Bioinspired Intelligent Solar-Responsive Thermally Conductive Pyramidal Phase Change Composites with Radially Oriented Layered Structures toward Efficient Solar–Thermal–Electric Energy Conversion

To remedy the drawbacks of weak solar-thermal conversion capability, low thermal conductivity, and poor structural stability of phase change materials, pyramidal graphitized chitosan/graphene aerogels (G-CGAs) with numerous radially oriented layers are constructed, in which the long-range radial alignment of graphene sheets is achieved by a novel directional-freezing strategy. A G-CGA/polyethylene glycol phase change composite exhibits a thermal conductivity of 2.90 W m⁻¹ K⁻¹ with a latent heat of 178.8 J g⁻¹, and achieves a superior solar-thermal energy conversion and storage efficiency of 90.4% and an attractive maximum temperature of 99.7 °C under a light intensity of 200 mW cm⁻². Inspired by waterlilies, solar-responsive phase change composites (SPCCs) are designed for the first time by assembling the G-CGA/polyethylene glycol phase change composites with solar-driven bilayer films, which bloom by day and close by night. The heat preservation effect of the solar-driven films leads to a higher temperature of SPCC for a longer period at night. The SPCC-based solar–thermal–electric generator achieves output voltages of 499.2 and 1034.9 mV under light intensities of 200 and 500 mW cm⁻², respectively. Even after stopping the solar irradiation, the voltage output still occurs because of the latent heat release and the heat preservation of the films.     

Flame-Retardant Host–Guest Films for Efficient Thermal Management of Cryogenic Devices

Phase change materials hold tremendous potential for thermal energy storage and temperature management due to their high latent heat and chemical stability. However, the manufacture of flame-retardant, form-stable phase change films working under a cryogenic environment remains difficult. Herein, an organic polydopamine-aramid nanofiber (PANF) aerogel film with a limiting oxygen index (LOI) of 32 is applied as a host to confine a unique phase change guest material (i.e., deep eutectic solvent, DES) to fabricate PANF-DES host–guest flame-retardant cryogenic phase change films. The PANF aerogel film is prepared through the in situ polymerization of dopamine within the aramid nanofiber hydrogel film, exhibiting a high specific surface area of 289 m² g⁻¹. The cryogenic phase change material is a ternary DES composed of ammonium chloride (NH₄Cl), ethylene glycol (Eg), and deionized water (H₂O). The as-prepared PANF-DES host–guest films with the phase transition temperature of −21 °C and melting enthalpy of 225 J g⁻¹ can withstand fire for 60 s without naked flame, and the peak of heat release rate (pkHRR) is only 26.0 MJ kg⁻¹. This study opens the way for developing ultra-low flammable phase change composite films, as well as shows great potential applications for thermal management in cryogenic devices.     

Effect of Rapid Thermal Annealing on Sputtered CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> Thin Films

Calcium copper titanium oxide (CaCu₃Ti₄O₁₂, abbreviated to CCTO) films were deposited on Pt/Ti/SiO₂/Si substrates at room temperature (RT) by radiofrequency magnetron sputtering. As-deposited CCTO films were treated by rapid thermal annealing (RTA) at various temperatures and in various atmospheres. X-ray diffraction patterns and scanning electron microscope (SEM) images demonstrated that the crystalline structures and surface morphologies of CCTO thin films were sensitive to the annealing temperature and ambient atmosphere. Polycrystalline CCTO films could be obtained when the annealing temperature was 700°C in air, and the grain size increased signifi- cantly with annealing in O₂. The 0.8-μm CCTO thin film that was deposited at RT for 2 h and then annealed at 700°C in O₂ exhibited a high dielectric constant (ε′) of 410, a dielectric loss (tan δ) of 0.17 (at 10 kHz), and a leakage current density (J) of 1.28 × 10⁻⁵ A/cm² (at 25 kV/cm).     

High performance sol–gel spin-coated titanium dioxide dielectric based MOS structures

High-κ TiO₂ thin films have been fabricated using cost effective sol–gel and spin-coating technique on p-Si (100) wafer. Plasma activation process was used for better adhesion between TiO₂ films and Si. The influence of annealing temperature on the structure-electrical properties of titania films were investigated in detail. Both XRD and Raman studies indicate that the anatase phase crystallizes at 400 °C, retaining its structural integrity up to 1000 °C. The thickness of the deposited films did not vary significantly with the annealing temperature, although the refractive index and the RMS roughness enhanced considerably, accompanied by a decrease in porosity. For electrical measurements, the films were integrated in metal-oxide-semiconductor (MOS) structure. The electrical measurements evoke a temperature dependent dielectric constant with low leakage current density. The Capacitance–voltage (C–V) characteristics of the films annealed at 400 °C exhibited a high value of dielectric constant (~34). Further, frequency dependent C–V measurements showed a huge dispersion in accumulation capacitance due to the presence of TiO₂/Si interface states and dielectric polarization, was found to follow power law dependence on frequency (with exponent ‘s’=0.85). A low leakage current density of 3.6×10⁻⁷ A/cm² at 1 V was observed for the films annealed at 600 °C. The results of structure-electrical properties suggest that the deposition of titania by wet chemical method is more attractive and cost-effective for production of high-κ materials compared to other advanced deposition techniques such as sputtering, MBE, MOCVD and ALD. The results also suggest that the high value of dielectric constant ‘κ‘ obtained at low processing temperature expands its scope as a potential dielectric layer in MOS device technology.     

PTFE nanoemulsions as ultralow-k dielectric materials

Modern integrated circuits require insulating materials with a dielectric constant as low as possible in order to obtain device speed improvements through lower RC delay. We have investigated the electrical and structural properties of PTFE thin films obtained from Algoflon^®-PTFE nanoemulsions, via spin coating deposition, followed by sintering. Films as thin as 160 nm with dielectric strength better than 4 MV/cm have been obtained. Breakdown mechanism is also discussed.     

Low-Temperature Pulsed-PECVD ZnO Thin-Film Transistors

We report high-quality ZnO thin films deposited at low temperature (200°C) by pulsed plasma-enhanced chemical vapor deposition (pulsed PECVD). Process byproducts are purged by weak oxidants N₂O or CO₂ to minimize parasitic CVD deposition, resulting in high-refractive-index thin films. Pulsed-PECVD-deposited ZnO thin-film transistors were fabricated on plasma-enhanced atomic layer deposition (PEALD) Al₂O₃ dielectric and have a field-effect mobility of 15 cm²/V s, subthreshold slope of 370 mV/dec, threshold voltage of 6.6 V, and current on/off ratio of 10⁸. Thin-film transistors (TFTs) on thermal SiO₂ dielectric have a field-effect mobility of 7.5 cm²/V s and threshold voltage of 14 V. For these devices, performance may be limited by the interface between the ZnO and the dielectric.     

Laminated Modulation of Tricritical Ferroelectrics Exhibiting Highly Enhanced Dielectric Permittivity and Temperature Stability

Ferroelectric materials with large dielectric response and high temperature‐stability have found significant applications in advanced electronics and electrical power/storage equipment. The effective approaches explored up to now mainly focus on improving dielectric response by employing the phase instability caused by the ferroelectric transition. Nevertheless, one inherent shortcoming is that the enhancement of dielectric permittivity is at the expense of the deterioration of its temperature stability. Here, a strategy that successfully achieves both enhanced dielectric response as well as excellent temperature reliability (with ε_r ≈ 2 × 10⁴ from 30 to 85 °C) by designing a laminated structure of tricritical ferroelectrics (LTF) with successive Curie temperatures is proposed. Moreover, the improvement in dielectric performance triggers the temperature‐stable energy‐storage performance as well as electrocaloric property in LTF specimens. Further microstructure investigation and phase‐field modeling reveal that these remarkable properties of laminated layers originate from the successive occurrence of tricritical transition with a nanodomain structure in a wide temperature range. The findings may shed a new light on developing advanced ferroelectrics with high performance and thermal reliability.     

Nanostructured Interfaces for Thermoelectrics

Temperature drops at the interfaces between thermoelectric materials and the heat source and sink reduce the overall efficiency of thermoelectric systems. Nanostructured interfaces based on vertically aligned carbon nanotubes (CNTs) promise the combination of mechanical compliance and high thermal conductance required for thermoelectric modules, which are subjected to severe thermomechanical stresses. This work discusses the property require- ments for thermoelectric interface materials, reviews relevant data available in the literature for CNT films, and characterizes the thermal properties of vertically aligned multiwalled CNTs grown on a candidate thermoelectric material. Nanosecond thermoreflectance thermometry provides thermal property data for 1.5-μm-thick CNT films on SiGe. The thermal interface resistances between the CNT film and surrounding materials are the dominant barriers to thermal transport, ranging from 1.4 m² K MW⁻¹ to 4.3 m² K MW⁻¹. The volumetric heat capacity of the CNT film is estimated to be 87 kJ m⁻³ K⁻¹, which corresponds to a volumetric fill fraction of 9%. The effect of 100 thermal cycles from 30°C to 200°C is also studied. These data provide the groundwork for future studies of thermoelectric materials in contact with CNT films serving as both a thermal and electrical interface.     

Highly transparent polyimide/nanocrystalline-zirconium dioxide hybrid materials for organic thin film transistor applications

A solution-processable high k dielectric materials based on polyimide/zirconium dioxide (PI-ZrO₂) for organic thin film transistors (OTFTs) is demonstrated. To study the effect of the ZrO₂ content on the properties of the dielectric layer, a series of PZn films (n = 0, 2, 5, 8, 10, 12, and 15, which are the weight percentage of ZrO₂ in the film) were prepared. The results showed that all of the prepared hybrid films had a high transmittance of 96–99%. The nondestructive Zr K-edge XANES analysis revealed that the absorption intensity was proportional to the ZrO₂ content. EXAFS analysis indicated that the ZrO₂ formed bigger clusters in the film than in the solution state. Water and diiodomethane contact angle analysis found that the PZ12 film had the largest contact angles, lowest surface energy, and lowest water absorbance, which results in the least structural defects and highest carrier mobility. Electrical property analysis indicated that the dielectric constant of the films increased from 4.04 for the PZ0 film to 8.10 for the PZ12 film, but then dropped for the PZ15 film. All current leakages (−2 MV/cm) were less than 10⁻⁹ A/cm. The carrier mobility in the PZ0 film was 2.78 × 10⁻¹, up to 4.15 × 10⁻¹ for the PZ12 film, but down to 3.34 × 10⁻¹ for the PZ15 film. The I_on/I_off ratio was 2.3 × 10³ for PZ0, up to 1.4 × 10⁵ for PZ12, but down to 1.8 × 10⁴ for PZ15. The hybrid dielectric devices showed better performance. This work reveals great potential for hybrid dielectric materials for OTFT applications.     

Photoresponse of composites of zinc oxide and poly(3-hexythiophene) under selective UV and white-light illumination

We investigate charge transport in UV sensing devices based on organic-inorganic semiconductor composites with the metal-semiconductor-metal (MSM) structure. Composite materials of zinc oxide (ZnO) nanoparticles and poly(3-hexylthiophene) (P3HT) were prepared by drop-casting their colloidal mixture in chloroform onto low-cost interdigitated copper electrodes. The current-voltage characteristics of the devices were investigated under both dark and illuminated conditions in the UV–visible range. The highest photoresponse was observed for an optimal P3HT:ZnO ratio of 1:8 w/w in the wavelength range between 310 and 380 nm. The dynamic response was investigated by pulsing a 365 nm UV light with a long period to reveal the response time of 4 s and the recovery time of less than 1 s. The photoresponse of the materials was also investigated for a shorter period of UV pulsing, using a rotating chopper. The response time and recovery time for the short UV pulse were found to be approximately 20 m and 25 m, respectively. The dual response times should stem from the presence of two types of semiconductor materials, namely ZnO with a high electron mobility and P3HT with a moderate hole mobility. To probe the charge generation and transport mechanisms, we further investigate the photoresponse using UV pulsing under background white light of different intensities, and vice versa. The background white light was found to deteriorate the UV photoresponse of the materials. On the other hand, the background UV illumination produced an anomalous photoresponse pattern with the white light pulsing. Understanding the charge transport mechanisms for composite materials is highly important for future applications in low-cost UV sensors and tunable optoelectronic devices.     

Synchronous Visual/Infrared Stealth Using an Intrinsically Flexible Self-Healing Phase Change Film

Phase change materials (PCMs) have been particularly concerned as infrared stealth functional materials due to their superior thermal management capability. However, traditional PCMs usually behave rigid solid or flowing liquid states with fixed transition temperature, greatly limiting their application especially in multi-band stealth and multiple scenes. Herein, an intrinsically flexible self-healing phase change film used for synchronous visual/infrared stealth for the first time is designed and constructed. The phase change film possesses a solid–solid phase transition behavior with adjustable transition temperature (from 38.8 to 51.1 °C) and enthalpy (from 79.7 to 116.7 J g⁻¹), long-term cycling stability (500 cycles), and outstanding flexible and self-healing performance. Remarkably, the phase change film can be customized with different colors and various configurations to exhibit attractive visual stealth functions in multiple scenes. Additionally, owing to phase transition property, this phase change film can possess a thermal management capability and behave infrared stealth performance for objectives at various temperatures. Combining the above unique functions, the intrinsically flexible self-healing phase change film developed in this work may show great potential for applications in the synchronous visual/infrared stealth across a wide range of scenarios and temperatures.     

Ultrahigh Energy Density of Antiferroelectric PbZrO3-Based Films at Low Electric Field

Dielectric capacitors play a vital role in advanced electronics and power systems as a medium of energy storage and conversion. Achieving ultrahigh energy density at low electric field/voltage, however, remains a challenge for insulating dielectric materials. Taking advantage of the phase transition in antiferroelectric (AFE) film PbZrO₃ (PZO), a small amount of isovalent (Sr²⁺) / aliovalent (La³⁺) dopants are introduced to form a hierarchical domain structure to increase the polarization and enhance the backward switching field E_A simultaneously, while maintaining a stable forward switching field E_F. An ultrahigh energy density of 50 J cm⁻³ is achieved for the nominal Pb_0.925La_0.05ZrO₃ (PLZ5) films at low electric fields of 1 MV cm⁻¹, exceeding the current dielectric energy storage films at similar electric field. This study opens a new avenue to enhance energy density of AFE materials at low field/voltage based on a gradient-relaxor AFE strategy, which has significant implications for the development of new dielectric materials that can operate at low field/voltage while still delivering high energy density.     

Al2O3/TiO2 nanolaminate gate dielectric films with enhanced electrical performances for organic field-effect transistors

Nanolamination has entered the spotlight as a novel process for fabricating highly dense nanoscale inorganic alloy films. OFET commercialization requires, above all, excellent dielectric properties of gate dielectric layer. Here, we describe the fabrication and characterization of Al–O–Ti (AT) nanolaminate gate dielectric films using a PEALD process, and their OFET applications. The AT films exhibited a very smooth surface (R_q < 0.3 nm), a high dielectric constant (17.8), and a low leakage current (8.6 × 10⁻⁹ A/cm² at 2 MV/cm) compared to single Al₂O₃ or TiO₂ films. Importantly, a 50 nm thick AT film dramatically enhanced the value of μFET (0.96 cm²/V) on a pentacene device, and the high off-current level in a single TiO₂ film was effectively reduced. The nanolamination process removes the drawbacks inherent in each single layer so that the AT film provides excellent dielectric properties suitable for fabricating high-performance OFETs. Triethylsilylethynyl anthradithiophene (TES-ADT), a solution-processable semiconductor, was combined with the AT film in an OFET, and the electrical properties of the device were characterized. The excellent dielectric properties of the AT film render nanolamination a powerful strategy for practical OFET applications.     

Wearable Janus-Type Film with Integrated All-Season Active/Passive Thermal Management,Thermal Camouflage,and Ultra-High Electromagnetic Shielding Efficiency Tunable by Origami Process

Multifunctional films with integrated temperature adjustment, electromagnetic interference (EMI) shielding, and thermal camouflage are remarkably desirable for wearable products. Herein, a novel Janus-type multifunctional ultra-flexible film is fabricated via continuous electrospinning followed by spraying. Interestingly, in the polyvinyl alcohol (PVA)/phase change capsules (PCC) layer (P₁), the PCC is strung on PVA fibers to form a stable “candied haws stick” structure that obviates slipping or falling off. The film with sufficient melting enthalpy (141.4 J g⁻¹) guarantees its thermoregulation capability. Simultaneously, its high mid-IR emissivity (90.15%) endows the film with radiative cooling properties (reducing temperature by 10.13 °C). Mechanical strength is significantly improved by superimposing a polylactic acid (PLA) layer (P₂) on its surface. By spraying a thin MXene layer on the PLA surface of P₂P₁ film, the obtained (MXene/P₂P₁) MP₂P₁ film is endowed with satisfactory low-voltage heating, photo-thermal and superior thermal camouflage performance, achieving all-season thermal comfort. Impressively, the flexible MP₂P₁ film achieves enhanced EMI shielding effect from 50.3 to 87.8 dB through a simple origami process, which simplifies the manufacturing process of high-performance EMI shielding materials. In brief, the multifunctional Janus-type MP₂P₁ film is an attractive candidate for future wearable products with personalized thermal management and anti-electromagnetic radiation.     

Effect of Sintering Temperature on the Properties of Fused Silica Ceramics Prepared by Gelcasting

Fused silica ceramics were fabricated by gelcasting, by use of a low-toxicity N′N-dimethylacrylamide gel system, and had excellent properties compared with those obtained by use of the low-toxicity 2-hydroxyethyl methacrylate and toxic acrylamide systems. The effect of sintering temperature on the microstructure, mechanical and dielectric properties, and thermal shock resistance of the fused silica ceramics was investigated. The results showed that sintering temperature has a critical effect. Use of an appropriate sintering temperature will promote densification and improve the strength, thermal shock resistance, and dielectric properties of fused silica ceramics. However, excessively high sintering temperature will greatly facilitate crystallization of amorphous silica and result in more cristobalite in the sample, which will cause deterioration of these properties. Fused silica ceramics sintered at 1275°C have the maximum flexural strength, as high as 81.32 MPa, but, simultaneously, a high coefficient of linear expansion (2.56 × 10^?6/K at 800°C) and dramatically reduced residual flexural strength after thermal shock (600°C). Fused silica ceramics sintered at 1250°C have excellent properties, relatively high and similar flexural strength before (67.43 MPa) and after thermal shock (65.45 MPa), a dielectric constant of 3.34, and the lowest dielectric loss of 1.20 × 10^?3 (at 1 MHz).     

Polyethylene Based Ionomers as High Voltage Insulation Materials

Polyethylene based ionomers are demonstrated to feature a thermo-mechanical and dielectric property portfolio that is comparable to cross-linked polyethylene (XLPE), which may enable the design of more sustainable high voltage direct-current (HVDC) power cables, a crucial component of future electricity grids that seamlessly integrate renewable sources of energy. A new type of ionomer is obtained via high-pressure/high-temperature free radical copolymerization of ethylene in the presence of small amounts of ion-pair comonomers comprising amine terminated methacrylates and methacrylic acid. The synthesized ionomers feature a crystallinity, melting temperature, rubber plateau modulus and thermal conductivity like XLPE but remain melt-processable. Moreover, the preparation of the ionomers is free of byproducts, which readily yields a highly insulating material with a low dielectric loss tangent and a low direct-current (DC) electrical conductivity of 1 to 6·10⁻¹⁴ S m⁻¹ at 70 °C and an electric field of 30 kV mm⁻¹. Evidently, the investigated ionomers represent a promising alternative to XLPE-based high voltage insulation, which may permit to ease the production as well as end-of-use recycling of HVDC power cables by combining the advantages of thermoset and thermoplastic materials while avoiding the formation of byproducts.     

Photo-patternable high-k ZrOx dielectrics prepared using zirconium acrylate for low-voltage-operating organic complementary inverters

Solution-processed dielectric materials with a high dielectric constant (k) have attracted considerable attention due to their potential applications in low-voltage-operating organic field-effect transistors (OFETs) for realizing large-area and low-power electronic devices. In terms of device commercialization, the patterning of each film component via a facile route is an important issue. In this study, we introduce a photo-patternable precursor, zirconium acrylate (ZrA), to fabricate photo-patterned high-k zirconium oxide (ZrO_x) dielectric layers with UV light. Solution-processed ZrA films were effectively micro-patterned with UV exposure and developing, and transitioned to ZrO_x through a sol-gel reaction during deep-UV annealing. The UV-assisted and ∼10 nm-thick ZrO_x dielectric films exhibited a high capacitance (917.13 nF/cm² at 1 KHz) and low leakage current density (10⁻⁷ A/cm² at 1.94 MV/cm). Those films could be utilized as gate dielectric layers of OFETs after surface modification with ultrathin cyclic olefin copolymer layers. Finally, we successfully fabricated organic complementary inverters exhibiting hysteresis-free operation and high voltage gains of over 42 at low voltages of ≤3 V.     

Effect of deposition methods on dielectric breakdown strength of PECVD low-k carbon doped silicon dioxide dielectric thin films

The effect of deposition methods on dielectric breakdown strength of PECVD low-k dielectric carbon doped silicon dioxide films is investigated. I-V measurements were performed using metal-insulator semiconductor structures for carbon doped silicon dioxide thin films with various thicknesses by single deposition station and six sequential deposition systems. I-t measurements are also performed for films with the thickness of 32 nm prepared using both deposition methods. Comparison studies have been carried out for the thickness dependence, temperature dependence, conduction mechanism and time dependence of dielectric breakdown for carbon doped silicon dioxide with single layer and six sub-layers. Results demonstrated that both films follow the newly obtained relationship between dielectric strength E_B and thickness d, i.e. E_B∝(d−d_c)⁻ⁿ, but with a lower exponential factor n and a larger thickness limit d_c for films with six sub-layers. It is also demonstrated that films with six sub-layers have a higher dielectric strength in all the thickness and temperature ranges, a thickness independent thermal behavior and a longer lifetime under constant voltage stressing. This indicates that by tuning the deposition methods smaller thickness with desired dielectric properties can be achieved.     

High-Energy-Density Waterborne Dielectrics from Polyelectrolyte-Colloid Complexes

To meet the demands of miniaturization and integration of next-generation power systems, a major challenge is to improve the energy density of used dielectric capacitors. Polymer nanocomposites are of great potential for high-energy-density capacitors. However, most of them are prepared via melt blending at high temperatures or solution processing in hazardous organic solvents, which are energy consuming and environmentally problematic. It has long remained economically and ecologically challenging to develop new dielectric materials. Here, a class of high-energy-density dielectrics made by electrostatically complexing polyvinylidene fluoride (PVDF) latex with oppositely charged chitosan in an aqueous phase is reported. At the charge neutralization point, the film of PVDF@Chitosan complexes demonstrates the highest breakdown strength (630 MV m⁻¹) and recoverable energy density (10.1 J cm⁻³), which are respectively 279% and 421% higher than the bare PVDF latex film, and far beyond most of the conventional solvent- or melt-processed polymer films. The largely improved capacitive performances are ascribed to the significant minimization of losses at the critical charge neutralization point. The concept can be extended to a wide range of colloids, including polystyrene latex and aqueous bentonite suspension, highlighting the versatility of the proposed approach to develop environmentally friendly high-performance capacitors.