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Abstract MXenes, a family of 2D transition‐metal carbides and nitrides, have excellent electrical conductivity and unique optical properties. However, MXenes oxidize in ambient conditions, which is accelerated upon heating. Intercalation of water also causes hydrolysis accelerating oxidation. Developing new tools to readily characterize MXenes’ thermal stability can enable deeper insights into their structure–property relationships. Here, in situ spectroscopic ellipsometry (SE) is employed to characterize the optical properties of three types of MXenes (Ti3C2Tx, Mo2TiC2Tx, and Ti2CTx) with varied composition and atomistic structures to investigate their thermal degradation upon heating under ambient environment. It is demonstrated that changes in MXene extinction and optical conductivity in the visible and near‐IR regions correlate well with the amount of intercalated water and hydroxyl termination groups and the degree of oxidation, measured using thermogravimetric analysis. Among the three MXenes, Ti3C2Txand Ti2CTx, respectively, have the highest and lowest thermal stability, indicating the role of transition‐metal type, synthesis route, and the number of atomic layers in MXene flakes. These findings demonstrate the utility of SE as a powerful in situ technique for rapid structure–property relationship studies paving the way for the further design, fabrication, and property optimization of novel MXene materials.
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Ultrafast dynamics of plasmons and free carriers in 2D MXenes
We use transient optical absorption and time-resolved terahertz THz spectroscopy to investigate photoexcitations in Ti3C2, Mo2Ti2C3, and Nb2C. Measurements reveal pronounced plasmonic effects. Monitoring them provides insights into thermal relaxation processes and low thermal conductivity.
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- PAR ID:
- 10466141
- Date Published:
- Journal Name:
- CLEO 2023, Technical Digest Series (Optica Publishing Group, 2023)
- Page Range / eLocation ID:
- FF1G.2
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract MXenes constitute a rapidly growing family of 2D materials that are promising for optoelectronic applications because of numerous attractive properties, including high electrical conductivity. However, the most widely used titanium carbide (Ti3C2Tx) MXene transparent conductive electrode exhibits insufficient environmental stability and work function (WF), which impede practical applications Ti3C2Txelectrodes in solution‐processed optoelectronics. Herein, Ti3C2TxMXene film with a compact structure and a perfluorosulfonic acid (PFSA) barrier layer is presented as a promising electrode for organic light‐emitting diodes (OLEDs). The electrode shows excellent environmental stability, highWFof 5.84 eV, and low sheet resistanceRSof 97.4 Ω sq−1. The compact Ti3C2Txstructure after thermal annealing resists intercalation of moisture and environmental contaminants. In addition, the PFSA surface modification passivates interflake defects and modulates theWF. Thus, changes in theWFandRSare negligible even after 22 days of exposure to ambient air. The Ti3C2TxMXene is applied for large‐area, 10 × 10 passive matrix flexible OLEDs on substrates measuring 6 × 6 cm. This work provides a simple but efficient strategy to overcome both the limited environmental stability and lowWFof MXene electrodes for solution‐processable optoelectronics.more » « less
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Abstract Ti3C2Txbelongs to the family of MXenes, 2D materials with an attractive combination of functional properties suitable for applications such as batteries, supercapacitors, and strain sensors. However, the fabrication of devices and functional coatings based on Ti3C2Txremains challenging as they are prone to chemical degradation by their oxidation to TiO2. In this paper, we examine the oxidation of Ti3C2Txin air, liquid, and solid media via conductivity measurements to assess the shelf life of Ti3C2TxMXenes. The oxidation of Ti3C2Txwas observed in all the media used in this study, but it is fastest in liquid media and slowest in solid media (including polymer matrices). We also show that the conventional indicators of MXene oxidation, such as changes in color and colloidal stability, are not always reliable. Finally, we demonstrate the acceleration of oxidation under exposure to UV light.more » « less
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Abstract 3D continuous mesoscale architectures of nanomaterials possess the potential to revolutionize real‐time electrochemical biosensing through higher active site density and improved accessibility for cell proliferation. Herein, 3D microporous Ti3C2TXMXene biosensors are fabricated to monitor antibiotic release in tissue engineering scaffolds. The Ti3C2TX‐coated 3D electrodes are prepared by conformal MXene deposition on 3D‐printed polymer microlattices. The Ti3C2TXMXene coating facilitates direct electron transfer, leading to the efficient detection of common antibiotics such as gentamicin and vancomycin. The 3D microporous architecture exposes greater electrochemically active MXene surface area, resulting in remarkable sensitivity for detecting gentamicin (10–1 mM) and vancomycin (100–1 mM), 1000 times more sensitive than control electrodes composed of 2D planar films of Ti3C2TXMXene. To characterize the suitability of 3D microporous Ti3C2TXMXene sensors for monitoring drug elution in bone tissue regeneration applications, osteoblast‐like (MG‐63) cells are seeded on the 3D MXene microlattices for 3, 5, and 7 days. Cell proliferation on the 3D microporous MXene is tracked over 7 days, demonstrating its promising biocompatibility and its clinical translation potential. Thus, 3D microporous Ti3C2TXMXene can provide a platform for mediator‐free biosensing, enabling new applications for in vivo monitoring of drug elution.more » « less
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Abstract To advance the MXene field, it is crucial to optimize each step of the synthesis process and create a detailed, systematic guide for synthesizing high‐quality MXene that can be consistently reproduced. In this study, a detailed guide is provided for an optimized synthesis of titanium carbide (Ti3C2Tx) MXene using a mixture of hydrofluoric and hydrochloric acids for the selective etching of the stoichimetric‐Ti3AlC2MAX phase and delamination of the etched multilayered Ti3C2TxMXene using lithium chloride at 65 °C for 1 h with argon bubbling. The effect of different synthesis variables is investigated, including the stoichiometry of the mixed powders to synthesize Ti3AlC2, pre‐etch impurity removal conditions, selective etching, storage, and drying of MXene multilayer powder, and the subsequent delamination conditions. The synthesis yield and the MXene film electrical conductivity are used as the two parameters to evaluate the MXene quality. Also the MXenes are characterized with scanning electron microscopy, x‐ray diffraction, atomic force microscopy, and ellipsometry. The Ti3C2Txfilm made via the optimized method shows electrical conductivity as high as ≈21,000 S/cm with a synthesis yield of up to 38 %. A detailed protocol is also provided for the Ti3C2TxMXene synthesis as the supporting information for this study.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Conference Paper:
- https://doi.org/10.1364/CLEO_FS.2023.FF1G.2
