An inorganic all-solid-state electric / optical dual-response variable infrared emissivity device and a preparation method thereof

Abstract

An inorganic all-solid-state electro / optic dual-response variable infrared emissivity device and its fabrication method are disclosed, belonging to the field of active intelligent thermal management materials technology. This invention addresses the problem that existing technologies for regulating infrared emissivity often limit materials and devices to a single stimulus signal response mode, making it difficult to achieve synergistic electro-optic dual-stimulation drive and meet the challenge of flexible and precise control of infrared emissivity performance in complex scenarios. The device comprises, from bottom to top, a substrate, a bottom electrode, an ion storage layer, a solid electrolyte layer, an infrared high-reflectivity top electrode, and an electro / optic dual-response plasmonic nanocrystalline layer. The method involves sequentially fabricating the bottom electrode, ion storage layer, solid electrolyte layer, and infrared high-reflectivity top electrode using physical vapor deposition (PVD), followed by fabrication of the electro / optic dual-response plasmonic nanocrystalline layer using PVD or wet chemical methods, and finally heat treatment. This invention relates to inorganic all-solid-state electro / optic dual-response variable infrared emissivity devices and their fabrication.

Description

Technical Field

[0001] This invention belongs to the field of active intelligent thermal management materials technology. Background Technology

[0002] The stringent requirements of the aerospace industry for adaptability to extreme environments, efficient energy utilization, and precise thermal control are driving the upgrade of spacecraft thermal control systems towards intelligence and multi-functionality. Spacecraft in orbit must cope with extreme conditions such as drastic fluctuations in solar radiation and high-low temperature cycles. Flexible adjustment of infrared emissivity is crucial for accurately maintaining cabin temperature, directly determining equipment reliability and mission lifespan. Against this backdrop, variable emissivity intelligent thermal control devices have become a key solution, dynamically adjusting infrared radiation characteristics through external stimuli such as electric fields and light to achieve adaptive thermal control. Mainstream thermal control devices are classified into three categories based on their response mechanisms: electrochromic (EC), photochromic (PC), and thermochromic (TC). EC devices can adjust emissivity over a wide range, quickly, and reversibly, meeting the requirements for precise control. However, they have weak optical memory effects and require intermittent or continuous power supply to maintain their state, increasing spacecraft energy consumption and system complexity. PC devices have the advantage of passive self-adaptation, autonomously adjusting emissivity according to solar irradiance intensity without additional energy input, conforming to the aerospace lightweight and low-power design concept. However, their adjustment range is small, their response speed is slow, and they are irreversible, making them difficult to adapt to the dynamic thermal control requirements of extreme operating conditions. Therefore, electro / optical dual-response all-solid-state devices that combine the core advantages of both are a key direction for breaking through the bottleneck of aerospace intelligent thermal control technology. However, most current aerospace variable infrared emissivity devices are still limited to a single stimulus response mode. Electro / optical dual-response functionality has not yet been realized in inorganic all-solid-state systems, failing to meet the core requirements for flexible, precise, and low-power control of infrared emissivity in complex orbital environments. Summary of the Invention

[0003] This invention addresses the problem that existing materials and devices for regulating infrared emissivity are mostly limited to a single stimulus signal response mode, making it difficult to achieve electro-optic dual-stimulation synergistic drive and meet the problem of flexible and precise control of infrared emissivity performance in complex scenarios. Therefore, this invention provides an inorganic all-solid-state electro / optic dual-response variable infrared emissivity device and its preparation method.

[0004] An inorganic all-solid-state electro / optical dual-response variable infrared emissivity device comprises, from bottom to top, a substrate, a bottom electrode, an ion storage layer, a solid electrolyte layer, an infrared high-reflectivity top electrode, and an electro / optical dual-response plasma nanocrystalline layer.

[0005] A method for fabricating an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device, comprising the following steps:

[0006] 1. A bottom electrode is fabricated on a substrate using physical vapor deposition.

[0007] II. An ion storage layer is prepared on the bottom electrode using physical vapor deposition.

[0008] III. A solid electrolyte layer is prepared on the ion storage layer using physical vapor deposition.

[0009] IV. An infrared high-reflectivity top electrode was prepared on a solid electrolyte layer using physical vapor deposition.

[0010] V. Prepare an electro / optic dual-response plasma nanocrystalline layer on an infrared high-reflectivity top electrode using physical vapor deposition or wet chemical methods;

[0011] VI. Heat treatment yields an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device.

[0012] Principle: This invention designs and fabricates an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device, which employs a unique six-layer structure consisting of a substrate, a bottom electrode, an ion storage layer, a solid electrolyte layer, an infrared high-reflectivity top electrode, and an electro / optical dual-response plasmonic nanocrystal layer. The electro / optical dual-response plasmonic nanocrystal layer, as the core functional layer, plays a crucial role in regulating infrared emissivity. Its unique plasmonic effect and crystal structure characteristics provide the foundation for carrier migration and optical performance modulation. The infrared high-reflectivity top electrode not only possesses high infrared reflectivity but also functions as an ion transport channel, ensuring both efficient optical regulation in the infrared band and ion conduction between the electrolyte layer and the nanocrystal layer. The ion storage layer is responsible for the temporary storage and release of ions, working in conjunction with the ion transport function of the solid electrolyte layer to construct a stable ion cycling system, ensuring the reversibility and long-term effectiveness of the device response.

[0013] Under the influence of an electric field, electrons are injected into or extracted from the electro / optic dual-response plasma nanocrystal layer driven by the applied electric field. This directly induces precise changes in the carrier concentration within the nanocrystal layer, thereby modulating infrared optical parameters through the plasma resonance effect and achieving active and rapid adjustment of infrared emissivity. Simultaneously, ions in the solid electrolyte layer pass through the ion channels of the infrared high-reflectivity top electrode under the influence of the electric field and are directionally adsorbed onto the surface of the plasma nanocrystal layer, forming a charge balance system. This effectively suppresses device structural distortion caused by oxygen vacancy migration, ensuring the stability and reliability of the device during long-term operation. Under solar irradiation, the electro / optic dual-response plasma nanocrystal layer generates photogenerated carriers (electron-hole pairs) upon illumination. The separation and migration of photogenerated carriers significantly modulate the carrier concentration and distribution of the nanocrystal layer, thereby altering the infrared LSPR absorption intensity and achieving adaptive control of infrared emissivity.

[0014] The beneficial effects of this invention are:

[0015] 1. The inorganic all-solid-state electro / optical dual-response variable infrared emissivity device prepared by this invention possesses a dual regulation mechanism: on the one hand, it can adaptively adjust the infrared emissivity to regulate the device surface temperature according to the dynamic changes in sunlight intensity, achieving passive thermal management without additional energy consumption; on the other hand, it can achieve precise regulation of infrared emissivity by actively regulating the carrier concentration under low applied voltage (low power consumption) conditions, achieving the goal of active temperature control. This dual regulation characteristic not only significantly improves the temperature control accuracy and response speed of spacecraft thermal control systems, but also significantly reduces system energy consumption, solving the technical bottleneck of traditional spacecraft thermal control devices with single regulation and high energy consumption.

[0016] 2. The inorganic all-solid-state electro / optical dual-response variable infrared emissivity device prepared by this invention can achieve precise control of infrared emissivity under dual stimulation of electric field and sunlight. Under sunlight, the infrared emissivity of the device exhibits a dynamic increasing trend: it can increase from an initial 0.3 to 0.5 within 20 minutes, and further increase to 0.79 after 60 minutes as the irradiation time continues to extend, ultimately achieving an infrared emissivity modulation amplitude as high as 0.49. This characteristic enables the device to adaptively enhance the intensity of infrared thermal radiation into space when the spacecraft is on the sun-facing side, effectively reducing the surface temperature of the spacecraft, significantly reducing the energy consumption required for heat dissipation of the spacecraft system, and achieving passive and efficient thermal management. Meanwhile, the device also features voltage-driven active regulation, meeting the thermal control requirements of spacecraft under different operating conditions: when the spacecraft needs rapid heat dissipation, applying a small voltage of -2.5V and maintaining it for 30 seconds allows the device to quickly switch to a high emissivity state (emissivity 0.79) for efficient heat dissipation; conversely, when the spacecraft needs heat preservation, applying a small voltage of +2.5V and maintaining it for 30 seconds allows the device to quickly return to a low emissivity state (emissivity 0.29), effectively locking in internal heat. This dual regulation mode of "passive adaptive + active rapid response" significantly improves the temperature control accuracy and response speed of the spacecraft's thermal control system, providing a reliable guarantee for the stable operation of the spacecraft in extreme environments. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the structure of the inorganic all-solid-state electro / optic dual-response variable infrared emissivity device of the present invention. 1 is the electro / optic dual-response plasma nanocrystalline layer, 2 is the infrared high-reflection top electrode, 3 is the solid electrolyte layer, 4 is the ion storage layer, 5 is the bottom electrode, and 6 is the substrate.

[0018] Figure 2 This is a schematic diagram of the electro / optical dual-response modulation mechanism of the inorganic all-solid-state electro / optical dual-response variable infrared emissivity device of the present invention;

[0019] Figure 3The infrared emissivity variation spectrum of the inorganic all-solid-state electro / optic dual-response variable infrared emissivity device prepared in Example 1 under different solar irradiation times;

[0020] Figure 4 The infrared emissivity variation spectrum of the inorganic all-solid-state electro / optical dual-response variable infrared emissivity device prepared in Example 1 under different voltages;

[0021] Figure 5 The infrared emissivity variation spectra of the inorganic all-solid-state electro / optic dual-response variable infrared emissivity device prepared in Example 2 are shown under solar irradiation and under voltage. Detailed Implementation

[0022] Specific implementation method one, combined with Figure 1 Detailed description: This embodiment is an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device, which consists of, from bottom to top, a substrate, a bottom electrode, an ion storage layer, a solid electrolyte layer, an infrared high-reflection top electrode, and an electro / optical dual-response plasma nanocrystal layer.

[0023] The bottom electrode is connected to an external circuit, and when an external voltage is applied, an electric field is formed, which drives the movement of electrons and ions in the device.

[0024] The ion storage layer is used to temporarily store / release ions in the electrolyte during the process of regulating infrared emissivity, balance the charge of the electro / optic dual-response plasma nanocrystal layer, and avoid ion accumulation that could lead to device performance degradation or failure.

[0025] The solid electrolyte layer is used to provide mobile ions to transfer charge to balance the surface charge of the electro / optic dual-response plasma nanocrystalline layer, ensuring the stable operation of the process of regulating infrared emissivity.

[0026] The infrared high-reflection top electrode has both electron conduction and infrared light reflection functions. By reflecting the infrared light incident on the device, the device presents an initial low infrared emissivity state.

[0027] The electro / optical dual-response plasma nanocrystalline layer plays a major role in regulating infrared emissivity.

[0028] Figure 2 This is a schematic diagram of the electro / optical dual-response modulation mechanism of the inorganic all-solid-state electro / optical dual-response variable infrared emissivity device of the present invention. The core modulation process is as follows:

[0029] Initial state: The electro-optic dual-response plasma nanocrystal layer in the device exhibits high infrared transmittance. Combined with the infrared emission suppression effect of the infrared high-reflection top electrode, the device as a whole exhibits a low infrared emission (high reflection) state.

[0030] Optical response modulation: Under solar irradiation, the electro-optic dual-response plasma nanocrystal layer is stimulated to generate photogenerated carriers; the separation and migration of carriers change the carrier concentration and distribution of the nanocrystal layer, triggering local surface plasmon resonance (LSPR) absorption, enhancing the infrared absorption capability of the device, and enabling the device to switch to the infrared high emissivity state.

[0031] Electro-response modulation: After applying an electric field, electrons are injected into the electro-optic dual-response plasma nanocrystalline layer under the drive of the external field, directly modulating the internal carrier concentration. Infrared absorption is enhanced through the LSPR effect, and the device also switches to a high infrared emissivity state. At the same time, ions in the solid electrolyte layer penetrate the infrared high-reflectivity top electrode and adsorb on the surface of the nanocrystalline layer to achieve charge balance, effectively suppressing device structure degradation caused by oxygen vacancy migration.

[0032] This specific embodiment designs and fabricates an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device. Under the influence of an electric field, electron injection or extraction from the plasma nanocrystalline layer induces changes in carrier concentration, enabling active control of infrared optical performance. Simultaneously, ions in the electrolyte layer pass through the infrared high-reflectivity top electrode and adsorb onto the surface of the nanocrystalline layer to balance the charge, preventing oxygen vacancy migration from causing structural changes in the device. Under solar irradiation, the plasma nanocrystalline layer generates photogenerated carriers, achieving adaptive control of infrared emission by adjusting the intensity of localized surface plasmon resonance (LSPR) of infrared light. This device can adaptively adjust its surface temperature according to changes in sunlight intensity and can also actively and precisely control the temperature under low applied voltage, significantly improving the thermal control accuracy of spacecraft while significantly reducing energy consumption, opening up a new path for the development of next-generation spacecraft thermal control systems.

[0033] The beneficial effects of this specific implementation method are:

[0034] 1. The inorganic all-solid-state electro / optical dual-response variable infrared emissivity device prepared in this specific embodiment possesses a dual regulation mechanism: on the one hand, it can adaptively adjust the infrared emissivity to regulate the device surface temperature according to the dynamic changes in sunlight intensity, achieving passive thermal management without additional energy consumption; on the other hand, it can achieve precise regulation of infrared emissivity by actively regulating the carrier concentration under low applied voltage (low power consumption) conditions, achieving the goal of active temperature control. This dual regulation characteristic not only significantly improves the temperature control accuracy and response speed of the spacecraft thermal control system, but also significantly reduces the system energy consumption, solving the technical bottleneck of traditional spacecraft thermal control devices with single regulation and high energy consumption.

[0035] 2. The inorganic all-solid-state electro / optical dual-response variable infrared emissivity device prepared in this specific embodiment can achieve precise control of infrared emissivity under dual stimulation of electric field and sunlight. Under sunlight conditions, the infrared emissivity of the device exhibits a dynamic increasing trend: it can increase from the initial 0.3 to 0.5 within 20 minutes, and further increase to 0.79 after 60 minutes as the irradiation time continues to extend, ultimately achieving an infrared emissivity modulation amplitude as high as 0.49. This characteristic enables the device to adaptively enhance the intensity of infrared thermal radiation into space when the spacecraft is on the sun-facing side, effectively reducing the surface temperature of the spacecraft, significantly reducing the energy consumption required for heat dissipation of the spacecraft system, and achieving passive and efficient thermal management. Meanwhile, the device also features voltage-driven active regulation, meeting the thermal control requirements of spacecraft under different operating conditions: when the spacecraft needs rapid heat dissipation, applying a small voltage of -2.5V and maintaining it for 30 seconds allows the device to quickly switch to a high emissivity state (emissivity 0.79) for efficient heat dissipation; conversely, when the spacecraft needs heat preservation, applying a small voltage of +2.5V and maintaining it for 30 seconds allows the device to quickly return to a low emissivity state (emissivity 0.29), effectively locking in internal heat. This dual regulation mode of "passive adaptive + active rapid response" significantly improves the temperature control accuracy and response speed of the spacecraft's thermal control system, providing a reliable guarantee for the stable operation of the spacecraft in extreme environments.

[0036] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the substrate is a rigid substrate or a flexible substrate; the bottom electrode is a metal conductive electrode or a semiconductor conductive electrode. Everything else is the same as in Specific Implementation Method One.

[0037] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in that: the rigid substrate is quartz glass or polycarbonate; the flexible substrate is polyethylene terephthalate, polydimethylsiloxane, or polyimide; the metal conductive electrode is silver, gold, aluminum, or copper; and the semiconductor conductive electrode is ITO, FTO, AZO, or a modified metal oxide. Everything else is the same as in Specific Implementation Method One or Two.

[0038] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that: the ion storage layer is nickel oxide, tungsten-doped nickel oxide, ITO, or AZO; the solid electrolyte layer is lithium fluoride, magnesium fluoride, calcium fluoride, lithium tantalate, lithium niobate, lithium nickelate, or lithium nickel manganese oxide; the infrared high-reflection top electrode is one or a combination of several of ITO, FTO, AZO, metal nanowires, metal meshes, and modified metal oxides; and the electro / optical dual-response plasma nanocrystalline layer is ITO, FTO, AZO, IGZO, or a modified metal semiconductor material. Everything else is the same as in Specific Implementation Methods One to Three.

[0039] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that: the thickness of the bottom electrode is 10nm~500nm; the thickness of the ion storage layer is 10nm~800nm; the thickness of the solid electrolyte layer is 10nm~2000nm; the thickness of the infrared high-reflectivity top electrode is 10nm~500nm; and the thickness of the electro / optical dual-response plasma nanocrystalline layer is 50nm~1000nm. Everything else is the same as in Specific Implementation Methods One to Four.

[0040] Specific Implementation Method Six: This implementation method describes a method for fabricating an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device, which is carried out according to the following steps:

[0041] 1. A bottom electrode is fabricated on a substrate using physical vapor deposition.

[0042] II. An ion storage layer is prepared on the bottom electrode using physical vapor deposition.

[0043] III. A solid electrolyte layer is prepared on the ion storage layer using physical vapor deposition.

[0044] IV. An infrared high-reflectivity top electrode was prepared on a solid electrolyte layer using physical vapor deposition.

[0045] V. Prepare an electro / optic dual-response plasma nanocrystalline layer on an infrared high-reflectivity top electrode using physical vapor deposition or wet chemical methods;

[0046] VI. Heat treatment yields an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device.

[0047] The crystal structure and internal plasma concentration of the electro / optic dual-response plasma nanocrystal layer described in this specific embodiment can be controlled by parameters of two preparation paths:

[0048] Firstly, for physical vapor deposition (PVD) processes, basic control can be achieved by adjusting the sputtering power and oxygen content during the material deposition process. Subsequently, further calibration can be achieved by optimizing key parameters of the heat treatment process (including heat treatment temperature, holding time, and heat treatment atmosphere) to reach the target control effect.

[0049] Secondly, for the wet chemical preparation process, the performance can be adjusted by controlling the precursor concentration, reaction temperature, reaction time, pH value and surface modifier dosage during the preparation process. Subsequently, the performance can also be adjusted and improved by controlling the number of washings, drying temperature, drying time and heat treatment atmosphere in the post-treatment process.

[0050] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Method Six in that: the physical vapor deposition method described in steps one to five is one or a combination of several of molecular beam epitaxy, magnetron sputtering, electron beam evaporation, and resistance evaporation; the wet chemical method described in step five is a high-temperature solid-state method, hydrothermal method, sol-gel method, or electrodeposition method. Everything else is the same as in Specific Implementation Method Six.

[0051] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Method Six or Seven in that: in step five, when using magnetron sputtering as the physical vapor deposition method to prepare an electro / optical dual-response plasma nanocrystalline layer on an infrared high-reflectivity top electrode, the specific steps are as follows: deposition is carried out under the conditions of a mixed atmosphere of oxygen and inert gas, a substrate temperature of 10℃~600℃, a sputtering pressure ≤5Pa, a sputtering rate of 1nm / min~100nm / min, and a sputtering power of 1kW~20kW; the mass percentage of oxygen in the mixed atmosphere of oxygen and inert gas is 1%~20%. Everything else is the same as in Specific Implementation Method Six or Seven.

[0052] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods Six to Eight in that: in step five, when using a hydrothermal method (wet chemical method) to prepare an electro / optical dual-response plasma nanocrystalline layer on an infrared high-reflection top electrode, the specific steps are as follows: The device prepared in step four is immersed in a precursor solution, and a hydrothermal reaction is carried out at a temperature of 20℃~400℃ for 30 min~1440 min. After the hydrothermal reaction, it is washed 1 to 5 times, and then vacuum dried at a temperature of 40℃~120℃ for 30 min~720 min; the precursor solution consists of a precursor, The surface modifier and solvent composition are as follows: the precursor is a metal salt precursor; the surface modifier is one or a combination of several of the following: polyvinylpyrrolidone, hexadecyltrimethylammonium bromide, citric acid, ethylenediaminetetraacetic acid, ethylene glycol, and polyvinyl alcohol; the solvent is one or a combination of several of the following: deionized water, anhydrous ethanol, ethylene glycol, and isopropanol; the total concentration of metal ions in the precursor solution is 0.01 mol / L to 0.5 mol / L, and the mass of the surface modifier is 0.5% to 20% of the precursor mass; the pH value of the precursor solution is 2 to 11. Other aspects are the same as in specific embodiments six to eight.

[0053] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Methods Six to Nine in that the heat treatment described in step six is ​​performed in a vacuum environment, argon atmosphere, nitrogen atmosphere, atmospheric environment, or nitrogen-hydrogen mixed atmosphere, at a heat treatment temperature of 10℃ to 600℃, and held at that temperature for 30 min to 600 min. Everything else is the same as in Specific Implementation Methods Six to Nine.

[0054] The beneficial effects of the present invention are verified using the following embodiments:

[0055] Example 1:

[0056] An inorganic all-solid-state electro / optical dual-response variable infrared emissivity device comprises, from bottom to top, a substrate, a bottom electrode, an ion storage layer, a solid electrolyte layer, an infrared high-reflectivity top electrode, and an electro / optical dual-response plasma nanocrystalline layer.

[0057] The substrate is quartz glass;

[0058] The bottom electrode is a gold electrode;

[0059] The ion storage layer is tungsten-doped nickel oxide (W-NiO).

[0060] The solid electrolyte layer is lithium fluoride (LiF).

[0061] The infrared high-reflection top electrode is ITO (indium-doped tin oxide);

[0062] The electro / optic dual-response plasma nanocrystalline layer is IGZO (indium gallium zinc oxide).

[0063] The thickness of the bottom electrode is 50 nm; the thickness of the ion storage layer is 190 nm; the thickness of the solid electrolyte layer is 200 nm; the thickness of the infrared high-reflectivity top electrode is 100 nm; and the thickness of the electro / optical dual-response plasma nanocrystalline layer is 450 nm.

[0064] The above-mentioned method for fabricating an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device is carried out according to the following steps:

[0065] I. A bottom electrode was fabricated on a substrate using magnetron sputtering with an Au target as the target material under the conditions of argon atmosphere, substrate temperature of 25℃, sputtering pressure of 1.0 Pa, sputtering power of 50 kW, and sputtering rate of 20 nm / min.

[0066] II. Using magnetron sputtering, an ion storage layer was prepared on the bottom electrode under the following conditions: oxygen atmosphere, substrate temperature of 200℃, sputtering pressure of 0.65Pa, sputtering power of 10kW, and sputtering rate of 15nm / min.

[0067] III. A solid electrolyte layer was prepared on the ion storage layer by electron beam evaporation with LiF as the evaporation particle under the conditions of a substrate temperature of 25℃, a deposition gas pressure of 0.005Pa, an evaporation beam current of 60A and an evaporation rate of 100 nm / min.

[0068] IV. Using electron beam evaporation with ITO as the evaporation particles, an infrared high-reflectivity top electrode was prepared on a solid electrolyte layer under the conditions of a substrate temperature of 100℃, a deposition pressure of 0.003Pa, an evaporation beam current of 35A, and an evaporation rate of 120nm / min.

[0069] V. Using magnetron sputtering with an IGZO target as the target material, an electro / optical dual-response plasma nanocrystalline layer was prepared on an infrared high-reflectivity top electrode under the conditions of a mixed atmosphere of oxygen and argon, a substrate temperature of 200℃, a sputtering pressure of 0.5Pa, a sputtering rate of 10nm / min, and a sputtering power of 8.2kW.

[0070] The oxygen content in the oxygen and argon mixture atmosphere is 2% by mass.

[0071] VI. Under an argon atmosphere and at a temperature of 350℃, a heat treatment of 120 min was performed to obtain an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device.

[0072] Example 2:

[0073] An inorganic all-solid-state electro / optical dual-response variable infrared emissivity device comprises, from bottom to top, a substrate, a bottom electrode, an ion storage layer, a solid electrolyte layer, an infrared high-reflectivity top electrode, and an electro / optical dual-response plasma nanocrystalline layer.

[0074] The substrate is quartz glass;

[0075] The bottom electrode is an aluminum electrode;

[0076] The ion storage layer is nickel oxide (NiO);

[0077] The solid electrolyte layer is magnesium fluoride (MgF2).

[0078] The infrared high-reflection top electrode is FTO (fluorine-doped tin oxide).

[0079] The electro / optic dual-response plasma nanocrystalline layer is AZO (aluminum-doped zinc oxide).

[0080] The thickness of the bottom electrode is 200 nm; the thickness of the ion storage layer is 180 nm; the thickness of the solid electrolyte layer is 180 nm; the thickness of the infrared high-reflectivity top electrode is 120 nm; and the thickness of the electro / optical dual-response plasma nanocrystalline layer is 1000 nm.

[0081] The above-mentioned method for fabricating an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device is carried out according to the following steps:

[0082] I. A bottom electrode was fabricated on a substrate using magnetron sputtering with an Al target as the target material under the conditions of argon atmosphere, substrate temperature of 100℃, sputtering pressure of 0.8Pa, sputtering power of 60kW, and sputtering rate of 15nm / min.

[0083] II. An ion storage layer was fabricated on the bottom electrode using magnetron sputtering with a Ni target as the target material under the conditions of a mixed atmosphere of oxygen and argon, a substrate temperature of 200℃, a sputtering pressure of 0.55Pa, a sputtering power of 10kW, and a sputtering rate of 12nm / min.

[0084] The mass percentage of oxygen in the oxygen and argon mixture is 80%.

[0085] III. A solid electrolyte layer was prepared on the ion storage layer by electron beam evaporation with MgF2 as the evaporation particle under the conditions of a substrate temperature of 100℃, a deposition gas pressure of 0.004Pa, an evaporation beam current of 80A and an evaporation rate of 80nm / min.

[0086] IV. Using electron beam evaporation with FTO as the evaporation particle, an infrared high-reflectivity top electrode was prepared on a solid electrolyte layer under the conditions of a substrate temperature of 25℃, a deposition gas pressure of 0.003Pa, an evaporation beam current of 35A, and an evaporation rate of 75nm / min.

[0087] 5. Using a hydrothermal method, the device prepared in step 4 was immersed in a precursor solution and subjected to a hydrothermal reaction at 80°C for 120 min. After the hydrothermal reaction, it was washed three times with deionized water and once with anhydrous ethanol. Then, it was vacuum dried at 60°C for 120 min to obtain an electro / optical dual-response plasma nanocrystalline layer on the infrared high-reflection top electrode.

[0088] The precursor solution comprises a precursor, a surface modifier, and a solvent; the precursor is a mixture of zinc nitrate hexahydrate and aluminum nitrate nonahydrate, with an Al to Zn molar ratio of 1:99; the surface modifier is PEG-400; the solvent is a mixture of deionized water and anhydrous ethanol in a volume ratio of 1:2; the total concentration of metal ions in the precursor solution is 0.1 mol / L, and the mass of the surface modifier is 0.5% of the precursor mass; the pH value of the precursor solution is 8.5.

[0089] VI. Under a nitrogen-hydrogen mixed atmosphere and a temperature of 350℃, heat treatment for 60 min yields an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device.

[0090] The volume ratio of nitrogen to hydrogen in the nitrogen-hydrogen mixed atmosphere is 95:5.

[0091] Figure 3 The infrared emissivity variation spectrum of the inorganic all-solid-state electro / optical dual-response variable infrared emissivity device prepared in Example 1 under different solar irradiation times. Under illumination, the average infrared emissivity of the device exhibits a dynamic increasing characteristic: it increases from an initial 0.3 to 0.5 within 20 minutes, further increases to 0.79 after 60 minutes, and finally achieves a high modulation amplitude of 0.49.

[0092] Figure 4 The infrared emissivity variation spectrum of the inorganic all-solid-state electro / optical dual-response variable infrared emissivity device prepared in Example 1 under different voltages is shown. When a small voltage of -2.5V is applied and maintained for 30 seconds, the device can quickly switch to a high emissivity state (average infrared emissivity 0.79); when a small voltage of +2.5V is applied and maintained for 30 seconds, it quickly returns to a low emissivity state (average infrared emissivity 0.29), exhibiting rapid and reversible electromodulation performance.

[0093] Figure 5 The infrared emissivity variation spectra of the inorganic all-solid-state electro / optical dual-response variable infrared emissivity device prepared in Example 2 are shown under solar irradiation and under voltage. Under illumination, the average infrared emissivity of the device increases from 0.15 to 0.56 after 60 minutes, ultimately achieving a high modulation amplitude of 0.41. Applying a small voltage of -2.5V and maintaining it for 30 seconds allows the device to quickly switch to a high emissivity state (average infrared emissivity 0.73), exhibiting rapid and reversible electromodulation performance (modulation amplitude 0.58).

Claims

1. An inorganic all-solid-state electro / optical dual-response variable infrared emissivity device, characterized in that... From bottom to top, it consists of a substrate, a bottom electrode, an ion storage layer, a solid electrolyte layer, an infrared high-reflectivity top electrode, and an electro / optical dual-response plasma nanocrystalline layer.

2. The inorganic all-solid-state electro / optical dual-response variable infrared emissivity device according to claim 1, characterized in that... The substrate is a rigid substrate or a flexible substrate; the bottom electrode is a metal conductive electrode or a semiconductor conductive electrode.

3. The inorganic all-solid-state electro / optical dual-response variable infrared emissivity device according to claim 2, characterized in that... The rigid substrate is quartz glass or polycarbonate; the flexible substrate is polyethylene terephthalate, polydimethylsiloxane or polyimide; the metal conductive electrode is silver, gold, aluminum or copper; the semiconductor conductive electrode is ITO, FTO, AZO or modified metal oxide.

4. The inorganic all-solid-state electro / optical dual-response variable infrared emissivity device according to claim 1, characterized in that... The ion storage layer is nickel oxide, tungsten-doped nickel oxide, ITO, or AZO; the solid electrolyte layer is lithium fluoride, magnesium fluoride, calcium fluoride, lithium tantalate, lithium niobate, lithium nickelate, or lithium nickel manganese oxide; the infrared high-reflection top electrode is one or a combination of several of ITO, FTO, AZO, metal nanowires, metal meshes, and modified metal oxides; the electro / optic dual-response plasma nanocrystalline layer is ITO, FTO, AZO, IGZO, or a modified metal semiconductor material.

5. The inorganic all-solid-state electro / optical dual-response variable infrared emissivity device according to claim 1, characterized in that... The thickness of the bottom electrode is 10nm~500nm; the thickness of the ion storage layer is 10nm~800nm; the thickness of the solid electrolyte layer is 10nm~2000nm; the thickness of the infrared high-reflectivity top electrode is 10nm~500nm; and the thickness of the electro / optical dual-response plasma nanocrystalline layer is 50nm~1000nm.

6. The method for fabricating an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device as described in claim 1, characterized in that... It is done in the following steps:

1. A bottom electrode is fabricated on a substrate using physical vapor deposition. II. An ion storage layer is prepared on the bottom electrode using physical vapor deposition. III. A solid electrolyte layer is prepared on the ion storage layer using physical vapor deposition. IV. An infrared high-reflectivity top electrode was prepared on a solid electrolyte layer using physical vapor deposition. V. Prepare an electro / optic dual-response plasma nanocrystalline layer on an infrared high-reflectivity top electrode using physical vapor deposition or wet chemical methods; VI. Heat treatment yields an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device.

7. The method for fabricating an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device according to claim 6, characterized in that... The physical vapor deposition method described in steps one to five is one or a combination of several of the following: molecular beam epitaxy, magnetron sputtering, electron beam evaporation, and resistance evaporation; the wet chemical method described in step five is a high-temperature solid-phase method, a hydrothermal method, a sol-gel method, or an electrodeposition method.

8. The method for fabricating an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device according to claim 6, characterized in that... In step five, when using magnetron sputtering as the physical vapor deposition method to prepare an electro / optical dual-response plasma nanocrystalline layer on an infrared high-reflectivity top electrode, the specific steps are as follows: deposition is carried out under the conditions of a mixed atmosphere of oxygen and inert gas, a substrate temperature of 10℃~600℃, a sputtering pressure ≤5Pa, a sputtering rate of 1nm / min~100nm / min, and a sputtering power of 1kW~20kW; the mass percentage of oxygen in the mixed atmosphere of oxygen and inert gas is 1%~20%.

9. The method for fabricating an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device according to claim 6, characterized in that... In step five, when using a hydrothermal method (a wet chemical method) to prepare an electro / optical dual-response plasma nanocrystalline layer on an infrared high-reflectivity top electrode, the specific steps are as follows: The device prepared in step four is immersed in a precursor solution, and a hydrothermal reaction is carried out at a temperature of 20℃~400℃ for 30 min~1440 min. After the hydrothermal reaction, it is washed 1~5 times, and then vacuum dried at a temperature of 40℃~120℃ for 30 min~720 min. The precursor solution consists of a precursor, a surface modifier, and a solvent. The precursor is a metal salt precursor; the surface modifier is one or a combination of several of the following: polyvinylpyrrolidone, hexadecyltrimethylammonium bromide, citric acid, ethylenediaminetetraacetic acid, ethylene glycol, and polyvinyl alcohol; the solvent is one or a combination of several of the following: deionized water, anhydrous ethanol, ethylene glycol, and isopropanol; the total concentration of metal ions in the precursor solution is 0.01 mol / L to 0.5 mol / L, and the mass of the surface modifier is 0.5% to 20% of the precursor mass; the pH value of the precursor solution is 2 to 11.

10. The method for fabricating an inorganic all-solid-state electro / optical dual-response variable infrared emissivity device according to claim 6, characterized in that... The heat treatment described in step six is ​​carried out in a vacuum environment, argon atmosphere, nitrogen atmosphere, atmospheric environment, or nitrogen-hydrogen mixed atmosphere, at a heat treatment temperature of 10℃ to 600℃, and held for 30 min to 600 min.

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