Mesoporous black TiO2 hollow shells with controlled cavity size for enhanced visible light photocatalysis.

Black TiO2 formed by introducing lattice disorder into pristine TiO2 has a narrowed band gap and suppresses the recombination of charge carriers. This provides a potential strategy for visible light photocatalysis. However, the microstructural design of black TiO2 for a higher optimization of visible light is still in high demand. In this work, we proposed the preparation of black TiO2 hollow shells with controllable cavity diameters using silica spheres as templates for the cavities and the NaBH4 reduction method. The decreased cavity size resulted in a hollow shell with an enhanced visible-light absorption and improved photocatalytic performance. Moreover, we demonstrated that this cavity can be combined with gold nanoparticles (AuNPs) to form AuNPs@black TiO2 yolk-shells. The AuNPs provided additional visible light absorption and promoted the separation of photogenerated carriers in the yolk-shell structures. This further improved the photocatalysis, the degradation rate of Cr(VI) can reach 0.066 min-1. Our work evaluated the effect of the cavity size on the photocatalytic performance of hollow and yolk-shell structures and provided concepts for the further enhancement of visible-light photocatalysis.

Thermal and mechanical THz modulation of flexible all-dielectric metamaterial.

The implementation of Terahertz (THz) modulation is critical for applications in high-speed wireless communications, security screening and so on. Therefore, it is particularly significant to obtain THz wave modulation devices with stable and flexible performance, easy manipulation of the modulation method, and multi-functionality. Here, we propose a flexible all-dielectric metamaterial by embedding zirconia (ZrO2) microspheres into a vanadium dioxide/polydimethylsiloxane (VO2/PDMS) composite, which can achieve thermal and mechanical tuning of THz wave transmission. When the temperature of the ZrO2/VO2/PDMS metamaterial increases, VO2 changes from the insulating phase to the metallic phase, and the 1st (at 0.304 THz) and 2nd (at 0.414 THz) order magnetic resonances exhibit the tunability of 20 GHz and 15 GHz, respectively. When stretched, the 1st and 2nd order magnetic resonances show the tunability of 12 GHz and 10 GHz, respectively. In the meantime, there are accompanying changes in transmittance at the resonances. The ZrO2/VO2/PDMS all-dielectric metamaterial presented in this work provides an alternative strategy for developing actively tunable, flexible, and versatile THz devices. In addition, it has the merits of simple preparation and low cost, promising large-area and rapid preparation of meta-arrays.

Impact of the uniaxial strain on terahertz modulation characteristics in flexible epitaxial VO2 film across the phase transition.

Exploring flexible electronics is on the verge of innovative breakthroughs in terahertz (THz) communication technology. Vanadium dioxide (VO2) with insulator-metal transition (IMT) has excellent application potential in various THz smart devices, but the associated THz modulation properties in the flexible state have rarely been reported. Herein, we deposited an epitaxial VO2 film on a flexible mica substrate via pulsed-laser deposition and investigated its THz modulation properties under different uniaxial strains across the phase transition. It was observed that the THz modulation depth increases under compressive strain and decreases under tensile strain. Moreover, the phase-transition threshold depends on the uniaxial strain. Particularly, the rate of the phase transition temperature depends on the uniaxial strain and reaches approximately 6 °C/% in the temperature-induced phase transition. The optical trigger threshold in laser-induced phase transition decreased by 38.9% under compressive strain but increased by 36.7% under tensile strain, compared to the initial state without uniaxial strain. These findings demonstrate the uniaxial strain-induced low-power triggered THz modulation and provide new insights for applying phase transition oxide films in THz flexible electronics.

Roles of MXenes in biomedical applications: recent developments and prospects.

....With the development of nanomedical technology, the application of various novel nanomaterials in the biomedical field has been greatly developed in recent years. MXenes, which are new inorganic nanomaterials with ultrathin atomic thickness, consist of layered transition metal carbides and nitrides or carbonitrides and have the general structural formula Mn+1XnTx (n = 1-3). Based on the unique structural features of MXenes, such as ultrathin atomic thickness and high specific surface area, and their excellent physicochemical properties, such as high photothermal conversion efficiency and antibacterial properties, MXenes have been widely applied in the biomedical field. This review systematically summarizes the application of MXene-based materials in biomedicine. The first section is a brief summary of their synthesis methods and surface modification strategies, which is followed by a focused overview and analysis of MXenes applications in biosensors, diagnosis, therapy, antibacterial agents, and implants, among other areas. We also review two popular research areas: wearable devices and immunotherapy. Finally, the difficulties and research progress in the clinical translation of MXene-based materials in biomedical applications are briefly discussed.

Improved chemical precipitation prepared rapidly NiCo2S4 with high specific capacitance for supercapacitors.

In this work, rapid chemical precipitation assisted annealing method is used to prepare flower-like NiCo2S4. And the flower-like structure after polyethylene glycol (PEG) modification yields an excellent specific capacitance (2198.9 F g-1 at 1 A g-1). And an asymmetric supercapacitor assembled with NiCo2S4 (PEG-modified) and activated carbon (AC) shows an energy density of 38.2 Wh kg-1 at 400 W kg-1, and outstanding stability (80% remained after 3000 cycles at 5 A g-1). Benefited by a larger specific surface area and suitable pore size of the aggregate structure, the specific capacitance of prepared NiCo2S4 is increased by about 2 times. This uncomplicated preparation method is proved to be suitable for NiCo2S4 with a high specific capacitance of supercapacitors.

Terahertz wave near-field compressive imaging with a spatial resolution of over λ/100.

We demonstrate terahertz (THz) wave near-field imaging with a spatial resolution of ∼4.5 µm using single-pixel compressive sensing enabled by femtosecond-laser (fs-laser) driven vanadium dioxide (VO2)-based spatial light modulator. By fs-laser patterning a 180 nm thick VO2 nanofilm with a digital micromirror device, we spatially encode the near-field THz evanescent waves. With single-pixel Hadamard detection of the evanescent waves, we reconstructed the THz wave near-field image of an object from a serial of encoded sequential measurements, yielding improved signal-to-noise ratio by one order of magnitude over a raster-scanning technique. Further, we demonstrate that the acquisition time was compressed by a factor of over four with 90% fidelity using a total variation minimization algorithm. The proposed THz wave near-field imaging technique inspires new and challenging applications such as cellular imaging.

Giant impact of self-photothermal on light-induced ultrafast insulator-to-metal transition in VO2 nanofilms at terahertz frequency.

Ultrafast detection and switching of light are key processes in high-speed optoelectronic devices. However, the performances of VO2-based optoelectronics are strongly degraded by photothermal. The mechanism of the latter is still unclear. Here, by using femtosecond-laser (fs-laser) driven kinetic terahertz wave absorption, we quantitatively separate slow photothermal response and ultrafast photodoping response (e.g. light-induced insulator-to-metal transition) from second- to picosecond-timescales, and discover the competing interplay between them. With self-photothermal (mainly determined by fs-laser pulse repetition rate and pump fluence), the ultrafast transition time was degraded by 190% from 50 ps to 95 ps, the ultrafast transition threshold was decreased to 82% from 11mJ/cm2 to 9mJ/cm2, while the amplitudes of the two photoresponse are competing. Percolation theory, along with the macroscopic conductivity response, is used to explain the competing interplay. Our findings are relevant for designing and optimizing VO2-based ultrafast optoelectronic devices.

Two-dimensional MXene nanosheets on nano-scale fibrils in hierarchical porous structure to achieve ultra-high sensitivity.

The complex hybrid nanostructure combining a two-dimensional (2D) conductive material and a hierarchical nanoscale skeleton plays an important role to enhance its piezoresistive sensitivity. To construct such a novel hybrid nanostructure, a piezoresistive sensor was designed with the following strategy to take the full advantages of 2D MXene and nanoscale fibrils: ethylene oxide propylene oxide random copolymer (EOPO) was grafted to ethylene-vinyl alcohol (EVOH) molecular chains and was foamed by an environmentally-friendly supercritical CO2 (scCO2) foaming technology to fabricate abundant nanoscale EVOH fibrils surrounding micropores; MXene featured as a 2D structure of nanoscale size that strongly interacted with this hierarchical nanoscale skeleton, and MXene not only convolved on nanoscale fibrils to generate bumps but also MXene covered the end of broken fibrils to build spots, and furthermore, MXene adhered on the soft EOPO embedded EVOH fibrils to form wrinkles, in which these bumps, spots and wrinkles assembled by highly conductive 2D MXene offered sufficient contacts when the hierarchical nanoscale skeleton was compressed (these contacts would then destruct when the skeleton recovered). Such an elaborated hybrid nanostructural design exploits the full potential of 2D MXene and hence achieves an ultra-high sensitivity of 6895.0 kPa-1 for this fabricated MXene piezoresistive sensor.

A terahertz meta-sensor array for 2D strain mapping.

Large-scale stretchable strain sensor arrays capable of mapping two-dimensional strain distributions have gained interest for applications as wearable devices and relating to the Internet of Things. However, existing strain sensor arrays are usually unable to achieve accurate directional recognition and experience a trade-off between high sensing resolution and large area detection. Here, based on classical Mie resonance, we report a flexible meta-sensor array that can detect the in-plane direction and magnitude of preloaded strains by referencing a dynamically transmitted terahertz (THz) signal. By building a one-to-one correspondence between the intrinsic electrical/magnetic dipole resonance frequency and the horizontal/perpendicular tension level, arbitrary strain information across the meta-sensor array is accurately detected and quantified using a THz scanning setup. Particularly, with a simple preparation process of micro template-assisted assembly, this meta-sensor array offers ultrahigh sensor density (~11.1 cm-2) and has been seamlessly extended to a record-breaking size (110 × 130 mm2), demonstrating its promise in real-life applications.

VO2 Films Decorated with an MXene Interface for Decreased-Power-Triggered Terahertz Modulation.

VO2, which exhibits semiconductor-metal phase transition characteristics occurring on a picosecond time scale, holds great promise for ultrafast terahertz modulation in next-generation communication. However, as of now, there is no reported prototype for an ultrafast device. The temperature effect has been proposed as one of the major obstacles. Consequently, reducing the excitation threshold for the phase transition would be highly significant. The traditional strategy typically involves chemical doping, but this approach often leads to a decrease in phase transition amplitude and a slower transition speed. In this work, we proposed a design featuring a highly conductive MXene interfacial layer between the VO2 film and the substrate. We demonstrate a significant reduction in the phase transition threshold for both temperature and laser-induced phase transition by adjusting the conductivity of the MXene layers with varying thicknesses. Our observations show that the phase transition temperature can be decreased by 9 °C, while the pump fluence for laser excitation can be reduced by as high as 36%. The ultrafast phase transition process on a picosecond scale, as revealed by the optical-pump terahertz-probe method, suggests that the MXene layers have minimal impact on the phase transition speed. Moreover, the reduced phase transition threshold can remarkably alleviate the photothermal effect and inhibit temperature rise and diffusion in VO2 triggered by laser. This study offers a blueprint for designing VO2/MXene hybrid films with reduced phase transition thresholds. It holds significant potential for the development of low-power, intelligent optical and electrical devices including, but not limited to, terahertz modulators based on phase transition phenomena.

[The characteristics and dielectric dynamics of hydrated TiO2 in THz frequency range].

Terahertz time-domain spectroscopy (THz-TDS) was used to measure the information of water, the terahertz time-domain and frequency spectroscopy, absorbance, refractive index and the complex dielectric permittivity in the frequency range of 0.21-1 THz of various hydrated TiO2 samples with heating for different times. The result reveals that the absorbance of hydrated TiCO2 reduces with heating time increasing, and the location of the absorption peak is corresponded to the refractive index. The response of electric polarization in THz field has no clear relations with the frequency. With frequency increasing, the dielectric dissipation of hydrated TiO2 firstly decreases and then tends to be stable. The dielectric response always reduces with heating time increasing.

Highly Flexible Ti3C2Tx MXene/Waterborne Polyurethane Membranes for High-Efficiency Terahertz Modulation with Low Insertion Loss.

The dynamic control of terahertz (THz) wave transmission on flexible functional materials is a fundamental building block for wearable electronics and sensors in the THz range. However, achieving high-efficiency THz modulation and low insertion loss is a great challenge while maintaining the excellent flexibility and stretchability of the materials. Herein, we report a Ti3C2Tx MXene/waterborne polyurethane (WPU) membrane prepared by a vacuum-assisted filtration method, which exhibits excellent THz modulation properties across stretching. The hydrophilic Ti3C2Tx MXene and WPU enable the uniform 3D distribution of Ti3C2Tx MXene in the WPU matrix. Particularly, the stretchability with the maximum strain of the membranes can reach 200%, accompanied by dynamic tuning of THz transmittance for more than 90% and an insertion loss as low as -4.87 dB. The giant THz modulation continuously decreases with MXene content per unit area, accompanied by a lower density of the MXene interface and diminished THz absorption during stretching. Such a design opens a pathway for achieving flexible THz modulators with a high modulation depth and low insertion loss, which would be used for THz flexible and wearable devices.

THz medical imaging: from in vitro to in vivo.

Terahertz (THz) radiation has attracted considerable attention in medical imaging owing to its nonionizing and spectral fingerprinting characteristics. To date, most studies have focused on in vitro and ex vivo objects with water-removing pretreatment because the water in vivo excessively absorbs the THz waves, which causes deterioration of the image quality. In this review, we discuss how THz medical imaging can be used for a living body. The development of imaging contrast agents has been particularly useful to this end. In addition, we also introduce progress in novel THz imaging methods that could be more suitable for in vivo applications. Based on our discussions, we chart a developmental roadmap to take THz medical imaging from in vitro to in vivo.

Photothermal conversion of Ti2O3 film for tuning terahertz waves.

Dynamic tuning of terahertz (THz) wave is vital for the development of next generation THz devices. Utilization of solar energy for tuning THz waves is a promising, eco-friendly, and sustainable way to expand THz application scenarios. Ti2O3 with an ultranarrow bandgap of 0.1eV exhibits intriguing thermal-induced metal-insulator transition (MIT), and possesses excellent photothermal conversion efficiency. Herein, Ti2O3 film was fabricated by a two-step magnetron sputtering method, and exhibited an excellent photothermal conversion efficiency of 90.45% and demonstrated temperature-dependent THz transmission characteristics with a wideband at 0.1-1 THz. We supposed to combine photothermal conversion characteristics with temperature-dependent THz transmission properties of Ti2O3 film, which could introduce solar light as the energy source for tuning THz waves. Our work will provide new sight for investigating MIT characteristics of Ti2O3 at THz regime and exhibit huge potential in the application of tuning terahertz waves in outdoor scenarios in the future.

Sol-Gel-Derived Ni3Al Coating on Nickel Alloy for Oxidation Resistance in Supercritical Water Environments.

Although nickel-based alloys are widely used in industries due to their oxidation and corrosion resistance, the pursuit of better performance in harsh environments is still a great challenge. In this work, we developed a sol-gel method to synthesize Ni3Al coating on a nickel alloy, assisted by a post-annealing process, and investigated the oxidation-resistant performance. The coating thickness can be controlled by designing the deposition times, which keep the pure Ni3Al phase stable. In addition, the surface morphologies indicate that the coating is compact without obvious voids or cracks. Furthermore, the oxidation-resistant property of the coating was investigated by carrying out a supercritical water oxidation experiment. The crystalline structure and surface morphology of the samples before and after 72-h oxidation demonstrated the superior oxidation resistance of the coating. This work provides a convenient method to fabricate an oxidation-resistant coating on a nickel-based alloy, which would be significant for prolonging the service life of vessels under oxidation conditions, especially for supercritical water reactions.

Fabrication and Supercritical Water Corrosion Resistance of TiN/TiNC/Al2O3 Multilayer Coating on Inconel 625 Alloy by CVD Method.

A TiN/TiNC/Al2O3 multilayer coating was deposited on an Inconel 625 alloy by the chemical vapor deposition method as a protective barrier to improve the corrosion resistance in supercritical water. The corrosion characteristics were evaluated in a reactor at 500 °C and 25 MPa for 72 h. The surface morphology of the coated samples was relatively dense with no obvious cracks or pores observed. The XRD analysis revealed that the coatings were composed of TiN, TiNC and α-Al2O3 phases. After exposure to supercritical water, the surface morphology of the coatings was still dense and kept integrity. The phase composition of the coatings was also not changed, with no obvious corrosion scales detected. This result demonstrates the effectiveness of TiN/TiNC/Al2O3 coatings as a protective coating under harsh supercritical water environments.

Reconfigurable Optical Physical Unclonable Functions Enabled by VO2 Nanocrystal Films.

Optical physical unclonable function (PUF) is one of the most promising hardware security solutions, which has been proven to be resistant to machine learning attacks. However, the disordered structures of the traditional optical PUFs are usually deterministic once they are manufactured and therefore exhibit fixed challenge-response behaviors. Herein, a reconfigurable PUF (R-PUF) is proposed and demonstrated by using the reversible phase transition behavior of VO2 nanocrystals combined with TiO2 disordered nanoparticles. Both the simulation and experiment results show that the near-infrared laser speckle pattern of the R-PUF can be almost completely altered after the phase transition of VO2 nanocrystals, resulting in a reconfigurable and reproducible optical response. The similarity of the response speckles shows an obvious hysteresis loop during the rise and drop of temperature, providing a simple way to regulate and control the response behaviors of the R-PUF. More importantly, the hysteretic characteristic provides a new dimension to describe the challenge-response behavior of the R-PUF besides the laser speckle, providing an effective way to improve the security and encoding capacity of the optical PUFs. The proposed R-PUF can be employed as a promising security primitive for high robustness and high-security authentication and encryption.

Volatile and Nonvolatile Switching of Phase Change Material Ge2Sb2Te5 Revealed by Time-Resolved Terahertz Spectroscopy.

Phase change materials exhibit unique advantages in reconfigurable photonic devices due to drastic tunability of photoelectric properties. Here, we systematically investigate the thermal equilibrium process and the ultrafast dynamics of Ge2Sb2Te5 (GST) driven by femtosecond (fs) pulses, using time-resolved terahertz spectroscopy. Both fs-pulse-driven crystallization and amorphization are demonstrated, and the threshold of photoinduced crystallization (amorphization) is determined to be 8.4 mJ/cm2 (10.1 mJ/cm2). The ultrafast carrier dynamics reveal that the cumulative photothermal effect plays a crucial role in the ultrafast crystallization, and modulation depth of volatile (nonvolatile) THz has switching limits up to 30% (15%). A distinctive phonon absorption at 1.1 THz is observed, providing fingerprint spectrum evidence of crystalline lattice formation driven by intense fs pulses. Finally, multistate volatile (nonvolatile) THz switching is implemented by tuning optical pump fluence. These results provide insight into the photoinduced phase change of GST and offer benefits for all optical THz functional devices.

The role of lattice dynamics in ferroelectric switching.

Reducing the switching energy of ferroelectric thin films remains an important goal in the pursuit of ultralow-power ferroelectric memory and logic devices. Here, we elucidate the fundamental role of lattice dynamics in ferroelectric switching by studying both freestanding bismuth ferrite (BiFeO3) membranes and films clamped to a substrate. We observe a distinct evolution of the ferroelectric domain pattern, from striped, 71° ferroelastic domains (spacing of ~100 nm) in clamped BiFeO3 films, to large (10's of micrometers) 180° domains in freestanding films. By removing the constraints imposed by mechanical clamping from the substrate, we can realize a ~40% reduction of the switching voltage and a consequent ~60% improvement in the switching speed. Our findings highlight the importance of a dynamic clamping process occurring during switching, which impacts strain, ferroelectric, and ferrodistortive order parameters and plays a critical role in setting the energetics and dynamics of ferroelectric switching.

[Terahertz spectroscopic investigation of lanthanide-doped nano-TiO2].

Lanthanide-doped nano-TiO2 samples with different Ti/Ln (Ln = Ce, Nd, and Sm) were synthesized by sol-gel method. The samples were characterized by X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy (XPS) and terahertz time-domain spectroscopy (THz-TDS). The results indicate that Ce, Nd, and Sm ions were uniformly dispersed into the TiO2; and the infrared activities of lanthanide-deped nano-TiO2 were much stronger than Undoped nano-TiO2, the refractive index of anatase TiO2 declines with frequency increasing in the frequency range of 0.2-1.70 THz at room temperature, and it exhibits anomalous dispersion. Unique characteristic absorption peaks at 1.35 and 1.58 THz were observed from Ce-doped nano-TiO2. Compared with undoped nano-TiO2, the absorption edges of Ce-doped nano-TiO2 were red-shifted remarkably and those of Nd and Sm ions doped nano-TiO2 were blue-shifted. Sm-doped nano-TiO2 has induced the least dielectric losses in the frequency range of 0.2-1.7 THz, and the average value is 0.05.