An electro / optical dual-response color-changing inorganic all-solid-state smart window and a preparation method thereof

Abstract

The application relates to an inorganic full-solid-state intelligent window with electric / optical dual-response color changing and a preparation method thereof. The application aims to solve the problem that the existing technology of stimulus-response color changing materials, devices and intelligent windows can only respond to a single stimulus and cannot simultaneously respond to electric and optical color changing. The inorganic full-solid-state intelligent window with electric / optical dual-response color changing is characterized by a seven-layer structure, which comprises a transparent substrate, a transparent bottom electrode, an ion storage layer, an ion conductive layer, an electric / optical dual-response color changing semiconductor coupled double layer and a transparent top electrode. The prepared inorganic full-solid-state intelligent window with electric / optical dual-response color changing can not only adaptively change the transmittance of the window according to the change of the sunlight intensity to adjust the indoor temperature, but also actively change the transmittance under a small applied voltage to adjust the indoor temperature.

Description

Technical Field

[0001] This invention relates to an inorganic all-solid-state smart window and its preparation method. Background Technology

[0002] The current global energy crisis and environmental problems necessitate that buildings, which account for nearly 40% of global energy consumption, move towards minimizing energy consumption and achieving carbon neutrality. In this context, smart windows are considered a reliable solution because they can regulate the input of visible light and solar irradiance based on weather conditions and personal preferences through external stimuli (such as electric fields, light, temperature, gas, and mechanical pressure), significantly improving indoor comfort and saving energy in lighting, heating, ventilation, and air conditioning. Based on the different external stimuli (electric fields, light, temperature, etc.), smart windows can be mainly divided into electrochromic (EC) smart windows, photochromic (PC) smart windows, and thermochromic (TC) smart windows. Unlike passive PC and TC smart windows, EC smart windows are active smart windows that can dynamically and reversibly control the sunlight and heat entering the room through manually applied external electrical stimulation. However, due to their poor optical memory effect, EC smart windows require intermittent or continuous power supply to operate, thus necessitating additional energy and human resources. In this respect, PC smart windows have an advantage because they require no energy consumption and can adaptively adjust their transmittance according to solar irradiance. Unfortunately, the small transmittance adjustment range and slow, irreversible light response of PC windows limit their practical applications. Therefore, designing an electro / optical dual-response color-changing smart window that combines the advantages of EC smart windows (large transmittance adjustment range, fast response speed, and good reversibility) with those of PC smart windows (large transmittance adjustment range, fast response speed, and good reversibility) has significant theoretical and practical implications. However, dual-response electrochromism and photochromism have not yet been achieved in inorganic all-solid-state devices; most smart windows can only respond to one stimulus and cannot achieve simultaneous responses to both electricity and light. Summary of the Invention

[0003] The purpose of this invention is to solve the problem that existing stimulus-responsive color-changing materials, devices, and smart windows can only respond to a single stimulus and are difficult to respond to both electricity and light simultaneously. The invention provides an inorganic all-solid-state smart window with dual electro-optical color-changing response and its preparation method.

[0004] An inorganic all-solid-state smart window with electro / optic dual-response color-changing structure is characterized by having a seven-layer structure, including a transparent substrate, a transparent bottom electrode, an ion storage layer, an ion conductive layer, an electro / optic dual-response color-changing semiconductor coupling double layer, and a transparent top electrode. The electrolyte and hydrogen source are water from the air environment, and the introduced water mainly permeates into the smart window through the porous surface or edges of the smart window.

[0005] The aforementioned electro / optic dual-response color-changing semiconductor coupled double layer is a double-layer structure composed of an electro / optic dual-response color-changing layer and a semiconductor functional layer;

[0006] The electro / optical dual-response color-changing layer is oxygen-deficient modified tungsten oxide or oxygen-deficient modified niobium oxide, with a thickness of 100-1000 nanometers.

[0007] The semiconductor functional layer is made of titanium oxide nanoparticles, zinc oxide nanoparticles, silicon oxide nanoparticles, or cadmium sulfide quantum dots, and is prepared by physical vapor deposition or wet chemical methods, with a thickness of 1-100 nanometers.

[0008] A method for fabricating an inorganic all-solid-state smart window with electro / optical dual-response color-changing properties, characterized in that the fabrication method is specifically completed according to the following steps:

[0009] I. Fabrication of transparent bottom electrodes on transparent substrates using physical vapor deposition;

[0010] II. Preparation of an ion storage layer on a transparent bottom electrode using physical vapor deposition;

[0011] III. An ion-conducting layer is prepared on an ion storage layer using physical vapor deposition.

[0012] IV. Preparing an electro / optic dual-response color-changing layer on an ion-conductive layer using physical vapor deposition;

[0013] 5. A semiconductor functional layer is deposited on the electro / optic dual-response color-changing layer using physical vapor deposition or wet chemical methods, so that the semiconductor functional layer and the electro / optic dual-response color-changing layer can be coupled to form a semiconductor coupled double layer with a heterojunction.

[0014] VI. A transparent top electrode was fabricated on an electro / optically dual-response color-changing semiconductor coupled bilayer using physical vapor deposition to obtain a seven-layer smart window structure.

[0015] 7. The prepared seven-layer smart window is subjected to heat treatment to obtain the heat-treated seven-layer smart window.

[0016] 8. The heat-treated seven-layer smart window is then subjected to a humidification process to introduce water as an electrolyte, resulting in an inorganic all-solid-state smart window with dual electro-optical response and color change.

[0017] The principle of this invention:

[0018] This invention prepares an electro / optic dual-response color-changing semiconductor coupled bilayer, which is a bilayer structure composed of an electro / optic dual-response color-changing layer and a semiconductor functional layer. The electro / optic dual-response color-changing layer plays the main role in color change. By controlling the surface morphology and internal oxygen vacancy concentration of the electro / optic dual-response color-changing layer, it promotes the chemisorption of water and the transfer of protons and electrons, significantly improving the EC and PC performance of the electro / optic dual-response color-changing layer. The semiconductor functional layer enhances the color-changing effect of the electro / optic dual-response color-changing layer. Through semiconductor coupling with the electro / optic dual-response color-changing layer, a heterojunction is formed at the interface, causing holes generated in the electro / optic dual-response color-changing layer under illumination to migrate along the valence band to the valence band of the semiconductor functional layer (the highest valence band value of the semiconductor functional layer is higher than that of the electro / optic dual-response color-changing layer), thereby decomposing the water adsorbed on the surface of the nanoparticles of the semiconductor functional layer and generating protons. Simultaneously, most of the photogenerated electrons from the electro / optic dual-response color-changing layer and the semiconductor functional layer are transferred to the conduction band of the semiconductor functional layer (the minimum conduction band value of the semiconductor functional layer is also higher than that of the electro / optic dual-response color-changing layer). This is accompanied by the injection of previously generated protons, leading to the coloring of the electro / optic dual-response color-changing layer. In summary, the photogenerated electrons and holes originally generated in the electro / optic dual-response color-changing layer and the semiconductor functional layer are more effectively separated and transferred, thus significantly improving the PC response of the electro / optic dual-response color-changing semiconductor coupled bilayer film. Furthermore, the semiconductor functional layer can also enhance water adsorption. Composed of nanoparticles, the semiconductor functional layer has a large surface area and significant surface adsorption capacity, enabling it to effectively adsorb large amounts of water through the surface effect of nanoparticles.

[0019] Based on this, the present invention designs an inorganic all-solid-state smart window with electro / optical dual-response color-changing properties. This smart window has a unique seven-layer structure, including a transparent substrate, a transparent bottom electrode, an ion storage layer, an ion-conducting layer, an electro / optical dual-response color-changing semiconductor coupling double layer (composed of an electro / optical dual-response color-changing layer and a semiconductor functional layer), and a transparent top electrode. The electrolyte (for electrochromism) and hydrogen source (for photochromism) are water vapor from the air. Introduced water mainly permeates into the smart window through its surface or edges. Under the action of an electric field, protons generated by ionizing water are transferred from the ion-conducting layer via proton hopping and embedded inside the electro / optical dual-response color-changing layer. Through small polaron absorption, the transmittance of visible light and near-infrared light is adjusted, thereby achieving the purpose of actively controlling sunlight (visible light) and heat (near-infrared light). Furthermore, under light irradiation, the electro / optical dual-response color-changing layer generates photogenerated holes and electrons, where the photogenerated holes can decompose the water adsorbed in the smart window to generate protons. Subsequently, these protons, along with photogenerated electrons, are transferred to the electro / optic dual-response color-changing layer, which colors the layer to reduce the visible light and near-infrared transmittance of the smart window, thereby achieving the purpose of adaptive control of sunlight and heat.

[0020] Advantages of this invention:

[0021] I. The electro / optical dual-response color-changing inorganic all-solid-state smart window prepared by this invention can not only adaptively change its transmittance to regulate indoor temperature according to changes in sunlight intensity, but also actively change its transmittance to regulate indoor temperature under a very small applied voltage. This not only greatly improves the indoor comfort of buildings, but also provides considerable energy-saving benefits by reducing dependence on artificial lighting and air conditioning, opening up new avenues for the development of high-performance smart windows;

[0022] II. The electro / optic dual-response color-changing inorganic all-solid-state smart window prepared by this invention can simultaneously respond to electric fields and light illumination to change color. Under light illumination, it can undergo photochromism, changing from colorless to blue within 4 hours, with a 41.2% decrease in transmittance. The photochromized smart window also exhibits excellent uniformity and stability, maintaining low visible light and near-infrared transmittance (38.8% and 28.5% at 633 and 1000 nm, respectively) even after prolonged dark treatment (approximately one day). This indicates that the electro / optic dual-response color-changing inorganic all-solid-state smart window can maintain a low transmittance state for a long time after photochromism. Therefore, the smart window can effectively block sunlight and heat from entering the room for a long time under photochromism, thereby greatly improving indoor comfort in hot weather and reducing energy consumption and labor costs. When the electro / optic dual-response color-changing inorganic all-solid-state smart window is subjected to an electric field, it can also rapidly undergo electro-fading, recovering to its initial state within 30 seconds. Even after returning to its initial state, the window can still perform electro-coloring normally, changing from colorless to deep blue within 30 seconds, with a 61.9% decrease in transmittance. Furthermore, the energy-saving building prototype composed of this smart window can not only adaptively adjust its transmittance to regulate indoor temperature based on changes in sunlight intensity (achieving a 4.7°C cooling effect), but also actively change its transmittance to regulate indoor temperature with a very small applied voltage (achieving a 5.3°C cooling effect). This not only significantly improves the indoor comfort of the building but also provides considerable energy-saving benefits by reducing reliance on artificial lighting and air conditioning. Moreover, the electro / optical dual-response color-changing inorganic all-solid-state smart window can repeatedly undergo light-coloring-electro-fading cycles. Even after 30 light-coloring-electro-fading cycles, the transmittance modulation amplitude only changes slightly, thus proving that the electro / optical dual-response color-changing inorganic all-solid-state smart window prepared in this invention is suitable for long-term operation. Attached Figure Description

[0023] Figure 1 SEM image of the electro / optic dual-response color-changing inorganic all-solid-state smart window prepared in Example 1;

[0024] Figure 2The visible-near-infrared transmittance spectrum of the electro / optic dual-response color-changing inorganic all-solid-state smart window prepared in Example 1 under different ultraviolet irradiation times;

[0025] Figure 3 The visible-near-infrared transmittance spectrum of the electro / optical dual-response color-changing inorganic all-solid-state smart window prepared in Example 1 under different voltages;

[0026] Figure 4 This is a graph showing the change in 633nm transmittance of the electro / optic dual-response color-changing inorganic all-solid-state smart window prepared in Example 1 during 30 photocoloring-electrodecolorization processes. Detailed Implementation

[0027] Specific implementation method one: The inorganic all-solid-state smart window with electro / optic dual-response color change in this implementation method has a seven-layer structure, including a transparent substrate, a transparent bottom electrode, an ion storage layer, an ion conductive layer, an electro / optic dual-response color change semiconductor coupling double layer, and a transparent top electrode. The electrolyte and hydrogen source are water in the air environment. The introduced water mainly permeates into the smart window through the porous surface or edge of the smart window.

[0028] The aforementioned electro / optic dual-response color-changing semiconductor coupled double layer is a double-layer structure composed of an electro / optic dual-response color-changing layer and a semiconductor functional layer;

[0029] The electro / optic dual-response color-changing layer plays the main role in color changing, and is oxygen-deficient modified tungsten oxide or oxygen-deficient modified niobium oxide with a thickness of 100-1000 nanometers.

[0030] The semiconductor functional layer enhances the color-changing effect of the electro / optic dual-response color-changing layer and increases the amount of water adsorption. It is made of titanium oxide nanoparticles, zinc oxide nanoparticles, silicon oxide nanoparticles or cadmium sulfide quantum dots, and is prepared by physical vapor deposition or wet chemical method, with a thickness of 1-100 nanometers.

[0031] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the transparent substrate is either a rigid substrate or a flexible substrate; the rigid substrate is quartz glass or polycarbonate; the flexible substrate is polyethylene terephthalate, polydimethylsiloxane, or polyimide. The other steps are the same as in Specific Implementation Method One.

[0032] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in that the transparent bottom electrode and transparent top electrode are one or more combinations of ITO, FTO, AZO, metal nanowires and metal meshes, and modified metal oxides, with a thickness of 10-500 nanometers. Other steps are the same as in Specific Implementation Method One or Two.

[0033] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that the ion storage layer is one of tungsten nickel oxide, nickel oxide, or iridium oxide, with a thickness of 10-800 nanometers. The other steps are the same as in Specific Implementation Methods One to Three.

[0034] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that the ion-conducting layer is one of tantalum pentoxide, zirconium dioxide, silicon dioxide, magnesium fluoride, calcium fluoride, and silicon nitride, with a thickness of 10-1000 nanometers. The other steps are the same as in Specific Implementation Methods One to Four.

[0035] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One through Five in that: the surface morphology and internal oxygen vacancy concentration of the electro / optical dual-response color-changing layer are controlled by regulating the evaporation rate of the material and the mass flow rate of oxygen during the electron beam evaporation process; the evaporation rate of the material during the electron beam evaporation process is... The oxygen mass flow rate is 0–20 sccm. Other steps are the same as in embodiments one through five.

[0036] Specific Implementation Method Seven: This implementation method is a preparation method for an electro / optical dual-response color-changing inorganic all-solid-state smart window, which is specifically completed according to the following steps:

[0037] I. Fabrication of transparent bottom electrodes on transparent substrates using physical vapor deposition;

[0038] II. Preparation of an ion storage layer on a transparent bottom electrode using physical vapor deposition;

[0039] III. An ion-conducting layer is prepared on an ion storage layer using physical vapor deposition.

[0040] IV. Preparing an electro / optic dual-response color-changing layer on an ion-conductive layer using physical vapor deposition;

[0041] 5. A semiconductor functional layer is deposited on the electro / optic dual-response color-changing layer using physical vapor deposition or wet chemical methods, so that the semiconductor functional layer and the electro / optic dual-response color-changing layer can be coupled to form a semiconductor coupled double layer with a heterojunction.

[0042] VI. A transparent top electrode was fabricated on an electro / optically dual-response color-changing semiconductor coupled bilayer using physical vapor deposition to obtain a seven-layer smart window structure.

[0043] 7. The prepared seven-layer smart window is subjected to heat treatment to obtain the heat-treated seven-layer smart window.

[0044] 8. The heat-treated seven-layer smart window is then subjected to a humidification process to introduce water as an electrolyte, resulting in an inorganic all-solid-state smart window with dual electro-optical response and color change.

[0045] Specific Implementation Method Eight: The difference between this implementation method and Specific Implementation Methods One through Seven is that the method for preparing the electro / optical dual-response color-changing layer on the ion-conductive layer using electron beam evaporation in step four is specifically completed according to the following steps:

[0046] A transparent substrate, already coated with a transparent bottom electrode, an ion storage layer, and an ion-conducting layer, is fixed onto a sample tray and then placed inside an evaporation chamber. The tungsten oxide or niobium oxide evaporation material is kept 25 cm away from the substrate, and a vacuum of 5 × 10⁻⁶ is applied. -4 Below Pa, then turn on the mass flow controller to introduce oxygen into the vacuum chamber, controlling the mass flow rate between 0 and 20 sccm, with the evaporation rate decreasing sequentially from fast to slow. and At an evaporation rate of [value missing], one-fifth of the required total thickness is deposited; simultaneously, the substrate is rotated at a speed of 20 revolutions per minute during the evaporation deposition process to ensure the uniformity of the film layer. Other steps are the same as in specific embodiments one through seven.

[0047] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that: the heat treatment described in step seven is performed in a vacuum, under argon gas, or in the atmosphere; the temperature of the heat treatment is 0℃ to 600℃, and the heat treatment time is 1 min to 600 min; the physical vapor deposition method is one or more of magnetron sputtering, electron beam evaporation, and vacuum resistance evaporation; the wet chemical method is a high-temperature solid-state method, a hydrothermal method, a sol-gel method, or an electrodeposition method. Other steps are the same as in Specific Implementation Methods One to Eight.

[0048] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Methods One through Nine in that: the humidification process described in step eight involves directly immersing the seven-layer smart window in water for 1 to 48 hours; or placing the seven-layer smart window in the air at a temperature of 20-30°C and a relative humidity of 10-90% for 1 to 72 hours; or placing the seven-layer smart window in a constant temperature and humidity chamber at a temperature of 10-35°C and a relative humidity of 0-100% for 1 to 72 hours. The other steps are the same as in Specific Implementation Methods One through Nine.

[0049] The beneficial effects of the present invention are verified using the following embodiments:

[0050] Example 1: A method for preparing an inorganic all-solid-state smart window with electro / optical dual-response color-changing properties, specifically completed according to the following steps:

[0051] 1. A transparent bottom electrode was fabricated on a transparent glass substrate using magnetron sputtering. The transparent bottom electrode was made of ITO and had a thickness of 180 nanometers.

[0052] The transparent glass substrate mentioned in step one is quartz glass;

[0053] II. An ion storage layer was prepared on a transparent bottom electrode by electron beam evaporation. The ion storage layer was nickel oxide and the thickness of the ion storage layer was 145 nanometers.

[0054] III. An ion-conducting layer was prepared on the ion storage layer by electron beam evaporation. The ion-conducting layer was tantalum oxide and the thickness of the ion-conducting layer was 280 nanometers.

[0055] IV. Preparation of electro / optic dual-response color-changing layers on ion-conductive layers using electron beam evaporation:

[0056] The electro / optic dual-response color-changing layer mentioned in step four is oxygen vacancy-modified tungsten oxide with a thickness of 430 nm. The surface morphology and internal oxygen vacancy concentration of the tungsten oxide are controlled by adjusting the material deposition rate and oxygen flow rate during electron beam evaporation. Specifically, a transparent substrate coated with a transparent bottom electrode, an ion storage layer, and an ion-conducting layer is fixed on a sample plate and placed inside the evaporation chamber. The distance between the tungsten oxide evaporation material and the substrate is maintained at 25 cm, and a vacuum of 5 × 10⁻⁶ is applied. -4 Below Pa, oxygen is introduced into the vacuum chamber by turning on the mass flow controller, with the mass flow rate controlled at 2.5 sccm. The evaporation rate gradually decreases, i.e., sequentially... and At the evaporation rate, one-fifth of the required total thickness is deposited; at the same time, the substrate is rotated at a speed of 20 revolutions per minute during the evaporation coating process to ensure the uniformity of the film layer;

[0057] 5. A semiconductor functional layer is deposited on the electro / optic dual-response color-changing layer using electron beam evaporation, so that the semiconductor functional layer and the electro / optic dual-response color-changing layer can interact to form a semiconductor coupled double layer with a heterojunction; the semiconductor functional layer is amorphous zinc oxide nanoparticles, and the thickness of the semiconductor functional layer is 40 nanometers.

[0058] VI. A top transparent conductive layer was prepared on an electro / optical dual-response color-changing semiconductor coupled bilayer using electron beam evaporation. The transparent top electrode was ITO, and the thickness of the transparent top conductive layer was 50 nanometers, resulting in a seven-layer smart window structure.

[0059] 7. The prepared seven-layer smart window is subjected to heat treatment to optimize the color-changing function; the heat treatment atmosphere is Ar, the heat treatment temperature is 400℃, and the time is 120 minutes.

[0060] 8. Place the heat-treated seven-layer smart window into a sealed box with constant temperature and humidity. The temperature inside the box is 25℃ and the humidity is 50-60%. The placement time is 48 hours to obtain an inorganic all-solid-state smart window with dual electro-optical response and color change.

[0061] Figure 1 SEM image of the electro / optic dual-response color-changing inorganic all-solid-state smart window prepared in Example 1;

[0062] from Figure 1 It can be seen that the electro / optic dual-response color-changing inorganic all-solid-state smart window prepared in Example 1 consists of, from bottom to top, a transparent glass substrate 1 (quartz glass), a transparent bottom electrode 2 (ITO, 180 nm), an ion storage layer 3 (NiO, 145 nm), an ion conductive layer 4 (Ta2O5, 280 nm), and an electro / optic dual-response color-changing layer 5 (O2O5, 280 nm). V -WO 3-x The film consists of a 430 nm semiconductor functional layer 6 (ZnO, 40 nm) and a transparent top electrode 7 (ITO, 50 nm). The interfaces between the layers are clear and free of cracks, which means that all the film layers have good physical and chemical stability.

[0063] Figure 2 The visible-near-infrared transmittance spectrum of the electro / optic dual-response color-changing inorganic all-solid-state smart window prepared in Example 1 under different ultraviolet irradiation times;

[0064] Figure 3 The visible-near-infrared transmittance spectrum of the electro / optical dual-response color-changing inorganic all-solid-state smart window prepared in Example 1 under different voltages;

[0065] from Figure 2 and Figure 3It is known that this electro / optic dual-response color-changing inorganic all-solid-state smart window can simultaneously respond to electric fields and light illumination, undergoing photochromism under light. Within 4 hours, its color changes from colorless to blue, with a 41.2% decrease in transmittance. Notably, the photochromic smart window also exhibits excellent uniformity and stability, maintaining low visible light and near-infrared transmittance (38.8% and 28.5% at 633 and 1000 nm, respectively) even after prolonged dark treatment (approximately one day). This indicates that the electro / optic dual-response color-changing inorganic all-solid-state smart window can maintain a low transmittance state for an extended period after photochromism. Therefore, this smart window can effectively block sunlight and heat from entering the room for a long time under photochromism, significantly improving indoor comfort in hot weather and reducing energy consumption and labor costs. When the electro / optic dual-response color-changing inorganic all-solid-state smart window is subjected to an electric field, it can also rapidly undergo electro-fading, returning to its initial state within 30 seconds. After returning to its initial state, it can still perform electro-coloring normally, changing from colorless to dark blue within 30 seconds, with a 61.9% decrease in transmittance. Furthermore, the energy-saving building prototype composed of this smart window can not only adaptively change its transmittance to regulate indoor temperature based on changes in sunlight intensity (achieving a 4.7℃ cooling effect), but also actively change its transmittance to regulate indoor temperature under a very small applied voltage (achieving a 5.3℃ cooling effect).

[0066] Figure 4 This is a graph showing the change in 633nm transmittance of the electro / optic dual-response color-changing inorganic all-solid-state smart window prepared in Example 1 during 30 photocoloring-electrodecolorization processes.

[0067] from Figure 4 It can be seen that the electro / optic dual-response color-changing inorganic all-solid-state smart window can repeatedly undergo photo-coloring-electro-fading cycles. Even after 30 photo-coloring-electro-fading cycles, the transmittance modulation amplitude only changes slightly, thus proving that the electro / optic dual-response color-changing inorganic all-solid-state smart window prepared by this invention is suitable for long-term operation.

Claims

1. An inorganic all-solid-state smart window with dual electro / optical response and color-changing properties, characterized in that... The electro / optic dual-response color-changing inorganic all-solid-state smart window has a seven-layer structure, including a transparent substrate, a transparent bottom electrode, an ion storage layer, an ion conductive layer, an electro / optic dual-response color-changing semiconductor coupling double layer, and a transparent top electrode. The electrolyte and hydrogen source are water in the air environment. The introduced water mainly permeates into the smart window through the porous surface or edge of the smart window. The aforementioned electro / optic dual-response color-changing semiconductor coupled double layer is a double-layer structure composed of an electro / optic dual-response color-changing layer and a semiconductor functional layer; The electro / optical dual-response color-changing layer is oxygen-deficient modified tungsten oxide or oxygen-deficient modified niobium oxide, with a thickness of 100-1000 nanometers. The semiconductor functional layer is composed of titanium oxide nanoparticles, zinc oxide nanoparticles, silicon oxide nanoparticles, or cadmium sulfide quantum dots, prepared using physical vapor deposition or wet chemical methods, with a thickness of 1-100 nanometers. The semiconductor functional layer enhances the color-changing effect of the electro / optic dual-response color-changing layer. Through semiconductor coupling with the electro / optic dual-response color-changing layer, a heterojunction is formed at the interface. This allows holes generated in the electro / optic dual-response color-changing layer under illumination to migrate along the valence band to the valence band of the semiconductor functional layer. The highest valence band value of the semiconductor functional layer is higher than that of the electro / optic dual-response color-changing layer, thereby decomposing water adsorbed on the surface of the nanoparticles in the semiconductor functional layer and generating protons. Simultaneously, photogenerated electrons from the electro / optic dual-response color-changing layer and the semiconductor functional layer are transferred to the conduction band of the semiconductor functional layer. The lowest conduction band value of the semiconductor functional layer is also higher than that of the electro / optic dual-response color-changing layer. This, along with the injection of previously generated protons, leads to the coloring of the electro / optic dual-response color-changing layer.

2. The inorganic all-solid-state smart window with electro / optical dual-response color-changing as described in claim 1, characterized in that... The transparent substrate can be a rigid substrate or a flexible substrate; the rigid substrate can be quartz glass or polycarbonate; the flexible substrate can be polyethylene terephthalate, polydimethylsiloxane or polyimide.

3. The inorganic all-solid-state smart window with electro / optical dual-response color-changing as described in claim 1, characterized in that... The transparent bottom electrode and transparent top electrode are one or a combination of ITO, FTO, AZO, metal nanowires and metal meshes, and modified metal oxides, with a thickness of 10-500 nanometers.

4. The inorganic all-solid-state smart window with electro / optical dual-response color-changing as described in claim 1, characterized in that... The ion storage layer is one of tungsten nickel oxide, nickel oxide, or iridium oxide, with a thickness of 10-800 nanometers.

5. The inorganic all-solid-state smart window with electro / optical dual-response color-changing as described in claim 1, characterized in that... The ion-conducting layer is one of tantalum pentoxide, zirconium dioxide, silicon dioxide, magnesium fluoride, calcium fluoride, and silicon nitride, with a thickness of 10-1000 nanometers.

6. The inorganic all-solid-state smart window with electro / optical dual-response color-changing as described in claim 1, characterized in that... The surface morphology and internal oxygen vacancy concentration of the electro / optic dual-response color-changing layer are controlled by adjusting the evaporation rate of the material and the mass flow rate of oxygen during the electron beam evaporation process; the evaporation rate of the material during the electron beam evaporation process is 5 Å / s to 25 Å / s, and the mass flow rate of oxygen is 0 to 20 sccm.

7. The method for preparing an inorganic all-solid-state smart window with electro / optical dual-response color change as described in claim 1, characterized in that... The preparation method is specifically carried out according to the following steps: I. Fabrication of transparent bottom electrodes on transparent substrates using physical vapor deposition; II. Preparation of an ion storage layer on a transparent bottom electrode using physical vapor deposition; III. An ion-conducting layer is prepared on an ion storage layer using physical vapor deposition. IV. Preparing an electro / optic dual-response color-changing layer on an ion-conductive layer using physical vapor deposition; 5. A semiconductor functional layer is deposited on the electro / optic dual-response color-changing layer using physical vapor deposition or wet chemical methods, so that the semiconductor functional layer and the electro / optic dual-response color-changing layer can be coupled to form a semiconductor coupled double layer with a heterojunction. VI. A transparent top electrode was fabricated on an electro / optically dual-response color-changing semiconductor coupled bilayer using physical vapor deposition to obtain a seven-layer smart window structure.

7. The prepared seven-layer smart window is subjected to heat treatment to obtain the heat-treated seven-layer smart window.

8. The heat-treated seven-layer smart window is then subjected to a humidification process to introduce water as an electrolyte, resulting in an inorganic all-solid-state smart window with dual electro-optical response and color change.

8. The method for preparing an inorganic all-solid-state smart window with electro / optical dual-response color change according to claim 7, characterized in that... Step four involves using electron beam evaporation to prepare an electro / optical dual-response color-changing layer on an ion-conductive layer. This process is specifically completed as follows: A transparent substrate, already coated with a transparent bottom electrode, an ion storage layer, and an ion-conducting layer, is fixed onto a sample tray and then placed inside an evaporation chamber. The tungsten oxide or niobium oxide evaporation material is kept 25 cm away from the substrate, and a vacuum of 5 × 10⁻⁶ is applied. -4 Below Pa, oxygen is introduced into the vacuum chamber by turning on the mass flow controller. The mass flow rate is controlled between 0 and 20 sccm. The evaporation rate is gradually reduced from fast to slow, that is, one-fifth of the required total thickness is deposited at evaporation rates of 25 Å / s, 20 Å / s, 15 Å / s, 10 Å / s and 5 Å / s respectively. At the same time, the substrate is rotated at a speed of 20 revolutions per minute during the evaporation coating process to ensure the uniformity of the film layer.

9. The method for preparing an inorganic all-solid-state smart window with electro / optical dual-response color change according to claim 7, characterized in that... The heat treatment described in step seven is carried out in a vacuum, under argon or atmospheric conditions; the temperature of the heat treatment is 0℃~600℃, and the heat treatment time is 1min~600min; the physical vapor deposition method is one or more of magnetron sputtering, electron beam evaporation and vacuum resistance evaporation; the wet chemical method is a high-temperature solid-state method, a hydrothermal method, a sol-gel method or an electrodeposition method.

10. The method for preparing an inorganic all-solid-state smart window with electro / optical dual-response color change according to claim 7, characterized in that... The humidification process described in step eight involves directly immersing the seven-layer smart window in water for 1 to 48 hours; or placing the seven-layer smart window in the air at a temperature of 20-30°C and a relative humidity of 10-90% for 1 to 72 hours; or placing the seven-layer smart window in a constant temperature and humidity chamber at a temperature of 10-35°C and a relative humidity of 0-100% for 1 to 72 hours.

Images