Use of nanomaterials for photocatalysis faces challenges such as complex synthesis, high cost, low scalability, and dependance on UV radiation for initiating the photocatalytic activity. We recently demonstrated scalable, one-pot syntheses of one-dimensional (1D) lepidocrocite-based nanofilaments (NFs), 1DL NFs, that have the potential to overcome some of the challenges. 1DL NFs are exceptionally stable in water, have a large surface to volume ratio, and sub-square-nanometer cross sections. Initial reports show the semiconducting nature of this material, with an indirect band gap energy of 4.0 eV, one of the highest ever reported for a titania material. In this work, we present a study of the electronic and optical properties of these newly discovered 1DL NFs using ultrafast transient optical absorption. We show that despite the large band gap of this material, sub-gap states can be accessed with visible light illumination only, and photoexcited species reveal decay times in the nanosecond scale. Long lived photoexcitations in the visible range, without assistance by UV illumination, pave the way for possible application in photocatalysis.
Discovered in 2013, 2D niobium carbide (Nb2C), a member of the MXene family, has been shown to have many extraordinary properties, such as high photothermal conversion efficiency, strong electron-phonon interactions, strong optical absorption in the near-infrared, and even saturable optical absorption. These unique properties of Nb2C render this MXene potentially useful for a variety of applications, including photonic and optoelectronic devices and even photothermal cancer therapy. Here, we employ both terahertz time-domain spectroscopy (TDS) and time-resolved terahertz spectroscopy (TRTS) to investigate intrinsic and photoinduced conductivity and dynamics of optically injected charge carriers with 1.55 eV excitations in order to understand the photoinduced processes taking place in Nb2C. We find that the photoinduced conductivity in this MXene shows an initial rapid decay over a picosecond time scale, followed by a much longer-lived component that lasts for nanoseconds. We also observe that the long-range conductivity is strongly limited by the nanoflake boundaries.
Germanium sulfide (GeS) is a 2D semiconductor with high carrier mobility, a moderate band gap of about 1.6 eV, and highly anisotropic optical properties. In-plane anisotropy and a large in-plane spontaneous electric polarization in GeS monolayers have been predicted to result in significant second order nonlinear effects in response to above-the-gap excitation with photon energy < 2.5 eV1. We have further confirmed it experimentally by demonstrating surface shift current generation in GeS using THz emission spectroscopy with 3.1 eV excitation.3 Here, we use time-resolved THz spectroscopy to investigate the dynamics and lifetimes of photoexcited carriers in GeS single crystals and nanoribbons in response to excitations with energies ranging from 1.5 eV, resonant with the bulk gap, to 3.1 eV. We find that resulting dynamics vary considerably. Lower energy (1.5 eV) excitation injects carriers directly into three low-lying valleys in the conduction band. Those carriers have long, which photoconductivity persisting for over 500 ps, as it can be seen in Fig. 1(a). On the other hand, injecting carriers high into the conduction band results in THz emission due to the shift current as well as into transient photoconductivity that recovers over <100 ps. Pronounced changes in the transient photoconductivity in response to optical excitation with photon energy across the visible-NIR range open intriguing possibilities for applications in ultrafast spectrally-sensitive photodetectors and solar energy conversion.
MXenes are a new class of intrinsically metallic 2D materials. Their wide range of optoelectronic properties they demonstrate as a function of their chemical composition suggest applications in electronic and photonic devices. In this work we present a comprehensive study of the optical properties of three members of the MXene family, Ti3C2Tz, Mo2Ti2C3Tz, and Nb2CTz, using ultrafast transient optical absorption and THz spectroscopy. We find that those properties result from a complicated interaction between free carriers, interband transitions and localized surface plasmon resonances. Elucidating the nature of photoexcitation and dynamics of carriers in these emergent materials will lay the foundation for their potential for optoelectronic applications.
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