one surface of the glass substrate.
2 is a schematic cross-sectional view of a thermochromic window according to one embodiment of the present invention.
Figure 3 is a graph showing the transmittance according to the thickness of the p-Si thin film in the thermochromic window consisting of a substrate / p-Si thin film / vanadium dioxide thin film in accordance with the present invention.
4 is a schematic cross-sectional view of a thermochromic window according to another embodiment of the present invention.
Figure 5 is a graph showing the resistivity of the seed layer according to the concentration of P doped in the seed layer consisting of p-Si.
Figure 6 is a graph showing the phase-transmission before and after transmittance of the thermochromic window consisting of a substrate / p-Si thin film / vanadium dioxide thin film / AlOx thin film in accordance with a preferred embodiment of the present invention.

Hereinafter, a thermochromic window according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

In addition, in describing the present invention, when it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

2 is a schematic cross-sectional view of a thermochromic window according to one embodiment of the present invention.

Referring to FIG. 2, the thermochromic window according to the present invention may include a substrate 100, a seed layer 200, and a thermochromic thin film 300.

The substrate 100 may be a support substrate, and soda-lime-based building glass may be preferably used.

The seed layer 200 is formed on the substrate 100 to improve the difference between the crystallinity of the thermochromic thin film 300 formed on the seed layer 200 and the transmittance before and after the phase transition of the thermochromic window.

To this end, the seed layer 200 has crystallinity and has a refractive index within 0.3 of a difference from the refractive index of the thermochromic thin film 300.

That is, since the seed layer 200 has crystallinity, the crystallinity of the thermochromic thin film 300 formed by coating the thermochromic material on the seed layer 200 is improved.

In addition, when the thermochromic window is formed of a multilayer of the seed layer 200 and the thermochromic thin film 300, the thermochromic window may be changed into the thermochromic by the refractive index due to the difference in refractive index between the seed layer 200 and the thermochromic thin film 300. There arises a problem that the phase change of the MIC window before and after the transmittance difference is smaller than the difference between the before and after transmittance of the thermochromic window having only the thermochromic thin film. However, in the present invention, the seed layer 200 has a refractive index that is similar to the refractive index of the thermochromic thin film 300, that is, the refractive index of which the difference between the seed layer 200 and the refractive index of the thermochromic thin film 300 is within 0.3 ( By having the refractive index of the thermochromic thin film-0.3 ≤ the refractive index of the seed layer ≤ the refractive index of the thermochromic thin film + 0.3), the transmittance before and after the phase change of the thermochromic window, the transmittance before and after the phase transition of the thermochromic window Improve the difference

In addition, the transmittance of the thermochromic window may be controlled by adjusting the thickness of the seed layer 200.

Figure 3 is a graph showing the transmittance according to the thickness of the p-Si thin film in the thermochromic window composed of a substrate / p-Si thin film / vanadium dioxide thin film in accordance with the present invention. As shown in FIG. 3, it can be seen that as the thickness of the p-Si thin film becomes thicker, a peak before phase transition in the near infrared region moves.

In addition, the seed layer 200 may prevent the ions in the substrate 100 from being eluted.

In general, the thermochromic thin film 300 to be described later is formed by sputtering a thermochromic material at a high temperature. In such a high temperature process, ions in the substrate are eluted to the outside. However, according to the present invention, the crystalline seed layer 200 having a large packing density is formed on the substrate 100, thereby preventing the ions in the substrate 100 from being eluted to the outside, thereby improving the performance of the thermochromic window. This deterioration can be prevented. In particular, when the substrate 100 is a soda-based glass substrate, the seed layer 200 may prevent the sodium (Na) ions in the glass substrate from being eluted by sodium diffusion.

In addition, a dopant may be doped into the seed layer 200.

By controlling the emissivity of the thermochromic window by adjusting the resistivity of the seed layer 200 through doping of the dopant, the thermal insulation performance of the thermochromic window may be improved. In general, the higher the doping concentration of the dopant, the lower the resistivity of the seed layer 200.

The thermochromic thin film 300 is formed on the seed layer 200 and may be formed by sputtering coating of a thermochromic material.

Thermochromic material is a material whose crystal structure changes due to a thermochromic phenomenon that is phase-transformed at a specific temperature (phase transition temperature), and thus the physical properties (electrical conductivity, infrared transmittance, etc.) change rapidly. Has the property of changing the blocking or reflectance. Such a thermochromic material may be made of any one of vanadium dioxide (VO 2 ), titanium (III) oxide (Ti 2 O 3 ), niobium oxide (NbO 2 ), and nickel sulfide (NiS).

In addition, the thermochromic thin film 300 may be formed of a thermochromic material doped with a dopant.

By doping the dopant in the thermochromic material, it is possible to control the phase transition temperature of the thermochromic thin film 300. In general, the higher the doping ratio of the dopant, the lower the phase transition temperature of the thermochromic thin film 300.

The dopant to be doped may be at least one of Mo, W, Nb, Ti, Sn, and Ni.

4 is a schematic cross-sectional view of a thermochromic window according to another embodiment of the present invention.

Referring to FIG. 4, the thermochromic window according to another embodiment of the present invention may further include an oxide or nitride thin film 400 formed on the thermochromic thin film 300.

The oxide or nitride thin film 400 has a structure in which the thermochromic window is a multilayer of the seed layer 200 and the thermochromic thin film 300, thereby improving transmittance of the visible light.

In addition, the oxide or nitride thin film 400 may prevent the thermochromic thin film 300 from being damaged by scratches or external contamination.

The oxide or nitride thin film 400 may include one of AlOx, SiOx, Nb 2 O 5 , TiO 2 , and Si 3 N 4 .

The thermochromic window according to the preferred embodiment of the present invention may include a substrate, a seed layer, and a vanadium dioxide thin film.

Here, the seed layer includes a material of any one of p-Si, CuO, Cu 2 O, AlAs, InGaAs, GaSb, and AlSb having crystallinity and having a refractive index similar to that of vanadium dioxide (n ≒ 3). Can be done.

In addition, when the seed layer includes p-Si, the seed layer may be doped with B or P to adjust the resistivity of the seed layer, thereby controlling the emissivity of the thermochromic window.

5 is a graph showing the resistivity of the seed layer according to the concentration of P doped in the seed layer made of p-Si. As shown in FIG. 5, the resistivity of the seed layer decreases as the concentration of the dopant P increases.

In addition, an oxide or nitride thin film may be formed on the vanadium dioxide thin film to improve visible light transmittance.

Preferably, the seed layer comprises p-Si, but has a thickness of 100 nm, the vanadium dioxide thin film has a thickness of 100 nm, and the oxide or nitride thin film comprises AlOx, but has a thickness of 50 nm. Will have

FIG. 6 is a graph showing before and after phase transition transmittance of a thermochromic window composed of a substrate / p-Si thin film / vanadium dioxide thin film / AlOx thin film according to a preferred embodiment of the present invention. Referring to FIG. 6, as a result of calculating the transmittance before and after the phase transition using the KSL2514 standard, which is a method of testing the transmittance, reflectance, emissivity, and solar heat acquisition rate of the plate glass, the difference in visible light transmittance compared to a thermochromic window composed of a conventional substrate / vanadium dioxide thin film is From 3.6% to 16.8%, the difference in solar transmittance was improved from 13.6% to 25.9% and the difference in near infrared transmittance was increased from 23% to 37%.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible.

Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the scope of the appended claims as well as the appended claims.

100: substrate 200: seed layer
300: thermochromic thin film 400: oxide or nitride thin film

Claims (10)

Board;
A seed layer formed on the substrate;
It comprises a thermochromic thin film formed on the seed layer,
The seed layer has a crystallinity, the thermochromic window, characterized in that the refractive index of the seed layer is within 0.3 difference from the refractive index of the thermochromic thin film.
The method of claim 1,
The thermochromic window,
The thermochromic window further comprises an oxide or nitride thin film formed on the thermochromic thin film.
3. The method of claim 2,
The oxide or nitride thin film is AlOx, SiOx, Nb 2 O 5 , TiO 2, Si 3 N 4 and any one of the thermoelectric electrochromic window, characterized in that comprises a material selected from the group consisting of.
The method of claim 1,
And the seed layer further comprises a dopant.
The method of claim 1,
Wherein the thermochromic thin film comprises a dopant-doped thermochromic material.
6. The method of claim 5,
And the dopant is at least one of Mo, W, Nb, Ti, Sn, and Ni.
The method of claim 1,
The thermochromic thin film is formed of any one material of vanadium dioxide (VO 2 ), titanium (III) oxide (Ti 2 O 3 ), niobium oxide (NbO 2 ), or nickel sulfide (NiS). Thermochromic window.
The method of claim 1,
The thermochromic thin film is made of vanadium dioxide (VO 2 ),
And the seed layer comprises any one of p-Si, CuO, Cu 2 O, AlAs, InGaAs, GaSb, and AlSb.
9. The method of claim 8,
The seed layer is made of p-Si,
The seed layer is thermochromic window, characterized in that doped with B or P.
3. The method of claim 2,
The seed layer comprises p-Si, but has a thickness of 100 nm,
The thermochromic thin film is made of vanadium dioxide (VO 2 ), but has a thickness of 100 nm,
The oxide or nitride thin film is made of AlOx, thermochromic window, characterized in that having a thickness of 50nm.

KR1020120080159A 2012-07-23 2012-07-23 Thermochromic window KR20140013376A (en)

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