Terahertz Spectroscopy of Charge-Carrier Dynamics in One-Dimensional Nanomaterials
Date: 14 February 2018
University of Exeter
PhD in Physics
One-dimensional (1D) nanomaterials are of great importance for a number of potential applications. However, in order to realize this potential a thorough understanding of the charge-carrier dynamics in these materials is required, since these largely determine the optoelectronic properties of the materials in question. This thesis ...
One-dimensional (1D) nanomaterials are of great importance for a number of potential applications. However, in order to realize this potential a thorough understanding of the charge-carrier dynamics in these materials is required, since these largely determine the optoelectronic properties of the materials in question. This thesis investigates the charge-carrier dynamics of two 1D nanomaterials, single-walled carbon nanotubes (CNTs) and tungsten-oxide nanowires (WOxNWs), with the goal of better understanding the nature of their optoelectronic responses, and how nanomaterial geometry and morphology influence these responses. We do this using terahertz time-domain spectroscopy (THz-TDS) and optical pump - terahertz probe time-domain spectroscopy (OPTP). Firstly, we discuss how to properly analyse and interpret the data obtained from these experiments when measuring 1D nanomaterials. While the data obtained from THz-TDS is fairly straight-forward to analyse, OPTP experimental data can be far from trivial. Depending on the relative size of the sample geometry compared to the probe wavelength, various approximations can be used to simplify the extraction of their ultrafast response. We present a general method, based on the transfer matrix method, for evaluating the applicability of these approximations for a given multilayer structure, and show the limitations of the most commonly used approximations. We find that these approximations are only valid in extreme cases where the thickness of the sample is several orders of magnitude smaller or larger than the wavelength, which highlight the danger originating from improper use of these approximations. We then move on to investigate how the charge-carrier dynamics of our CNTs is influenced by nanotube length and density. This is done through studying the nature of the broad THz resonance observed in finite-length CNTs, and how the nanotube length and density affects this resonance. We do this by measuring the conductivity spectra of thin films comprising bundled CNTs of different average lengths in the frequency range 0.3-1000 THz and temperature interval 10-530 K. From this we show that the observed temperature-induced changes in the terahertz conductivity spectra depend strongly on the average CNT length, with a conductivity around 1 THz that increases/decreases as the temperature increases for short/long tubes. This behaviour originates from the temperature dependence of the electron scattering rate, which results in a subsequent broadening of the observed THz conductivity peak at higher temperatures and a shift to lower frequencies for increasing CNT length. Finally, we show that the change in conductivity with temperature depends not only on tube length, but also varies with tube density. We record the effective conductivities of composite films comprising mixtures of WS2 nanotubes and CNTs vs CNT density for frequencies in the range 0.3-1 THz, finding that the conductivity increases/decreases for low/high density films as the temperature increases. This effect arises due to the density dependence of the effective length of conducting pathways in the composite films, which again leads to a shift and temperature dependent broadening of the THz conductivity peak. Next, we investigate the conflicting reports regarding the ultrafast photoconductive response of films of CNTs, which apparently exhibit photoconductivities that can vastly differ, even in sign. Here we observe explicitly that the THz photoconductivity of CNT films is a highly variable quantity which correlates with the length of the CNTs, while the specific type of CNT has little influence. Moreover, by comparing the photo-induced change in THz conductivity with heat-induced changes, we show that both occur primarily due to heat-generated modification of the Drude electron relaxation rate, resulting in a broadening of the plasmonic resonance present in finite-length metallic and doped semiconducting CNTs. This clarifies the nature of the photo-response of CNT films and demonstrates the need to carefully consider the geometry of the CNTs, specifically the length, when considering them for application in optoelectronic devices. We then move on to consider our WOxNWs. We measure the terahertz conductivity and photoconductivity spectra of thin films compromising tungsten-oxide (WOx) nanowires of average diameters 4 nm and 100 nm, and oxygen deficiencies WO2.72 and WO3 using THz-TDS and OPTP. From this we present the first experimental evidence of a metal-to-insulator transition in WOx nanowires, which occurs when the oxygen content is increased from x=2.72->3 and manifests itself as a massive drop in the THz conductivity due to a shift in the Fermi level from the conduction band down into the bandgap. Furthermore we present the first experimental measurements of the photoexcited charge-carrier dynamics of WOx nanowires on a picosecond timescale and map the influence of oxygen-content and nanowire diameter. From this we show that the decay-dynamics of the nanowires is characterized by a fast decay of <1 ps, followed by slow decay of 3-10 ps, which we attribute to saturable carrier trapping at the surface of the nanowires.
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