An improved electrically controlled all-solid-state intelligent dimming device
By introducing dielectric composite reinforcement and protective layer into all solid state intelligent dimming products, the film layer structure is optimized, the problems of high production costs and low light transmittance are solved, and the color selection range and visual effect are improved.
Patent Information
- Application Number
- CN201810090833.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2018-01-30
- Publication Date
- 2024-12-13
- Estimated Expiration
- 2038-01-30
AI Technical Summary
The existing all-solid-state intelligent dimming products have high production costs, single color when fully transmissive, poor visual effect, small size of the finished product, too low light transmittance when fully transmissive, and high-temperature preparation of conductive films.
The structure of an improved electronically controlled all-solid-state intelligent dimming device includes a transparent substrate, a dielectric composite reinforcement layer, a lower transparent electrode layer, a lower electrochromic layer, an ion conductive layer, an upper electrochromic layer, an upper transparent electrode layer and a dielectric The composite protective layer is enhanced by the preferred film layer materials and process methods, especially the addition of the dielectric composite reinforcement layer and the dielectric composite protective layer, and the visible light transmittance and color selection range.
The color selection range during full transmission and discoloration is improved, and the visible light transmittance is improved, solving the problems of high cost and low light transmittance, while reducing the preparation temperature.
Smart Images
Figure CN108227328B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to an improved electrically controlled all-solid-state intelligent dimming device, belonging to the technical field of energy saving. Background Art
[0002] Conventional solid-state electrochromic systems currently available in the field of electrochromic technology are based on a so-called "six-layer" basic model architecture including a transparent substrate: transparent substrate (1) / lower transparent electrode layer (2) / lower electrochromic layer (3) / ion conduction layer (4) / upper electrochromic layer (5) / upper transparent electrode layer (6).
[0003] In the above model, the electrochromic system includes two layers of reversibly oxidized or reduced materials, one of which is generally transparent in an oxidized state and the other is generally transparent in a reduced state. The transparent conductive layer is connected to an external power source. An appropriate positive DC voltage is applied between the upper and lower transparent conductive electrodes. The ions in the ion storage layer are extracted and enter the electrochromic layer through the ion conductor to achieve zero-power memory. When the reverse voltage is applied, the ions in the electrochromic layer are extracted and then enter the storage layer again, and the glass returns to transparency. By controlling the different changes in the transmittance and color of the product, the external thermal radiation and internal heat diffusion are selectively absorbed or reflected. In some application fields, a combination of two substrates can be used, each of which can maintain part of the electrochromic function, and the entire dimming color system is a combination of the two substrates.
[0004] Among the basic electrochromic materials, the cathode color-changing material amorphous tungsten oxide is the most practical. The counter electrode generally uses another electrochromic material that is complementary to the electrochromic layer, that is, if the color-changing layer is a cathode electrochromic material, the counter electrode uses an anode electrochromic material. Under the action of an external voltage, the cathode and anode will be colored and faded at the same time, making the color of the colored state darker and the light transmittance of the faded state higher. The typical combination of this complementary color change is WO-NiO, WO is colored in a reduced state, and NiO is colored in an oxidized state, so that the color change can be deepened. Similarly, when WO is in an oxidized state, NiO is in a reduced state, so that high-transmittance glass can be produced. In addition, solid ion conductors have also received great attention. LiF, LiA1F4, LiN, LiA1C1 and other ion conductor films have good comprehensive properties. Summary of the invention
[0005] In order to solve the problems of high production cost, single color when fully transparent and discolored, poor visual effect, small size of finished products, too low transmittance when fully transparent, and high temperature preparation of conductive films in the original all-solid-state intelligent dimming products, the present invention provides an improved electrically controlled all-solid-state intelligent dimming device. The present invention improves the visible light transmittance through preferred film materials, film structures, and process methods, especially by adding a dielectric composite strengthening layer and a dielectric composite protective layer, while also increasing the range of color choices when fully transparent and discolored.
[0006] In order to solve the above technical problems, the present invention provides an improved electrically-controlled all-solid-state intelligent dimming device, characterized in that the improved electrically-controlled all-solid-state intelligent dimming device is stacked from bottom to top in sequence: a transparent substrate, a dielectric composite strengthening layer, a lower transparent electrode layer, a lower electrochromic layer, an ion conduction layer, an upper electrochromic layer, an upper transparent electrode layer, and a dielectric composite protective layer.
[0007] Preferably, the dielectric composite strengthening layer includes one or more of a SiO2 layer, a TiO2 layer, a Si3N4 layer, a Si2N2O layer, a ZnSnO2 layer, a Nb2O5 layer, a ZnO layer, a ZrO2 layer, a NbZr layer, a BiO2 layer, an Al2O3 layer, and a Cr2N layer.
[0008] Preferably, the dielectric composite protective layer includes one or more of a TiO2 layer, a Cr2N layer, a ZnSnO2 layer, a ZnO layer, a ZrO2 layer, a NbZr layer, a Si3N4 layer, a SiO2 layer, a Si2N2O layer, a BiO2 layer, an Al2O3 layer, a Nb2O5 layer, a Cr layer, an Al layer, and a Pd layer.
[0009] Preferably, the lower transparent electrode layer includes at least one of an oxide-doped, metal-doped or undoped FTO layer, an ATO layer, an ITO layer, an Ag layer, an Au layer, a Cu layer, an AZO layer, a GZO layer, a GXO layer, an Al layer, a Cr layer, and a Pt layer.
[0010] Preferably, the upper transparent electrode layer includes at least one of an oxide-doped, metal-doped or undoped Cr layer, Al layer, ITO layer, Ni layer, FTO layer, Au layer, ATO layer, Ag layer, Cu layer, AZO layer, and Pt layer.
[0011] Preferably, the lower electrochromic layer includes at least one of a WO3 layer, a Ta2O5 layer, a V2O5 layer, a MoO3 layer, a Nb2O5 layer, a TiO2 layer, and an Ir2O3 layer.
[0012] Preferably, the lower electrochromic layer includes at least one of an oxide-doped WO3 layer, Ta2O5 layer, V2O5 layer, MoO3 layer, Nb2O5 layer, TiO2 layer, and SnO2 layer.
[0013] Preferably, the ion-conducting layer includes one or more of a solid-state lithium salt such as a LiTaO3 layer, Li3N layer, LiNbO3 layer, LiBO2 layer, LiF layer, LiA1F4 layer, LiA1C1 layer, and LiPON layer.
[0014] Preferably, the upper electrochromic layer includes NiO x layer, Ir2O3 layer, Rh2O3 layer, CoO2 layer, and InN layer.
[0015] Preferably, the upper electrochromic layer includes one or more of an oxide-doped NiO x layer, Ir2O3 layer, Rh2O3 layer, and CoO2 layer.
[0016] Preferably, x in the NiO x is a stoichiometric number different from that of nickel oxide NiO, and NiO x has a specific value range: 0 < x < 1, or 0.2 < x < 0.9, or 0.4 < x < 0.8.
[0017] Preferably, the transparent substrate is at least one of glass, PMMA, PC, and PET.
[0018] Preferably, the thickness of the dielectric composite strengthening layer is 60 - 100 nm, the thickness of the lower transparent electrode layer is 50 - 150 nm, the thickness of the lower electrochromic layer is 200 - 400 nm, the thickness of the ion-conducting layer is 10 - 2000 nm, the thickness of the upper electrochromic layer is 150 - 350 nm, the thickness of the upper transparent electrode layer is 50 - 250 nm, and the thickness of the dielectric composite protection layer is 50 - 150 nm.
[0019] Preferably, the resistance of both the lower transparent electrode layer and the upper transparent electrode layer is less than 20 Ω.
[0020] Preferably, it further includes one or a combination of a low-emissivity functional film, a sunscreen functional film, a hydrophobic functional film, a hydrophilic functional film, an antireflection functional film, an electromagnetic shielding functional film, and an anti-dust photocatalytic functional film.
[0021] Preferably, the light-to-heat ratio of the improved electronically controlled all-solid-state intelligent dimming device is 4.0 - 7.8.
[0022] Preferably, the dielectric composite strengthening layer, the lower transparent electrode layer, the lower electrochromic layer, the ion conducting layer, the upper electrochromic layer, the upper transparent electrode layer, and the dielectric composite protective layer are all prepared by vacuum magnetron sputtering process.
[0023] Preferably, the vacuum magnetron sputtering process uses at least one of dual AC rotating cathodes, dual AC planar cathodes, dual DC planar cathodes, single DC planar cathodes, and single DC rotating cathodes to deposit films in an argon-oxygen, argon-nitrogen, or argon-oxygen-nitrogen atmosphere.
[0024] Preferably, the lower transparent electrode layer and the upper transparent electrode layer are both prepared by a vacuum high temperature annealing process.
[0025] The present invention also provides a glass window, characterized in that the glass window has the above-mentioned improved electrically controlled all-solid-state intelligent dimming device.
[0026] Beneficial effects achieved by the present invention: The present invention improves the visible light transmittance through the preferred film material, film structure, and process method, especially by adding a dielectric composite strengthening layer and a dielectric composite protective layer, while also increasing the range of color choices for full transparency and color change. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Figure 1 It is a basic structural diagram of an improved electrically controlled all-solid-state intelligent dimming device;
[0028] Figure 2 It is a schematic diagram of the film manufacturing process of the improved electrically controlled all-solid-state intelligent dimming device;
[0029] Figure 3 It is a schematic diagram of the structure of the first and second embodiments of the improved electrically controlled all-solid-state intelligent dimming product;
[0030] Figure 4 It is a schematic diagram of the structure of the third and fourth embodiments of the improved electrically controlled all-solid-state intelligent dimming product. DETAILED DESCRIPTION
[0031] The present invention will be further described below in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and cannot be used to limit the protection scope of the present invention.
[0032] like Figure 1 As shown, an improved electrically controlled all-solid-state intelligent dimming device is stacked from bottom to top on a transparent substrate 1: a transparent substrate 1, a dielectric composite strengthening layer 2, a lower transparent electrode layer 3, a lower electrochromic layer 4, an ion conduction layer 5, an upper electrochromic layer 6, an upper transparent electrode layer 7, and a dielectric composite protective layer 8.
[0033] The transparent substrate 1 can be made of various transparent substrates such as glass, PMMA, PC, PET, etc., preferably glass substrate, including various functional glass original plates such as automotive-grade coated plates, solar ultra-clear plates, colored glass, etc.
[0034] The dielectric composite strengthening layer 2 can be conductive or insulating; it has the function of visible light transmission enhancement or reflection. The dielectric composite strengthening layer 2 includes one or more of SiO2 layer, TiO2 layer, Si3N4 layer, Si2N2O layer, ZnSnO2 layer, Nb2O5 layer, ZnO layer, ZrO2 layer, NbZr layer, BiO2 layer, Al2O3 layer, and Cr2N layer. The dielectric composite strengthening layer 2 has a thickness of 10 to 150 nm, preferably 40 to 120 nm, and more preferably 60 to 100 nm.
[0035] The lower transparent electrode layer 3 has high conductivity and low visible light absorption; when there is a need for reflection, a metal performance material can be selected. The lower transparent electrode layer 3 has a resistance of less than 20Ω. The lower transparent electrode layer 3 includes at least one of an oxide-doped, metal-doped or undoped FTO layer, ATO layer, ITO layer, Ag layer, Au layer, Cu layer, AZO layer, GZO layer, GXO layer, Al layer, Cr layer, and Pt layer. The thickness of the lower transparent electrode layer 3 is 10 to 600 nm, preferably 30 to 300 nm, and more preferably 50 to 150 nm.
[0036] The lower electrochromic layer 4 can be added with non-color-changing or / and electrolytic materials to improve the interface performance and durability; the multilayer or material produced by the addition is not defined as an electrolyte because it does not participate in ion conduction. The lower electrochromic layer 4 includes at least one of an oxide-doped or undoped WO3 layer, a Ta2O5 layer, a V2O5 layer, a MoO3 layer, a Nb2O5 layer, a TiO2 layer, an Ir2O3 layer, and a SnO2 layer. The thickness of the lower electrochromic layer 4 is 100 to 800 nm, preferably 150 to 600 nm, and more preferably 200 to 400 nm.
[0037] The ion conducting layer 5 has electronic insulation and ion conducting functions; the visible light absorption rate is less than 6%; the nitride electrolyte can increase the system life and reduce the difficulty of film deposition. The ion conducting layer 5 includes one or more of the solid lithium salt LiTaO3 layer, Li3N layer, LiNbO3 layer, LiBO2 layer, LiF layer, LiA1F4 layer, LiA1C1 layer, and LiPON layer. The thickness of the ion conducting layer 5 is 10 to 2000 nm, preferably 50 to 300 nm, and more preferably 100 to 200 nm.
[0038] The upper electrochromic layer 6 and the lower electrochromic layer 4 can be interchanged under different application requirements to achieve color complementation and / or charge balance requirements. The upper electrochromic layer 6 includes oxide-doped or undoped NiOx One or several of a layer, an Ir2O3 layer, a Rh2O3 layer, a CoO2 layer, and an InN layer. The NiO x where x in is a stoichiometric number different from that of nickel oxide NiO, and NiO x The specific value range is: 0 < x < 1, preferably 0.2 < x < 0.9, more preferably 0.4 < x < 0.8. The thickness of the electrochromic layer 6 is 1 to 600 nm, preferably 50 to 500 nm, and more preferably 150 to 350 nm.
[0039] The upper transparent electrode layer 7 has high conductivity and low visible light absorption; when reflection is required, a metal property material can be selected. The resistance of the lower transparent electrode layer 3 is less than 20 Ω. The upper transparent electrode layer 7 includes at least one of an oxide-doped or metal-doped or undoped Cr layer, Al layer, ITO layer, Ni layer, FTO layer, Au layer, ATO layer, Ag layer, Cu layer, AZO layer, and Pt layer. The thickness of the upper transparent electrode layer 7 is 10 to 600 nm, preferably 30 to 300 nm, and more preferably 50 to 250 nm.
[0040] The dielectric composite protective layer 8 can be conductive or insulating. The dielectric composite protective layer 8 includes one or several of a TiO2 layer, a Cr2N layer, a ZnSnO2 layer, a ZnO layer, a ZrO2 layer, a NbZr layer, a Si3N4 layer, a SiO2 layer, a Si2N2O layer, a BiO2 layer, an Al2O3 layer, a Nb2O5 layer, a Cr layer, an Al layer, and a Pd layer, and they can be single-layer or multi-layer. The thickness of the dielectric composite protective layer 8 is 1 to 200 nm, preferably 20 to 180 nm, and more preferably 50 to 150 nm.
[0041] The light-to-heat ratio of the improved electro-control all-solid-state intelligent dimming device is 4.0 to 7.8.
[0042] Basic target position architecture and process parameters
[0043]
[0044]
[0045]
[0046] As Figure 2 shown, the present invention also provides a preparation method of an improved electro-control all-solid-state intelligent dimming device, including the following steps:
[0047] a. After the transparent substrate 1 is ground, polished, cleaned, and dried, it is heated under vacuum conditions;
[0048] b. A dielectric composite strengthening layer 2, a lower transparent electrode layer 3, a lower electrochromic layer 4, an ion conducting layer 5, an upper electrochromic layer 6, an upper transparent electrode layer 7, and a dielectric composite protective layer 8 are sequentially prepared on a transparent substrate 1 by a vacuum magnetron sputtering process;
[0049] c. After online testing and finished product inspection, the product will be packaged.
[0050] The vacuum magnetron sputtering process uses at least one of dual AC rotating cathodes, dual AC planar cathodes, dual DC planar cathodes, single DC planar cathodes, and single DC rotating cathodes to deposit films in an argon-oxygen, argon-nitrogen, or argon-oxygen-nitrogen atmosphere.
[0051] The lower transparent electrode layer 3 and the upper transparent electrode layer 7 may also be prepared by vacuum high temperature annealing process.
[0052] The present invention also provides a glass window, which has the above-mentioned improved electrically controlled all-solid-state intelligent dimming device.
[0053] Embodiment 1
[0054] The hollow glass of the structure of 6mm EC+12A+6mm+12A+6mm (the color-changing film layer is on the inner surface of the outdoor sheet and is filled with inert gas) is made by using the present invention, and the measured data are as follows (the glass is 6mm ordinary white glass):
[0055] Test items Test Data Visible light transmittance on / off T＝63％～5％ Solar Heat Gain Coefficient (SHGC) 0.50～0.08 <![CDATA[Heat transfer coefficient U value (W / m 2 ·K)]]> 1.28 <![CDATA[Maximum dimension (m 2 )]]> 3,300×6,000 <![CDATA[Minimum power consumption (Wh / m 2 )]]> 0.4
[0056] Embodiment 2
[0057] The hollow glass of the structure of 6mm+1.52SGP+6mm EC+12A+6mm (the color-changing film layer is on the inner surface of the outdoor sheet and filled with inert gas) is made by using the present invention, and the measured data are as follows (the glass is 6mm ordinary white glass):
[0058] Test items Test Data Visible light transmittance on / off T＝57％～3％ UV transmittance on / off 3.9％～0.6％ Solar Heat Gain Coefficient (SHGC) 0.46～0.11 <![CDATA[Heat transfer coefficient U value (W / m 2 ·K)]]> 1.10 <![CDATA[Maximum dimension (m 2 )]]> 3,300×6,000 <![CDATA[Minimum power consumption (Wh / m 2 )]]> 0.35
[0059] Embodiment 3
[0060] The laminated glass of the structure of 6mm+1.52SGP+6mm EC+12A+6mm (the color-changing film layer is on the inner surface of the outdoor sheet, and the interior is filled with inert gas) is made by using the present invention, and the measured data are as follows:
[0061] Test items Test Data Visible light transmittance on / off T＝52％～17％ UV transmittance on / off 4％～0 Solar Heat Gain Coefficient (SHGC) 0.40～0.13 <![CDATA[Heat transfer coefficient U value (W / m 2 ·K)]]> 1.13 <![CDATA[Maximum dimension (m 2 )]]> 3,300×6,000 <![CDATA[Power consumption (Wh / m 2 )]]> 0.5
[0062] Embodiment 4
[0063] The laminated glass of the structure of 6mm+1.52SGP+6mm EC+12A+6mm (the color-changing film layer is on the inner surface of the outdoor sheet, and the interior is filled with inert gas) is made by using the present invention, and the measured data are as follows:
[0064]
[0065]
[0066] The present invention improves the visible light transmittance by optimizing the film material, film structure, and process method, especially by adding a dielectric composite strengthening layer and a dielectric composite protective layer, and also increases the color selection range for full transparency and color change.
[0067] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. An improved electrically controlled all-solid-state intelligent dimming device, Its characteristics are: The improved electrically controlled all-solid-state intelligent dimming device is stacked on the transparent substrate (1) in order from bottom to top: a transparent substrate (1), a dielectric composite strengthening layer (2), a lower transparent electrode layer (3), a lower electrochromic layer (4), an ion conducting layer (5), an upper electrochromic layer (6), an upper transparent electrode layer (7), and a dielectric composite protective layer (8); The upper electrochromic layer (6) comprises an oxide-doped NiOx layer; The x in NiOx is a stoichiometric number different from nickel oxide NiO. The specific value range of NiOx is: <x<0.8; The dielectric composite strengthening layer (2) has a thickness of 60 to 100 nm, the lower transparent electrode layer (3) has a thickness of 50 to 150 nm, the lower electrochromic layer (4) has a thickness of 200 to 400 nm, the ion conduction layer (5) has a thickness of 10 to 2000 nm, the upper electrochromic layer (6) has a thickness of 150 to 350 nm, the upper transparent electrode layer (7) has a thickness of 50 to 250 nm, and the dielectric composite protective layer (8) has a thickness of 50 to 150 nm; The resistance of the lower transparent electrode layer (3) and the upper transparent electrode layer (7) are both less than 20Ω; It also includes one or a combination of low-radiation functional film, sunscreen functional film, hydrophobic functional film, hydrophilic functional film, anti-reflection functional film, electromagnetic shielding functional film, and anti-dust photocatalytic functional film; The light-to-heat ratio of the improved electrically controlled all-solid-state intelligent dimming device is 4.0 to 7.8; The lower transparent electrode layer (3) and the upper transparent electrode layer (7) are both prepared by a vacuum high-temperature annealing process.
2. According to claim 1, an improved electrically controlled all-solid-state intelligent dimming device, Its characteristics are: The dielectric composite strengthening layer (2) comprises one or more of a SiO2 layer, a TiO2 layer, a Si3N4 layer, a Si2N2O layer, a ZnSnO2 layer, a Nb2O5 layer, a ZnO layer, a ZrO2 layer, a NbZr layer, a BiO2 layer, an Al2O3 layer, and a Cr2N layer.
3. The improved electrically controlled all-solid-state intelligent dimming device according to claim 1, Its characteristics are: The dielectric composite protective layer (8) comprises one or more of a TiO2 layer, a Cr2N layer, a ZnSnO2 layer, a ZnO layer, a ZrO2 layer, a NbZr layer, a Si3N4 layer, a SiO2 layer, a Si2N2O layer, a BiO2 layer, an Al2O3 layer, a Nb2O5 layer, a Cr layer, an Al layer, and a Pd layer.
4. The improved electrically controlled all-solid-state intelligent dimming device according to claim 1, Its characteristics are: The lower transparent electrode layer (3) comprises at least one of an oxide-doped, metal-doped or undoped FTO layer, an ATO layer, an ITO layer, an Ag layer, an Au layer, a Cu layer, an AZO layer, a GZO layer, a GXO layer, an Al layer, a Cr layer, and a Pt layer.
5. The improved electrically controlled all-solid-state intelligent dimming device according to claim 1, Its characteristics are: The upper transparent electrode layer (7) comprises at least one of an oxide-doped, metal-doped or undoped Cr layer, an Al layer, an ITO layer, a Ni layer, a FTO layer, an Au layer, an ATO layer, an Ag layer, a Cu layer, an AZO layer, and a Pt layer.
6. The improved electrically controlled all-solid-state intelligent dimming device according to claim 1, Its characteristics are: The lower electrochromic layer (4) comprises at least one of a WO3 layer, a Ta2O5 layer, a V2O5 layer, a MoO3 layer, a Nb2O5 layer, a TiO2 layer, and an Ir2O3 layer.
7. The improved electrically controlled all-solid-state intelligent dimming device according to claim 1, Its characteristics are: The lower electrochromic layer (4) comprises at least one of an oxide-doped WO3 layer, a Ta2O5 layer, a V2O5 layer, a MoO3 layer, a Nb2O5 layer, a TiO2 layer, and a SnO2 layer.
8. The improved electrically controlled all-solid-state intelligent dimming device according to claim 1, Its characteristics are: The ion conducting layer (5) comprises one or more of a solid lithium salt LiTaO3 layer, a Li3N layer, a LiNbO3 layer, a LiBO2 layer, a LiF layer, a LiA1F4 layer, a LiA1C1 layer, and a LiPON layer.
9. The improved electrically controlled all-solid-state intelligent dimming device according to claim 1, Its characteristics are: The upper electrochromic layer (6) comprises at least one of a NiOx layer, an Ir2O3 layer, a Rh2O3 layer, a CoO2 layer, and an InN layer.
10. The improved electrically controlled all-solid-state intelligent dimming device according to claim 1, Its characteristics are: The transparent substrate (1) is at least one of glass, PMMA, PC and PET.
11. The improved electrically controlled all-solid-state intelligent dimming device according to claim 1, Its characteristics are: The dielectric composite strengthening layer (2), the lower transparent electrode layer (3), the lower electrochromic layer (4), the ion conduction layer (5), the upper electrochromic layer (6), the upper transparent electrode layer (7), and the dielectric composite protective layer (8) are all prepared by a vacuum magnetron sputtering process.
12. The improved electrically controlled all-solid-state intelligent dimming device according to claim 11, Its characteristics are: The vacuum magnetron sputtering process uses at least one of dual AC rotating cathodes, dual AC planar cathodes, dual DC planar cathodes, single DC planar cathodes, and single DC rotating cathodes to deposit films in an argon-oxygen, argon-nitrogen, or argon-oxygen-nitrogen atmosphere.
13. A glass window, Its characteristics are: The glass window has the improved electrically controlled all-solid-state intelligent dimming device as described in any one of claims 1-12.