INORGANIC MULTI-COLOR TRANSMISSION ELECTROCHROMIC FILMS, ELECTROCHROMIC COATED GLASS ELECTRODES AND THE DESIGN METHOD

Abstract

The present invention discloses an inorganic multi-color transmission electrochromic film, coated glass and a design method. The coated glass comprises a glass substrate and the inorganic multi-color transmission electrochromic film stacked in sequence. The inorganic multi-color transmission electrochromic film comprises a dielectric layer (optionally added), a current collecting interference layer, a sacrificial layer, an electrochromic layer, and an electron blocking layer (optionally added) stacked in sequence. With the help of thin film optics principle to design transmittance and color coordinates, optimize the material selection and thickness parameters of each film layer, and further use large-area coating technology to prepare a multilayer film structure on a clean flat glass substrate, and finally a large-area coated glass product with multi-color transmission color and electro-control effect is obtained.

Claims

1. An inorganic multi-color transmission electrochromic thin film, comprising a current collecting interference layer, a sacrificial layer and an electrochromic layer stacked in sequence; wherein the thickness of the current collecting interference layer is 8-20 nm, and the material is a metal or alloy whose resistivity is less than 2.1?10?7 ?.Math.m; the thickness of the electrochromic layer is 100-300 nm, and the material is an inorganic electrochromic material, specifically a transition metal oxide; the thickness of the sacrificial layer is 1-10 nm, and the material is the metal or its alloy in the transition metal oxide.

2. The inorganic multi-color transmission electrochromic thin film according to claim 1, wherein, the material of the current collecting interference layer is Ag, Au, Cu, Al or their alloys.

3. The inorganic multi-color transmission electrochromic thin film according to claim 1, wherein, the transition metal oxide is at least one of WO.sub.3, TiO.sub.2, and V.sub.2O.sub.5.

4. The inorganic multi-color transmission electrochromic thin film according to claim 1, wherein, the thickness of the current collecting interference layer is 8-10 nm.

5. The inorganic multi-color transmission electrochromic thin film according to claim 1, wherein, the thickness of the sacrificial layer is 1-5 nm.

6. The inorganic multi-color transmission electrochromic thin film according to claim 1, wherein, a dielectric layer is provided on the other side of the current collecting interference layer, the thickness of the dielectric layer is 1-10 nm, and the material is at least one of TiO.sub.2, SnO.sub.2, ZnO, Si.sub.3N.sub.4, and SiO.sub.2.

7. The inorganic multi-color transmission electrochromic thin film according to claim 1, wherein, an electron blocking layer is provided on the other side of the electrochromic layer, the thickness of the electron blocking layer is 1-10 nm, and the material is at least one of SiO.sub.2, Si.sub.3N.sub.4, and Ta.sub.2O.sub.5.

8. An inorganic multi-color transmission electrochromic coated glass, comprising a glass substrate and the inorganic multi-color transmission electrochromic film according to claim 1 which are stacked in sequence, in the inorganic multi-color transmission electrochromic thin film, the closest to the glass substrate is a current collecting interference layer or a dielectric layer.

9. A preparation method of the inorganic multi-color transmission electrochromic coated glass, comprising: adopting a coating method of DC reactive magnetron sputtering or electron beam evaporation, on the glass substrate, each layer is sequentially deposited according to the structure of the inorganic multi-color transmission electrochromic film according to claim 1.

10. A design method of the inorganic multi-color transmission electrochromic film according to claim 1, comprising the steps of: (1) using spectroscopic ellipsometry to measure the ellipsometry parameters of various constituent materials that can be used to make each layer of the inorganic multi-color transmission electrochromic film, denoted as cos ?.sub.i and tan ?.sub.i, A represents relative phase change, and ? represents relative amplitude attenuation. Selecting the corresponding dispersion model according to the constituent materials, and using the Fresnel formula to establish the functional relationship between the refractive index n, extinction coefficient k and film thickness d of each constituent material and the ellipsometry parameter, denoted as cos ?.sub.i(n,k,d) and tan ?.sub.i(n,k,d). Regression algorithm is used to obtain the refractive index n and extinction coefficient k of each of the constituent materials. The mean square error function MSE between cos ?.sub.i, tan ?.sub.i and cos ?.sub.i(n,k,d), tan ?.sub.i(n,k,d) is used as regression judging standard formula:
MSE=?.sub.Vis[(cos ?.sub.i?cos ?.sub.i(n,k,d)).sup.2+(tan ?.sub.i?tan ?.sub.i(n,k,d)).sup.2]; (2) According to the color change requirements and service requirements, based on the thin film optics principle, and according to the refractive index n and extinction coefficient k of each of the constituent materials, determining the specific materials composing each layer of the inorganic multi-color transmission electrochromic film, and determining the film layer structure; (3) based on the thin film optics principle, using the refractive index n and extinction coefficient k of the specific materials of each layer, according to the determined film layer structure, the color change state of the electrochromic layer and the thickness of each layer being used as variables to calculate the transmittance in the visible light range, then optimizing the target thickness of each layer according to the transmittance-chromaticity relationship.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0038] FIG. 1 is the structural representation of the inorganic multi-color transmission electrochromic coated glass of the present invention.

[0039] FIG. 2 is the ellipsometry fitting result diagram of the W thin film sample, wherein, the solid line is the model simulation value, and the dotted line is the measured value.

[0040] FIG. 3 is the ellipsometry fitting result diagram of AgW thin film sample, wherein, the solid line is the model simulation value, and the dotted line is the measured value.

[0041] FIG. 4 is the ellipsometry fitting result diagram of the faded WO.sub.3 film sample, wherein the solid line is the model simulation value, and the dotted line is the measured value.

[0042] FIG. 5 is the ellipsometry fitting result diagram of the colored WO.sub.3 thin film sample, wherein, the solid line is the simulated value of the model, and the dotted line is the measured value.

[0043] FIG. 6 is a graph of the refractive index and extinction coefficient of W.

[0044] FIG. 7 is a graph of the refractive index and extinction coefficient of Ag.

[0045] FIG. 8 is a graph of the refractive index and extinction coefficient of WO.sub.3 in a faded state and a colored state.

[0046] FIG. 9 is the transmittance diagram of the example glass/Ag (10 nm)/W (2 nm)/WO.sub.3 (210 nm) multilayer structure coated glass under different voltages.

[0047] FIG. 10 is a graph showing the variation of transmission color with voltage according to the CIE1931x-y chromaticity coordinates of the example glass/Ag (10 nm)/W (2 nm)/WO.sub.3 (210 nm) multilayer structure coated glass.

PREFERRED EMBODIMENTS OF THE INVENTION

[0048] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. The operation method without specifying the specific conditions in the following examples is usually in accordance with the conventional conditions, or in accordance with the conditions suggested by the manufacturer.

[0049] Ultraviolet-visible spectrum: The transmission spectrum is observed with a spectrophotometer, and the equipment model is Agilent's Cary5000.

[0050] Measurement and analysis of ellipsometry: a photometric ellipsometry is used, the equipment model is GES-5E of Semilab, and the software SEA (WinElli 3) v1.6.1 is used for data analysis.

[0051] The structure of the inorganic multi-color transmission electrochromic coated glass of the present invention is shown in FIG. 1, including a glass substrate, a dielectric layer (optionally added), a current collecting and interference layer, a sacrificial layer, an electrochromic layer and an electron blocking layer (optionally added) stacked in sequence.

[0052] The design idea and preparation method of inorganic multi-color transmission electrochromic thin films are now described with specific materials as examples. Metal Ag is used as the current collecting interference layer material, metal W is used as the sacrificial layer material, and WO3 is used as the electrochromic layer material. Among them, the dielectric layer and the electron blocking layer are optional, and are not added in this embodiment.

[0053] In order to obtain the ellipsometric parameters of the single-layer material, the corresponding thin film material was prepared on the silicon wafer by the DC reactive magnetron sputtering method. The working power used to prepare the Ag layer: 100 W, the working pressure: 0.2 Pa, and the argon flow rate: 30 sccm. The working power used to prepare the W layer: 80 W, the working pressure: 0.8 Pa, and the argon flow rate: 30 sccm. The working power used to prepare the WO.sub.3 layer: 80 W, the working air pressure: 0.8 Pa, the argon flow rate: 30 sccm, and the oxygen flow rate: 15 sccm.

[0054] Spectroscopic ellipsometry was used to measure the samples respectively, the measurement spectral range was 350 nm?1000 nm, the incident angle was set to 62?, and the ellipsometry parameters cos ?.sub.i and tan ? were obtained. A suitable dispersion model was established for each material. The Ag layer useD a Drude dispersion equation and a Lorentz oscillator model to describe the optical parameters. The initial values are set to E.sub.P=7.4, E.sub.?=0.6, f=0.6, E.sub.0=4.2, ?=0.15. The W layer used a Drude dispersion equation and three Lorentz oscillator models to describe the dispersion relationship, the initial value is set to E.sub.P=8.5, E.sub.?=3.7, {circle around (1)} (f=2.6, E.sub.0=5.8, ?=0.17), {circle around (2)} (f=6.3, E.sub.0=1.8, ?=2.16), {circle around (3)} (f=9.7, E.sub.0=3.9, ?=4.95). The faded WO.sub.3 layer adopted a Sellmeier oscillator model and a Lorentz oscillator model to describe the optical parameters, the initial value is set to B=4.2, ?.sub.0=0.2, f=0.1, E.sub.0=3.7, ?=0.12. The colored WO.sub.3 layer used a Drude dispersion equation and three Lorentz oscillator models to describe the dispersion relationship, and the initial values were set to E.sub.P=3.2, E.sub.?=3.6. {circle around (1)} (f=0.4, E.sub.0=5.2, ?=0.88), {circle around (2)} (f=3.0, E.sub.0=5.6, ?=0.00), {circle around (3)} (f=3.2, E.sub.0=1.3, ?=2.97). The functional relationship cos ?.sub.i(n,k,d) and tan ?.sub.i(n,k,d) of the refractive index n, extinction coefficient k and film thickness d of Ag, W and WO.sub.3 and the ellipsometry parameters were established by using the above-established structural model and dispersion model combined with the Fresnel formula, and giving the MSE function to find a set of parameters that make MSE get the minimum value. The cos ?.sub.i(n,k,d) and tan ?.sub.i(n,k,d) (calculated values) regressed by this method have a high degree of fit with cos ?.sub.i(n,k,d) and tan ?.sub.i(n,k,d) (measured values), as shown in FIG. 2-5, the best fit result returns the minimum value of MSE of 1.89?10.sup.?3. FIGS. 6-8 are graphs of the relationship between refractive index n/extinction coefficient k-wavelength ? fitted to Ag, W and WO.sub.3 thin film samples.

[0055] According to the optical parameters of each material obtained in FIGS. 6-8, the glass/Ag/W/WO.sub.3 multilayer film was used as the design structure, and the transmittance and corresponding chromaticity of the target structure were calculated based on the optical principle of thin films, and high transmittance and high saturation multi-color were the optimization target, the theoretical parameters of Ag layer thickness not greater than 10 nm, W layer thickness not greater than 5 nm, and WO.sub.3 layer thickness ranging from 100 to 300 nm were determined.

[0056] Coated glass with glass/Ag/W/WO.sub.3 multilayer structure was prepared by DC reactive magnetron sputtering method. Taking the prepared glass/Ag(10 nm)/W(2 nm)/WO.sub.3 (210 nm) sample as an example, FIG. 9 and FIG. 10 were the transmittance and the corresponding CIE1931x-y chromaticity coordinates of the sample under different voltages, showing multi-color changes.

[0057] In addition, it should be understood that after reading the above description of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.