J. Lloyd-Hughes, P.M. Oppeneer, T. Pereira dos Santos, A. Schleife, S. Meng, M.A. Sentef, M. Ruggenthaler, A. Rubio, I. Radu, M. Murnane, X. Shi, H. Kapteyn, B. Stadtmüller, K.M. Dani, F.H. da Jornada, E. Prinz, M. Aeschlimann, R.L. Milot, M. Burdanova, J. Boland, T. Cocker and F. Hegmann
J. Phys.: Cond. Matt. 33 353001 (July 2021)
C.Q. Xia, M. Monti, J.L. Boland, L.M. Herz, J. Lloyd-Hughes, M.R. Filip and M.B. Johnston
Phys. Rev. B 103 245205 (June 2021)
M.G. Burdanova, G.M. Katybab, R. Kashtiban, G.A. Komandin, E. Butler-Caddle, M. Staniforth, A.A. Mkrtchyan, D.V. Krasnikov, Y.G. Gladush, J.Sloan, A.G. Nasibulin and J. Lloyd-Hughes
Carbon 173 245 (Mar 2021)
Hot carriers in mixed Pb-Sn halide perovskite semiconductors cool slowly while retaining their electrical mobility
An Ultrafast Shakedown Reveals the Energy Landscape, Relaxation Dynamics and Concentration of the N3VH0 Defect in Diamond
Ultrafast Optoelectronic Processes in 1D Radial van der Waals Heterostructures: Carbon, Boron Nitride, and MoS2 Nanotubes with Coexisting Excitons and Highly Mobile Charges
M.G. Burdanova, R.J. Kashtiban, Y. Zheng, R. Xiang, S. Chiashi, J.M. Woolley, M. Staniforth, E. Sakamoto-Rablah, X. Xie, M. Broome, J. Sloan, A. Anisimov, E.I. Kauppinen, S. Maruyama and J. Lloyd-Hughes
Nano Lett. 20 5, 3560 (Apr 2020) [ free e-print ] [ preprint pdf ] [ ref ]
Heterostructures built from 2D, atomically thin crystals are bound by the van der Waals force and exhibit unique optoelectronic properties. Here, we report the structure, composition and optoelectronic properties of 1D van der Waals heterostructures comprising carbon nanotubes wrapped by atomically thin nanotubes of boron nitride and molybdenum disulfide (MoS2). The high quality of the composite was directly made evident on the atomic scale by transmission electron microscopy, and on the macroscopic scale by a study of the heterostructure’s equilibrium and ultrafast optoelectronics. Ultrafast pump–probe spectroscopy across the visible and terahertz frequency ranges identified that, in the MoS2 nanotubes, excitons coexisted with a prominent population of free charges. The electron mobility was comparable to that found in high-quality atomically thin crystals. The high mobility of the MoS2 nanotubes highlights the potential of 1D van der Waals heterostructures for nanoscale optoelectronic devices.
J. Keller, G. Scalari, F. Appugliese, S. Rajabali, M. Beck, J. Haase, C.A. Lehner, W. Wegscheider, M. Failla, M. Myronov, D.R. Leadley, J. Lloyd-Hughes, P. Nataf, and J. Faist
Physical Review B 101:075301 (Feb 2020) [ pdf ][ ref ]
We probe ultrastrong light-matter coupling between metallic terahertz metasurfaces and Landau-level transitions in high-mobility two-dimensional electron and hole gases. We utilize heavy-hole cyclotron resonances in strained Ge and electron cyclotron resonances in InSb quantum wells, both within highly nonparabolic bands, and compare our results to well-known parabolic AlGaAs/GaAs quantum well systems. Tuning the coupling strength of the system by two methods, lithographically and by optical pumping, we observe a behavior clearly deviating from the standard Hopfield model previously verified in cavity quantum electrodynamics: an opening of a lower polaritonic gap.
K.D.G.I. Jayawardena, R.M.I. Bandara, M. Monti, E. Butler-Caddle, T. Pichler, H. Shiozawa, Z. Wang, S. Jenatsch, S.J. Hinder, M.G. Masteghin, M. Patel, H.M. Thirimanne, W. Zhang, R.A. Sporea, J. Lloyd-Hughes and S. R. P. Silva
J. Mater. Chem. A 8 693 (Jan 2020) [ pdf ] [ ref ]
The performance of all solar cells is dictated by charge recombination. A closer to ideal recombination dynamics results in improved performances, with fill factors approaching the limits based on Shockley-Queisser analysis. It is well known that for emerging solar materials such as perovskites, there are several challenges that need to be overcome to achieve high fill factors, particularly for large area lead-tin mixed perovskite solar cells. Here we demonstrate a strategy towards achieving fill factors above 80% through post-treatment of a lead-tin mixed perovskite absorber with guanidinium bromide for devices with an active area of 0.43 cm2. This bromide post-treatment results in a more favourable band alignment at the anode and cathode interfaces, enabling better bipolar extraction. The resulting devices demonstrate an exceptional fill factor of 83%, approaching the Shockley–Queisser limit, resulting in a power conversion efficiency of 14.4% for large area devices.
Y. Gladush, A. Mkrtchyan, D. Kopylova, A. Ivanenko, B. Nyushkov, S. Kobtsev, A. Kokhanovskiy, A. Khegai, M. Melkumov, M.G. Burdanova, M. Staniforth, J. Lloyd-Hughes and A.G. Nasibulin
Nano Letters 19 5836 (Aug 2019) [ pdf ] [ ref ]
Materials with electrically tunable optical properties offer a wide range of opportunities for photonic applications. The optical properties of the single-walled carbon nanotubes (SWCNTs) can be significantly altered in the near infrared region by means of electrochemical doping. The states’ filling, which is responsible for the optical absorption suppression under doping, also alters the nonlinear optical response of the material. Here, for the first time, we report that the electrochemical doping can tailor the nonlinear optical absorption of SWCNT films and demonstrate its application to control pulsed fiber laser generation. With a pump-probe technique we show that under an applied voltage below 2 V the photo-bleaching of the material can be gradually reduced and even turned to photo-induced absorption. Furthermore, we integrated a carbon nanotube electrochemical cell on a side-polished fiber to tune the absorption saturation and implemented it into the fully polarization-maintaining fiber laser. We show that the pulse generation regime can be reversibly switched between femtosecond mode locking and microsecond Q-switching using different gate voltages. This approach paves the road towards carbon nanotube optical devices with tunable nonlinearity.
Scalable interdigitated photoconductive emitters for the electrical modulation of terahertz beams with arbitrary linear polarization
A multi-element interdigitated photoconductive emitter for broadband THz polarization rotation is proposed and experimentally verified. The device consists of separate pixels for the emission of horizontally and vertically polarized THz radiation. The broadband (0.3–5.0 THz) nature of the device is demonstrated, and the polarization angle of the generated far-field THz radiation is shown to be readily controlled by varying the relative bias voltage applied to the horizontally and vertically emitting pixels. The device is scalable in design, and with its simple method of polarization rotation it allows the modulation of the generated THz polarization at rates significantly faster than those achievable in ellipsometry systems based on mechanically rotating components.
In this paper, we numerically and experimentally demonstrate the inverse polarization effect in three-dimensional (3-D) printed polarizers for the frequency range of 0.5 - 2.7 THz. The polarizers simply consist of 3-D printed strip lines of conductive polylactic acid (CPLA, Proto-Pasta) and do not require a substrate or any further metallic deposition. The experimental and numerical results show that the proposed structure acts as a broadband polarizer between the range of 0.3 THz to 2.7 THz, in which the inverse polarization effect is clearly seen for frequencies above 0.5 THz. In the inverse polarization effect, the transmission of the transverse electric (TE) component exceeds that of the TM component, in contrast to the behavior of a typical wire-grid polarizer. We show how the performance of the polarizers depends on the spacing and thickness of the CPLA structure; extinction ratios higher than 20 dB are achieved. This is the first report using CPLA to fabricate THz polarizers, demonstrating the potential of using conductive polymers to design THz components efficiently and robustly.
M.G. Burdanova, A.P. Tsapenko, D.A. Satco, R.J. Kashtiban, C.D.W. Mosley, M. Monti, M. Staniforth, J. Sloan, Y. Gladush, A.G. Nasibulin and J. Lloyd-Hughes
ACS Photonics 6 1058 (Mar 2019) [ preprint pdf ] [ supplemental info ] [ ref ]
A strong negative photoconductivity was identified in thin film networks of single-walled carbon nanotubes using optical pump, THz probe spectroscopy. The films were controllably doped, using either adsorption doping with different p-type dopant concentrations, or ambipolar doping using an ionic gate. While doping enhanced the THz conductivity and increased the momentum scattering rate, interband photoexcitation lowered the spectral weight and reduced the momentum scattering rate. This negative THz photoconductivity was observed for all doping levels, regardless of the chemical potential, and decayed within a few picoseconds. The strong many-body interactions inherent to these 1D conductors led to trion formation under photoexcitation, lowering the overall conductivity of the carbon nanotube network. The large amplitude of negative THz photoconductivity and the tunability of its recovery time with doping offer promise for spectrally wide-band ultrafast devices including THz detectors, polarizers and modulators.
Efficient Intraband Hot Carrier Relaxation in the Perovskite Semiconductor Cs1-xRbxSnI3 Mediated by Strong Electron-Phonon Coupling
The dynamic increase in THz photoconductivity resulting from energetic intraband relaxation was used to track the formation of highly mobile charges in thin films of the tin iodide perovskite Cs1-xRbxSnI3, with x=0 and x=0.1. Energy relaxation times were found to be around 500fs, comparable to those in the prototypical inorganic semiconductor GaAs. At low excess energies the efficient intraband energy relaxation in the lowest conduction and valence bands of Cs1-xRbxSnI3 can be understood within the context of the Fröhlich electron-phonon interaction, with a strong coupling strength. For higher excess energies the photoconductivity rise time lengthens in accordance with carrier injection into multiple bands, identified by quantitative first-principles bandstructure calculations and photoluminescence spectroscopy. The findings contribute to the development of design rules for photovoltaic devices capable of extracting hot carriers from perovskite semiconductors.
Highly Sensitive Terahertz Thin-Film Total Internal Reflection Spectroscopy Reveals in Situ Photoinduced Structural Changes in Methylammonium Lead Halide Perovskites
Terahertz (THz) thin-film total internal reflection (TF-TIR) spectroscopy is shown to have an enhanced sensitivity to the vibrational properties of thin films in comparison with standard THz transmission spectroscopy. This increased sensitivity was used to track photoinduced modifications to the structure of thin films of methylammonium (MA) lead halide, MAPbI3–xBrx (x = 0, 0.5, 1, and 3). Initially, illumination strengthened the phonon modes around 2 THz, associated with Pb–I stretch modes coupled to the MA ions, whereas the 1 THz twist modes of the inorganic octahedra did not alter in strength. Under longer term illumination, the 1 THz phonon modes of encapsulated films slowly reduced in strength, whereas in films exposed to moisture and oxygen, these phonons weaken more rapidly and blue-shift in frequency. The rapid monitoring of environmentally induced changes to the vibrational modes afforded by TF-TIR spectroscopy offers applications in the characterization and quality control of the perovskite thin-film solar cells and other thin-film semiconductors.
We show that films of the 3-dimensional perovskite Cs1−xRbxSnI3 can be prepared from room temperature N,N-dimethylformamide solutions of RbI, CsI and SnCl2 for x ≤ 0.5, and that for x ≤ 0.2 film stability is sufficient for utility as the light harvesting layer in inverted photovoltaic (PV) devices. Electronic absorption and photoluminescence spectroscopy measurements supported by computational simulation, show that increasing x increases the band gap, due to distortion of the lattice of SnI6 octahedra that occurs when Cs is substituted with Rb, although it also reduces the stability towards decomposition. When Cs0.8Rb0.2SnI3 perovskite is incorporated into the model inverted PV device structure; ITO|perovskite|C60|bathocuproine|Al, an ∼120 mV increase in open-circuit is achieved which is shown to correlate with an increase in perovskite ionisation potential. However, for this low Rb loading the increase in band gap is very small (∼30 meV) and so a significant increase in open circuit-voltage is achieved without reducing the range of wavelengths over which the perovskite can harvest light. The experimental findings presented are shown to agree well with the predictions of density functional theory (DFT) simulations of the stability and electronic structure, also performed as part of this study.
D. Shao, P. Yotprayoonsak, V. Saunajoki, M. Ahlskog, J. Virtanen, V. Kangas, A. Volodin, C. Van Haesendonck, M. Burdanova, C. D. W. Mosley and J. Lloyd-Hughes
Nanotechnology 29 145203 (Feb 2018) [ pdf ] [ ref ]
We have examined the conductive properties of a carbon nanotube (CNT) based thin film, which were prepared via dispersion in water by non-covalent functionalization of the nanotubes with xylan, a type of hemicellulose. Measurements of low temperature conductivity, Kelvin Probe Force Microscopy, and high frequency (THz) conductivity elucidated the intra-tube and inter-tube charge transport processes in this material. The measurements show excellent conductive properties of the as prepared thin films, with bulk conductivity up to 2000 S/cm. The transport results demonstrate that the hemicellulose does not seriously interfere with the inter-tube conductance.
Tracking a hysteretic and disorder-broadened phase transition via the electromagnon response in improper ferroelectrics
We demonstrate that electromagnons can be used to directly probe the nature of a phase transition between magnetically ordered phases in an improper ferroelectric. The antiferromagnetic/paraelectric to antiferromagnet/ferroelectric phase transition in Cu1-xZnxO (x = 0, 0.05) alloys was tracked via the electromagnon response using terahertz time-domain spectroscopy, on heating and cooling through the phase transition. The transition was found to exhibit thermal hysteresis, confirming its first-order nature, and to broaden under the influence of spin-disorder upon Zn substitution. The energy of the electromagnon increases upon alloying, as a result of the non-magnetic ions modifying the magnetic interactions that give rise to the multiferroic phase and electromagnons. We describe our findings in the context of recent theoretical work that examined improper ferroelectricity and electromagnons in CuO from phenomenological and first-principles approaches.
We introduce a polarization-resolved terahertz time-domain spectrometer with a broadband (0.3-2.5THz), rotatable THz polarization state, and which exhibits minimal change in the electric field amplitude and polarization state upon rotation. This was achieved by rotating an interdigitated photoconductive emitter, and by detecting the orthogonal components of the generated THz pulse via electro-optic sampling. The high precision (<0.1°) and accuracy (<1.0°) of this approach is beneficial for the study of anisotropic materials without rotating the sample, which can be impractical, for instance for samples held in a cryostat. The versatility of this method was demonstrated by studying the anisotropic THz optical properties of uniaxial and biaxial oxide crystals. For uniaxial ZnO and LaAlO3, which have minimal THz absorption across the measurement bandwidth, the orientations of the eigenmodes of propagation were conveniently identified as the orientation angles that produced a transmitted THz pulse with zero ellipticity, and the birefringence was quantified. In CuO, a multiferroic with improper ferroelectricity, the anisotropic THz absorption created by an electromagnon was investigated, mapping its selection rule precisely. For this biaxial crystal, which has phonon and electromagnon absorption, the polarization eigenvectors exhibited chromatic dispersion, as a result of the monoclinic crystal structure and the frequency-dependent complex refractive index.
Colossal terahertz magnetoresistance at room temperature in epitaxial La0.7Sr0.3MnO3 nanocomposites and single-phase thin films
We show that colossal magnetoresistance persists up to THz frequencies, in manganite nanocomposites and thin films. At the metal-insulator transition the THz conductivity of the nanocolumn film was dramatically enhanced by the application of a magnetic field, creating a non-Drude conductivity that increased with frequency. Surprisingly, the observed colossal THz magnetoresistance is large for ac motion on nanometre length scales, even when the dc magnetoresistance on macroscopic length scales is negligible.
Papers from 2015 (JLH only)
- Narrow heavy-hole cyclotron resonances split by the cubic Rashba spin-orbit interaction in strained germanium quantum wells
M. Failla, M. Myronov, C. Morrison, D. R. Leadley, and J. Lloyd-Hughes
Physical Review B, 92:045303 (July 2015) [ pdf ][ supplemental info ][ ref ]
The spin-orbit interaction was found to split the cyclotron resonance of heavy holes confined in high-mobility, compressively strained germanium quantum wells. The interference between coherent spin-split cyclotron resonances was tracked on picosecond time scales using terahertz time-domain spectroscopy. Analysis in the time domain, or using a time-frequency decomposition based on the Gabor-Morlet wavelet, was necessary when the difference between cyclotron frequencies was comparable to the linewidth. The cubic Rashba spin-orbit coefficient β was determined via two methods: (i) the magnetic-field dependence of the cyclotron frequencies, and (ii) the spin-resolved subband densities. An enhanced β and spin polarization was created by tailoring the strain to enhance the spin-orbit interaction. The amplitude modulation of the narrow, interfering cyclotron resonances is a signature of spin coherences persisting for more than 10 ps.
- Interfacial and bulk polaron masses in Zn1-xMgxO/ZnO heterostructures examined by terahertz time-domain cyclotron spectroscopy
J. Lloyd-Hughes, M. Failla, J. Ye, S.P.P. Jones, K.L. Teo, and C. Jagadish
Appl. Phys. Lett. 106:202103 (May 2015) [ pdf ][ ref ]
The cyclotron resonance of polarons in Zn1-xMgxO/ZnO heterostructures (with 0.15<x<0.22) was studied by terahertz time-domain spectroscopy. Low-temperature magnetoconductivity spectra of the 2D electron gas at the Zn1-xMgxO/ZnO interface determined the polaron density, mass, and scattering rate. The cyclotron mass of 2D polarons was found to increase significantly with magnetic field B from 0.24me at B=2T to 0.37me at B=7.5T. A nonlinear cyclotron frequency with B was also observed for 3D polarons in ZnO. The findings are discussed in the context of polaron mass renormalization driven by the electron-LO-phonon and electron-acoustic phonon interactions.
- Structural, optical and vibrational properties of self-assembled Pbn+1(Ti1-xFex)nO3n+1-δ Ruddlesden-Popper superstructures
K. I. Doig, J. J. P. Peters, S. Nawaz, D. Walker, M. Walker, M. R. Lees, R. Beanland, A. M. Sanchez, C. F. McConville, V. R. Palkar, J. Lloyd-Hughes
Scientific Reports, 5:7719 (Jan 2015) [ pdf ][ Supp. Info. ][ ref ]
Bulk crystals and thin films of PbTi1−xFexO3−δ (PTFO) are multiferroic, exhibiting ferroelectricity and ferromagnetism at room temperature. Here we report that the Ruddlesden-Popper phase Pbn+1(Ti1-xFex)nO3n+1-δ forms spontaneously during pulsed laser deposition of PTFO on LaAlO3 substrates. High-resolution transmission electron microscopy, x-ray diffraction and x-ray photoemission spectroscopy were utilised to perform a structural and compositional analysis, demonstrating that n~8 and x~0.5. The complex dielectric function of the films was determined from far-infrared to ultraviolet energies using a combination of terahertz time-domain spectroscopy, Fourier transform spectroscopy, and spectroscopic ellipsometry. The simultaneous Raman and infrared activity of phonon modes and the observation of second harmonic generation establishes a non-centrosymmetric point group for Pbn+1(Ti0.5Fe0.5)nO3n+1−δ, a prerequisite for (but not proof of) ferroelectricity. No evidence of macroscopic ferromagnetism was found in SQUID magnetometry. The ultrafast optical response exhibited coherent magnon oscillations compatible with local magnetic order, and additionally was used to study photocarrier cooling on picosecond timescales. An optical gap smaller than that of BiFeO3 and long photocarrier lifetimes may make this system interesting as a ferroelectric photovoltaic.
Papers from 2014 (JLH only)
- Terahertz spectroscopy of quantum 2D electron systems
J. Phys. D: Appl. Phys., 47:374006 (Sept 2014) [ pdf ][ ref ]
Terahertz time-domain spectroscopy permits the coherent motion of charges to be examined in a diverse range of two-dimensional semiconductor heterostructures. Studies of the THz conductivity and magnetoconductivity of two-dimensional quantum systems are reviewed, including cyclotron resonance spectroscopy and the transverse conductivity in the Hall and quantum Hall regimes. Experiments are described that demonstrate quantum phenomena at THz frequencies, principally coherent control and enhanced light–matter coupling in electromagnetic cavities.
- Influence of nonmagnetic Zn substitution on the lattice and magnetoelectric dynamical properties of the multiferroic material CuO
S.P.P. Jones, N.C. Wurz, M. Failla, D. Prabhakaran, C.F. McConville, J. Lloyd-Hughes
Phys. Rev. B, 90:064405 (Aug 2014) [ pdf ][ ref ]
Electromagnons were observed in the high-temperature multiferroic CuO even after Zn substitution disturbed the spin structure. The results demonstrate that electromagnons and dynamic magnetoelectric coupling can be maintained in disordered spin systems. Further, the dynamic lattice response of CuZnO was investigated by Raman and Fourier-transform spectroscopy, and was used to show strong spin-phonon coupling in both the antiferromagnetic low-temperature phase and the intermediate-temperature multiferroic phase.
- High-temperature electromagnons in the magnetically induced multiferroic cupric oxide driven by intersublattice exchange
S.P.P. Jones, S.M. Gaw, K.I. Doig, D. Prabhakaran, E.M. Hétroy Wheeler, A.T. Boothroyd, J. Lloyd-Hughes
Nat. Commun., 5:3787 (Apr 2014) [ pdf with Supp. Info. ][ ref ]
Magnetically induced ferroelectric multiferroics present an exciting new paradigm in the design of multifunctional materials, by intimately coupling magnetic and polar order. Magnetoelectricity creates a novel quasiparticle excitation - the electromagnon - at terahertz frequencies, with spectral signatures that unveil important spin interactions. To date, electromagnons have been discovered at low temperature (<70K) and predominantly in rare-earth compounds such as RMnO3. Here we demonstrate using terahertz time-domain spectroscopy that intersublattice exchange in the improper multiferroic cupric oxide (CuO) creates electromagnons at substantially elevated temperatures (213-230K). Dynamic magnetoelectric coupling can therefore be achieved in materials, such as CuO, that exhibit minimal static cross-coupling. The electromagnon strength and energy track the static polarization, highlighting the importance of the underlying cycloidal spin structure. Polarized neutron scattering and terahertz spectroscopy identify a magnon in the antiferromagnetic ground state, with a temperature dependence that suggests a significant role for biquadratic exchange.
- Modifying the polarization state of terahertz radiation using anisotropic twin-domains in LaAlO3
J. Lloyd-Hughes, S.P.P. Jones, E. Castro-Camus, K.I. Doig, J.L. Macmanus-Driscoll
Optics Lett., 39 1121 (Mar 2014) [ pdf ][ ref ]
Polarization-resolved terahertz (THz) time-domain spectroscopy was utilized to examine the complex refractive index of lanthanum aluminate (LaAlO3), a rhombohedrally distorted perovskite that exhibits crystallographic twin domains. The uniaxial anisotropy of the refractive index was quantified. The ellipticity of THz radiation pulses after transmission through single domains indicated that LaAlO3 can be used as a quarter- or half-wave plate. The effective anisotropy of -oriented LaAlO3 was found to be reduced when the material exhibited multiple, narrow twin domains.