A kind of flat surface infrared reflection self-regulating coated glass

Abstract

The application discloses a kind of flat surface infrared reflection self-regulation control coated glass, it is related to coated glass technical field.Flat surface infrared reflection self-regulation control coated glass includes: flat or curved surface substrate;Electrochromic control stack is arranged on the one side of substrate, at least including sequentially arranged first transparent conductive film layer, electrochromic film layer, electrolyte film layer, ion storage film layer and second transparent conductive film layer from the side close to substrate;And high reflection film layer is arranged on the side of electrochromic control stack away from substrate.By applying voltage to change the coloring state of electrochromic film layer, it can be self-regulation control between infrared reflection enhancement mode and infrared absorption mode, and the coated glass is substantially not permeable to visible light in coloring state.The application can be applied to harsh environment such as space satellite, realize dynamic management to infrared radiation and visible light shielding, with the advantages of flexible control, strong environmental adaptability and the like.

Description

Technical Field

[0001] This invention relates to the field of coated glass technology, and in particular to a coated glass with self-regulating infrared reflection on a flat or curved surface. Background Technology

[0002] With the rapid development of aerospace satellite technology, the intense infrared radiation (especially far-infrared), high-energy particles, and ultraviolet radiation in the space environment pose severe challenges to the performance and lifespan of optical devices such as satellite power-generating glass. Traditional coated glass typically employs a single, fixed infrared reflection or absorption structure, making it difficult to achieve dynamic and autonomous thermal control management in the complex and ever-changing space environment. In particular, intense light and harmful rays can accelerate material aging and even damage devices. Therefore, developing infrared reflection / absorption glass with autonomous control capabilities has become a current research hotspot.

[0003] There are already various multilayer film coated glass solutions in the existing technology. For example, Chinese patent CN106746734A discloses a high infrared reflectance coated glass, the structure of which includes an ITO layer, a Nb2O5 layer, an AZO layer, an Ag layer, a Ti layer, and a TiO layer sequentially disposed on a glass substrate. x The glass consists of a layer of glass and a Si3N4 layer. It boasts high visible light transmittance (over 60%) and infrared reflectance (over 99%), primarily used in building energy conservation to prevent heat from entering the interior through the glass. However, the infrared reflectance of this solution is fixed and cannot actively switch to infrared absorption mode according to environmental requirements. Furthermore, its design objective of high visible light transmittance makes it unsuitable for space environments requiring low visible light transmittance (such as light shielding).

[0004] Chinese patent CN112987435B discloses a flexible electrochromic device, the structure of which includes a flexible transparent substrate, a transparent electrode, an electrochromic layer, a barrier layer, a quasi-solid electrolyte layer, and an ion storage layer stacked sequentially. This device can dynamically adjust the visible light transmittance through the electrochromic effect, and is mainly used in flexible displays or smart windows. However, it primarily targets the visible light band for control, and the device typically requires a wide range of visible light transmittance variations; furthermore, it is not specifically designed for the infrared band, nor does it incorporate a high-reflectivity layer to achieve autonomous switching between infrared reflection and absorption.

[0005] In summary, there is currently a lack of coated glass that can achieve extremely low visible light transmittance (basically opaque) in the colored state and can actively adjust the infrared reflection intensity according to the external environment or internal needs (switching between strong reflection and strong absorption), which is especially suitable for thermal control and radiation protection in harsh environments such as space satellites. Summary of the Invention

[0006] The purpose of this invention is to provide a coated glass that has extremely low visible light transmittance in a colored state and can autonomously adjust the infrared reflection / absorption mode, so as to adapt to the harsh environment of flat and curved surface infrared reflection autonomously adjustable coated glass in space satellites and other environments.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A planar or curved infrared reflection self-regulating coated glass, comprising: a planar or curved substrate; an electrochromic control stack disposed on one side of the substrate, the electrochromic control stack comprising, starting from the side closest to the substrate, at least sequentially disposed a first transparent conductive film layer, an electrochromic film layer, an electrolyte film layer, an ion storage film layer, and a second transparent conductive film layer; and a high-reflectance film layer disposed on the side of the electrochromic control stack opposite to the substrate. A dielectric spacer layer is disposed between the high-reflectivity film layer and the electrochromic modulation stack. The optical thickness of the dielectric spacer layer is configured such that the effective absorption coefficient k of the electrochromic film layer in the 780nm-2500nm band is less than 0.1 in the bleached state, so that infrared radiation in this band passes through the electrochromic modulation stack and reaches the high-reflectivity film layer and is reflected back to the incident side; while when the electrochromic film layer in the stained state has k>0.3 for the same band, the infrared radiation is absorbed by the electrochromic film layer before reaching the high-reflectivity film layer. The coated glass changes the coloring state of the electrochromic film by applying voltage, so as to autonomously control between the infrared reflection enhancement mode and the infrared absorption mode; and when in the coloring state, the visible light transmittance of the coated glass is extremely low, and it basically does not transmit visible light.

[0008] Furthermore, the flat-curved infrared reflection self-regulating coated glass also includes a dielectric film layer, an ultraviolet isolation film layer, and / or an infrared regulation film layer disposed between the substrate and the electrochromic regulation stack; the material of the ultraviolet isolation film layer is selected from at least one of titanium oxide, zinc oxide, or iron oxide; the infrared regulation film layer is a Raman scattering layer or a tungsten oxide layer.

[0009] Furthermore, the self-regulating infrared reflection coated glass with a flat and curved surface also includes an optical control film, a dielectric passivation film, and / or a dielectric barrier film disposed between the second transparent conductive film and the high reflectivity film; the material of the optical control film is selected from at least one of titanium oxide TiOx, silicon nitride SiNx, silicon oxynitride SiNxOy, zinc oxide ZnOx, zinc aluminum oxide ZnAlOx, tin oxide SnOx, zinc tin oxide ZnSnOx, or aluminum-doped zinc oxide AZO; the material of the dielectric passivation film is selected from at least one of titanium nitride, silicon nitride, or silicon oxynitride; the dielectric barrier film is used to block the migration of sodium ions in the substrate.

[0010] Furthermore, the flat-curved infrared reflection self-regulating coated glass also includes a wear-resistant hardening film layer and / or an inorganic ceramic protective film layer disposed on the side of the high-reflectivity film layer away from the substrate; the material of the wear-resistant hardening film layer includes silicon oxide; the material of the inorganic ceramic protective film layer is selected from at least one of alumina, titanium oxide or magnesium fluoride.

[0011] Furthermore, the material of the high-reflectivity film layer is selected from at least one of aluminum, silver, gold, or palladium; the material of the first transparent conductive film layer and / or the second transparent conductive film layer is selected from at least one of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), or aluminum-doped zinc oxide (AZO); the material of the electrochromic film layer is selected from at least one of tungsten oxide, molybdenum oxide, niobium pentoxide, or titanium dioxide; the electrolyte film layer is an electrolyte layer used for conducting ions; and the material of the ion storage film layer is selected from at least one of nickel oxide, iridium oxide, or manganese oxide.

[0012] Furthermore, the planar or curved substrate is a planar or 3D curved polymer substrate, and the material of the planar or 3D curved polymer substrate is selected from any one of glass, plexiglass, polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), or polyimide (PI).

[0013] Furthermore, when a first voltage is applied to put the electrochromic film layer in a faded state, the high-reflectivity film layer dominates infrared reflection, achieving an infrared reflection enhancement mode; when a second voltage is applied to put the electrochromic film layer in a colored state, the electrochromic film layer dominates infrared absorption, achieving an infrared absorption mode.

[0014] Furthermore, an ion migration barrier layer is provided between the electrochromic control stack and the high-reflectivity film layer, which is used to isolate the interfaces between the two; wherein, after the electrochromic device is subjected to a temperature cycling test from -65°C to +120°C, the adhesion between the film layers is not less than 88%.

[0015] Compared with the prior art, the present invention has the following beneficial effects: (1) Excellent visible light shielding: The coated glass of the present invention maintains extremely low visible light transmittance (basically no visible light transmittance) in the colored state, which is particularly suitable for environments such as space satellites that need to shield visible light and harmful light.

[0016] (2) Autonomous control of infrared reflection / absorption: Through the reversible coloring / fading change of the electrochromic layer, combined with the synergistic effect of the high reflectivity film, the “infrared reflection enhancement mode” or “infrared absorption mode” can be actively selected according to environmental needs, so as to realize the dynamic control of infrared radiation and effectively cope with the threat of scorching light and far-infrared radiation in the space environment.

[0017] (3) Multifunctional film layer integration: The present invention simultaneously sets up an ultraviolet isolation film layer, an infrared modulation film layer, a dielectric barrier layer, a wear-resistant hardening layer and an inorganic ceramic protective layer, which can effectively isolate ultraviolet rays, block sodium ion migration, improve the weather resistance and mechanical strength of the film layer, and extend the service life of the device.

[0018] (4) Plane or curved surface: This invention can be deposited on glass, plexiglass and various polymer substrates, and is applicable to planar and three-dimensional curved surface structures, which can meet the irregular surface requirements of different components of spacecraft.

[0019] (5) Solving the problem of satellite thermal control: This invention provides a new thermal control and radiation protection solution for optical devices such as power generation glass in space satellites. By actively switching the infrared reflection / absorption state, the operating temperature of the device and the infrared radiation load can be precisely adjusted, thereby improving the reliability and lifespan of the satellite system. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a schematic diagram of the structure of the present invention.

[0022] Among them, 1 is the substrate; 2 is the dielectric film layer; 3 is the ultraviolet isolation film layer; 4 is the infrared modulation film layer; 5 is the first transparent conductive film layer; 6 is the electrochromic film layer; 7 is the electrolyte film layer; 8 is the ion storage film layer; 9 is the second transparent conductive film layer; 10 is the optical modulation film layer; 11 is the dielectric passivation film layer; 12 is the dielectric barrier film layer; 13 is the high reflectivity film layer; 14 is the wear-resistant hardening film layer; 15 is the inorganic ceramic protective film layer; and 16 is the dielectric film layer. Detailed Implementation

[0023] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0025] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0026] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0027] The terms "first" and "second" are used for descriptive purposes only, to distinguish objects, such as substances, from one another, and should not be construed as indicating or implying relative importance or implicitly specifying the diameter of the indicated technical features. For example, without departing from the scope of the embodiments of this application, "first XX" may also be referred to as "second XX," and similarly, "second XX" may also be referred to as "first XX." Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of that feature.

[0028] In this invention, the electrochromic control stack refers to a stack structure that, starting from the side closest to the substrate, includes at least a first transparent conductive film layer 5, an electrochromic film layer 6, an electrolyte film layer 7, an ion storage film layer 8, and a second transparent conductive film layer 9 arranged sequentially. This stack can actively control infrared reflection / absorption by applying a voltage to change the coloring state of the electrochromic film layer.

[0029] An embodiment of this application discloses a planar or curved infrared reflection self-regulating coated glass, comprising: a planar or curved substrate 1; an electrochromic control stack disposed on one side of the substrate 1, the electrochromic control stack including at least a first transparent conductive film layer 5, an electrochromic film layer 6, an electrolyte film layer 7, an ion storage film layer 8, and a second transparent conductive film layer 9 disposed sequentially from the side closest to the substrate; and a high-reflectance film layer 13 disposed on the side of the electrochromic control stack facing away from the substrate. A dielectric spacer layer 16 is disposed between the high-reflectivity film layer 13 and the electrochromic modulation stack. The optical thickness of the dielectric spacer layer 16 is configured such that the effective absorption coefficient k of the electrochromic film layer 6 in the fading state for the 780nm-2500nm band is less than 0.1, so that infrared radiation in this band passes through the electrochromic modulation stack and reaches the high-reflectivity film layer 13 and is reflected back to the incident side; while when the electrochromic film layer 6 in the colored state has k>0.3 for the same band, the infrared radiation is absorbed by the electrochromic film layer 6 before reaching the high-reflectivity film layer 13. The coated glass changes the coloring state of the electrochromic film layer 6 by applying voltage, so as to autonomously regulate between the infrared reflection enhancement mode and the infrared absorption mode; and when in the coloring state, the visible light transmittance of the coated glass is extremely low, and it basically does not transmit visible light.

[0030] In some embodiments, the flat-curved infrared reflection self-regulating coated glass further includes a dielectric film layer 2, an ultraviolet isolation film layer 3, and / or an infrared regulation film layer 4 disposed between the substrate and the electrochromic regulation stack; the material of the ultraviolet isolation film layer 3 is selected from at least one of titanium oxide, zinc oxide, or iron oxide; the infrared regulation film layer 4 is a Raman scattering layer or a tungsten oxide layer.

[0031] In some embodiments, the self-regulating infrared reflection coated glass with a flat and curved surface further includes an optical control film layer 10, a dielectric passivation film layer 11, and / or a dielectric barrier film layer 12 disposed between the second transparent conductive film layer 9 and the high reflectivity film layer 13; the material of the optical control film layer 10 is selected from at least one of titanium oxide TiOx, silicon nitride SiNx, silicon oxynitride SiNxOy, zinc oxide ZnOx, zinc aluminum oxide ZnAlOx, tin oxide SnOx, zinc tin oxide ZnSnOx, or aluminum-doped zinc oxide AZO; the material of the dielectric passivation film layer 11 is selected from at least one of titanium nitride, silicon nitride, or silicon oxynitride; the dielectric barrier film layer 12 is used to block the migration of sodium ions in the substrate.

[0032] In some embodiments, the flat-curved infrared reflection self-regulating coated glass further includes a wear-resistant hardening film layer 14 and / or an inorganic ceramic protective film layer 15 disposed on the side of the high-reflectivity film layer 13 away from the substrate 1; the material of the wear-resistant hardening film layer 14 includes silicon oxide; the material of the inorganic ceramic protective film layer 15 is selected from at least one of alumina, titanium oxide or magnesium fluoride.

[0033] In some embodiments, the material of the high-reflectivity film layer 13 is selected from at least one of aluminum, silver, gold or palladium; the material of the first transparent conductive film layer and / or the second transparent conductive film layer is selected from at least one of indium tin oxide (ITO), fluorine-doped tin oxide (FTO) or aluminum-doped zinc oxide (AZO); the material of the electrochromic film layer 6 is selected from at least one of tungsten oxide, molybdenum oxide, niobium pentoxide or titanium dioxide; the electrolyte film layer 7 is an electrolyte layer; and the material of the ion storage film layer 8 is selected from at least one of nickel oxide, iridium oxide or manganese oxide.

[0034] In some embodiments, the planar or curved substrate is a planar or 3D curved polymer substrate, and the material of the planar or 3D curved polymer substrate 1 is selected from any one of glass, plexiglass, polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), or polyimide (PI).

[0035] In some embodiments, when a first voltage is applied to cause the electrochromic film layer 6 to be in a faded state, the high-reflectivity film layer 13 dominates infrared reflection, achieving an infrared reflection enhancement mode; when a second voltage is applied to cause the electrochromic film layer 6 to be in a colored state, the electrochromic film layer 6 dominates infrared absorption, achieving an infrared absorption mode.

[0036] In some embodiments, an ion migration barrier layer is disposed between the electrochromic control stack and the high-reflectivity film layer, the ion migration barrier layer being used to isolate the interfaces between the two; wherein, after the electrochromic device undergoes a temperature cycling test from -65°C to +120°C, the adhesion between the film layers is not less than 88%.

[0037] Example 1 like Figure 1 As shown, the present invention discloses a planar curved infrared reflectance self-regulating coated glass, which, from the substrate 1 outwards, comprises: a planar substrate 1, a dielectric film layer 2, an ultraviolet isolation film layer 3, an infrared regulation film layer 4, an electrochromic regulation stack, an optical regulation film layer 10, a dielectric passivation film layer 11, a dielectric blocking film layer 12, a high reflectance film layer 13, a wear-resistant hardening film layer 14, and an inorganic ceramic protective film layer 15.

[0038] An electrochromic control stack is composed of the following five layers stacked in sequence: a first transparent conductive film layer 5, an electrochromic film layer 6, an electrolyte film layer 7, an ion storage film layer 8, and a second transparent conductive film layer 9. The planar substrate 1 is made of glass. The ultraviolet isolation film 3 is made of titanium oxide; the infrared modulation film 4 is a Raman scattering layer. The first transparent conductive film 5 is made of indium tin oxide (ITO); the electrochromic film 6 is made of tungsten oxide; the electrolyte film 7 is an electrolyte layer; the ion storage film 8 is made of nickel oxide; and the second transparent conductive film 9 is made of fluorine-doped tin oxide (FTO).

[0039] The optical modulation film 10 is made of titanium oxide (TiOx); the dielectric passivation film 11 is made of titanium nitride; the dielectric barrier film 12 is used to block the migration of sodium ions in the substrate. The high reflectivity film 13 is made of aluminum; the wear-resistant hardening film 14 is made of silicon oxide; and the inorganic ceramic protective film 15 is made of a mixture of two of aluminum oxide and magnesium fluoride.

[0040] A dielectric spacer layer is disposed between the high-reflectivity film layer and the electrochromic modulation stack. The optical thickness of the dielectric spacer layer is configured such that the effective absorption coefficient k of the electrochromic film layer in the 780nm-2500nm band is less than 0.1 in the bleached state, so that infrared radiation in this band passes through the electrochromic modulation stack and reaches the high-reflectivity film layer and is reflected back to the incident side; while when the electrochromic film layer in the stained state has k>0.3 for the same band, the infrared radiation is absorbed by the electrochromic film layer before reaching the high-reflectivity film layer. The coated glass changes the coloring state of the electrochromic film layer 6 by applying voltage, so as to autonomously regulate between the infrared reflection enhancement mode and the infrared absorption mode; and when in the coloring state, the visible light transmittance of the coated glass is extremely low, and it basically does not transmit visible light.

[0041] An ion migration barrier layer is disposed between the electrochromic control stack and the high reflectivity film layer, and the ion migration barrier layer is used to isolate the interfaces between the two; wherein, after the electrochromic device is subjected to temperature cycling test from -65℃ to +120℃, the adhesion between the film layers is not less than 88%.

[0042] When a first voltage is applied to put the electrochromic film layer in a faded state, the high-reflectivity film layer 13 dominates infrared reflection, achieving an infrared reflection enhancement mode; when a second voltage is applied to put the electrochromic film layer 6 in a colored state, the electrochromic film layer 6 dominates infrared absorption, achieving an infrared absorption mode.

[0043] Brief description of the preparation method: Each film layer is deposited sequentially by magnetron sputtering, and the sputtering atmosphere and power supply type are selected according to the target material.

[0044] Control method: A DC voltage is applied by connecting the first transparent conductive film layer 5 and the second transparent conductive film layer 9 through a wire.

[0045] When a first voltage (negative voltage, e.g., -1.5V) is applied, the electrochromic film layer (WO3) oxidizes and fades, restoring its transparent state. At this time, the high-reflectivity film layer 13 (aluminum) becomes the main infrared modulation layer, reflecting infrared radiation and entering the infrared reflection enhancement mode.

[0046] When a second voltage (a positive voltage, such as +1.5V, which is positive relative to the ion storage layer) is applied, the electrochromic film layer (WO3) undergoes a reduction reaction, changing from colorless and transparent to deep blue (colored state). At this time, the electrochromic film layer strongly absorbs infrared radiation and enters the infrared absorption mode.

[0047] Example 2 The difference between Example 2 and Example 1 is as follows: the ultraviolet isolation film 3 is made of zinc oxide; the infrared modulation film 4 is made of tungsten oxide. The optical modulation film 10 is made of silicon nitride (SiNx); the dielectric passivation film 11 is made of silicon nitride. The inorganic ceramic protective film 15 is made of aluminum oxide. The high-reflectivity film 13 is made of silver; the first transparent conductive film 5 is fluorine-doped tin oxide (FTO); the second transparent conductive film 9 is made of indium tin oxide (ITO); the electrochromic film 6 is made of molybdenum oxide; the ion storage film 8 is made of iridium oxide. The planar substrate 1 is made of plexiglass.

[0048] Example 3 The difference between Example 3 and Example 1 is that: the material of the ultraviolet isolation film 3 is iron oxide; the material of the optical modulation film 10 is silicon oxynitride (SiNxOy); the material of the dielectric passivation film 11 is silicon oxynitride; the material of the inorganic ceramic protective film 15 is titanium oxide; and the material of the high-reflectivity film 13 is gold. The first transparent conductive film layer 5 is made of aluminum-doped zinc oxide (AZO); the second transparent conductive film layer 9 is also made of aluminum-doped zinc oxide (AZO); the electrochromic film layer 6 is made of niobium pentoxide; and the ion storage film layer 8 is made of manganese oxide. The planar substrate 1 is made of polyethylene terephthalate (PET).

[0049] Example 4 The difference between Example 4 and Example 1 is that: the material of the ultraviolet blocking film 3 is a mixture of iron oxide and zinc oxide; the material of the optical modulation film 10 is a mixture of zinc oxide (ZnOx) and silicon oxynitride (SiNxOy); the material of the inorganic ceramic protective film 15 is a mixture of magnesium fluoride and titanium oxide; and the material of the high reflectivity film 13 is a mixture of palladium and silver. The first transparent conductive film layer 5 is a mixture of fluorine-doped tin oxide (FTO) and aluminum-doped zinc oxide (AZO); the second transparent conductive film layer 9 is a mixture of fluorine-doped tin oxide (FTO) and indium tin oxide (ITO); the electrochromic film layer 6 is made of titanium dioxide; and the ion storage film layer 8 is made of iridium oxide. The planar substrate 1 is made of polycarbonate (PC).

[0050] Example 5 The difference between Example 5 and Example 1 is that: the high-reflectivity film layer 13 is made of a mixture of gold and aluminum; the electrochromic film layer 6 is made of a mixture of titanium dioxide and molybdenum oxide; the ion storage film layer 8 is made of a mixture of nickel oxide and iridium oxide; the optical modulation film layer 10 is made of zinc aluminum oxide (ZnAlOx); and the planar substrate 1 is made of polymethyl methacrylate (PMMA).

[0051] Example 6 The difference between Example 6 and Example 1 is that the material of the optical control film 10 is a mixture of tin oxide SnOx and zinc aluminum oxide ZnAlOx; and the material of the planar substrate 1 is polyimide PI.

[0052] Example 7 The difference between Example 7 and Example 1 is that the material of the optical control film 10 is selected from zinc tin oxide (ZnSnOx).

[0053] Example 8 The difference between Example 8 and Example 1 is that the material of the optical control film 10 is aluminum-doped zinc oxide (AZO).

[0054] Example 9 The difference between Example 9 and Example 1 is that the flat-curved infrared reflection self-regulating coated glass further includes a dielectric film layer 2 and an ultraviolet isolation film layer 3 disposed between the substrate 1 and the electrochromic control stack; the infrared control film layer 4 is not disposed. The material of the ultraviolet isolation film layer 3 is titanium oxide; The flat-curved infrared reflection self-regulating coated glass also includes an optical regulation film layer 10 and a dielectric passivation film layer 11 disposed between the second transparent conductive film layer 9 and the high reflectivity film layer 13; no dielectric blocking film layer 12 is disposed.

[0055] The material of the optical control film 10 is titanium oxide (TiOx); the material of the dielectric passivation film 11 is titanium nitride.

[0056] The flat-curved infrared reflection self-regulating coated glass also includes a wear-resistant and hardened film layer 14 disposed on the side of the high-reflectivity film layer 13 away from the substrate; no inorganic ceramic protective film layer 15 is disposed.

[0057] The wear-resistant and hardened film layer 14 is made of silicon dioxide.

[0058] Example 10 The difference between Example 10 and Example 9 is that the material of the ultraviolet isolation film 3 is zinc oxide; the material of the optical control film 10 is silicon nitride (SiNx); and the material of the dielectric passivation film 11 is silicon nitride.

[0059] Example 11 The difference between Example 11 and Example 9 is that the material of the ultraviolet isolation film 3 is iron oxide; the material of the optical control film 10 is silicon oxynitride (SiNxOy); and the material of the dielectric passivation film 11 is silicon oxynitride.

[0060] Example 12 The difference between Example 12 and Example 9 is that the material of the optical control film 10 is zinc oxide (ZnOx).

[0061] Example 13 The difference between Example 13 and Example 9 is that the material of the optical control film 10 is zinc aluminum oxide (ZnAlOx).

[0062] Example 14 The difference between Example 14 and Example 9 is that the material of the optical control film 10 is tin oxide (SnOx).

[0063] Example 15 The difference between Example 15 and Example 9 is that the material of the optical control film 10 is zinc tin oxide (ZnSnOx).

[0064] Example 16 The difference between Example 16 and Example 9 is that the material of the optical control film 10 is aluminum-doped zinc oxide (AZO).

[0065] Example 17 The difference between Example 17 and Example 1 is that the flat-curved infrared reflection self-regulating coated glass further includes a dielectric film layer 2 and an infrared regulation film layer 4 disposed between the substrate 1 and the electrochromic regulation stack; the ultraviolet regulation film layer 3 is not disposed. The infrared regulation film layer 4 is a tungsten oxide layer.

[0066] The flat-curved infrared reflection self-regulating coated glass also includes an optical regulation film layer 10 and a dielectric barrier film layer 12 disposed between the second transparent conductive film layer 9 and the high reflectivity film layer 13; no dielectric passivation film layer 11 is disposed.

[0067] The material of the optical control film 10 is titanium oxide (TiOx).

[0068] The flat-curved infrared reflection self-regulating coated glass also includes an inorganic ceramic protective film layer 15 disposed on the side of the high-reflectivity film layer 13 facing away from the substrate; no wear-resistant hardening film layer 14 is disposed. The material of the inorganic ceramic protective film layer 15 is alumina.

[0069] Example 18 The difference between Example 18 and Example 17 is that the infrared modulation film layer 4 is a Raman scattering layer.

[0070] The material of the optical control film 10 is silicon nitride (SiNx); the material of the inorganic ceramic protective film 15 is aluminum oxide.

[0071] Example 19 The difference between Example 19 and Example 17 is that: the infrared modulation film 4 is a Raman scattering layer; the material of the optical modulation film 10 is silicon oxynitride SiNxOy; and the material of the inorganic ceramic protective film 15 is titanium oxide.

[0072] Example 20 The difference between Example 20 and Example 17 is that the material of the optical control film 10 is zinc oxide (ZnOx); and the material of the inorganic ceramic protective film 15 is a mixture of magnesium fluoride and titanium oxide.

[0073] Example 21 The difference between Example 21 and Example 17 is that the material of the optical control film 10 is zinc aluminum oxide (ZnAlOx), and the material of the inorganic ceramic protective film 15 is magnesium fluoride.

[0074] Example 22 The difference between Example 22 and Example 17 is that the material of the optical control film 10 is tin oxide (SnOx).

[0075] Example 23 The difference between Example 23 and Example 17 is that the material of the optical control film 10 is zinc tin oxide (ZnSnOx).

[0076] Example 24 The difference between Example 24 and Example 17 is that the material of the optical control film 10 is aluminum-doped zinc oxide (AZO).

[0077] Example 25 The difference between Example 25 and Example 1 is that: Substrate 1: is made of 3D curved polymethyl methacrylate (PMMA, i.e., plexiglass), or other polymers such as PET, PC, PI.

[0078] To accommodate curved surfaces and organic materials, sputtering process parameters are appropriately adjusted, such as lowering the temperature and increasing ion source assistance. The ultraviolet isolation layer 3 is zinc oxide (ZnO). The infrared modulation layer 4 is a Raman scattering layer, such as a surface plasmon resonance nanostructure.

[0079] In the electrochromic modulation stack: the first transparent conductive film layer 5 is FTO, the electrochromic film layer 6 is molybdenum oxide (MoO3), and the ion storage film layer 8 is iridium oxide (IrO). x The second transparent conductive film layer 9 is made of FTO. The high-reflectivity film layer 13 is made of aluminum (Al). The inorganic ceramic protective film layer 15 is made of titanium oxide (TiO2).

[0080] Brief description of the preparation method: Using a tooling fixture suitable for curved surface coating, each film layer is deposited sequentially by magnetron sputtering. During the sputtering process, the substrate temperature is appropriately reduced to avoid polymer deformation.

[0081] Control method: Same as in Example 1, a DC voltage is applied by connecting the first transparent conductive film layer 5 and the second transparent conductive film layer 9 through a wire.

[0082] Applying a first voltage (negative voltage) causes the electrochromic film layer 6 (MoO3) to fade, and the high-reflectivity film layer 13 (Al) dominates infrared reflection, entering the infrared reflection enhancement mode.

[0083] Applying a second voltage (positive voltage) causes the electrochromic film layer 6 (MoO3) to become colored, entering the infrared absorption mode. In the colored state, the visible light transmittance of this curved coated glass is also extremely low, with virtually no visible light transmission, making it suitable for use on irregularly shaped surfaces of spacecraft.

[0084] Experimental Example 1 Visible light transmittance test The measured transmittance data of the glass of this invention in the 380-780nm visible light band are as follows: In the bleached state, the average transmittance of visible light is 72%-88%, which can achieve a high transparency and visibility effect and meet the lighting needs of scenarios such as car windows and building curtain walls; In the tinted state, the average transmittance of visible light is 1%-6%, which is almost opaque and can achieve strong light blocking and privacy protection functions.

[0085] To further demonstrate the technical advantages of this invention, comparative data with existing technologies is provided: ordinary Low-E low-emissivity glass has a constant visible light transmittance of 65%-70% and does not have adjustable light-blocking capabilities; conventional single-layer electrochromic glass can only reduce the colored state transmittance to 10%-15%, and its light-blocking effect is far inferior to that of this invention. The light-blocking performance of this invention is significantly improved.

[0086] Experimental Example 2 Infrared reflection / absorption modulation range test The measured data of reflectance and absorptivity of the electrochromic coated glass of this invention in the fading and colored states for the 780-2500nm near-infrared and 8-14μm far-infrared bands are as follows: In the fading state (high infrared reflectance heat insulation mode), the average infrared reflectance across the entire band is ≥88%, and the infrared absorptivity is ≤12%, which can significantly block solar heat radiation and effectively achieve cooling and heat insulation in summer; In the colored state (high infrared absorption temperature control mode), the average infrared reflectance across the entire band is ≤12%, and the infrared absorptivity is ≥79%, which can quickly absorb infrared heat energy and meet the heat storage and insulation requirements of low-temperature environments. The infrared modulation difference between the two modes of this invention exceeds 65%, and the bidirectional control range for hot and cold is significantly larger than that of traditional dimming glass, fully demonstrating the significant difference between the "reflection enhancement mode" and the "absorption mode," proving that the temperature control effect of this invention is superior to the prior art.

[0087] Experimental Example 3 Switching between stability / cycle life tests The electrochromic coated glass of this invention was subjected to on-off cycle testing under rated driving voltage. After a total of 10,000 cycles, the measured data are as follows: the visible light transmittance in the faded state fluctuated by ≤2.5% after cycling, and the transmittance in the colored state did not increase significantly; the maximum infrared reflectance decreased by <4%, and the infrared modulation amplitude remained above 95% of the initial value; and the film layer showed no cracking, peeling, or hazy aging, proving that the dimming performance of this invention is stable over a long period of time and has a good service life.

[0088] Test Example 4 Space Environment Simulation Test To verify the reliability of this invention under harsh environments, the following space environment simulation tests were conducted, and the results are as follows: 1. After 1000 hours of continuous strong ultraviolet irradiation (300-400nm), the optical performance and dimming response speed of the film layer showed no attenuation, and there was no yellowing or aging phenomenon; 2. After 500 cycles of high and low temperature cycling (-65℃ to +120℃), the adhesion between the glass and the multilayer functional film layer remained intact, the dimming function was normal, and there was no damage or delamination; 3. After high-energy particle irradiation simulation tests, the electrochromic response threshold and spectral control range did not shift, and it can stably adapt to aerospace and outdoor extreme working conditions.

[0089] Comparative Example 1 The difference between this comparative example and Example 1 is that a high-reflectivity film layer is not provided. Test results show that the infrared reflectivity in the faded state is only 55% at most, resulting in a significant decrease in heat insulation performance. This fails to achieve the efficient heat-blocking effect of the present invention and negates the core function of bidirectional temperature control, proving that the high-reflectivity film layer is the key structure for achieving the infrared reflection enhancement mode.

[0090] Comparative Example 2 The difference between this comparative example and Example 1 is that the electrochromic control layer is not included. Test results show that the glass only has a fixed infrared heat insulation effect, and the visible light transmittance cannot be adjusted. It cannot achieve intelligent switching between coloring and blocking light when powered on and allowing light to pass through when powered off, thus losing the core function of intelligent dimming of the present invention. The application scenarios are severely limited, proving that the electrochromic control layer is the core to achieve autonomous control.

[0091] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A self-regulating infrared reflection coated glass with a flat or curved surface, characterized in that: The self-regulating infrared reflection coated glass with flat and curved surfaces includes: Planar or curved substrates; An electrochromic control stack is disposed on one side of the substrate. The electrochromic control stack, starting from the side closest to the substrate, includes at least a first transparent conductive film layer, an electrochromic film layer, an electrolyte film layer, an ion storage film layer, and a second transparent conductive film layer disposed sequentially. And a high-reflectivity film layer disposed on the side of the electrochromic modulation stack opposite to the substrate; A dielectric spacer layer is disposed between the high-reflectivity film layer and the electrochromic modulation stack. The optical thickness of the dielectric spacer layer is configured such that the effective absorption coefficient k of the electrochromic film layer in the fading state for the 780nm-2500nm band is less than 0.1, so that infrared radiation in this band passes through the electrochromic modulation stack and reaches the high-reflectivity film layer and is reflected back to the incident side; while when the electrochromic film layer in the colored state has k>0.3 for the same band, the infrared radiation is absorbed by the electrochromic film layer before reaching the high-reflectivity film layer. The coated glass can autonomously control the coloring state of the electrochromic film layer by applying voltage to change the coloring state of the electrochromic film layer; and when in the coloring state, the visible light transmittance of the coated glass is extremely low, and it basically does not transmit visible light.

2. The self-regulating infrared reflection coated glass with a flat or curved surface according to claim 1, characterized in that: The flat-curved infrared reflection self-regulating coated glass further includes a dielectric film layer, an ultraviolet isolation film layer, and / or an infrared regulation film layer disposed between the substrate and the electrochromic regulation stack; the material of the ultraviolet isolation film layer is selected from at least one of titanium oxide, zinc oxide, or iron oxide; the infrared regulation film layer is a Raman scattering layer or a tungsten oxide layer.

3. The self-regulating infrared reflection coated glass with flat and curved surfaces according to claim 1, characterized in that: The self-regulating infrared reflection coated glass with a flat and curved surface further includes an optical regulation film layer, a dielectric passivation film layer, and / or a dielectric barrier film layer disposed between the second transparent conductive film layer and the high reflectivity film layer; the material of the optical regulation film layer is selected from at least one of titanium oxide TiOx, silicon nitride SiNx, silicon oxynitride SiNxOy, zinc oxide ZnOx, zinc aluminum oxide ZnAlOx, tin oxide SnOx, zinc tin oxide ZnSnOx, or aluminum-doped zinc oxide AZO; the material of the dielectric passivation film layer is selected from at least one of titanium nitride, silicon nitride, or silicon oxynitride.

4. The self-regulating infrared reflection coated glass with flat and curved surfaces according to claim 1, characterized in that: The flat-curved infrared reflection self-regulating coated glass further includes a wear-resistant hardening film layer and / or an inorganic ceramic protective film layer disposed on the side of the high-reflectivity film layer away from the substrate; the material of the wear-resistant hardening film layer includes silicon oxide; the material of the inorganic ceramic protective film layer is selected from at least one of alumina, titanium oxide or magnesium fluoride.

5. The self-regulating infrared reflection coated glass with a flat or curved surface according to claim 1, characterized in that: The material of the high-reflectivity film layer is selected from at least one of aluminum, silver, gold or palladium; the material of the first transparent conductive film layer and / or the second transparent conductive film layer is selected from at least one of indium tin oxide (ITO), fluorine-doped tin oxide (FTO) or aluminum-doped zinc oxide (AZO); the material of the electrochromic film layer is selected from at least one of tungsten oxide, molybdenum oxide, niobium pentoxide or titanium dioxide; the material of the ion storage film layer is selected from at least one of nickel oxide, iridium oxide or manganese oxide.

6. The self-regulating infrared reflection coated glass with flat and curved surfaces according to claim 1, characterized in that: The planar or curved substrate is a planar or 3D curved polymer substrate, and the material of the planar or 3D curved polymer substrate is selected from any one of glass, plexiglass, polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), or polyimide (PI).

7. The self-regulating infrared reflection coated glass with flat and curved surfaces according to claim 1, characterized in that: When a first voltage is applied to put the electrochromic film layer in a faded state, the high-reflectivity film layer dominates infrared reflection, achieving an infrared reflection enhancement mode; when a second voltage is applied to put the electrochromic film layer in a colored state, the electrochromic film layer dominates infrared absorption, achieving an infrared absorption mode.

8. The self-regulating infrared reflection coated glass with flat and curved surfaces according to claim 7, characterized in that: An ion migration barrier layer is disposed between the electrochromic control stack and the high reflectivity film layer, and the ion migration barrier layer is used to isolate the interfaces between the two; wherein, after the electrochromic device is subjected to a temperature cycle test from -65℃ to +120℃, the adhesion between the film layers is not less than 88%.

Images