WO2010098200A1

WO2010098200A1 - Stack article

Info

Publication number: WO2010098200A1
Application number: PCT/JP2010/051866
Authority: WO
Inventors: 英雄大本; 和広加藤; 徹蘆田; 由貴中西
Original assignee: セントラル硝子株式会社
Priority date: 2009-02-26
Filing date: 2010-02-09
Publication date: 2010-09-02

Abstract

Provided is a glass stack characterized by being provided with a glass substrate and a thin-layer stack formed on the glass substrate, wherein the thin-layer stack comprises, in order from the substrate side, a first layer configured from a dielectric, a second layer configured from metal consisting mainly of Ag, a third layer configured from a dielectric, a fourth layer configured from metal consisting mainly of Ag, and a fifth layer configured from a dielectric, the sum of the geometric thicknesses of the second layer and the fourth layer falls within the range of 22-29 nm, the geometric thickness of the second layer is 0.3-0.8 times the thickness of the geometric thickness of the fourth layer, the sum of the optical thicknesses of the first, third, and fifth layers falls within the range of 220-380 nm, the optical thickness of the third layer falls within the range of 140-200 nm, the optical thickness of the first layer is 0.4-1.5 times the optical thickness of the fifth layer, and regarding the reflection color tone from the glass substrate side, a* in the CIE L*a*b* chromaticity coordinate diagram is less than 3 when the incident angle falls within the range of 0°-60°. The glass stack achieves a reduction in reddish reflection tone and an improvement in the reflectivity of a near-infrared region, and thus is suitably used for window glass in order to improve the cooling/heating efficiency in a room.

Description

Laminate article

The present invention relates to a laminated article, and in particular, to a glass laminated body having a glass substrate and a laminated film formed on the glass substrate and applicable to window glass or the like as Low-E (low emission) glass.

In the window glass, in the summer, the solar heat that flows from the outdoor to the interior is reflected (suppresses the rise in the temperature of the indoor atmosphere due to sunlight and blocks the inflow of heat from the outdoor to the indoors), and in the winter, from the indoor to the outdoor. It is required to improve the cooling / heating efficiency and to save energy (reduction of heating / cooling costs) by reflecting the heating heat flowing out into the window, that is, by providing the window glass with heat insulation (heat insulation). . Currently, the window glass is a multilayer in which the periphery of two opposing glass substrates is sealed with a spacer and a sealing material, and dry gases and rare gases such as Ar are sealed in the two glass substrates. Glass is widely used. For the purpose of improving the heat shielding property of the multilayer glass, a glass laminate in which a low-radiation laminated film is formed on at least one of glass substrates is applied.

A glass laminate in which a low-emission laminated film is formed is known as Low-E (low emission) glass, and a first layer composed of a metal oxide, Ag as a main component, is sequentially formed on a glass substrate. Two layers, a third layer made of a metal oxide, a fourth layer mainly composed of Ag, and a fifth layer made of a metal oxide are becoming popular. When the metal layer is thickened to improve the heat shielding property of the glass laminate, the visible light transmittance of the glass laminate is reduced, but the first layer made of a dielectric, Ag as a main component, is sequentially formed on the glass substrate. A second layer made of a metal, a third layer made of a dielectric, a fourth layer made of a metal containing Ag as a main component, and a fifth layer made of a dielectric. By making two layers, the visible light transmittance is adjusted using the interference effect of light.

In Patent Document 1, in the glass laminate in which the laminated film having the above five-layer structure is formed, the optical thickness of the first layer is 32 nm to 41 nm, the geometric thickness of the second layer is 6 nm to 9 nm, Reflection from the glass substrate side by setting the optical thickness of the three layers to 113 nm to 145 nm, the geometric thickness of the fourth layer to 8 nm to 12 nm, and the optical thickness of the fifth layer to 45 nm to 60 nm. It discloses that a glass laminate having a small change in color tone even when the incident angle is changed and excellent in heat shielding performance is obtained.

Patent Document 2 discloses that in a glass laminate in which a laminated film having the above five-layer structure is formed, the thickness of the first layer is 0.45 to 0.9 times the thickness of the third layer. It discloses that the redness of the reflected color tone is reduced when the laminate is viewed from an oblique direction.

Patent Documents

3 and 4 disclose a method for producing Low-E glass having high heat shielding properties and high visible light transmittance.

Moreover, the laminated article which has a silver thin film layer is utilized for the electrode member of an electronic device, such as a solar cell and a display by utilizing the electrical conductivity of a silver thin film layer (nonpatent literature 1), and is integrated in a plasma display etc. Application to a near-infrared cut filter for a front panel (Non-Patent Document 2) has been proposed.

JP 11-34216 A JP 2004-58592 A JP 2006-206424 A JP 2007-191384 A

In order to save energy, such as improving air-conditioning efficiency, window glass laminates are required to have not only low radiation properties but also further improved heat shielding properties. If the thickness of the metal layer containing Ag as a main component is increased, the reflectance in the near-infrared region is increased, and the heat shielding property can be improved. However, the more the thermal barrier property of the laminated film, that is, the reflectance in the near infrared region is improved, the influence on the reflectance near 700 nm which is the boundary region between the visible region and the near infrared region is affected. The reflected color tone becomes reddish, and the reflected color tone in the oblique direction is particularly reddish. When the laminate is used for a window glass of a building or a house, it is preferable to avoid a reddish reflection color tone because a gentle appearance color tone is preferred in these applications. In order to meet social demands, the reflection color tone of the glass laminate should not be reddish, and the reflectance in the near infrared region should be improved (the total thickness of the metal layer mainly composed of Ag is increased). Was a conflicting issue.

Also, the heat shielding property, visible light transmittance, electrical conductivity, etc. of the thin film laminate including the silver thin film layer are greatly affected by the surface resistance value of the silver thin film layer. The heat shielding property, visible light transmittance, electrical conductivity, etc. of the thin film laminate are also affected by the thickness of the silver thin film layer, and increasing the thickness of the silver thin film layer brings about an improvement in the heat shielding property, electrical conductivity, Since it leads to a decrease in visible light transmittance and an increase in cost, it cannot be a good solution. Therefore, in order to obtain a thin film laminate having excellent heat shielding properties, visible light transmittance, and electrical conductivity, it is important to reduce the surface resistance value of the silver thin film layer.

It is an object of the present invention to provide a laminated article that has overcome the above-mentioned problems, and in particular, a glass laminated body that has a reduced reddish reflection color tone including an oblique direction and an improved near-infrared reflectance. To do.

That is, according to the present invention, it comprises a glass substrate and a thin film laminate formed on the glass substrate, and the thin film laminate comprises, in order from the substrate side, a first layer made of a dielectric. , A second layer made of a metal containing Ag as a main component, a third layer made of a dielectric, a fourth layer made of a metal containing Ag as a main component, and a fifth layer made of a dielectric. The total geometric thickness of the second layer and the fourth layer is 22 to 29 nm, and the geometric thickness of the second layer is 0.3 to 0.8 times the geometric thickness of the fourth layer. The total optical thickness of the first, third, and fifth layers is 220 to 380 nm, the optical thickness of the third layer is 140 to 200 nm, and the optical thickness of the first layer is the optical thickness of the fifth layer. The reflection color tone from the glass substrate side is 0.4 to 1.5 times, and the a * in the CIE L * a * b * chromaticity coordinate diagram is 3 when the incident angle is in the range of 0 ° to 60 °. Not yet And characterized in that the glass laminate is provided.

It is a cross-sectional schematic diagram of the glass laminated body which is embodiment of the laminated body article of this invention. It is a cross-sectional schematic diagram of other embodiment of the laminated body article of this invention. It is the schematic of a magnetron sputtering apparatus. It is a figure which shows the reflectance spectrum of the glass laminated body of Example 1-1 and Comparative Example 1-1. FIG. 3 is a schematic cross-sectional view of glass laminates of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 and 2-5. It is a cross-sectional schematic diagram of the glass laminated body of Comparative Example 2-4. It is a figure showing the relationship between the film thickness of the silver thin film in a glass laminated body of a reference example, and a relative packing density.

Hereinafter, the present invention will be described in detail.

FIG. 1 shows a glass laminate as a first embodiment of the laminate article of the present invention. The glass laminated body of 1st Embodiment consists of a glass base material and the thin film laminated body formed on this glass base material. The thin film laminate is composed of a first layer made of a dielectric, a second layer made of a metal containing Ag as a main component, a third layer made of a dielectric, and a metal made mainly of Ag. It has four layers and a fifth layer made of a dielectric. The thin film stack is preferably formed using a vapor deposition process such as sputtering.

The glass substrate is not particularly limited. For example, the glass substrate has an inorganic transparency such as a building window glass, a commonly used float plate glass, or a soda-lime glass produced by a roll-out method. A certain plate glass is mentioned. The plate glass can be used for both colorless glass such as clear glass and high transmission glass, and green colored such as heat ray absorbing glass, and is not particularly limited to the shape of the glass, but visible light. In consideration of the transmittance, it is preferable to use colorless glass such as clear glass and high transmittance glass. In addition to flat glass, bent glass, various glass such as air-cooled tempered glass and chemically tempered glass, netted glass can be used. Furthermore, various glass substrates such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, and zero expansion crystallized glass can be used.

The first, third, and fifth layers made of dielectric (hereinafter also referred to as “dielectric layers”) may be layers having the same composition or layers having different compositions. In addition, each of the first, third, and fifth layers may be configured by a layer having a single composition as a whole, or may be formed by stacking layers having a plurality of different compositions. In particular, the first, third, and fifth layers are zinc oxide, aluminum oxide, silicon oxide, titanium oxide, tantalum oxide, tin oxide, zirconium oxide, zinc-tin alloy oxide, silicon nitride, aluminum nitride, silicon oxynitride, It is preferable to include a layer made of at least one dielectric selected from the group consisting of aluminum oxynitride, titanium oxynitride, zirconium oxynitride, and tin oxynitride.

The second and fourth layers containing Ag as a main component (hereinafter also referred to as “silver thin film layer”) may be made of Ag alone or a silver alloy containing Ag as a main component. In the case of a silver alloy, it may contain up to 5% by mass of a metal such as Pd, Au, Pt, Ni, Cu.

In the glass laminate of the first embodiment, the total geometric thickness of the second layer and the fourth layer is 22 to 29 nm, and the geometric thickness of the second layer is the geometric thickness of the fourth layer. The total optical thickness of the first, third, and fifth layers is 220 to 380 nm, and the optical thickness of the third layer is 140 to 200 nm. CIE L * a * b when the optical thickness is 0.4 to 1.5 times the optical thickness of the fifth layer and the reflection color tone from the substrate side is in the range of 0 ° to 60 ° incident angle * It is characterized in that a * in the chromaticity coordinate diagram is less than 3.

The configuration of the second layer and the fourth layer is important in order to reduce the reddish reflection color tone of the glass laminate and improve the reflectance in the near infrared region. Therefore, in the first embodiment, the total geometric thickness of the second layer and the fourth layer is set to 22 to 29 nm, preferably 24 to 29 nm. If the sum of the geometric thicknesses of the second layer and the fourth layer is less than 22 nm, the near infrared region (for example, the light wavelength region of 750 to 2000 nm, particularly close to the visible region) where the thermal action is large in the sunlight. The effect of improving the reflectance in a light wavelength region of 750 to 1000 nm (where the radiant energy intensity is particularly large) is reduced. For example, at a light wavelength of 750 nm, when the total geometric thickness of the second layer and the fourth layer is about 20 nm, the reflectance from the film surface direction is 20 to 25%, whereas the second layer When the sum of the geometric thicknesses of the film and the fourth layer is about 25 nm, the reflectance from the film surface direction is 40 to 60%, and it is recognized that a large difference of 2 to 3 times occurs. When the total geometric thickness of the second layer and the fourth layer exceeds 29 nm, the visible light transmittance is likely to decrease, and it becomes difficult to achieve a visible light transmittance of 70% or more in the glass laminate. .

The geometric thickness of the second layer is 0.3 to 0.8 times, preferably 0.5 to 0.7 times the geometric thickness of the fourth layer. If the geometric thickness of the second layer is 0.3 to 0.8 times the geometric thickness of the fourth layer, the reflection color tone from the substrate side is determined so that the incident angle is 0 ° to 60 °. In the range, a * in the CIE L * a * b * chromaticity coordinate diagram is easily set to less than 3. By setting the a * to less than 3, the reddish color in the reflected color tone is not only viewed from the front (corresponding to an incident angle near 0 °) but also in an oblique direction (considering an incident angle of up to 60). As a result, it is possible to provide a window glass having a mild appearance color tone. When the geometric thickness of the second layer is less than 0.3 times the geometric thickness of the fourth layer, the geometric thickness of the fourth layer must be increased, and the glass laminate is visible. In addition to the low light transmittance, the reflected color tone tends to exhibit a reddish color tone even when viewed from the front. When the geometric thickness of the second layer is more than 0.8 times the geometric thickness of the fourth layer, the reflection color tone from the oblique direction tends to exhibit a reddish color tone. In order to obtain good solar shading performance and visible light transmittance, the thickness of each of the second and fourth layers is preferably 8 to 20 nm.

The sum of the optical thicknesses of the first, third and fifth layers is set to 220 to 380 nm, preferably 260 to 360 nm, and the optical thickness of the third layer is set to 140 to 200 nm, preferably 160 to 190 nm. . When the optical thickness of the third layer is less than 140 nm, the reflected color tone in the front view tends to exhibit a reddish color tone. On the other hand, when it exceeds 200 nm, the visible light transmittance of the glass laminate tends to be low.

Furthermore, the optical thickness of the first layer is 0.4 to 1.5 times, preferably 0.8 to 1.4 times the optical thickness of the fifth layer. When the optical thickness of the first layer is less than 0.4 times the optical thickness of the fifth layer, the second layer metal layer tends to have low crystallinity and low visible light transmittance. It is easy to become. On the other hand, when the optical thickness of the first layer is more than 1.5 times the optical thickness of the fifth layer, the reflected color tone tends to exhibit a reddish color tone even in front view.

In the first embodiment, at least one of the second and fourth layers containing Ag as a main component is an oxide layer (hereinafter referred to as a “zinc oxide layer”) in which the base material side has Zn as the main component of the cationic metal. .). The first and third layers may be formed as zinc oxide films so as to be in contact with the second and fourth layers, and a separate zinc oxide layer is formed between the first and second layers or between the third and fourth layers. May be. The zinc oxide layer tends to improve the crystallinity of the silver thin film layer. The zinc oxide layer may be made of zinc oxide alone, or may be made of a composite zinc oxide compound containing at least one metal selected from Sn, Al, Ti, Si, Cr, Mg, and Ga. These metals may be contained up to 0.4 times the number of Zn atoms.

From the viewpoint of improving the crystallinity of the silver thin film layer, the zinc oxide layer shows a diffraction peak due to the (002) crystal plane of zinc oxide by an X-ray diffraction method using CuKα rays. The diffraction angle 2θ is preferably 33.9 ° or less, and more preferably 33.8 ° or less.

Moreover, it is preferable that the diffraction angle 2theta of the diffraction peak by a silver (111) crystal plane is 38.1 degrees or more, and a silver thin film layer is 38.11 degrees or more by the X-ray-diffraction method using a CuK alpha ray. It is more preferable that A silver thin film layer having a diffraction angle 2θ of silver (111) crystal plane of 38.1 ° or more is formed on a zinc oxide thin film layer having a diffraction angle 2θ of zinc oxide (002) crystal plane of 33.9 ° or less. Then, the surface resistance value of the silver thin film layer can be lowered. For example, a silver thin film layer with a thickness of 10 nm can have a surface resistance value of 5.5 Ω / □ or less, and 4.3 Ω / □, which is much lower than the conventional product of 6-8 Ω / □. A silver thin film layer having a value can be obtained. Further, the product nk of the refractive index n and the extinction coefficient k of the silver thin film layer can be reduced. For example, a silver thin film having a thickness of 10 nm, an nk of 0.5 or less with respect to a light wavelength of 550 nm, a small absorption of visible light by the silver thin film layer, and a good visible light transmittance A layer can be obtained.

The lower limit value of the diffraction angle 2θ of the diffraction peak due to the (002) crystal plane of zinc oxide is not particularly limited, but if it is less than 33.3 °, the deviation from the diffraction angle 34.421 ° of the unstrained zinc oxide powder is large. The residual strain (compressive stress) of the zinc oxide thin film layer increases, and the thin film laminate may be deteriorated over time, such as peeling from the substrate. Therefore, the diffraction angle 2θ of the diffraction peak due to the (002) crystal plane of zinc oxide may be set to 33.3 ° or more.

The upper limit of the diffraction angle 2θ of the diffraction peak due to the (111) crystal plane of silver is not particularly limited, but when it exceeds 38.6 °, there is a large deviation from the diffraction angle of the undistorted silver agglomeration of 38.116 °. Residual strain (tensile stress) increases, silver thin films tend to aggregate over time, and point defects may occur in the thin film stack. Therefore, the diffraction angle 2θ of the diffraction peak due to the silver (111) crystal plane may be set to 38.6 ° or less.

X-ray diffraction measurement using CuKα rays is performed using an X-ray diffraction measurement device (Rigaku, RINT-UtimaIII), and the measurement results are analyzed by a general-purpose program attached to the device, and diffraction of zinc oxide and silver is performed. The angle 2θ can be obtained.

Also, the surface resistance value of the silver thin film layer decreases as the root mean square roughness (Rms) of the surface of the zinc oxide thin film layer decreases. Therefore, it is preferable that Rms of the zinc oxide thin film layer is 1.5 nm or less. The lower limit of Rms of the zinc oxide thin film layer is not particularly limited, but may be 0.2 nm or more. When the thickness exceeds 1.5 nm, not only the surface resistance of the silver thin film layer becomes high, but also the visible light transmittance may decrease due to the scattering of visible light due to high Rms.

The mean square roughness (Rms) of the surface of the zinc oxide thin film layer was measured using an X-ray diffraction measurement device (Rigaku, RINT-UltimaIII), and the results were measured using a general-purpose program attached to the device. It can be obtained by analysis.

In the first embodiment, the thin film laminate is formed by sequentially laminating the first layer, the second layer, the third layer, the fourth layer, and the fifth layer from the base material side. When five layers (dielectric layers) are formed, the second layer and the fourth layer (metal layer mainly composed of Ag) are affected by atmospheric conditions at the time of forming the dielectric layer and are oxidized or nitrided. May occur. In order to prevent this, a sacrificial layer made of a thin metal layer, metal oxide layer, or metal nitride layer may be laminated between the second layer and the third layer and between the fourth layer and the fifth layer. .

As the sacrificial layer, a metal, a metal oxide, or a metal nitride can be used. For example, at least one metal selected from the group consisting of Zn, Ti, Sn, Ta, Nb, Si, Al, and Cr, or Metal oxides, nitrides, oxynitrides can be used and the sacrificial layers are transparent in a laminated state, or are oxidized or nitrided when the third and fifth layers are formed and become transparent In particular, an alloy of zinc and aluminum, aluminum, or zinc oxide doped with aluminum oxide is preferable.

The geometric thickness of the sacrificial layer is preferably about 1 to 7 nm, more preferably about 2 to 6 nm.

Some sacrificial layers may remain as metal. In this case, unlike the metal containing Ag as a main component, the metal contributes little to the improvement of near-infrared reflectivity and is not included in the geometric thickness of the second and fourth layers, but turns into a dielectric. In the case where it is a dielectric or originally a dielectric, since it acts as an optical interference film, it is included in the optical thicknesses of the third layer and the fifth layer.

The glass laminate is suitably used as a multi-layer glass by facing the other glass substrate and sealing the periphery with a spacer, an adhesive or the like. At this time, it is preferable that the laminated film is directed to the internal space formed by the facing. This internal space is occupied by an inert gas such as Ar, He, Kr, and Xe, dry air, nitrogen, and the like. When forming a window using this multilayer glass, it is preferable to arrange | position a glass laminated body on the outdoor side from a viewpoint of making heat-shielding property favorable.

The glass laminate of the first embodiment is not only excellent in low radiation, but also has improved near-infrared reflectivity. Therefore, by using the laminate for window glass, the indoor heating and cooling efficiency can be improved. It helps and saves energy. In addition, since the reflection color tone of the glass laminate is not reddish from the front to the diagonal direction, it is possible to meet the social demand that the window glass has a gentle appearance color tone.

FIG. 2 shows a laminated article according to the second embodiment of the present invention. The laminate article of the second embodiment comprises a substrate and a thin film laminate formed on the substrate, and the thin film laminate is opposite to the zinc oxide thin film layer and the zinc oxide thin film layer substrate. It has a thin film stacking part composed of a silver thin film layer in contact with the side. The thin film stack is preferably formed using a vapor deposition process such as sputtering.

The base material is not particularly limited. Also in the second embodiment, various glass substrates can be used as in the first embodiment. Moreover, in 2nd Embodiment, you may use amorphous resin base materials, such as a polyethylene terephthalate resin, a polycarbonate resin, a polyvinyl chloride resin, a polyethylene resin other than a glass base material.

The zinc oxide layer may be composed of zinc oxide (ZnO) alone, or may be composed of a composite zinc oxide compound containing at least one metal selected from Sn, Al, Ti, Si, Cr, Mg, Ga, In this case, these metals may be contained up to 0.4 times the number of Zn atoms.

The silver thin film layer may be composed of Ag alone or a silver alloy containing Ag as a main component. In the case of a silver alloy, it may contain up to 5% by mass of a metal such as Pd, Au, Pt, Ni, Cu.

In the laminated article of the second embodiment, the zinc oxide layer is preferably 33.9 ° or less at a diffraction angle 2θ of a diffraction peak due to the (002) crystal plane of zinc oxide by an X-ray diffraction method using CuKα rays. Is 33.8 ° or less, and the silver thin film layer is 38.1 ° or more at a diffraction angle 2θ of a diffraction peak by a silver (111) crystal plane by X-ray diffraction using CuKα rays, preferably 38 .11 ° or more. With such a configuration, similarly to the first embodiment, the surface resistance value of the silver thin film layer can be lowered also in the second embodiment. The lower limit value of the diffraction angle 2θ of the diffraction peak due to the (002) crystal plane of zinc oxide is not particularly limited, but is set to 33.3 ° or more from the viewpoint of suppressing the change with time due to the residual strain of the zinc oxide layer. May be. Further, the upper limit of the diffraction angle 2θ of the diffraction peak due to the (111) crystal plane of silver is not particularly limited, but may be set to 38.6 ° or less from the viewpoint of suppressing the temporal change due to the residual strain of the silver thin film layer. Good.

In the second embodiment, as in the first embodiment, the surface mean square roughness (Rms) of the surface of the zinc oxide thin film layer is set to 1.5 nm or less in order to reduce the surface resistance value of the silver thin film layer. Is preferred. The lower limit of Rms of the zinc oxide thin film layer is not particularly limited, but may be 0.2 nm or more from the viewpoint of lowering the surface resistivity of the silver thin film layer and improving the visible light transmittance.

The thin film laminate of the second embodiment preferably has 1 or 2 to 3 and more preferably 2 thin film laminate portions. As the number of thin film layers is increased, the wavelength at which the reflectance can be reduced to near 0% increases due to the effect of optical interference, and the ratio (bandwidth ratio) of two wavelengths that are below a certain reflectance can be increased. The antireflection effect is large, and a neutral transmission color tone and reflection color tone can be obtained.

In the second embodiment, the thickness of the silver thin film layer is preferably 8 to 20 nm, and more preferably 10 to 18 nm. When the thickness of the silver thin film layer is less than 8 nm, it may be difficult to obtain solar shading performance by the silver thin film layer. In addition, the thin film is too thin, there are discontinuous regions, and local defects may occur. On the other hand, if it exceeds 20 nm, good visible light transmittance may not be obtained.

Furthermore, in the second embodiment, the thin film stack preferably has a protective thin film layer and a metal oxide thin film layer in addition to the thin film stack portion.

The protective thin film layer may be formed directly on the silver thin film layer for the purpose of functioning as a sacrificial layer that prevents oxidation of the silver thin film layer by oxygen plasma generated when the metal oxide thin film layer is formed. preferable. After forming the metal oxide thin film layer, the protective thin film layer is partially or completely oxidized. The protective thin film layer includes Zn, Sn, Ti, Al, NiCr, Cr, Zn alloy, Sn alloy, and each metal containing 0.0 to 10.0% by weight of Al, Sb metal, A metal or a lower oxide thin film of the alloy or the like can be used, and is appropriately selected in consideration of adhesion to the metal oxide thin film layer.

The metal oxide thin film layer can be used for the purpose of reducing visible light reflection on the surface of the thin film by an interference effect. In addition to the zinc oxide film, the metal oxide thin film layer includes oxide films such as Si, Sn, Al, and Ti, nitride films such as Si, Sn, Zn, Al, and Ti, and nitride oxide films. Alternatively, a metal oxide film selected from at least one kind may be used. This metal oxide thin film layer may be provided between the thin film laminated portion and the substrate.

Since the laminate article of the second embodiment has a surface resistance value of the silver thin film layer lower than that of the conventional product, it is possible to improve various performances such as heat shielding properties, visible light transmittance, and electrical conductivity of the laminate article. . Moreover, the product of the refractive index and the extinction coefficient of the silver thin film layer in the laminate is smaller than that of the conventional product, and the visible light transmittance can be improved.

As described above, in the first and second embodiments, the thin film stack is preferably formed by a vapor deposition process such as a sputtering method. In particular, a magnetron sputtering method is preferably used in which a magnet is disposed behind a sputtering target, plasma is confined in the vicinity of the target surface by a generated magnetic field, and film formation is performed with particles sputtered from the target. Moreover, in the sputtering method, a DC power source, an AC power source, or a power source in which AC and DC are superimposed is suitably used as a plasma generation source, but a power source in which AC and DC are superimposed has excellent continuous productivity. And is preferably used.

As a suitable method for setting the diffraction angle 2θ of the diffraction peak due to the (002) crystal plane of zinc oxide to 33.9 ° or less in the X-ray diffraction method using CuKα rays, A zinc oxide thin film layer can be formed by introducing oxygen gas or the like and adjusting the pressure in the vacuum chamber to 1.0 Pa or less, preferably 0.5 Pa or less. As the sputtering target, zinc metal is most preferably used, but a zinc alloy containing at least one metal selected from Sn, Al, Ti, Si, Cr, Mg, Ga and the like may be used.

In addition, when a sputtering method is used as a suitable method for setting the diffraction angle 2θ of the diffraction peak due to the (111) crystal plane of silver to 38.1 ° or more by X-ray diffraction using CuKα rays, The silver thin film layer can be formed by adjusting the applied voltage to 400 V or less, preferably 350 V or less. The lower the voltage applied to the sputtering target, the lower the residual stress of the silver thin film layer and the higher the silver packing density (see the reference example described later). In general, when the thickness of the silver thin film layer is constant, the surface resistance value is said to decrease as the packing density increases, and lowering the voltage applied to the sputtering target is equivalent to the surface resistance value of the silver thin film layer. It is presumed that it will succeed in lowering As a method of adjusting the voltage applied to the sputtering target, the magnetic flux density in the vertical direction generated on the surface by the magnet disposed on the back side of the sputtering target may be 70 mT or more, preferably 100 mT or more. As the sputtering target, silver is most preferably used, but a silver alloy containing at least one kind of metal such as palladium, gold, platinum, nickel, and copper may be used for silver.

FIG. 3 shows a magnetron sputtering apparatus as an example of a film forming apparatus. The apparatus includes a vacuum chamber 3 provided with a substrate holder 2, a gas introduction pipe 5 and a target 8, a vacuum pump 4 connected to the vacuum chamber 3 via an exhaust valve 6, and a film formation in the vacuum chamber 3. A gas introduction pipe 5 for introducing gas, a magnet 7 disposed on the back side of the target 8, and a power source 10 connected to the target 8 via a power cable 9 are provided. After the substrate 1 is held by the substrate holder 2, the inside of the vacuum chamber 3 is evacuated by the vacuum pump 4, and atmospheric gas is introduced into the vacuum chamber 3 from the gas introduction pipe 5. During film formation, the vacuum pump 4 is continuously operated. The pressure in the vacuum chamber 3 during film formation is adjusted by controlling the opening degree of the exhaust valve 6. The flow rate of the atmospheric gas is adjusted by a mass flow controller (not shown). When the power supply 10 is turned on, a film forming material is generated from the target 8 and a thin film is formed on the substrate 1. During film formation, the substrate holder 2 can be rotated to minimize the film thickness distribution. The type of vacuum pump 4, the number and type of targets 8, and the type of power source 10 (selection of DC power source and AC power source) may be selected as appropriate, and are not particularly limited.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

[Experiment 1]
1-1. Sample preparation (Examples 1 to 4 and Comparative Examples 1 to 7)
A thin film laminate having a five-layer structure was formed on a glass substrate by a DC magnetron sputtering method. For the glass substrate, soda lime silicate glass (clear glass) by a float method with a plate thickness of 5.8 mm was used. A zinc oxide layer is formed from a Zn target on the first layer and the third layer of the thin film stack, an Ag layer is formed from an Ag target on the second layer and the fourth layer, and an Sn layer is formed on the fifth layer. A tin oxide layer was formed from the target. In each example, the geometric thickness of the second and fourth layers and the optical thickness of the first, third, and fifth layers were adjusted. In addition, before forming the third zinc oxide layer and before forming the fifth tin oxide layer, aluminum having a geometric thickness of 6 nm was formed with an Al-doped ZnO target (ZnO containing 3% by mass of Al ₂ O ₃ ). A doped zinc oxide film was formed as a sacrificial layer.

Table 1 shows the film configurations of Examples 1 to 4 and Comparative Examples 1 to 7. Table 2 shows the film forming conditions of each layer.

1-2. Evaluation of sample The optical characteristics of the obtained sample were measured by irradiating measurement light from the glass substrate side using a spectrophotometer (U-4000 manufactured by Hitachi, Ltd.), and in accordance with JIS R 3106 (1998). The visible light transmittance, solar transmittance, solar reflectance, vertical emissivity, dominant wavelength of reflection, and stimulus purity were determined. Also, the reflection color tone on the glass substrate side was measured using an instantaneous multi-photometry system (MCPD-3000 manufactured by Otsuka Electronics Co., Ltd.) and a variable incident angle measuring jig, and CIE L * at incident angles of 0 ° and 60 °. a * in the a * b * chromaticity coordinate diagram was obtained.

Table 3 shows the evaluation results of Examples 1 to 4 and Comparative Examples 1 to 7.

Moreover, the reflectance spectrum of the obtained sample was measured. As a representative example, FIG. 4 shows reflectance spectra of Example 1 and Comparative Example 1 (measurement light is incident from the glass substrate side).

As is clear from Table 3 and FIG. 1, the samples of Examples 1 to 4 were excellent in various indices. On the other hand, the glass laminates of Comparative Examples 1 to 7 are inferior in any index, such as a visible light transmittance of less than 70%, a solar reflectance of less than 30%, or a * exceeding 3. It was a thing.

From the above results, by satisfying the thickness dimensional condition of the first embodiment, it is possible to ensure excellent low radiation of the glass laminate, improve the reflectance in the near infrared region, and reduce the reddish reflection color tone. Was confirmed.

[Experiment 2]
2-1. Sample preparation (Reference Example 1-1)
A sample in which a zinc oxide thin film 11 and a silver thin film 12 were sequentially laminated on a substrate 1 as shown in FIG. As the substrate 1, soda lime glass having a thickness of 1.1 mm was used. The zinc oxide thin film 11 and the silver thin film 12 were formed by the following procedure using the magnetron sputtering apparatus of FIG. 3 in order to appropriately adjust the X-ray diffraction angle 2θ of these thin films 11 and 12. In this apparatus, a turbo molecular pump was used as the vacuum pump 4 and a DC power source was used as the power source 10. As the target 8, a Zn target was used for forming the zinc oxide thin film 11, and an Ag target was used for forming the silver thin film 12.

The zinc oxide thin film 11 is formed by holding the glass substrate 1 on the substrate holder 2 and then evacuating the vacuum chamber 3 with the vacuum pump 4 while supplying oxygen gas into the vacuum chamber 3 from the gas introduction tube 5. The Zn target 8 was supplied with power of 100 W through the power cable 9 from the power supply 10 in the formed film formation atmosphere. During the film formation, the vacuum pump 4 was continuously operated, and the pressure in the vacuum chamber-3 during the film formation was adjusted to 0.1 Pa by the exhaust valve 6. The flow rate of oxygen gas was adjusted by a mass flow controller (not shown). The maximum magnetic flux density at the center of the target by the magnet 7 during film formation was measured with a Tesla meter (manufactured by Kanetech Co., Ltd., TM-701) and found to be 92 mT. By controlling the deposition time, the thickness of the zinc oxide thin film 11 was set to 37 nm. (Hereinafter, also in each example, a desired film thickness was obtained by controlling the film formation time, and intentional substrate heating was not performed.)

Next, a silver thin film 12 was continuously formed on the zinc oxide thin film 11 while maintaining the vacuum in the vacuum chamber 3. That is, the silver thin film 12 is formed by introducing argon gas from the gas introduction pipe 5 while evacuating the vacuum chamber 3 by the vacuum pump 4 and supplying power from the power source 10 to the Ag target 8 in the formed film formation atmosphere. 50 W of power was supplied through the cable 9. The pressure in the vacuum chamber 3 during film formation was adjusted to 0.5 Pa by the exhaust valve 6. When the maximum magnetic flux density at the center of the target by the magnet 7 during film formation was measured, it was 149 mT. The film formation time was controlled so that the thickness of the silver thin film 12 was 10 nm.

(Reference Example 1-2)
A sample in which the zinc oxide thin film 11 and the silver thin film 12 were sequentially laminated on the substrate 1 was prepared in the same manner as in Reference Example 1-1 except that the pressure during the formation of the zinc oxide thin film 11 was adjusted to 0.3 Pa. Created.

(Reference Example 1-3)
A sample in which the zinc oxide thin film 11 and the silver thin film 12 were sequentially laminated on the substrate 1 was prepared in the same manner as in Reference Example 1-1 except that the pressure during the formation of the zinc oxide thin film 11 was adjusted to 1.1 Pa. Created.

(Reference Comparative Example 1-1)
A sample in which the zinc oxide thin film 11 and the silver thin film 12 were sequentially laminated on the substrate 1 was prepared in the same manner as in Reference Example 1-1 except that the pressure during the formation of the zinc oxide thin film 11 was adjusted to 1.6 Pa. Created.

(Reference Comparative Example 1-2)
The same as in Reference Example 1-1 except that the pressure during deposition of the zinc oxide thin film 11 was adjusted to 0.6 Pa and the magnet 7 having a magnetic flux density of 57 mT at the center of the target was used. Thus, a sample in which the zinc oxide thin film 11 and the silver thin film 12 were sequentially laminated on the substrate 1 was prepared.

(Reference Comparative Example 1-3)
The same as in Reference Example 1-1 except that the pressure during the deposition of the zinc oxide thin film 11 was adjusted to 1.5 Pa and the magnet 7 having a magnetic flux density of 57 mT at the center of the target was used for the deposition of the silver thin film 12. Thus, a sample in which the zinc oxide thin film 11 and the silver thin film 12 were sequentially laminated on the substrate 1 was prepared.

(Reference Comparative Example 1-4)
As shown in FIG. 6, a sample in which a silver thin film 12 was formed on a substrate 1 was produced. As the substrate 1, soda lime glass having a thickness of 1.1 mm was used. The silver thin film 12 was formed using the magnetron sputtering apparatus of FIG. 3 under the same silver thin film 12 deposition conditions as in Reference Example 1-1.

(Reference Comparative Example 1-5)
As shown in FIG. 5, a sample in which a tin oxide thin film 11 and a silver thin film 12 were sequentially laminated on a substrate 1 was produced. As the substrate 1, soda lime glass having a thickness of 1.1 mm was used. The tin oxide thin film 11 and the silver thin film 12 were formed using the magnetron sputtering apparatus shown in FIG. 3 as in Reference Example 1-1. In forming the tin oxide thin film 11, a Sn target is used as the target 8, the vacuum pump 4 is continuously operated, and oxygen gas is introduced from the gas introduction pipe 5 so that the pressure in the vacuum chamber 3 is increased. Was adjusted to 0.4 Pa. The maximum magnetic flux density at the center of the target when the tin oxide thin film 11 was formed was measured to be 92 mT. The film formation time was controlled so that the thickness of the tin oxide thin film was 37 nm.

Table 4 shows the film formation conditions of Reference Examples 1-1 to 1-3 and Comparative Reference Examples 1-1 to 1-5.

2-2. Evaluation of Sample The surface resistance Rs of the obtained sample was measured using a surface resistance measuring instrument (Napson, Resistest VIII). The emissivity ε of the sample was calculated from the surface resistance Rs using the following formula (reference: J. Szczyrbowski et al., New low emissivity coating based on TwinMagsputtered TiOTM2 and Si3N4 layers, Thin Solid Films, Vol.351, Issues. 1-2, 1999, p 254-259)
ε = 0.0129 × Rs−6.7 × 10−5 × Rs2

Further, the optical characteristics of each sample were measured using a self-recording spectrophotometer (Hitachi, U-4000). A refractive index n and an extinction coefficient k at a wavelength of 550 nm were calculated from the measured optical characteristics (transmittance, film surface reflectance).

Furthermore, X-ray diffraction measurement using CuKα rays was performed using an X-ray diffraction measurement device (RINT-UltimaIII, manufactured by Rigaku), and diffraction angles 2θ of zinc oxide and silver were determined by a general-purpose program attached to the device.

In order to investigate the surface roughness and packing density of the zinc oxide layer, X-ray reflectivity measurement was performed using an X-ray diffractometer on a single layer film of zinc oxide produced under the same conditions as in Examples 5 to 7 and Comparative Example 8. And the mean square roughness (Rms) and packing density of the surface of the zinc oxide thin film layer were measured. Rms and packing density were determined by a general purpose program attached to the apparatus. The measured packing density was divided by the maximum value of the packing density and calculated as a relative packing density.

Table 5 shows evaluation results of electrical characteristics, emissivity, and optical characteristics in the visible light region of Reference Examples 1-1 to 1-3 and Comparative Reference Examples 1-1 to 1-5. Tables 5 and 6 show the evaluation results of the optical characteristics, the X-ray diffraction measurement results, and the X-ray reflectivity measurement results with respect to solar radiation in Reference Examples 1-1 to 1-3 and Comparative Reference Examples 1-1 to 1-5. .

As shown in Tables 5 and 6, in all of the samples of Reference Examples 1-1 to 1-3, the X-ray diffraction angle 2θ of the zinc oxide thin film is 33.9 ° or less, and the X-ray diffraction angle 2θ of the silver thin film is It was 38.1 ° or more, indicating low surface resistance and low emissivity. Therefore, it can be said that the samples of Reference Examples 1-1 to 1-3 had high infrared reflectance corresponding to room heating heat and excellent heat insulation.

The samples of Reference Examples 1-1 to 1-3 had a high visible light reflectance and a low absorption rate. From this, it can be said that the formation of the oxide film exhibits an optical interference effect and can easily improve the visible light transmittance. Further, the samples of Reference Examples 1-1 to 1-3 had a small product of nk. Since the product of nk is proportional to the absorption coefficient of the material (“Asakura Shoten, Matsumura Atsushi, Physics Library 9 Optics (1983), first edition, pages 26-27”), Reference Examples 1-1-1 It can be said that the sample of -3 had a low optical absorptance.

In addition, since the samples of Reference Examples 1-1 to 1-3 had high solar radiation transmittance and low absorptance, the solar reflectance could be easily improved by slightly increasing the thickness of the silver thin film. It can be said.

Furthermore, the zinc oxide thin film layers of the samples of Reference Examples 1-1 to 1-3 had a small Rms and a high packing density. The smaller the Rms of the zinc oxide thin film layer, the lower the surface resistance of the silver thin film layer. Therefore, it can be said that the surface resistance of the silver thin film can be reduced by decreasing the Rms of the zinc oxide thin film layer.

On the other hand, in the samples of Comparative Reference Examples 1-1 to 1-3, the X-ray diffraction angle 2θ of the zinc oxide thin film is smaller than 33.9 °, and the X-ray diffraction angle 2θ of the silver thin film is larger than 38.1 °. High surface resistance. Due to this, the samples of Comparative Reference Examples 1-1 to 1-3 have poor heat insulation properties and higher absorption rates of visible light and solar radiation than the samples of Reference Examples 1-1 to 1-3. It was. Even in the samples of Reference Examples 1-4 and 1-5 that do not have a zinc oxide thin film, the surface resistance is high, and the heat insulation is worse than the samples of Reference Examples 1-1 to 1-3. The absorption rate of was high.

From the above results, even if the thickness of the silver thin film is increased, by making the X-ray diffraction angle 2θ of the zinc oxide thin film and the silver thin film within the above-mentioned preferable range, the visible light transmittance of the silver thin film can be increased and visible. It was confirmed that various performances such as visible light transmittance, heat insulation, and solar shading of the laminated article can be improved by reducing the light and solar absorptivity.

[Experiment 3]
3-1. Sample preparation (Reference Example 2-1)
As shown in FIG. 6, a sample having a silver thin film 12 on a substrate 1 was produced. As the substrate 1, soda lime glass having a thickness of 1.1 mm was used. The silver thin film 12 was formed using the magnetron sputtering apparatus shown in FIG. In this apparatus, a turbo molecular pump was used as the vacuum pump 4, a DC power source was used as the power source 10, and an Ag target was used as the target 8. A magnet 7 having a magnetic flux density of 57 mT at the center of the target was used. More specifically, the silver thin film 12 is formed by holding the glass substrate 1 on the substrate holder 2 and then evacuating the inside of the vacuum chamber 3 with the vacuum pump 4 while using the vacuum chamber 3 through the gas introduction pipe 5. Ar gas was introduced therein, and 200 W of power was supplied from the power source 10 through the power cable 9 to the Zn target 8 in the formed film formation atmosphere. During the film formation, the vacuum pump 4 was continuously operated, and the pressure in the vacuum chamber-3 during the film formation was adjusted to 0.5 Pa by the exhaust valve 6. The flow rate of oxygen gas was adjusted by a mass flow controller (not shown). When the maximum magnetic flux density at the center of the target by the magnet 7 during film formation was measured, it was 149 mT.

(Reference Example 2-2)
A sample having a silver thin film on a glass substrate was produced in the same manner as in Reference Example 1 except that the magnet 7 having a magnetic flux density of 91 mT at the target center was used.

3-2. Sample evaluation

For the samples of Reference Examples 2-1 and 2-2, the packing density of the silver thin film was determined by X-ray reflectivity measurement using an X-ray diffractometer. The packing density was measured by a general-purpose program attached to the apparatus, and calculated as a relative packing density obtained by dividing the measured packing density by the maximum value of the packing density. In addition, the residual stress of the silver thin film was calculated by a general-purpose program attached to the apparatus using the 2θ-sin2ψ drawing method applying X-ray diffraction measurement (reference: X-ray diffraction handbook, published by Rigaku Corporation) June 2003, 4th edition, pages 103-104). The optical system employed the parallel tilt method, and the diffraction line measurement employed the lattice plane normal constant method.

Table 7 shows the film formation conditions and evaluation results of Reference Examples 2-1 and 2-2.

According to Reference Examples 2-1 and 2-2, it was confirmed that by reducing the voltage applied to the Ag target, the packing density of the silver thin film was increased and the residual stress was decreased.

Although the present invention has been described based on specific embodiments, the present invention is not limited to the above embodiments, and includes various modifications and changes without departing from the spirit of the present invention. For example, although 1st Embodiment was formed as a glass laminated body using a glass substrate, you may form a laminated body article using a resin substrate instead of a glass substrate.

Claims

A glass substrate, and a thin film laminate formed on the glass substrate, wherein the thin film laminate comprises, in order from the substrate side, a first layer made of a dielectric, and a metal containing Ag as a main component. A second layer made of a dielectric, a third layer made of a dielectric, a fourth layer made of a metal containing Ag as a main component, and a fifth layer made of a dielectric. The total geometric thickness is 22 to 29 nm, the geometric thickness of the second layer is 0.3 to 0.8 times the geometric thickness of the fourth layer, and the first, third, fifth layers The total optical thickness is 220 to 380 nm, the optical thickness of the third layer is 140 to 200 nm, and the optical thickness of the first layer is 0.4 to 1.5 times the optical thickness of the fifth layer. The reflection color tone from the glass substrate side is characterized in that a * in the CIE における L * a * b * chromaticity coordinate diagram is less than 3 in an incident angle range of 0 ° to 60 °. , Scan laminate.
First, third, and fifth layers are zinc oxide, aluminum oxide, silicon oxide, titanium oxide, tantalum oxide, tin oxide, zirconium oxide, zinc-tin alloy oxide, silicon nitride, aluminum nitride, silicon oxynitride, oxynitride 2. The glass laminate according to claim 1, comprising a layer made of at least one dielectric selected from the group consisting of aluminum, titanium oxynitride, zirconium oxynitride, and tin oxynitride.
3. The glass laminate according to claim 1, wherein at least one of the second layer and the fourth layer is in contact with an oxide layer containing Zn as a main component of a cation metal on the substrate side.
The oxide layer containing Zn as the main component of the cation metal shows a diffraction peak due to the (002) crystal plane of zinc oxide by an X-ray diffraction method using CuKα rays, and the diffraction angle 2θ of the peak is 33. It is 9 degrees or less, The glass laminated body of any one of Claims 1 thru | or 3 characterized by the above-mentioned.
The second layer and the fourth layer made of a metal containing Ag as a main component have a diffraction angle 2θ of a diffraction peak due to a silver (111) crystal plane of 38.1 ° or more by an X-ray diffraction method using CuKα rays. The glass laminate according to claim 4, wherein
The glass laminate according to claim 5, wherein the thickness of each of the second layer and the fourth layer is 8 to 20 nm.
The glass laminate according to any one of claims 3 to 6, wherein the root mean square roughness Rms on the thin film surface of the oxide layer containing Zn as a main component of the cationic metal is 1.5 nm or less. body.
A multi-layer glass comprising the glass laminate according to any one of claims 1 to 7.