Mechanism of the Terahertz Wave-MXene Interaction and Surface/Interface Chemistry of MXene for Terahertz Absorption and Shielding.

ConspectusOver the past two decades, terahertz (THz) technology has undergone rapid development, driven by advancements and the growing demand for THz applications across various scientific and technological domains. As the cornerstone of THz technology, strong THz-matter interactions, especially realized as high THz intrinsic absorption in nanometer-thick materials, play a highly important role in various applications including but not limited to THz absorption/shielding, detection, etc. The rigorous electromagnetic theory has posited a maximum intrinsic absorption of 50% for electromagnetic waves by thin films, and the succinct impedance matching condition has also been formulated to guide the design of highly intrinsically absorbing materials. However, these theories face challenges when applied to the THz spectrum with an ultrabroad bandwidth. Existing thin films typically achieve a maximum intrinsic absorption within a narrow frequency range, significantly limiting the performance of THz absorbers and detectors. To date, both theoretical frameworks and experimental solutions are lacking in overcoming the challenge of achieving broadband maximum intrinsic absorption in the THz regime.In this Account, we describe how two-dimensional (2D) transition-metal carbide and/or nitride (MXene) films with nanometer thickness can realize the maximum intrinsic absorption in the ultrabroad THz band, which successfully addresses the forementioned longstanding issue. Surprisingly, traditional DC impedance matching theory fails to explain this phenomenon, while we instead propose a novel theory of AC impedance matching to provide a satisfactory explanation. By delving into the microscopic transport behavior of free electrons in MXene, we discover that intraflake transport dominates terahertz conductivity under THz wave excitation, while interflake transport primarily dictates DC conductivity. This not only elucidates the significant disparities between DC and AC impedance in MXenes but also underscores the suitability of AC impedance matching for achieving broadband THz absorption limits. Furthermore, we identify a high electron concentration and short relaxation time as crucial factors for achieving broadband maximum absorption in the THz regime. Although approaching the THz intrinsic absorbing limits, it still faces hurdles to the use of MXene in practical applications. First, diverse and uncontrollable terminations exist on the surface of MXene stemming from the synthesis process, which largely influence the electron structure and THz absorbing property of MXene. Second, MXene suffers from poor stability in the presence of oxygen and water. To address the above issues, we have undertaken distinctive works to precisely control the terminations and suppress the oxidation of MXene even at high temperature through surface and interface chemistry, such as low-temperature Lewis basic halide treatment and building a Ti3C2Tx/extracted bentonite (EB) interface. For practical application consideration, we proposed a copolymer-polyacrylic latex (PAL)-based MXene waterborne paint (MWP) with a strong intermolecular polar interaction between MWP and the substrate provided by the cyano group in PAL. This not only has strong THz EMI shielding/absorption efficiency but also can easily adhere to various substrates that are commonly used in the THz band. These studies may have significant implications for future applications of MXene nanofilms in THz optoelectronic devices.

Organohydrogel-based transparent terahertz absorber via ionic conduction loss.

The fast-growing terahertz technologies require high-performance terahertz absorber for suppressing electromagnetic interference. Since the dissipation mechanism in terahertz band usually focuses on electronic conduction loss, almost all terahertz absorbers are constructed with electronically conducting materials being opaque, which limits their applications in scenarios requiring high visible transmittance. Here, we demonstrate a transparent terahertz absorber based on permittivity-gradient elastomer-encapsulated-organohydrogel. Our organohydrogel-based terahertz absorber exhibits a high absorbing property (average reflection loss of 49.03 dB) in 0.5-4.5 THz band with a thin thickness of 700 µm and a high average visible transmittance of 85.51%. The terahertz absorbing mechanism mainly derives from the ionic conduction loss of the polar liquid in organohydrogel. Besides, the hydrophobic and adhesive elastomer coating endows this terahertz absorber high absorbing stability and interfacial adhesivity. This work paves a viable way to designing transparent terahertz absorbers.

Charge Carriers Localization Effect Revealed through Terahertz Spectroscopy of MXene: Ti3C2Tx.

The transport properties of charge carriers in MXene, a promising material, have been studied using terahertz time-domain spectroscopy (THz-TDS) to examine its potential applications in optical and electronic devices. However, previous studies have been limited by narrow frequency ranges, which have hindered the understanding of the intrinsic mechanisms of carrier transport in MXenes. To address this issue, ultrabroadband THz-TDS with frequencies of up to 15 THz to investigate the complex photoconductances of MXene (Ti3C2Tx) films with different thicknesses are employed. The findings indicate that the electronic localization is substrate-dependent, and this effect decreases with an increase in the number of layers. This is attributed to the screening effect of the high carrier density in Ti3C2Tx. Additionally, the layer-independent photocarrier relaxations revealed by optical pump THz probe spectroscopy (OPTP) provide evidence of the carrier heating-induced screening effect. These results are significant for practical applications in both scientific research and various industries.

Electrically Tunable MXene Nanomechanical Resonators Vibrating at Very High Frequencies.

As an emerging class of two-dimensional (2D) layered nanomaterial, MXene exhibits a number of intriguing properties, such as good electrical conductivity and high elastic modulus, and has witnessed continued growth in related device research. However, nanoscale MXene devices which leverage both the intrinsic electrical and mechanical properties of these 2D crystals have not been experimentally studied. Here we demonstrate nanoelectromechanical resonators based on 2D MXene crystals, where Ti3C2Tx drumheads with a wide range of thickness, from more than 50 layers all the way down to a monolayer, exhibit robust nanomechanical vibrations with fundamental-mode frequency f0 up to >70 MHz in the very high frequency (VHF) band, a displacement noise density down to 52 fm/Hz1/2, and a fundamental-mode frequency-quality factor product up to f0 × Q ≈ 6.85 × 109 Hz. By combining experimental results with theoretical calculations, we independently derive the Young's modulus of 2D Ti3C2Tx crystals to be 270-360 GPa, in excellent agreement with nanoindentation measurements, based on which we elucidate frequency scaling pathways toward microwave frequencies. We further demonstrate electrical tuning of resonance frequency in MXene resonators and frequency-shift-based MXene vacuum gauges with responsivity of 736%/Torr and detection range down to 10-4 Torr. Our study can lead to the design and creation of nanoscale vibratory devices that exploit the intrinsic electrical and mechanical properties in 2D MXene crystals.

Simultaneously tuning interlayer spacing and termination of MXenes by Lewis-basic halides.

The surface and interface chemistry are of significance on controlling the properties of two-dimensional transition metal carbides and nitrides (MXenes). Numerous efforts have been devoted to the regulation of Ti3C2Tx MXene, however, tuning interlayer spacing and surface halogen termination of other MXenes (besides Ti3C2Tx) is rarely reported while demanded. Here we propose a Lewis-basic halides treatment, which is capable of simultaneously engineering the interlayer spacing and surface termination of various MXenes. Benefited from the abundant desolvated halogen anions and cations in molten state Lewis-basic halides, the -F termination was substituted by nucleophilic reaction and the interlayer spacing was enlarged. Ti3C2Tx MXene treated by this method showed a high specific capacity of 229 mAh g-1 for Li+ storage, which is almost 2 times higher than pristine one. Considering the universality, our method provides an approach to regulating the properties of MXenes, which may expand their potential applications in energy storage, optoelectronics and beyond.

High-temperature stability in air of Ti3C2Tx MXene-based composite with extracted bentonite.

Although Ti3C2Tx MXene is a promising material for many applications such as catalysis, energy storage, electromagnetic interference shielding due to its metallic conductivity and high processability, it's poor resistance to oxidation at high temperatures makes its application under harsh environments challenging. Here, we report an air-stable Ti3C2Tx based composite with extracted bentonite (EB) nanosheets. In this case, oxygen molecules are shown to be preferentially adsorbed on EB. The saturated adsorption of oxygen on EB further inhibits more oxygen molecules to be adsorbed on the surface of Ti3C2Tx due to the weakened p-d orbital hybridization between adsorbed O2 and Ti3C2Tx, which is induced by the Ti3C2Tx/EB interface coupling. As a result, the composite is capable of tolerating high annealing temperatures (above 400 °C for several hours) both in air or humid environment, indicating highly improved antioxidation properties in harsh condition. The above finding is shown to be independent on the termination ratio of Ti3C2Tx obtained through different synthesis routes. Utilized as terahertz shielding materials, the composite retains its shielding ability after high-temperature treatment even up to 600 °C, while pristine Ti3C2Tx is completely oxidized with no terahertz shielding ability. Joule heating and thermal cycling performance are also demonstrated.

Substrate-Independent Ti3C2Tx MXene Waterborne Paint for Terahertz Absorption and Shielding.

With the development of terahertz (THz) technology, there is a booming demand of THz shielding/absorption materials to avoid electromagnetic interference (EMI) or pollution. Paints that can be fast solidified to form a film and stably adherent on arbitrary substrates are especially desired for the shielding/absorption applications. Recently, MXenes with high electron conductivity and hydrophilicity have attracted a great interest for EMI shielding. Here, we demonstrate a copolymer-polyacrylic latex (PAL) based MXene waterborne paint (MWP), which not only has strong THz EMI shielding/absorption efficiency but also can easily adhere onto various substrates that are commonly used in the THz band. The viscosity of MWP can be tuned by adjusting the colloidal and viscous forces, and the cyano group in PAL provides a strong intermolecular polar interaction between MWP and the substrate. As a result, a 38.3-µm-thick MWP on quartz exhibits EMI shielding value of 64.9 dB, and an excellent reflection-loss of 32.8 dB is obtained on MWP coated sponge foam. This substrate-independent MWP provides a simple and efficient way to achieving high-performance THz shielding/absorption.