KR102040201B1 - Flexible low emissivity film with multilayered amorphous SilnZnO structure - Google Patents

Abstract

The present invention uses a multilayer amorphous silicon indium zinc oxide film structure in which an amorphous indium zinc oxide layer used as a base layer and a protective layer of a metal layer includes silicon, and a base layer, a metal layer, and a protective layer have a multilayer structure formed on a substrate. A flexible heat radiation prevention film, comprising: a flexible substrate; A first amorphous silicon indium zinc oxide layer formed on the flexible substrate as a base layer; A metal layer formed on the first amorphous silicon indium zinc oxide layer; And a second amorphous silicon indium zinc oxide layer formed as a protective layer on the metal layer. By providing a flexible thermal radiation prevention film using a multi-layer amorphous silicon indium zinc oxide film structure, the existing silver (Ag) -based crystalline transparent In the oxide multilayer thin film, a conventional amorphous silicon indium zinc oxide film free from grain boundaries, roughness, and defects according to the crystallinity of the base layer and the protective layer of silver (Ag) is used. Provided is a flexible thermal radiation preventing film using a multilayer amorphous silicon indium zinc oxide film structure having a thinner thickness than the Ag) layer and having high conductivity and low emissivity.

Description

Flexible low emissivity film with multilayered amorphous SilnZnO structure

The present invention relates to a heat radiation prevention film, and in particular, a base layer, a metal layer, and an upper layer are formed on a flexible substrate, and the upper layer is used as a base layer and a protective layer of the metal layer. The amorphous indium zinc oxide layer includes silicon. The present invention relates to a flexible heat radiation prevention film using a multilayer amorphous silicon indium zinc oxide film structure in which a base layer, a metal layer, and an upper layer are formed on a flexible substrate.

1A to 1C are cross-sectional views of a low emission substrate for blocking infrared radiation loss according to the prior art, and show various embodiments of a low emission substrate having a first metal oxide layer, a metal layer, and a second metal oxide layer formed on the metal substrate, respectively. It is.

First, the low-emissivity substrate shown in FIG. 1A is a first metal oxide layer made of a metal oxide coated on a glass substrate, and has a low emissivity and excellent heat resistance. The metal oxide is selected from antimony tin oxide (ATO), zinc oxide (ZnO), indium tin oxide (ITO), tin oxide (SnO ₂ ) or magnesium oxide (MgO).

The metal substrate used in the low-emission substrate according to the prior art shown in Figure 1a should not only have excellent heat dissipation, but also should use a material having excellent durability with low corrosion or thermal damage at high temperature heat generation, so that the metal substrate may be melt-deformed even at 300 ° C. A metal or alloy material having no metal is used, and usually, one metal selected from the group consisting of stainless steel, copper, aluminum, silver, and gold or an alloy composed of one or more metals is used.

The low-emission substrate according to the prior art is coated with a immersion coating method using a coating solution containing 1 to 10% by weight of the cleaned stainless steel ATO, ZnO, ITO, SnO ₂ or MgO or a mixture thereof and 230 to Prepared by heat treatment at 270 ℃.

The low-emission substrate shown in FIG. 1B is formed by sequentially coating and stacking a metal layer and a first metal oxide layer made of a metal oxide on the metal substrate. The metal material used as the base material of the low-emissivity substrate of FIG. 1b also has to be excellent in heat dissipation as well as the low-emission substrate shown in FIG. It is preferable to use a metal or alloy material having no melt deformation even at 300 ° C or higher. Silver (Ag) forming a metal layer is known to be effective in increasing the electrical conductivity and reducing the emissivity of the low-emissivity coating film. In consideration of the low radiation performance of the low-emissivity substrate, some elements such as Ni, Pd, Pt, Cu, or Au are added in an amount of 0.5 to 5 wt% to improve durability of the metal layer.

Since the low-emission substrate of FIG. 1B has a metal oxide layer formed on the metal layer, a layer for protecting oxidation or deterioration of the metal layer is not required. The low-emissivity substrate is coated with stainless steel using a bar coating method, which is a kind of wet coating method, using a coating liquid containing 1 to 10% by weight of ATO, ZnO, ITO, SnO ₂ or MgO or a mixture thereof. After the heat treatment at ℃ 270 ℃, a metal layer made of silver by a spray coating method is formed and heat treatment to increase the crystallinity of silver. Finally, the coating solution containing 1 to 10% by weight of the metal oxide is coated using the spray coating method.

The low-emission substrate shown in FIG. 1C is formed by sequentially coating and stacking a first metal oxide layer, a metal layer, and a second metal oxide layer, which are made of a metal oxide, on a metal substrate.

The second metal oxide layer serves to prevent the metal layer from being deteriorated or oxidized by the high temperature heat of the low emission substrate. The second metal oxide layer comprises at least one member selected from the group consisting of ATO, ZnO, ITO, SnO ₂ and MgO.

The low-emissivity substrate is coated with a bar coating method, which is a kind of wet coating method, with a coating liquid containing stainless steel in an amount of 1 to 10% by weight of ATO, ZnO, ITO, SnO ₂ or MgO, or a mixture thereof. After the heat treatment at 270 ℃, by forming a metal layer made of silver by the spray coating method and heat treatment to increase the crystallinity of the silver, and finally to protect the silver layer using a coating liquid containing 1 to 10% by weight of the metal oxide ( bar) it is prepared by coating.

The low-emissivity substrate shown in FIGS. 1A to 1C is generally manufactured by a wet coating method such as a dip coating method, a spray coating method, a bar coating method, and the like. The low-radiation substrate can produce an oxide film having excellent durability against erosion of water and gas, and has an advantage in producing a low-emission substrate having a large area, but by sputtering coating or vapor deposition. Compared with the formation of the low-emissivity coating film, there is a disadvantage that the thickness of the metal oxide layer is uneven.

FIG. 2 is a cross-sectional view of another conventional low emissivity film composed of three layers coated on glass, the substrate 1, the oxide film 2, the metal film 4A and Si, Ti, And zinc oxide film layers 4B and ZnO to which at least one is added in the group consisting of Cr, B, Mg, Sn and Ga.

Although the low emissivity film of FIG. 2 also has very fine spots observed in the film after the moisture resistance test, no remarkable white point or rare part is observed and has good moisture resistance, whereas the low emissivity film has a thickness to have high conductivity and low emissivity required. Too thick, there is a problem that the cost of energy efficiency increases.

In particular, the crystalline transparent multilayer film using the silver (Ag) heat insulating layer is due to the problems of grain boundaries, roughness, defects, etc. according to the crystallinity of the base layer and the protective layer. There is a limit to the thickness.

KR 10-2009-0099759 A (Published on September 23, 2009) KR 10-0299552 B1 (registered on June 11, 2001) KR 10-0763543 B1 (registered Sep. 27, 2007) KR 10-2014-0024416 A (released February 28, 2014) KR 10-1576517 B1 (registered Dec. 4, 2015)

An object of the present invention for solving the above problems is a grain boundary, roughness according to the crystallinity of the underlying layer and protective layer of silver (Ag) in the conventional silver (Ag) -based crystalline transparent oxide multilayer thin film Flexible using multi-layered amorphous silicon indium zinc oxide structure that can have high conductivity and low emissivity while using thinner amorphous silicon indium zinc oxide film free from defects, defects, etc. It is to provide a heat radiation prevention film.

In order to achieve the above object, a flexible thermal radiation prevention film using a multilayer amorphous silicon indium zinc oxide film structure according to the present invention includes a flexible substrate, comprising: a flexible substrate; A first amorphous silicon indium zinc oxide layer formed on the flexible substrate as a base layer; A metal layer formed on the first amorphous silicon indium zinc oxide layer (SIZO); And a second amorphous silicon indium zinc oxide layer formed on the metal layer as a protective layer.

In this case, in the flexible heat radiation prevention film using the multilayer amorphous silicon indium zinc oxide film structure according to the present invention, the content of silicon contained in each of the first and second amorphous silicon indium zinc oxide layers is 0.01-30 wt%. desirable.

In addition, in the flexible heat radiation prevention film using the multilayer amorphous silicon indium zinc oxide film structure according to the present invention, the metal layer is deposited by a thermal vapor deposition method or a sputtering method, the thickness of the metal layer is characterized in that 1nm to 20nm.

In addition, in the flexible thermal radiation prevention film using the multilayer amorphous silicon indium zinc oxide film structure according to the present invention, the metal layer is characterized by being made of any one of silver (Ag), copper (Cu), and aluminum (Al).

In addition, in the flexible thermal radiation prevention film using the multilayer amorphous silicon indium zinc oxide film structure according to the present invention, the first and second amorphous silicon indium zinc oxide layers are deposited by a sputtering method, and the first and second amorphous films. The thickness of the silicon indium zinc oxide layer is characterized in that 10nm to 1000nm.

In addition, in the flexible heat radiation prevention film using the multilayer amorphous silicon indium zinc oxide film structure according to the present invention, aluminum (Al), gallium (Ga), and hafnium (Hf) are formed on the first and second amorphous silicon indium zinc oxide layers. At least one element of zirconium (Zr), lithium (Li), potassium (K), titanium (Ti), germanium (Ge), and niobium (Nb) may be further included.

In addition, in the flexible heat radiation prevention film using the multilayer amorphous silicon indium zinc oxide film structure according to the present invention, the substrate is a polyimide (polyimide, PI), polyamide (PA), polyamide-imide (polyamide) -imide, polyurethane (PU), polyurethane acrylate (PUA), polyacrylamide (PA), polyethylene terephthalate (PET), polyether sulfone (PES), Polyethylene naphthalate (PEN), polycarbonate (PC), polymethylmethacrylate (PMMA), polyetherimide (PEI), polydimethylsiloxane (polydimethylsiloxane, PDMS), polyethylene (polyethylene, PE), polyvinyl alcohol (PVA), polystyrene (PS), biaxially oriented polystyrene (biaxially oriented PS, BOPS), acrylic Resin, characterized in that at least one of silicone resin, fluorine resin, modified epoxy resin.

Moreover, it is preferable to heat-process the flexible heat radiation prevention film | membrane using the multilayer amorphous silicon indium zinc oxide film structure which concerns on this invention at 50-900 degreeC.

As described above, the present invention provides a flexible thermal radiation prevention film structure using an amorphous silicon indium zinc oxide layer, so that the crystalline transparent multilayer film using the silver (Ag) heat insulating layer has a grain boundary depending on the crystallinity of the underlying layer and the protective layer. Solving the problem that the thickness of the silver (Ag) heat insulating layer was limited due to problems such as roughness, defects, etc., to provide high conductivity and low emissivity even at a thinner thickness than the conventional silver (Ag) layer. There is an advantage that can provide a thermal barrier that can have.

Accordingly, the present invention can achieve low cost, high energy efficiency and can be used as an eco-friendly technology.

In addition, the present invention can be easily attached on the existing glass by coating on a film substrate, there is an advantage that can be applied to a complex structure according to the flexible properties.

1A to 1C are cross-sectional views schematically showing low-emission substrates according to the prior art;
2 is a cross-sectional view schematically showing a low emissivity film according to the prior art,
3 is a perspective view of a flexible heat radiation prevention film using a multilayer amorphous silicon indium zinc oxide film structure according to the present invention;
4 is an AFM (atomic forced measurement) photograph according to the thickness of the multilayer amorphous silicon indium zinc oxide film of the flexible thermal radiation protection film according to the present invention,
5 is a graph showing the transmittance (transmittance) of the flexible heat radiation prevention film using a multilayer amorphous silicon indium zinc oxide film structure according to the present invention,
Figure 6 is a graph showing the resistance change according to the bending test (Bending test) of the flexible thermal radiation protection film according to the present invention.

Hereinafter, an embodiment of a flexible thermal radiation prevention film using a multilayer amorphous silicon indium zinc oxide film structure according to the present invention will be described in detail with reference to the accompanying drawings. The embodiments described below are provided to completely inform the scope of the invention to those skilled in the art, and the present invention may be implemented in various forms without being limited to the embodiments disclosed below.

Like configurations in the figures represent like reference numerals wherever possible. Specific details appear in the following description, which is provided to help a more general understanding of the present invention, and is not intended to limit the present invention to specific embodiments, and all modifications included in the spirit and technical scope of the present invention. It should be understood to include equivalents and substitutes. In the following description of the present invention, if 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.

Here, the accompanying drawings show an exaggerated or simplified part of the description and explanation for the structure and operation of the technology and for convenience and clarity, and it will be understood that each component does not exactly match the actual size.

Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

In addition, when a part includes a certain component, this means that the component may not include other components, but may further include other components unless specifically stated otherwise.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the dictionary generally used are defined in consideration of functions in the present invention, which should be construed as concepts consistent with the technical idea of the present invention and commonly understood or commonly recognized in the art. And, unless expressly defined in this application, is not to be construed in an ideal or excessively formal sense.

3 is a perspective view of a flexible heat radiation prevention film using a multilayer amorphous silicon indium zinc oxide film structure according to the present invention. Referring to FIG. 3, the flexible heat radiation prevention film according to the present invention is provided on a substrate 10 and a substrate 10. It may be configured to include a base layer 20, a heat insulating layer 30 on the base layer 20 and a protective layer 40 on the heat insulating layer 30.

In FIG. 3, the underlayer 20, the heat insulation layer 30, and the protective layer 40 are stacked on the substrate 10 once. However, the flexible thermal radiation prevention film according to another embodiment may be the underlayer 20. ), The heat insulating layer 30 and the protective layer 40 may have a repeating structure in which a plurality of times are repeatedly stacked.

The substrate 10 is a substrate on which a multilayer amorphous silicon indium zinc oxide (SIZO) structure of the flexible thermal radiation protection film according to an embodiment is stacked. For example, the type of the substrate 10 is not particularly limited, and for example, polyimide (PI), polyamide (PA), polyamide-imide, polyurethane, PU ), Polyurethane acrylate (PUA), polyacrylamide (PA), polyethylene terephthalate (PET), polyether sulfone (PES), polyethylene naphthalate (PEN), Polycarbonate (PC), polymethylmethacrylate (PMMA), polyetherimide (PEI), polydimethylsiloxane (PDMS), polyethylene (polyethylene, PE), polyvinyl alcohol ( Polyvinyl alcohol (PVA), polystyrene (PS), biaxially oriented polystyrene (BOPS), acrylic resin, silicone resin, fluorine resin, modified epoxy resin Smoke or plate, it may be glass or tempered glass. The substrate 10 may be washed before the base layer 20, the heat insulating layer 30, and the protective layer 40 are stacked.

The heat insulation layer 30 is a low-emissivity layer made of a metal layer, and has a low emissivity, thereby reducing the transmittance in the infrared region, thereby limiting heat transfer. For example, the heat insulation layer 30 may be a thin layer of silver (Ag). Deposition of the insulating layer 30 may be made by a sputtering method or a thermal evaporation (thermal evaporation). In one embodiment, the thickness of the thermal insulation layer 30 may be several nanometers to tens of nanometers. For example, the thickness of the heat insulation layer 30 may be about 1 nm to 20 nm.

The underlayer 20 may be formed of an amorphous silicon indium zinc oxide layer (SIZO) containing silicon (Si) in indium zinc oxide (InZnO). Here, the amorphous structure means a structure that is not a crystalline structure. In general, solids are roughly classified into crystalline and amorphous in their internal structure. In crystalline, while the arrangement of atoms or molecules has periodic regularity, amorphous generally lacks such regularity. Therefore, the amorphous can form a uniform and flat surface compared to the crystalline and is not affected by grain boundaries, roughness, defects. Therefore, by using the amorphous silicon indium zinc oxide layer (SIZO), the flexible thermal radiation prevention film according to an embodiment will be relatively thin, but can have a relatively high conductivity and low emissivity.

The amorphous silicon indium zinc oxide layer (SIZO) that is the base layer 20 may be deposited by a sputtering method. In one embodiment, the thickness of the underlying layer 20 may be several tens of nanometers to several hundred nanometers. For example, the thickness of the first amorphous silicon indium zinc oxide layer (SIZO) may be about 10 nm to 1000 nm.

The protective layer 40 serves to protect the heat insulating layer 30, and is a layer for improving abrasion resistance of the flexible thermal radiation preventing film according to an embodiment, and like the base layer 20, an amorphous silicon indium zinc oxide layer ( SIZO) allows the flexible thermal radiation protection film according to the embodiment to have high conductivity and low emissivity. In addition, the thickness of the protective layer 40 may be several tens of nanometers to several hundred nanometers. For example, the thickness of the protective layer 40 may be about 10nm to 1000nm. In this case, the thicknesses of the base layer 20 and the protective layer 40 may be the same or different from each other.

The produced amorphous silicon indium zinc oxide flexible thermal radiation prevention film may be subjected to a heat treatment process in the range of 50-900 ℃.

The manufacturing method of the flexible heat radiation prevention film which concerns on this invention is as follows.

First, it begins by forming the underlayer 20 on the substrate 10. The substrate 10 may be PI (polyimide). In this case, the base layer 20 may be stacked on the substrate 10 by using a sputtering method, and may be washed with the substrate 10 before the base layer 20 is formed.

After the base layer 20 is formed, a silver (Ag) layer is formed on the base layer 20 as the heat insulating layer 30. In this case, the heat insulation layer 30 may be formed by a sputtering method or a thermal evaporation method.

After the heat insulation layer 30 is formed, the protective layer 40 is formed on the heat insulation layer 30. The protective layer 40 may also be laminated using the sputtering method similarly to the base layer 20.

As such, each of the base layer 20 and the protective layer 40 stacked on the lower and upper portions of the heat insulating layer 30 is formed of a multilayer silicon indium zinc oxide layer (SIZO) having an amorphous structure, wherein the silicon content is 0.01-. It can be set as 30 wt%.

FIG. 4 is a view showing an atomic forced measurement (AFM) photograph of a multilayer amorphous silicon indium zinc oxide film structure of the flexible thermal radiation protection film according to the present invention, wherein a single amorphous constituting the flexible thermal radiation protection film using the AFM results shown in FIG. The roughness of the surface of the silicon indium zinc oxide film can be known. An AFM photograph captures the surface atomically to reveal the curvature of the surface. The curvature of the surface is zero when it is obtained through the mean, so it is difficult to obtain an accurate value for the actual curvature. Therefore, the root mean square (RMS) can be used to determine the actual roughness by averaging only the upper part rather than the lower part based on zero. In FIG. 4, it can be seen that the square mean of the amorphous silicon indium zinc oxide single layer of the flexible thermal radiation protection film according to the embodiment has a substantially flat surface of less than 0.1 nm. These results show that they can be less affected by grain boundaries, roughness, and defects than existing crystalline oxide layers used as base layers and protective layers.

5 is a graph showing the transmittance of the flexible thermal radiation prevention film using the multilayer amorphous silicon indium zinc oxide film structure according to the present invention, using a silver (Ag) layer as the heat insulating layer 30 and the base layer 20 and The result of measuring the flexible heat radiation prevention film which consists of an amorphous silicon indium zinc oxide (SIZO) layer containing silicon as the protective layer 40 is shown. 5 is a transmittance of the multilayer amorphous silicon indium zinc oxide film structure when the silver (Ag) layer 30 has a thickness of 3 nm, 5 nm, 7 nm, 9 nm, 11 nm, 13 nm, and 15 nm, respectively. Referring to FIG. 5, since the transmittance is about 80% or more in the visible light region of 380 to 780 nm, the transmittance is visually transparent and the transmittance gradually decreases toward the longer wavelength of the infrared region. It can be seen that the multilayer amorphous indium zinc oxide film structure of the flexible heat radiation prevention film according to the present invention plays a role of preventing heat radiation.

FIG. 6 is a graph illustrating a resistance change according to a bending test of a flexible thermal radiation prevention film using a multilayer amorphous silicon indium zinc oxide film structure according to the present invention.

As shown in FIG. 6, it can be seen that there is almost no resistance change according to the number of bending tests, so that the oxide / metal / oxide structure is not destroyed, and the mechanical flexibility is excellent, and thus the level is sufficiently applicable to the flexible substrate. Can be.

Table 1 below shows the results of the resistance change according to the bending test of the heat radiation prevention film using the multilayer amorphous silicon indium zinc oxide film structure according to the present invention.

Meanwhile, in the above-described exemplary embodiment, only a multilayer structure in which the base layer 20, the heat insulating layer 30, and the protective layer 40 are stacked on the substrate is illustrated once, but according to another exemplary embodiment, the flexible thermal radiation protection film A multi-layered structure in which the silver base layer 20, the heat insulation layer 30, and the protective layer 40 are repeatedly stacked several times may be repeatedly formed.

As described above, the flexible thermal radiation prevention film using the multilayer amorphous silicon indium zinc oxide film structure according to the present invention can be easily attached onto existing glass by coating on a film substrate.

In addition, the flexible heat radiation prevention film using the multilayer amorphous silicon indium zinc oxide film structure according to the present invention provides a flexible heat radiation prevention film structure using the amorphous silicon indium zinc oxide layer, thereby providing a crystalline transparent multilayer film using a silver (Ag) heat insulating layer. Solving the problem that the thickness of the Ag (Ag) heat insulating layer was limited due to problems such as grain boundaries, roughness, and defects according to the crystallinity of the base layer and the protective layer, It is possible to provide a thermal barrier that can have high conductivity and low emissivity even at a thickness thinner than the Ag) layer, and thus can be used as an eco-friendly technology while achieving low cost and high energy efficiency.

On the other hand, in the detailed description of the present invention has been described in detail with reference to the preferred embodiment referenced by the accompanying drawings, various modifications are possible without departing from the scope of the invention. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the scope of the following claims, but also by the equivalents of the claims.

Claims (8)

In the heat radiation prevention film forming a multilayer structure,
Flexible substrate;
A first amorphous silicon indium zinc oxide layer formed on the flexible substrate as a base layer;
A metal layer formed on the first amorphous silicon indium zinc oxide layer (SIZO); And
And a second amorphous silicon indium zinc oxide layer formed on the metal layer as a protective layer.
The flexible substrate is a polyimide (PI), polyamide (polyamide, PA), polyamide-imide, polyurethane (PU), polyurethane acrylate (polyurethaneacrylate, PUA), Polyacrylamide (PA), polyethylene terephthalate (PET), polyether sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), polymethylmethacryl Polymethylmethacrylate (PMMA), polyetherimide (PEI), polydimethylsiloxane (PDMS), polyethylene (PE, PE), polyvinyl alcohol (PVA), polystyrene (PS) , Biaxially oriented polystyrene (BOPS), acrylic resin, silicone resin, fluorine resin, modified epoxy resin,
The first and second amorphous silicon indium zinc oxide layers are deposited with a thickness of 10 nm to 1000 nm by a sputtering method, and the content of silicon contained in the first and second amorphous silicon indium zinc oxide layers is 0.01 to 30 wt%, respectively. , Lithium (Li), potassium (K), titanium (Ti), germanium (Ge), and niobium (Nb) at least any one of the elements further,
The metal layer is any one of silver (Ag), copper (Cu), and aluminum (Al), and is deposited at a thickness of 1 nm to 20 nm by thermal evaporation or sputtering.
The heat radiation prevention film having the multilayer structure is a flexible heat radiation prevention film using a multi-layer amorphous silicon indium zinc oxide film structure, characterized in that formed by heat treatment at 50 ~ 900 ℃. delete delete delete delete delete delete delete

Images