Tunable High-Performance Electromagnetic Interference Shielding of VO2 Nanowires-Based Composite.

The unique metal-insulator transition of VO2 is very suitable for dynamic electromagnetic (EM) regulation materials due to its sharp change in electrical conductivity. Here, we have developed an off/on switchable electromagnetic interference (EMI) shielding composite by interconnecting VO2 nanowires (NWs) in poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) to form conductive networks, resulting in outstanding performance at the X and Ku bands with maximum change values of 44.8 and 59.4 dB, respectively. The unique insulator-to-metal transition (IMT) of VO2 NWs has dominated the variation of polarization loss (εp″) and conductivity loss (εσ″) for the composites, which is the mechanism of EMI shielding switching between off and on states. Furthermore, the composite exhibits good cycling stability of the off/on switchable EMI shielding performance and has excellent mechanical properties, especially with 200 times abrasion resistance without obvious weight loss. This study provides a unique approach for dynamic switching of EM response with the potential to construct practical intelligent EM response systems for next-generation smart electromagnetic devices in various scenarios.

Unprecedented Spatial Manipulation and Transformation of Dynamic Thermal Radiation Based on Vanadium Dioxide.

Reconfigurable infrared (IR) materials have widespread applications in thermal management and smart IR concealment. Although various reconfigurable IR materials can be customized by positive or negative differential VO2-based resonators, their insightful mechanism remains unknown. Here, we comprehensively investigate the fundamental design rule of reconfigurable thermal radiation between positive and negative differential thermal radiation properties for the first time. Importantly, the skin depth of VO2 film in the metal state is investigated to clarify the transformation from positive to negative differential thermal radiation properties, and the critical thickness is further derived, providing important guidance in designing the reconfigurable thermal radiation regulator. Furthermore, the reconfigurable multistate thermal images had been presented into one plate. The resulting emittance variation (△ε8-14 µm) of the VO2-based resonator can change from 0.61 to -0.53, which consummates the ability for diverse demands such as infrared concealment, thermal illusion, and thermal management. This work constitutes a promising and universal route toward designing whole smart devices and may create new scientific and technological opportunities for platforms that can benefit from reconfigurable electromagnetic manipulation.

Tunable VO2 cavity enables multispectral manipulation from visible to microwave frequencies.

Optical materials capable of dynamically manipulating electromagnetic waves are an emerging field in memories, optical modulators, and thermal management. Recently, their multispectral design preliminarily attracts much attention, aiming to enhance their efficiency and integration of functionalities. However, the multispectral manipulation based on these materials is challenging due to their ubiquitous wavelength dependence restricting their capacity to narrow wavelengths. In this article, we cascade multiple tunable optical cavities with selective-transparent layers, enabling a universal approach to overcoming wavelength dependence and establishing a multispectral platform with highly integrated functions. Based on it, we demonstrate the multispectral (ranging from 400 nm to 3 cm), fast response speed (0.9 s), and reversible manipulation based on a typical phase change material, vanadium dioxide. Our platform involves tandem VO2-based Fabry-Pérot (F-P) cavities enabling the customization of optical responses at target bands independently. It can achieve broadband color-changing capacity in the visible region (a shift of ~60 nm in resonant wavelength) and is capable of freely switching between three typical optical models (transmittance, reflectance, and absorptance) in the infrared to microwave regions with drastic amplitude tunability exceeding 0.7. This work represents a state-of-art advance in multispectral optics and material science, providing a critical approach for expanding the multispectral manipulation ability of optical systems.

Effects of Film Thickness on the Residual Stress of Vanadium Dioxide Thin Films Grown by Magnetron Sputtering.

Vanadium dioxide (VO2) thin films of different thicknesses were prepared by regulating the deposition time (2, 2.5, 3, and 3.5 h). The impact of deposition time on the microstructure, surface morphology, and cross-section morphology was investigated. The results showed that the grain size increased with the film thickness. Meanwhile, the influence of film thickness on the residual stress was evaluated by X-ray diffraction. The phenomenon of "compressive-to-tensile stress transition" was illustrated as the thickness increased. The change of dominant mechanism for residual stress was used for explaining this situation. First, the composition of residual stress indicates that growth stress play a key role. Then, the effect of "atomic shot peening" can be used to explain the compressive stress. Lastly, the increased grain size, lower grain boundary density, and "tight effect" in the progress of film growth cause tensile stress.

Measurement of Mechanical Properties of VO2 Films by Nanoindentation.

The present work reported the intrinsic mechanical behavior of vanadium dioxide (VO2) thin film deposited on a SiO2 substrate using a combination of nanoindentation tests and a theoretical model. The effect of phase transition on mechanical parameters was studied by adjusting the test temperature. A new model that can simultaneously extract the elastic modulus and hardness was derived by introducing a dimensional analysis. The results showed that the thin film exhibits a hardness of 9.43 GPa and a Young's modulus of about 138.5 GPa at room temperature, compared with the values of 5.71 GPa and 126.9 GPa at a high temperature, respectively. It can be seen that the intrinsic mechanical parameters decrease to a certain extent after a phase transition. Finally, the numerical simulation results were consistent with those of the experiments, which verified the effectiveness of the new method. In addition, this study also provided useful guidance for mechanical tests on other ultra-thin films.

Analysis of Thermal Stress in Vanadium Dioxide Thin Films by Finite Element Method.

The buckling, de-lamination, and cracking of the thin film/substrate system caused by thermal stress is the main obstacle for functional failure. Moreover, the thermal stress of vanadium dioxide (VO2) thin film may be more complicated due to the stress re-distribution caused by phase transition. Therefore, the thermal stress of VO2 thin films deposited on four substrates with different materials (fused silica, silicon slice, sapphire, and glass) has been studied by finite element method in the present work. The influences of external temperature, substrate, and interlayer on thermal stress were analyzed. It was found that the substrates can greatly affect the thermal stresses, which were mainly caused by the mismatch of coefficient of thermal expansion (CTE). The thermal stress had a linear relationship with the external temperature, but this tendency would be redistributed or even change direction when phase transition occurred. The simulated results were in tandem with the analytical method. Meanwhile, the radial stress and shear stress distribution under the influence of phase transition were calculated. In addition, the reduction of thermal stress and shear stress showed that the appropriate interlayer can enhance the adhesive strength effectively.

Passive and Dynamic Phase-Change-Based Radiative Cooling in Outdoor Weather.

Radiative cooling has attracted considerable attention due to its tremendous potential in exploiting the cold reservoir of deep sky. However, overcooling always occurs in the conventional static radiative coolers because they operate only in the cooling mode in both hot and cold. Therefore, a dynamic radiative cooler based on phase change materials is highly desired. Nevertheless, the practical outdoor phase-change-based dynamic radiative cooling has not yet been experimentally demonstrated. To satisfy the stringent requirement of the phase-change-based radiative cooler in outdoor weather conditions, we engineered the phase-change material (VO2) to possess the room-temperature phase-transition capability for typical weather conditions. Second, the reconfigurable cavity consists of the lossless spacer to ensure the magnitude of thermal modulation and suppress the solar absorption simultaneously. Third, the practical selective-filtering method is devised to shield the solar irradiance while permitting the thermal emission. Our experiment demonstrates that these materials and photonic measures can work together to realize the dynamic radiative cooling in actual weather conditions, which shows a self-adaptive switch between the ON-cooling state in hot daytime and the OFF-cooling state in cold nighttime. The study pushes the radiative cooler toward multifunctionality and provides beneficial guidance for the phase-change-based intelligent thermal control.

VO2-Based Infrared Radiation Regulator with Excellent Dynamic Thermal Management Performance.

Dynamic thermal management materials attract fast-increasing interest due to their adaptability to changing environments and greater energy savings as compared to static materials. However, the high transition temperature and the low emittance tunability of the vanadium dioxide (VO2)-based infrared radiation regulators limit their practical applications. This study addresses these issues by proposing a smart infrared radiation regulator based on a Fabry-Pérot cavity structure (VO2/HfO2/Al), which is prepared by high-power impulse magnetron sputtering (HiPIMS) and has the potential for large-scale production. Remarkably, the outstanding emittance tunability reaches 0.51, and the phase transition temperature is lowered to near a room temperature of 27.5 °C by tungsten (W) doping. In addition, a numerical thermal management power of 196.3 W/m2 (at 8-14 µm band) can be obtained from 0 to 60 °C. As a proof-of-concept, the demonstrated capabilities of the VO2 infrared radiation regulator show great potentials in a wide range of applications for the thermal management of buildings and vehicles.

Smart Materials for Dynamic Thermal Radiation Regulation.

Thermal radiation in the mid-infrared region profoundly affects human lives in various fields, including thermal management, imaging, sensing, camouflage, and thermography. Due to their fixed emissivities, radiance features of conventional materials are usually proportional to the quadruplicate of surface temperature, which set the limit, that one type of material can only present a single thermal function. Therefore, it is necessary and urgent to design materials for dynamic thermal radiation regulations to fulfill the demands of the age of intelligent machines. Recently, the ability of some smart materials to dynamically regulate thermal radiation has been evaluated. These materials are found to be competent enough for various commands, thereby, providing better alternatives and tremendously promoting the commercial potentials. In this review, the dynamic regulatory mechanisms and recent progress in the evaluation of these smart materials are summarized, including thermochromic materials, electrochromic materials, mechanically and humidity responsive materials, with the potential applications, insufficient problems, and possible strategies highlighted.

Effect of Unit Cell Shape on Switchable Infrared Metamaterial VO2 Absorbers/Emitters.

Metamaterial absorber/emitter is an important aspect of infrared radiation manipulation. In this paper, we proposed four simple switchable infrared metamaterial absorbers/emitters with Ag/VO2 disks on the Ag plane employing triangle, square, hexagon, and circle unit cells. The spectral absorption peaks whose intensities are above 0.99 occur at ~4 µm after structure optimization when VO2 is in insulating state and disappear when VO2 becomes metallic state. The simulated electromagnetic field reveals that the spectral absorption peaks are attributed to the excitation of magnetic polariton within the insulating VO2 spacer layer, whose values exceed 1.59 orders of magnitude higher than the incident magnetic field. Longer resonant wavelength would be excited in square arrays because its configuration is a better carrier of charges at the same spans. For absorption stability, the absorbers/emitters with square and circular structures do not have any change with the polarization angles changing from 0° to 90°, due to the high rotational symmetric structure. And four absorbers/emitters reveal similar shifts and attenuations under different incident angles. We believed that the switchable absorber/emitter demonstrates promising applications in the sensing technology and adaptive infrared system.

Flexible Daytime Radiative Cooling Enhanced by Enabling Three-Phase Composites with Scattering Interfaces between Silica Microspheres and Hierarchical Porous Coatings.

Daytime radiative cooling has attracted considerable attention recently due to its tremendous potential for passively exploiting the coldness of the universe as clean and renewable energy. Many advanced materials with novel photonic micro/nanostructures have already been developed to enable highly efficient daytime radiative coolers, among which the flexible hierarchical porous coatings (HPCs) are a more distinguished category. However, it is still hard to precisely control the size distribution of the randomized pores within the HPCs, usually resulting in a deficient solar reflection at the near-infrared optical regime under diverse fabrication conditions of the coatings. We report here a three-phase (i.e., air pore-phase, microsphere-phase, and polymer-phase) self-assembled hybrid porous composite coating, which dramatically increases the average solar reflectance and yields remarkable temperature drops of ∼10 and ∼ 30 °C compared to the ambient circumstance and black paint, respectively, according to the rooftop measurements. Mie theory and Monte Carlo simulations reveal the origin of the low reflectivity of as-prepared two-phase porous HPCs, and the optical cooling improvement of the three-phase porous composite coatings is attributed to the newly generated interfaces possessing the high scattering efficiency between the hierarchical pores and silica microspheres hybridized with appropriate mass fractions. As a result, the hybrid porous composite approach enhances the whole performance of the coatings, which provides a promising alternative to the flexible daytime radiative cooler.

Bioinspired Microstructured Materials for Optical and Thermal Regulation.

Precise optical and thermal regulatory systems are found in nature, specifically in the microstructures on organisms' surfaces. In fact, the interaction between light and matter through these microstructures is of great significance to the evolution and survival of organisms. Furthermore, the optical regulation by these biological microstructures is engineered owing to natural selection. Herein, the role that microstructures play in enhancing optical performance or creating new optical properties in nature is summarized, with a focus on the regulation mechanisms of the solar and infrared spectra emanating from the microstructures and their role in the field of thermal radiation. The causes of the unique optical phenomena are discussed, focusing on prevailing characteristics such as high absorption, high transmission, adjustable reflection, adjustable absorption, and dynamic infrared radiative design. On this basis, the comprehensive control performance of light and heat integrated by this bioinspired microstructure is introduced in detail and a solution strategy for the development of low-energy, environmentally friendly, intelligent thermal control instruments is discussed. In order to develop such an instrument, a microstructural design foundation is provided.

Influence of Coagulation Bath Temperature on the Structure and Dielectric Properties of Porous Polyimide Films in Different Solvent Systems.

In this work, the effect of coagulation bath temperature in different solvent systems [1,4-butyrolactone (GBL)/N,N-dimethylacetamide (DMAC)] on the structure and dielectric properties of polyimide (PI) films was investigated for the first time. The solubility parameter was introduced to explain the formation process of porous PI films. The results showed that the changed tendency of the dielectric constant versus temperature is opposite for the single-solvent system and cosolvent system. For a single DMAC and GBL solvent, the dielectric constants of the films decreased with increasing temperature. In contrast, the dielectric constants increased with the increase in temperature for the GBL/DMAC cosolvent system. Moreover, the measured porosities were applied to estimate the dielectric constants of the PI films. This showed that the porosity increased with increasing temperature for a single-solvent system, while it decreased for a cosolvent system. Scanning electron microscopy images suggested that the variation trends are derived from the different influences of the temperature on the structure and morphology. Thus, this study reveals the effect of coagulation bath temperature on the structure and dielectric properties of porous PI films and provides the guidance for the design and optimization of architectures for high-performance porous films.

All solid state electrochromic devices based on the LiF electrolyte.

The unsafe deposition process and slow deposition rate of the electrolyte layers are the main obstacles for electrochromic devices (ECDs) toward commercial application. In this work, an ECD with a structure of glass/ITO/WO3/LiF/NiO/ITO has been prepared by electron beam and resistance evaporation methods. The LiF electrolyte is deposited by resistance evaporation with the LiF particles and shows promising potential as the Li+ based electrolyte in ECDs owing to its high transparency and good ionic conductivity. The ECD shows a fast response (4.0 s for bleaching and 9.6 s for coloring), large optical transmittance modulations (∼58.9% at 625 nm, 100 s for coloring), good stability and high coloration efficiency (88.5 cm2 C-1). This work not only indicates that LiF can be used as a Li+ based electrolyte in an ECD, but also paves a new way to fast and safe preparation of ECDs with high performance.

A Universal Approach To Achieve High Luminous Transmittance and Solar Modulating Ability Simultaneously for Vanadium Dioxide Smart Coatings via Double-Sided Localized Surface Plasmon Resonances.

Vanadium dioxide (VO2)-based thermochromic coatings has attracted considerable attention in the application of smart windows as a result of their intriguing property of metal-insulator transition at moderate temperatures. However, the practical requirements of smart windows, i.e., the high luminous transmittance of Tlum > 60% and large solar modulating ability of ΔTsol > 10%, are competing to a large extent and hardly satisfied simultaneously. Here, we proposed a facile and universal method to prepare VO2 coatings for exceeding the criteria above using double-sided localized surface plasmon resonances (LSPRs), which are excited by the VO2 nanoparticles dispersed evenly on both surfaces of the fused silica substrate. With subtle engineering of the sol-gel and heat treatment processes, the morphology of as-prepared VO2 nanoparticles and corresponding LSPRs are controlled to achieve a high luminous transmittance (Tlum = 68.2%) and solar modulating ability (ΔTsol = 11.7%) simultaneously. Further simulation suggests that the double-sided LSPRs can collectively enhance the performance of VO2 smart coatings. Moreover, the double-sided VO2 nanoparticle coatings demonstrate stable performance with no more than 1% degradation of Tlum and ΔTsol after 1500 cycles. This study provides an alternative strategy to obtain high-quality VO2 (M) solar modulating coatings.

A nanostructured Fc(COCH3)2 film prepared using silica monolayer colloidal crystal templates and its electrochromic properties.

Since oxidation and reduction reactions mainly take place on surfaces, enlarging the specific surface of redox materials is the key to achieving excellent electrochemical performance. In this work, by using silica monolayer colloidal crystal templates (MCCTs), a nanostructured Fc(COCH3)2 film is prepared successfully, and such a nanostructure could exhibit the following unique electrochemical properties: the MCCTs could impede the aggregation tendency of Fc(COCH3)2 and possess high electrochemical activity; Fc(COCH3)2 enlarges the contact area and offers more active sites and faster electronic transmission channels. The structure, optical and electrochemical properties of the nanostructured Fc(COCH3)2 were tested and then compared with those of compact Fc(COCH3)2 films to evaluate the role of the nanoarchitecture. The unique structure design of the Fc(COCH3)2 film enables outstanding performance, showing a large transmittance change (ΔT) of 37% at 550 nm when switched between 0.5 V and -2.5 V, which is approximately ninefold higher than that of the compact Fc(COCH3)2 film (approximately 4%). Response times of coloration and bleaching are found to be only 16.15 s and 5.56 s. Furthermore, the nanostructured Fc(COCH3)2 film shows much better cycling stability than the compact one. The results indicate that the nanostructure could significantly improve the electrochemical performance of the Fc(COCH3)2 film due to the increase in electrochemical active sites and the enhancement of the "D-to-A" redox switch of ferrocene.