Tip-Enhanced Raman Scattering Imaging of Single- to Few-Layer Ti3C2Tx MXene.

MXenes are among the most widely researched materials due to a unique combination of high electronic conductivity and hydrophilic surface, confined in a 2D structure. Therefore, comprehensive characterization of individual MXene flakes is of great importance. Here we report on nanoscale Raman imaging of single-layer and few-layer flakes of Ti3C2Tx MXene deposited on a gold substrate using tip-enhanced Raman scattering (TERS). TERS spectra of MXene monolayers are dominated by an intense peak at around 201 cm-1 and two well-defined peaks at around 126 and 725 cm-1. Absolute intensities of these peaks decrease with increasing number of layers, though the relative intensity of the 126 and 725 cm-1 bands as compared to the 201 cm-1 band increases. The peak positions of the main MXene bands do not significantly change in flakes of different number of layers, suggesting weak coupling between the MXene layers. In addition, we observed stiffening of the 201 cm-1 vibration over the wrinkles in MXene flakes. Using TERS for nanoscale spectroscopic characterization of Ti3C2Tx allows fast Raman mapping with deep subdiffraction resolution at the laser power density on the sample about an order of magnitude lower as compared to confocal Raman measurements. Finally, we demonstrate very high environmental stability of stoichiometric single-layer MXenes and show that the intensity of TERS response from the single- and few-layer flakes of Ti3C2Tx can be used to track early stages of degradation, well before significant morphological changes appear.

Deformation of and Interfacial Stress Transfer in Ti3C2 MXene-Polymer Composites.

Transitional metal carbides and nitrides (MXenes) have promise for incorporation into multifunctional composites due to their high electrical conductivity and excellent mechanical and tribological properties. It is unclear, however, to what extent MXenes are also able to improve the mechanical properties of the composites and, if so, what would be the optimal flake size and morphology. Herein, Ti3C2Tx MXene is demonstrated to be indeed a good candidate for mechanical reinforcement in polymer matrices. In the present work, the strain-induced Raman band shifts of mono-/few-/multilayer MXenes flakes have been used to study the mechanical properties of MXene and the interlayer/interfacial stress transfer on a polymer substrate. The mechanical performance of MXene was found to be less dependent upon flake thickness compared to that of graphene. This enables Ti3C2Tx MXene to offer an efficient mechanical reinforcement to a polymer matrix with a flake length of >10 µm and a thickness of 10s of nanometers. Therefore, the degree of exfoliation of MXenes is not as demanding as other two-dimensional (2D) materials for the purpose of mechanical enhancement in polymers. In addition, the active surface chemistry of MXene facilitates possible functionalization to enable a stronger interface with polymers for applications, such as strain engineering and mechanical enhancement, and in materials including membranes, coatings, and textiles.

Modified MAX Phase Synthesis for Environmentally Stable and Highly Conductive Ti3C2 MXene.

One of the primary factors limiting further research and commercial use of the two-dimensional (2D) titanium carbide MXene Ti3C2, as well as MXenes in general, is the rate at which freshly made samples oxidize and degrade when stored as aqueous suspensions. Here, we show that including excess aluminum during synthesis of the Ti3AlC2 MAX phase precursor leads to Ti3AlC2 grains with improved crystallinity and carbon stoichiometry (termed Al-Ti3AlC2). MXene nanosheets (Al-Ti3C2) produced from this precursor are of higher quality, as evidenced by their increased resistance to oxidation and an increase in their electronic conductivity up to 20 000 S/cm. Aqueous suspensions of stoichiometric single- to few-layer Al-Ti3C2 flakes produced from the modified Al-Ti3AlC2 have a shelf life of over ten months, compared to 1 to 2 weeks for previously published Ti3C2, even when stored in ambient conditions. Freestanding films made from Al-Ti3C2 suspensions stored for ten months show minimal decreases in electrical conductivity and negligible oxidation. Furthermore, oxidation of the improved Al-Ti3C2 in air initiates at temperatures that are 100-150 °C higher than that of conventional Ti3C2. The observed improvements in both the shelf life and properties of Al-Ti3C2 will facilitate the widespread use of this material.

Tailoring Electronic and Optical Properties of MXenes through Forming Solid Solutions.

Alloying is a long-established strategy to tailor properties of metals for specific applications, thus retaining or enhancing the principal elemental characteristics while offering additional functionality from the added elements. We propose a similar approach to the control of properties of two-dimensional transition metal carbides known as MXenes. MXenes (Mn+1Xn) have two sites for compositional variation: elemental substitution on both the metal (M) and carbon/nitrogen (X) sites presents promising routes for tailoring the chemical, optical, electronic, or mechanical properties of MXenes. Herein, we systematically investigated three interrelated binary solid-solution MXene systems based on Ti, Nb, and/or V at the M-site in a M2XTx structure (Ti2-yNbyCTx, Ti2-yVyCTx, and V2-yNbyCTx, where Tx stands for surface terminations) showing the evolution of electronic and optical properties as a function of composition. All three MXene systems show unlimited solubility and random distribution of metal elements in the metal sublattice. Optically, the MXene systems are tailorable in a nonlinear fashion, with absorption peaks from ultraviolet to near-infrared wavelength. The macroscopic electrical conductivity of solid solution MXenes can be controllably varied over 3 orders of magnitude at room temperature and 6 orders of magnitude from 10 to 300 K. This work greatly increases the number of nonstoichiometric MXenes reported to date and opens avenues for controlling physical properties of different MXenes with a limitless number of compositions possible through M-site solid solutions.

Tunable electrochromic behavior of titanium-based MXenes.

Two-dimensional transition metal carbides, nitrides and carbonitrides, popular by the name MXenes, are a promising class of materials as they exhibit intriguing optical, optoelectronic and electrochemical properties. Taking advantage of their metallic conductivity and hydrophilicity, titanium carbide MXenes (Ti3C2Tx and others) are used to fabricate solution processable transparent conducting electrodes (TCEs) for the design of three-electrode electrochromic cells. However, the tunable electrochromic behavior of various titanium-based MXene compositions across the entire visible spectrum has not yet been demonstrated. Here, we investigate the intrinsic electrochromic properties of titanium-based MXenes, Ti3C2Tx, Ti3CNTx, Ti2CTx, and Ti1.6Nb0.4CTx, where individual MXenes serve as a transparent conducting, electrochromic, and plasmonic material layer. Plasmonic extinction bands for Ti3C2Tx, Ti2CTx and Ti1.6Nb0.4CTx are centered at 800, 550 and 480 nm, which are electrochemically tunable to 630, 470 and 410 nm, respectively, whereas Ti3CNTx shows a reversible change in transmittance in the wide visible range. Additionally, the switching rates of MXene electrodes with no additional transparent conductor electrodes are estimated and correlated with the respective electrical figure of merit values. This study demonstrates that MXene-based electrochromic cells are tunable in the entire visible spectrum and suggests the potential of the MXene family of materials in optoelectronic, plasmonic, and photonic applications, such as tunable visible optical filters and modulators, to name a few.

Synthesis of Mo4VAlC4 MAX Phase and Two-Dimensional Mo4VC4 MXene with Five Atomic Layers of Transition Metals.

MXenes are a family of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides with a general formula of Mn+1XnTx, in which two, three, or four atomic layers of a transition metal (M: Ti, Nb, V, Cr, Mo, Ta, etc.) are interleaved with layers of C and/or N (shown as X), and Tx represents surface termination groups such as -OH, ═O, and -F. Here, we report the scalable synthesis and characterization of a MXene with five atomic layers of transition metals (Mo4VC4Tx), by synthesizing its Mo4VAlC4 MAX phase precursor that contains no other MAX phase impurities. These phases display twinning at their central M layers which is not present in any other known MAX phases or MXenes. Transmission electron microscopy and X-ray diffraction were used to examine the structure of both phases. Energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and high-resolution scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy were used to study the composition of these materials. Density functional theory calculations indicate that other five transition metal-layer MAX phases (M'4M″AlC4) may be possible, where M' and M″ are two different transition metals. The predicted existence of additional Al-containing MAX phases suggests that more M5C4Tx MXenes can be synthesized. Additionally, we characterized the optical, electronic, and thermal properties of Mo4VC4Tx. This study demonstrates the existence of an additional subfamily of M5X4Tx MXenes as well as a twinned structure, allowing for a wider range of 2D structures and compositions for more control over properties, which could lead to many different applications.

Tuning the Electrochemical Performance of Titanium Carbide MXene by Controllable In Situ Anodic Oxidation.

MXenes are a class of two-dimensional (2D) transition metal carbides, nitrides and carbonitrides that have shown promise for high-rate pseudocapacitive energy storage. However, the effects that irreversible oxidation have on the surface chemistry and electrochemical properties of MXenes are still not understood. Here we report on a controlled anodic oxidation method which improves the rate performance of titanium carbide MXene (Ti3 C2 Tx, Tx refers to -F, =O, -Cl and -OH) electrodes in acidic electrolytes. The capacitance retention at 2000 mV s-1 (with respect to the lowest scan rate of 5 mV s-1 ) increases gradually from 38 % to 66 % by tuning the degree of anodic oxidation. At the same time, a loss in the redox behavior of Ti3 C2 Tx is evident at high anodic potentials after oxidation. Several analysis methods are employed to reveal changes in the structure and surface chemistry while simultaneously introducing defects, without compromising electrochemically active sites, are key factors for improving the rate performance of Ti3 C2 Tx . This study demonstrates improvement of the electrochemical performance of MXene electrodes by performing a controlled anodic oxidation.

Automated Scalpel Patterning of Solution Processed Thin Films for Fabrication of Transparent MXene Microsupercapacitors.

A simple and generic strategy is proposed to pattern thin films deposited by a solution processable route. A soft approach based on an automated scalpel technique is developed to engrave thin films in a single step for sculpting functional planar devices. MXenes-the emerging family of 2D transition metal carbides and nitrides-combine metallic conductivity and hydrophilicity, enabling solution processing of transparent conducting electrodes (TCEs) under ambient conditions. Scalable dip coating is employed to process titanium carbide, Ti3 C2 , MXene thin films with excellent optoelectronic properties, achieving electrical Figure of merit up to 14. Automated scalpel engraving is adopted to fabricate transparent and semi-transparent MXene microsupercapacitors in a single step, hitherto not reported. Combining TCE and pseudocapacitive characteristics, MXene devices show excellent capacitive storage capabilities at high rates, without the aid of external metal current collectors. This technique allows for maskless patterning of solution processed thin films without losing intrinsic physicochemical properties and can be extended to fabricate heterostructured hybrid devices out of solution processable materials.

2D titanium carbide (MXene) for wireless communication.

With the development of the Internet of Things (IoT), the demand for thin and wearable electronic devices is growing quickly. The essential part of the IoT is communication between devices, which requires radio-frequency (RF) antennas. Metals are widely used for antennas; however, their bulkiness limits the fabrication of thin, lightweight, and flexible antennas. Recently, nanomaterials such as graphene, carbon nanotubes, and conductive polymers came into play. However, poor conductivity limits their use. We show RF devices for wireless communication based on metallic two-dimensional (2D) titanium carbide (MXene) prepared by a single-step spray coating. We fabricated a ~100-nm-thick translucent MXene antenna with a reflection coefficient of less than -10 dB. By increasing the antenna thickness to 8 µm, we achieved a reflection coefficient of -65 dB. We also fabricated a 1-µm-thick MXene RF identification device tag reaching a reading distance of 8 m at 860 MHz. Our finding shows that 2D titanium carbide MXene operates below the skin depth of copper or other metals as well as offers an opportunity to produce transparent antennas. Being the most conductive, as well as water-dispersible, among solution-processed 2D materials, MXenes open new avenues for manufacturing various classes of RF and other portable, flexible, and wearable electronic devices.

Selective Etching of Silicon from Ti3 SiC2 (MAX) To Obtain 2D Titanium Carbide (MXene).

Until now, MXenes could only be produced from MAX phases containing aluminum, such as Ti3 AlC2 . Here, we report on the synthesis of Ti3 C2 (MXene) through selective etching of silicon from titanium silicon carbide-the most common MAX phase. Liters of colloidal solutions of delaminated Ti3 SiC2 -derived MXene (0.5-1.3 mg mL-1 ) were produced and processed into flexible and electrically conductive films, which show higher oxidation resistance than MXene synthesized from Ti3 AlC2 . This new synthesis method greatly widens the range of precursors for MXene synthesis.