Ultrafast & Terahertz Photonics Group

Electro-optic sampling allows the electric field of THz, mid-infrared and visible light pulses to be measured directly as a function of time, with data analysis often performed in the frequency domain after fast Fourier transform. Here, we review aspects of Fourier theory relevant to the frequency-domain analysis of light pulses recorded in the time domain. We describe a “best practise” approach to using the discrete Fourier transform that ensures consistency with analytical results from the continuous Fourier transform. We summarise a phenomenological time-domain model of THz pulses, based on carrier and envelope waves, and show that it can reproduce a wide variety of experimental single- to multi-cycle THz pulses, with exemplary data from lab-based sources (photoconductive antennae, optical rectification, spintronic emitters) and a THz free-electron laser. A quantitative comparison of the spectral energy density of these distinct sources is enabled by the amplitude-accurate discrete Fourier transform. We describe a method that ensures the accurate calculation of the absolute spectral phase (valid for arbitrary sampling windows in the time domain) and summarise how the carrier-envelope phase, pulse arrival time, and chirp can be obtained from the phase. Our aim with this overview of THz pulse analysis is to highlight algorithms and concepts that are useful to newcomers to time-domain spectroscopy and experts, alike.

In perovskite solar cells, photovoltaic action is created by charge transport layers (CTLs) either side of the light-absorbing metal halide perovskite semiconductor. Hence, the rates for desirable charge extraction and unwanted interfacial recombination at the perovskite-CTL interfaces play a critical role for device efficiency. Here, the electrical properties of perovskite-CTL bilayer heterostructures are obtained using ultrafast terahertz and optical studies of the charge carrier dynamics after pulsed photoexcitation, combined with a physical model of charge carrier transport that includes the prominent Coulombic forces that arise after selective charge extraction into a CTL, and cross-interfacial recombination. The charge extraction velocity at the interface and the ambipolar diffusion coefficient within the perovskite are determined from the experimental decay profiles for heterostructures with three of the highest-performing CTLs, namely C60, PCBM and Spiro-OMeTAD. Definitive targets for the further improvement of devices are deduced: fullerenes deliver fast electron extraction, but suffer from a large rate constant for cross-interface recombination or hole extraction. Conversely, Spiro-OMeTAD exhibits slow hole extraction but does not increase the perovskite’s surface recombination rate, likely contributing to its success in solar cell devices.

Layered hybrid perovskites (LPKs) are promising as alternatives or additives to 3D metal halide perovskites for optoelectronic applications including photovoltaic cells, LEDs and lasers due to their increased stability. However, high exciton binding energies in these materials mean that excitons are the majority species under the operating conditions of many devices. Although the efficiency of devices that incorporate LPKs has been increasing, much is still unknown about the interplay of excitons and free charge-carriers in these materials, which is vital information for understanding how optoelectronic properties dictate device efficiency. In this work, we employ optical pump/THz probe spectroscopy (OPTP) and visible transient absorption spectroscopy (TAS) to analyse the optoelectronic properties and charge-carrier dynamics of phenylethylammonium lead iodide (PEA)2PbI4. By combining these techniques, we are able to disentangle the contributions from excitons and free charge-carriers. We observe fast cooling of free charge-carriers and exciton formation on a timescale of ∼400 fs followed by slower bimolecular recombination of residual free charge-carriers with a rate constant k2 ∼ 109 cm3s−1. Excitons recombine via two monomolecular processes with lifetimes t1 ∼ 11 ps and t2 ∼ 83 ps. Furthermore, we detect signatures of exciton–phonon coupling in the transient absorption kinetic traces. These findings provide new insight into the interplay between free charge-carriers and excitons as well as a possible mechanism to further understand the charge-carrier dynamics in LPKs.

The dynamics of the 3237 cm−1 local vibrational mode in diamond, associated with an unknown defect, was investigated using ultrafast infrared pump-probe spectroscopy. When pumped at 3237 cm−1, a degenerate probe was used to study the ground state's recovery, while a non-degenerate probe tracked excited state absorption at 3029 cm−1, corresponding to the 1 → 2 vibrational state transition. The similar population lifetimes for the ground state recovery and excited state absorption suggests a single population decay pathway, with a lifetime of T₁=2.2+-0.1ps. Perturbed free induction decay signals observed in negative time delays gave the dephasing time of the coherent state between the 0 and 1 vibrational states, and further predicted the 3029 cm−1 transition. Images from FTIR microscopy show that the 3237 cm−1 feature and the 3107 cm−1 absorption line from the N3VH0 defect are not correlated, and our pump-probe study shows the 3237 cm−1 feature does not share a common ground state with the N3VH0 defect, both of which suggest that this local vibrational mode does not originate from the N3VH0 defect. A calibration factor was obtained via a Morse potential model constrained by the observed transition energies, which relates the concentration of the defect producing the 3237 cm−1 feature to its absorption coefficient measured by FTIR spectroscopy. Based on FTIR absorption spectroscopy under uniaxial stress, we further assign a trigonal symmetry character to the defect that gives the 3237 cm−1 feature. The results presented are consistent with the theory that the 3237 cm−1 feature originates from the N4VH defect, the quantification of which allows better tracking of the nitrogen content in diamond.