Oxygen deficient titanium dioxide (TiO$_{2-x}$) is a very attractive material for several applications ranging from photocatalysis to resistive switching. Oxygen vacancies turn insulating anatase titanium dioxide into a polaronic conductor, while creating a defect state band below the ultraviolet semiconducting gap. Here we employ a combination of broadband infrared (IR) reflectivity and THz-pump/IR-probe measurements to investigate the relationship between localized defect states and delocalized conducting polaronic states. We show that the THz pump allows to convert deeply localized electrons into metastable polarons with a lifetime in the ns range. These long-lived metastable states may find application in novel opto-electronic applications exploiting the interplay of dc resistivity, with terahertz and infrared signals.
Thanks to its tunable infrared band-gap and to its anisotropic conduction properties, black phosphorus represents a very unique 2D material, whose potential in the engineering of new devices still needs to be fully explored. We investigate here the nonlinear terahertz (THz) electrodynamics of black phosphorus along the more conducting armchair direction. Similarly to the case of other 2D systems like graphene and topological insulators, the THz saturable absorption properties of black phosphorus can be understood within a thermodynamic model by assuming a fast thermalization of the electron bath. While black phosphorus does not display the presence of massless fermions at ambient pressure and temperature, our analysis shows that its anomalous THz nonlinear properties can be accounted for by a relativistic massive Dirac dispersion, provided the Fermi temperature is low enough. An optimal tuning of the Fermi level therefore represents a strategy to engineer strong THz nonlinear response in other massive Dirac materials as in transition metal dichalchogenides or high-temperature superconductors.
Angela Montanaro, Francesca Giusti, Matteo Zanfrognini, Paola Di Pietro, Filippo Glerean, Giacomo Jarc, Enrico Maria Rigoni, Shahla Y. Mathengattil, Daniele Varsano, Massimo Rontani, Andrea Perucchi, Elisa Molinari, Daniele Fausti The competition between the electron-hole Coulomb attraction and the three-dimensional dielectric screening dictates the optical properties of layered semiconductors. In low-dimensional materials, the equilibrium dielectric environment can be significantly altered by the ultrafast excitation of photo-carriers, leading to renormalized band gap and exciton binding energies. Recently, black phosphorus emerged as a 2D material with strongly layer-dependent electronic properties. Here, we resolve the coherent response of screening to sub-gap photo-excitation in bulk black phosphorus and find that mid-infrared pulses tuned across the band gap drive a transient non-thermal suppression of the dielectric screening, which is revealed by the emergence of the single-layer exciton resonance. Our work exposes the role of interlayer interactions in determining the electronic properties of 2D materials and discloses the possibility of optically manipulate them, which is of great relevance for the engineering of versatile van der Waals low-dimensional materials.
R. Mincigrucci, Jeremy Rouxel, Barbara Rossi, Emiliano Principi, Cettina Bottari, Sara Catalini, Danny Fainozzi, Laura Foglia, Alberto Simoncig, Alessia Matruglio, Gabor Kurdi, Flavio Capotondi, Emanuele Pedersoli, Andrea Perucchi, Federica Piccirilli, Alessandro Gessini, Marco Giarola, Gino Mariotto, Shaul Mukamel, Filippo Bencivenga, et al (2) In chemistry, biology and materials science, the ability to access interatomic interactions and their dynamical evolution has become possible with the advent of femtosecond lasers. In particular, the observation of vibrational wave packets via optical (UV-visible-IR) spectroscopies has been a major achievement as it can track the motion of nuclei within the system. However, optical spectroscopies only detect the effect of the interatomic vibrations on the global electronic surfaces. New tuneable, pulsed and polarized sources of short-wavelength radiation, such as X-Ray Free electron lasers, can overcome this limitation, allowing for chemical and, of primary importance in biochemistry, enantiomeric selectivity. This selectivity may be complemented by taking into account the chemical shifts of atoms belonging to different molecular moieties
Light can be strongly confined in sub-wavelength spatial regions through the interaction with plasmons, the collective electronic modes appearing in metals and semiconductors. This confinement, which is particularly important in the terahertz spectral region, amplifies light-matter interaction and provides a powerful mechanism for efficiently generating non-linear optical phenomena. These effects are particularly relevant in Dirac materials like graphene and Topological Insulators, where massless fermions show a naturally non-linear optical behavior in the terahertz range. The strong interaction scenario has been considered so far from the point of view of light. In this paper, we investigate instead the effect of strong interaction on the plasmon itself. In particular, we will show that Dirac plasmons in Bi$_2$Se$_3$ Topological Insulator are strongly renormalized when excited by high-intensity terahertz radiation by displaying a huge red-shift down to 60% of its characteristic frequency. This opens the road towards tunable terahertz non-linear optical devices based on Topological Insulators.
Flavio Giorgianni, Enrica Chiadroni, Andrea Rovere, Mariangela Cestelli-Guidi, Andrea Perucchi, Marco Bellaveglia, Michele Castellano, Domenico Di Giovenale, Giampiero Di Pirro, Massimo Ferrario, Riccardo Pompili, Cristina Vaccarezza, Fabio Villa, Alessandro Cianchi, Andrea Mostacci, Massimo Petrarca, Matthew Brahlek, Nikesh Koirala, Sean Oh, Stefano Lupi Electrons with a linear energy/momentum dispersion are called massless Dirac electrons and represent the low-energy excitations in exotic materials like Graphene and Topological Insulators (TIs). Dirac electrons are characterized by notable properties like a high mobility, a tunable density and, in TIs, a protection against backscattering through the spin-momentum looking mechanism. All those properties make Graphene and TIs appealling for plasmonics applications. However, Dirac electrons are expected to present also a strong nonlinear optical behavior. This should mirror in phenomena like electromagnetic induced transparency (EIT) and harmonic generation. Here, we demonstrate that in Bi2Se3 Topological Insulator, an EIT is achieved under the application of a strong terahertz (THz) electric field. This effect, concomitant determined by harmonic generation and charge-mobility reduction, is exclusively related to the presence of Dirac electron at the surface of Bi2Se_3, and opens the road towards tunable THz nonlinear optical devices based on Topological Insulator materials.
P. Di Pietro, M. Mitrano, S. Caramazza, F. Capitani, S. Lupi, P. Postorino, F. Ripanti, B. Joseph, N. Ehlen, A. Grüneis, A. Sanna, G. Profeta, P. Dore, A. Perucchi The phase diagrams of correlated systems like cuprates or pnictides high-temperature superconductors are characterized by a topological change of the Fermi surface under continuous variation of an external parameter, the so-called Lifshitz transition. However, the large number of low-temperature instabilities and the interplay of multiple energy scales complicate the study of this phenomenon. Here we first identify the optical signatures of a pressure-induced Lifshitz transition in a clean elemental system, black phosphorus. By applying external pressures above 1.5 GPa, we observe a change in the pressure dependence of the Drude plasma frequency due to the appearance of massless Dirac fermions. At higher pressures, optical signatures of two structural phase transitions are also identified. Our findings suggest that a key fingerprint of the Lifshitz transition in solid state systems, and in absence of structural phase transitions, is a discontinuity of the Drude plasma frequency due to the change of Fermi surface topology.
V. Tayari, B.V. Senkovskiy, D. Rybkovskiy, N. Ehlen, A. Fedorov, C.-Y. Chen, J. Avila, M. Asensio, A. Perucchi, P. di Pietro, L. Yashina, I. Fakih, N. Hemsworth, M. Petrescu, G. Gervais, A. Grüneis, T. Szkopek Stannous selenide is a layered semiconductor that is a polar analogue of black phosphorus, and of great interest as a thermoelectric material. Unusually, hole doped SnSe supports a large Seebeck coefficient at high conductivity, which has not been explained to date. Angle resolved photo-emission spectroscopy, optical reflection spectroscopy and magnetotransport measurements reveal a multiple-valley valence band structure and a quasi two-dimensional dispersion, realizing a Hicks-Dresselhaus thermoelectric contributing to the high Seebeck coefficient at high carrier density. We further demonstrate that the hole accumulation layer in exfoliated SnSe transistors exhibits a field effect mobility of up to $250~\mathrm{cm^2/Vs}$ at $T=1.3~\mathrm{K}$. SnSe is thus found to be a high quality, quasi two-dimensional semiconductor ideal for thermoelectric applications.
We perform infrared conductivity measurements on a series of CaCuO$_2$/SrTiO$_3$ heterostructures made by the insulating cuprate CaCuO$_2$ (CCO) and the insulating perovkite SrTiO$_3$ (STO). We estimate the carrier density of various heterostructures, with different level of hole doping from the integral of the optical conductivity and we measure the corresponding degree of correlation by estimating the ratio between the Drude weight and the integral of the infrared spectrum. The analysis demonstrates a large degree of correlation, which increases as the doping is reduced. The experimental results can be reproduced by Dynamical Mean-Field Theory calculations which strongly support the role of correlations in the CCO/STO heterostructures and their similarities with the most common cuprate superconductors. Our results suggest that cuprate superconductors can be looked at as natural superlattices, where the properties of the CuO$_2$ conducting planes and charge reservoir blocks can be completely disentangled.
Optical excitation at terahertz frequencies has emerged as an effective means to manipulate complex solids dynamically. In the molecular solid K3C60, coherent excitation of intramolecular vibrations was shown to transform the high temperature metal into a non-equilibrium state with the optical conductivity of a superconductor. Here we tune this effect with hydrostatic pressure, and we find it to disappear around 0.3 GPa. Reduction with pressure underscores the similarity with the equilibrium superconducting phase of K3C60, in which a larger electronic bandwidth is detrimental for pairing. Crucially, our observation excludes alternative interpretations based on a high-mobility metallic phase. The pressure dependence also suggests that transient, incipient superconductivity occurs far above the 150 K hypothesised previously, and rather extends all the way to room temperature.
Antonio Caretta, Barbara Casarin, Paola Di Pietro, Andrea Perucchi, Stefano Lupi, Valeria Bragaglia, Raffaella Calarco, Felix Rolf Lutz Lange, Matthias Wuttig, Fulvio Parmigiani, Marco Malvestuto The extraordinary electronic and optical properties of the crystal-to-amorphous transition in phase-change materials led to important developments in memory applications. A promising outlook is offered by nanoscaling such phase-change structures. Following this research line, we study the interband optical transmission spectra of nanoscaled GeTe/Sb$_2$Te$_3$ chalcogenide superlattice films. We determine, for films with varying stacking sequence and growth methods, the density and scattering time of the free electrons, and the characteristics of the valence-to-conduction transition. It is found that the free electron density decreases with increasing GeTe content, for sub-layer thickness below $\sim$3 nm. A simple band model analysis suggests that GeTe and Sb$_2$Te$_3$ layers mix, forming a standard GeSbTe alloy buffer layer. We show that it is possible to control the electronic transport properties of the films by properly choosing the deposition layer thickness and we derive a model for arbitrary film stacks.
LiOsO$_3$ has been recently identified as the first unambiguous "ferroelectric metal", experimentally realizing a prediction from 1965 by Anderson and Blount. In this work, we investigate the metallic state in LiOsO$_3$ by means of infrared spectroscopy supplemented by Density Functional Theory and Dynamical Mean Field Theory calculations. Our measurements and theoretical calculations clearly show that LiOsO$_3$ is a very bad metal with a small quasiparticle weight, close to a Mott-Hubbard localization transition. The agreement between experiments and theory allows us to ascribe all the relevant features in the optical conductivity to strong electron-electron correlations within the $t_{2g}$ manifold of the osmium atoms.
M. Mitrano, A. Cantaluppi, D. Nicoletti, S. Kaiser, A. Perucchi, S. Lupi, P. Di Pietro, D. Pontiroli, M. Riccò, A. Subedi, S. R. Clark, D. Jaksch, A. Cavalleri The control of non-equilibrium phenomena in complex solids is an important research frontier, encompassing new effects like light induced superconductivity. Here, we show that coherent optical excitation of molecular vibrations in the organic conductor K3C60 can induce a non-equilibrium state with the optical properties of a superconductor. A transient gap in the real part of the optical conductivity and a low-frequency divergence of the imaginary part are measured for base temperatures far above equilibrium Tc=20 K. These findings underscore the role of coherent light fields in inducing emergent order.
Vanadium sesquioxide V2O3 is considered a textbook example of Mott-Hubbard physics. In this paper we present an extended optical study of its whole temperature/doping phase diagram as obtained by doping the pure material with M=Cr or Ti atoms (V1-xMx)2O3. We reveal that its thermodynamically stable metallic and insulating phases, although macroscopically equivalent, show very different low-energy electrodynamics. The Cr and Ti doping drastically change both the antiferromagnetic gap and the paramagnetic metallic properties. A slight chromium content induces a mesoscopic electronic phase separation, while the pure compound is characterized by short-lived quasiparticles at high temperature. This study thus provides a new comprehensive scenario of the Mott-Hubbard physics in the prototype compound V2O3.
We have studied the optical properties of four (LaNiO$_3$)$_n$/(LaMnO$_3$)$_2$ superlattices (SL) ($n$=2, 3, 4, 5) on SrTiO$_3$ substrates. We have measured the reflectivity at temperatures from 20 K to 400 K, and extracted the optical conductivity through a fitting procedure based on a Kramers-Kronig consistent Lorentz-Drude model. With increasing LaNiO$_3$ thickness, the SLs undergo an insulator-to-metal transition (IMT) that is accompanied by the transfer of spectral weight from high to low frequency. The presence of a broad mid-infrared band, however, shows that the optical conductivity of the (LaNiO$_3$)$_n$/(LaMnO$_3$)$_2$ SLs is not a linear combination of the LaMnO$_3$ and LaNiO$_3$ conductivities. Our observations suggest that interfacial charge transfer leads to an IMT due to a change in valence at the Mn and Ni sites.
We report an infrared spectroscopy study of a 200 nm thick FeSe$_{0.5}$Te$_{0.5}$ film grown on LaAlO$_3$ with T$_c$=13.7 K. We analyze the 20 K normal state absolute reflectance R$_N$ measured over a broad infrared range and the reflectance ratio R$_S$/R$_N$, R$_S$ being the superconducting state reflectance, measured at 6 K in the terahertz range down to 12 cm$^{-1}$. We show that the normal state model conductivity is given by two Drude components, one of which much broader and intense than the other. In the superconducting state, we find that a gap $\Delta$=37$\pm$3 cm$^{-1}$ opens up in the narrow Drude band only, while the broad Drude band results to be ungapped, at least in the explored spectral range. Our results show that only a two-band model can coherently describe both normal and superconducting state data.
The optical properties of a V4O7 single crystal have been investigated from the high temperature metallic phase down to the low temperature antiferromagnetic insulating one. The temperature dependent behavior of the optical conductivity across the metal-insulator transition (MIT) can be explained in a polaronic scenario. Charge carriers form strongly localized polarons in the insulating phase as suggested by a far-infrared charge gap abruptly opening at T_MIT = 237 K. In the metallic phase instead the presence of a Drude term is indicative of fairly delocalized charges with a moderately renormalized mass m* = 5m_e. The electronic spectral weight is almost recovered on an energy scale of 1 eV, which is much narrower compared to VO2 and V2O3 cases. Those findings suggest that electron-lattice interaction rather than electronic correlation is the driving force for V4O7 metal-insulator transition.
A. Perucchi, F. Capitani, P. Di Pietro, S. Lupi, S. Lee, J.H. Kang, J. Jiang, J.D. Weiss, E.E. Hellstrom, C.B. Eom, P. Dore It has been recently reported (S. Lee et al., Nature Materials 12, 392, 2013) that superlattices where layers of the 8% Co-doped BaFe2As2 superconducting pnictide are intercalated with non superconducting ultrathin layers of either SrTiO3 or of oxygen-rich BaFe2As2, can be used to control flux pinning, thereby increasing critical fields and currents, without significantly affecting the critical temperature of the pristine superconducting material. However, little is known about the electron properties of these systems. Here we investigate the electrodynamics of these superconducting pnictide superlattices in the normal and superconducting state by using infrared reflectivity, from THz to visible range. We find that multi-gap structure of these superlattices is preserved, whereas some significant changes are observed in their electronic structure with respect to those of the original pnictide. Our results suggest that possible attempts to further increase the flux pinning may lead to a breakdown of the pnictide superconducting properties.
Fabio Novelli, Giulio De Filippis, Vittorio Cataudella, Martina Esposito, Ignacio Vergara Kausel, Federico Cilento, Enrico Sindici, Adriano Amaricci, Claudio Giannetti, Dharmalingam Prabhakaran, Simon Wall, Andrea Perucchi, Stefano Dal Conte, Giulio Cerullo, Massimo Capone, Andrey Mishchenko, Markus Grüninger, Naoto Nagaosa, Fulvio Parmigiani, Daniele Fausti The non-equilibrium semiconductors physics is based on the paradigm that different degrees of freedom interact on different timescales. In this context the photo-excitation is often treated as an impulsive injection of electronic energy that is transferred to other degrees of freedom only at later times. Here, by studying the ultrafast particles dynamics in a archetypal strongly correlated charge-transfer insulator (La2CuO4), we show that the interaction between electrons and bosons manifest itself directly in the photo-excitation processes of a correlated material. With the aid of a general theoretical framework (Hubbard Holstein Hamiltonian), we reveal that sub-gap excitation pilots the formation of itinerant quasi-particles which are suddently dressed (<100 fs) by an ultrafast reaction of the bosonic field.
The magnetically driven metal-insulator transition (MIT) was predicted by Slater in the fifties. Here a long-range antiferromagnetic (AF) order can open up a gap at the Brillouin electronic band boundary regardless of the Coulomb repulsion magnitude. However, while many low-dimensional organic conductors display evidence for an AF driven MIT, in three-dimensional (3D) systems the Slater MIT still remains elusive. We employ terahertz and infrared spectroscopy to investigate the MIT in the NaOsO3 3D antiferromagnet. From the optical conductivity analysis we find evidence for a continuous opening of the energy gap, whose temperature dependence can be well described in terms of a second order phase transition. The comparison between the experimental Drude spectral weight and the one calculated through Local Density Approximation (LDA) shows that electronic correlations play a limited role in the MIT. All the experimental evidence demonstrates that NaOsO3 is the first known 3D Slater insulator.
M. Mitrano, G. Cotugno, S.R. Clark, R. Singla, S. Kaiser, J. Staehler, R. Beyer, M. Dressel, L. Baldassarre, D. Nicoletti, A. Perucchi, T. Hasegawa, H. Okamoto, D. Jaksch, A. Cavalleri Femtosecond relaxation of photo-excited quasiparticles in the one dimensional Mott insulator ET-F2TCNQ are measured as a function of external pressure, which is used to tune the electronic structure. By fitting the static optical properties and measuring femtosecond decay times at each pressure value, we correlate the relaxation rates with the electronic bandwidth t and on the intersite correlation energy V. The scaling of relaxation times with microscopic parameters is different than for metals and semiconductors. The competition between localization and delocalization of the Mott-Hubbard exciton dictates the efficiency of the decay, as exposed by a fit based on the solution of the time-dependent extended Hubbard Hamiltonian.
Here we report an optical investigation in the terahertz region of a 40 nm ultrathin BaFe$_{1.84}$Co$_{0.16}$As$_2$ superconducting film with superconducting transition temperature T$_c$ = 17.5 K. A detailed analysis of the combined reflectance and transmittance measurements showed that the optical properties of the superconducting system can be described in terms of a two-band, two-gap model. The zero temperature value of the large gap $\Delta_B$, which seems to follow a BCS-like behavior, results to be $\Delta_B$(0) = 17 cm$^{-1}$. For the small gap, for which $\Delta_A$(0) = 8 cm$^{-1}$, the temperature dependence cannot be clearly established. These gap values and those reported in the literature for the BaFe$_{2-x}$Co$_{x}$As$_2$ system by using infrared spectroscopy, when put together as a function of T$_c$, show a tendency to cluster along two main curves, providing a unified perspective of the measured optical gaps. Below a temperature around 20 K, the gap-sizes as a function of T$_c$ seem to have a BCS-like linear behavior, but with different slopes. Above this temperature, both gaps show different supra-linear behaviors.
L. Baldassarre, A. Perucchi, P. Postorino, S. Lupi, C. Marini, L. Malavasi, J. Jiang, J.D. Weiss, E.E. Hellstrom, I. Pallecchi, P. Dore We report on an infrared study on the undoped compound BaFe2As2 as a function of both pressure (up to about 10 GPa) at three temperatures (300, 160, and 110 K). The evolution with pressure and temperature of the optical conductivity shows that, by increasing pressure, the mid-infrared absorptions associated with magnetic order are lowered while the Drude term increases, indicating the evolution towards a conventional metallic state. We evaluate the spectral weight dependence on pressure comparing it to that previously found upon doping. The whole optical results indicate that lattice modifications can not be recognized as the only parameter determining the low-energy electrodynamics in these compounds.
F. Capitani, M. Hoeppner, B. Joseph, L. Malavasi, G. A. Artioli, L. Baldassarre, A. Perucchi, M. Piccinini, S. Lupi, P. Dore, L. Boeri, P. Postorino We present high-quality optical data and density functional perturbation theory calculations for the vibrational spectrum of solid picene (C$_{22}$H$_{14}$) under pressure up to 8 GPa. First-principles calculations reproduce with a remarkable accuracy the pressure effects on both frequency and intensities of the phonon peaks experimentally observed . Through a detailed analysis of the phonon eigenvectors, We use the projection on molecular eigenmodes to unambiguously fit the experimental spectra, resolving complicated spectral structures, in a system with hundreds of phonon modes. With these projections, we can also quantify the loss of molecular character under pressure. Our results indicate that picene, despite a ∼20 % compression of the unit cell, remains substantially a molecular solid up to 8 GPa, with phonon modes displaying a smooth and uniform hardening with pressure. The Grueneisen parameter of the 1380 cm^-1 a_1 Raman peak ($\gamma_p=0.1$) is much lower than the effective value ($\gamma_d=0.8$) due to K doping. This is an indication that the phonon softening in K doped samples is mainly due to charge transfer and electron-phonon coupling.
B. Joseph, L. Boeri, L. Malavasi, F. Capitani, G. A. Artioli, S. Protti, M. Fagnoni, A. Albini, C. Marini, L. Baldassarre, A. Perucchi, S. Lupi, P. Postorino, P. Dore Recently, Mitsuhashi et al., have observed superconductivity with transition temperature up to 18 K in potassium doped picene (C22H14), a polycyclic aromatic hydrocarbon compound [Nature 464 (2010) 76]. Theoretical analysis indicate the importance of electron-phonon coupling in the superconducting mechanisms of these systems, with different emphasis on inter- and intra-molecular vibrations, depending on the approximations used. Here we present a combined experimental and ab-initio study of the Raman and infrared spectrum of undoped solid picene, which allows us to unanbiguously assign the vibrational modes. This combined study enables the identification of the modes which couple strongly to electrons and hence can play an important role in the superconducting properties of the doped samples.
We address the in-plane pressure-dependent electrodynamics of graphite through synchrotron based infrared spectroscopy and ab initio Density Functional Theory calculations. The Drude term remarkably increases upon pressure application, as a consequence of an enhancement of both electron and hole charge densities. This is due to the growth of the band dispersion along the k_z direction between the K and H points of the Brillouin zone. On the other hand, the mid-infrared optical conductivity between 800 and 5000 cm-1 is almost flat, and very weakly pressure dependent, at least up to 7 GPa. This demonstrates a surprising robustness of the graphene-like universal quantum conductance of graphite, even when the interlayer distance is significantly reduced.
We measure the optical conductivity of (SrMnO3)n/(LaMnO3)2n superlattices (SL) for n=1,3,5, and 8 and 10 < T < 400 K. Data show a T-dependent insulator to metal transition (IMT) for n ≤3, driven by the softening of a polaronic mid-infrared band. At n = 5 that softening is incomplete, while at the largest-period n=8 compound the MIR band is independent of T and the SL remains insulating. One can thus first observe the IMT in a manganite system in the absence of the disorder due to chemical doping. Unsuccessful reconstruction of the SL optical properties from those of the original bulk materials suggests that (SrMnO3)n/(LaMnO3)2n heterostructures give rise to a novel electronic state.
S. Lupi, L. Baldassarre, B. Mansart, A. Perucchi, A. Barinov, P. Dudin, E. Papalazarou, F. Rodolakis, J.-P. Rueff, J.-P. Itié, S. Ravy, D. Nicoletti, P. Postorino, P. Hansmann, N. Parragh, A. Toschi, T. Saha-Dasgupta, O. K. Andersen, G. Sangiovanni, K. Held, et al (1) V2O3 is the prototype system for the Mott transition, one of the most fundamental phenomena of electronic correlation. Temperature, doping or pressure induce a metal to insulator transition (MIT) between a paramagnetic metal (PM) and a paramagnetic insulator (PI). This or related MITs have a high technological potential, among others for intelligent windows and field effect transistors. However the spatial scale on which such transitions develop is not known in spite of their importance for research and applications. Here we unveil for the first time the MIT in Cr-doped V2O3 with submicron lateral resolution: with decreasing temperature, microscopic domains become metallic and coexist with an insulating background. This explains why the associated PM phase is actually a poor metal. The phase separation can be associated with a thermodynamic instability near the transition. This instability is reduced by pressure which drives a genuine Mott transition to an eventually homogeneous metallic state.
We present reflectance measurements in the infrared region on a single crystal the rare earth scandate DyScO3. Measurements performed between room temperature and 10 K allow to determine the frequency of the infrared-active phonons, never investigated experimentally, and to get information on their temperature dependence. A comparison with the phonon peak frequency resulting from ab-initio computations is also provided. We finally report detailed data on the frequency dependence of the complex refractive index of DyScO3 in the terahertz region, which is important in the analysis of terahertz measurements on thin films deposited on DyScO3.
A. Perucchi, L. Baldassarre, C. Marini, S. Lupi, J. Jiang, J.D. Weiss, E.E. Hellstrom, S. Lee, C.W. Bark, C.B. Eom, M. Putti, I. Pallecchi, P. Dore We measured the THz reflectance properties of a high quality epitaxial thin film of the Fe-based superconductor BaFe$_{1.84}$Co$_{0.16}$As$_2$ with T$_c$=22.5 K. The film was grown by pulsed laser deposition on a DyScO$_3$ substrate with an epitaxial SrTiO$_3$ intermediate layer. The measured $R_S/R_N$ spectrum, i.e. the reflectivity ratio between the superconducting and normal state reflectance, provides clear evidence of a superconducting gap $\Delta_A$ close to 15 cm$^{-1}$. A detailed data analysis shows that a two-band, two-gap model is absolutely necessary to obtain a good description of the measured $R_S/R_N$ spectrum. The low-energy $\Delta_A$ gap results to be well determined ($\Delta_A$=15.5$\pm$0.5 cm$^{-1}$), while the value of the high-energy gap $\Delta_B$ is more uncertain ($\Delta_B$=55$\pm$7 cm$^{-1}$). Our results provide evidence of a nodeless isotropic double-gap scenario, with the presence of two optical gaps corresponding to 2$\Delta/kT_c$ values close to 2 and 7.
A. Perucchi, D. Nicoletti, M. Ortolani, C. Marini, R. Sopracase, S. Lupi, U. Schade, M. Putti, I. Pallecchi, C. Tarantini, M. Ferretti, C. Ferdeghini, M. Monni, F. Bernardini, S. Massidda, P. Dore The possibility of multi-band conductivity and multi-gap superconductivity is explored in oriented V3Si thin films by means of reflectance and transmittance measurements at terahertz frequencies. The temperature dependence of the transmittance spectra in the normal state gives evidence of two bands contributing to the film conductivity. This outcome is consistent with electronic structure calculations performed within density functional theory. On this basis, we performed a detailed data analysis and found that all optical data can be consistently accounted for within a two-band framework, with the presence of two optical gaps in the superconducting state corresponding to 2D=kTc values close to 1.8 and 3.8.
A. Perucchi, C. Marini, M. Valentini, P. Postorino, R. Sopracase, P. Dore, P. Hansmann, O. Jepsen, G. Sangiovanni, A. Toschi, K. Held, D. Topwal, D. D. Sarma, S. Lupi The metal to insulator transition in the charge transfer NiS2-xSex compound has been investigated through infrared reflectivity. Measurements performed by applying pressure to pure NiS2 (lattice contraction) and by Se-alloying (lattice expansion) reveal that in both cases an anomalous metallic state is obtained. We find that optical results are not compatible with the linear Se-alloying vs Pressure scaling relation previously established through transport, thus pointing out the substantially different microscopic origin of the two transitions.
M. Lavagnini, A. Sacchetti, C. Marini, M. Valentini, R. Sopracase, A. Perucchi, P. Postorino, S. Lupi, J.-H. Chu, I.R. Fisher, L. Degiorgi We present new data on the pressure dependence at 300 K of the optical reflectivity of CeTe$_3$, which undergoes a charge-density-wave (CDW) phase transition well above room temperature. The collected data cover an unprecedented broad spectral range from the infrared up to the ultraviolet, which allows a robust determination of the gap as well as of the fraction of the Fermi surface affected by the formation of the CDW condensate. Upon compressing the lattice there is a progressive closing of the gap inducing a transfer of spectral weight from the gap feature into the Drude component. At frequencies above the CDW gap we also identify a power-law behavior, consistent with findings along the $R$Te$_3$ series (i.e., chemical pressure) and suggestive of a Tomonaga-Luttinger liquid scenario at high energy scales. This newest set of data is placed in the context of our previous investigations of this class of materials and allows us to revisit important concepts for the physics of CDW state in layered-like two-dimensional systems.
C. Marini, C. Mirri, G. Profeta, S. Lupi, D. Di Castro, R. Sopracase, P. Postorino, P. Calvani, A. Perucchi, S. Massidda, G. M. Tropeano, M. Putti, A. Martinelli, A. Palenzona, P. Dore We measured the Raman and the Infrared phonon spectrum of SmFeAsO polycrystalline samples. We also performed Density Functional Theory calculations within the pseudopotential approximation to obtain the structural and dynamical lattice properties of both the SmFeAsO and the prototype LaFeAsO compounds. The measured Raman and Infrared phonon frequencies are well predicted by the optical phonon frequencies computed at the Gamma point, showing the capability of the employed ab-initio methods to describe the dynamical properties of these materials. A comparison among the phonon frequencies of different oxypnictides suggests a possible role of the high frequency phonons in the pairing mechanism leading to superconductivity in these materials.
M. Tropeano, C. Fanciulli, C. Ferdeghini, D. Marre', A.S. Siri, M. Putti, A. Martinelli, M. Ferretti, A. Palenzona, M. R. Cimberle, C. Mirri, S. Lupi, R. Sopracase, P. Calvani, A. Perucchi We report measurements of resistivity, magnetoresistivity, Hall effect, Seebeck coefficient, infrared reflectivity of undoped SmFeAsO and lightly doped SmFeAs(O0.93F0.07) oxypnictides. All the properties measured on SmFeAsO are characterized by clear signatures of the magnetic instability. A self-consistent picture emerges in which below the magnetic transition carrier condensation occurs due to the opening of spin density wave (SDW) gap. This is accompanied by the mobility increase of not gapped carriers due to the suppression of electron-electron scattering. SmFeAs(O0.93F0.07) exhibits an increase of the metallic character on cooling consistent with electron doping, even though at room temperature values of all the properties nearly overlaps with those of SmFeAsO. However, with temperature decrease all anomalies related to the SDW instability are missed and the superconducting transition occurs. This suggests that doping breaks abruptly the symmetries of the Fermi surface inhibiting the SDW formation in favor of the superconducting transition, with no substantial changes in the density of states or in the effective mass.
The optical response of the two-band superconductor MgB$_2$ has been studied in the 0.7-4 THz range on films with very low impurity level. The effect of the high-energy $\sigma$-gap is observed in the ratio $R_S/R_N$ between the normal and superconducting state reflectance, while in a neutron irradiated film with a slightly higher impurity level mainly the effect of the $\pi$-gap is evident as reported in previous experiments. At terahertz frequencies, the electrodynamic of MgB$_2$ can be well described by the two-band parallel conductivity model and is dominated by the $\pi$-bands when the impurity level is only slightly higher than that of an ultra-clean sample.
We report the pressure dependence of the optical response of LaTe$_2$, which is deep in the charge-density-wave (CDW) ground state even at 300 K. The reflectivity spectrum is collected in the mid-infrared spectral range at room temperature and at pressures between 0 and 7 GPa. We extract the energy scale due to the single particle excitation across the CDW gap and the Drude weight. We establish that the gap decreases upon compressing the lattice, while the Drude weight increases. This signals a reduction in the quality of nesting upon applying pressure, therefore inducing a lesser impact of the CDW condensate on the electronic properties of LaTe$_2$. The consequent suppression of the CDW gap leads to a release of additional charge carriers, manifested by the shift of weight from the gap feature into the metallic component of the optical response. On the contrary, the power-law behavior, seen in the optical conductivity at energies above the gap excitation and indicating a weakly interacting limit within the Tomonaga-Luttinger liquid scenario, seems to be only moderately dependent on pressure.
L. Baldassarre, A. Perucchi, D. Nicoletti, A. Toschi, G. Sangiovanni, K. Held, M. Capone, M. Ortolani, L. Malavasi, M. Marsi, P. Metcalf, P. Postorino, S. Lupi The infrared conductivity of V2O3 is measured in the whole phase diagram. Quasiparticles appear above the Neel temperature TN and eventually disappear further enhancing the temperature, leading to a pseudogap in the optical spectrum above 425 K. Our calculations demonstrate that this loss of coherence can be explained only if the temperature dependence of lattice parameters is considered. V2O3 is therefore effectively driven from the metallic to the insulating side of the Mott transition as the temperature is increased.
The electrodynamics near the metal-to-insulator transitions (MIT) induced, in V3O5 single crystals, by both temperature (T) and pressure (P) has been studied by infrared spectroscopy. The T- and P-dependence of the optical conductivity may be explained within a polaronic scenario. The insulating phase at ambient T and P corresponds to strongly localized small polarons. Meanwhile the T-induced metallic phase at ambient pressure is related to a liquid of polarons showing incoherent dc transport, in the P-induced metallic phase at room T strongly localized polarons coexist with partially delocalized ones. The electronic spectral weight is almost recovered, in both the T and P induced metallization processes, on an energy scale of 1 eV, thus supporting the key-role of electron-lattice interaction in the V3O5 metal-to-insulator transition.
Raman and combined trasmission and reflectivity mid infrared measurements have been carried out on monoclinic VO$_2$ at room temperature over the 0-19 GPa and 0-14 GPa pressure ranges, respectively. The pressure dependence obtained for both lattice dynamics and optical gap shows a remarkable stability of the system up to P*$\sim$10 GPa. Evidence of subtle modifications of V ion arrangements within the monoclinic lattice together with the onset of a metallization process via band gap filling are observed for P$>$P*. Differently from ambient pressure, where the VO$_2$ metal phase is found only in conjunction with the rutile structure above 340 K, a new room temperature metallic phase coupled to a monoclinic structure appears accessible in the high pressure regime, thus opening to new important queries on the physics of VO$_2$.
We investigate the pressure dependence of the optical properties of CeTe$_3$, which exhibits an incommensurate charge-density-wave (CDW) state already at 300 K. Our data are collected in the mid-infrared spectral range at room temperature and at pressures between 0 and 9 GPa. The energy for the single particle excitation across the CDW gap decreases upon increasing the applied pressure, similarly to the chemical pressure by rare-earth substitution. The broadening of the bands upon lattice compression removes the perfect nesting condition of the Fermi surface and therefore diminishes the impact of the CDW transition on the electronic properties of $R$Te$_3$.
Substituting $Eu$ by $Ca$ in ferromagnetic $EuB_6$ leads to a percolation limited magnetic ordering. We present and discuss magneto-optical data of the $Eu_{1-x}Ca_{x}B_6$ series, based on measurements of the reflectivity $R(\omega)$ from the far infrared up to the ultraviolet, as a function of temperature and magnetic field. Via the Kramers-Kronig transformation of $R(\omega)$ we extract the complete absorption spectra of samples with different values of $x$. The change of the spectral weight in the Drude component by increasing the magnetic field agrees with a scenario based on the double exchange model, and suggests a crossover from a ferromagnetic metal to a ferromagnetic Anderson insulator upon increasing $Ca$-content at low temperatures.
We present a comprehensive optical study of the narrow gap $FeSb_2$ semiconductor. From the optical reflectivity, measured from the far infrared up to the ultraviolet spectral range, we extract the complete absorption spectrum, represented by the real part $\sigma_1(\omega)$ of the complex optical conductivity. With decreasing temperature below 80 K, we find a progressive depletion of $\sigma_1(\omega)$ below $E_g\sim 280$ cm$^{-1}$, the semiconducting optical gap. The suppressed (Drude) spectral weight within the gap is transferred at energies $\omega>E_g$ and also partially piles up over a continuum of excitations extending in the spectral range between zero and $E_g$. Moreover, the interaction of one phonon mode with this continuum leads to an asymmetric phonon shape. Even though several analogies between $FeSb_2$ and $FeSi$ were claimed and a Kondo-insulator scenario was also invoked for both systems, our data on $FeSb_2$ differ in several aspects from those of $FeSi$. The relevance of our findings with respect to the Kondo insulator description will be addressed.
The chain-like $ZrTe_3$ compound undergoes a charge-density-wave (CDW) transition at $T_{CDW}=63$ $K$, most strongly affecting the conductivity perpendicular to the chains. We measure the temperature ($T$) dependence of the optical reflectivity from the far infrared up to the ultraviolet with polarized light. The CDW gap $\Delta(T)$ along the direction perpendicular to the chains is compatible for $T<T_{CDW}$ with the behavior of an order parameter within the mean-field Bardeen-Cooper-Schrieffer (BCS) theory. $\Delta(T)$ also persists well above $T_{CDW}$, which emphasizes the role played by fluctuation effects.
We present a detailed study of the electronic transport properties on a single crystalline specimen of the moderately disordered heavy fermion system URh$_2$Ge$_2$. For this material, we find glassy electronic transport in a single crystalline compound. We derive the temperature dependence of the electrical conductivity and establish metallicity by means of optical conductivity and Hall effect measurements. The overall behavior of the electronic transport properties closely resembles that of metallic glasses, with at low temperatures an additional minor spin disorder contribution. We argue that this glassy electronic behavior in a crystalline compound reflects the enhancement of disorder effects as consequence of strong electronic correlations.
We have measured the optical reflectivity $R(\omega)$ of the quasi one-dimensional conductor $NbSe_{3}$ from the far infrared up to the ultraviolet between 10 and 300 $K$ using light polarized along and normal to the chain axis. We find a depletion of the optical conductivity with decreasing temperature for both polarizations in the mid to far-infrared region. This leads to a redistribution of spectral weight from low to high energies due to partial gapping of the Fermi surface below the charge-density-wave transitions at 145 K and 59 K. We deduce the bulk magnitudes of the CDW gaps and discuss the scattering of ungapped free charge carriers and the role of fluctuations effects.
We have measured the optical reflectivity $R(\omega)$ of $Eu_{0.6}Ca_{0.4}B_{6}$ as a function of temperature between 1.5 and 300 $K$ and in external magnetic fields up to 7 $T$. The slope at the onset of the plasma edge feature in $R(\omega)$ increases with decreasing temperature and increasing field but the plasma edge itself does not exhibit the remarkable blue shift that is observed in the binary compound $EuB_{6}$. The analysis of the magnetic field dependence of the low temperature optical conductivity spectrum confirms the previously observed exponential decrease of the electrical resistivity upon increasing, field-induced bulk magnetization at constant temperature. In addition, the individual exponential magnetization dependences of the plasma frequency and scattering rate are extracted from the optical data.
J.Karpinski, M.Angst, J.Jun, S.M.Kazakov, R.Puzniak, A.Wisniewski, J.Roos, H.Keller, A. Perucchi, L. Degiorgi, M.Eskildsen, P.Bordet, L.Vinnikov, A.Mironov Single crystals of MgB2 with a size up to 1.5x0.9x0.2 mm3 have been grown with a high pressure cubic anvil technique. The crystal growth process is very peculiar and involves an intermediate nitride, namely MgNB9. Single crystals of BN and MgB2 grow simultaneously by a peritectic decomposition of MgNB9. Magnetic measurements in fields of 1-5 Oe show sharp transitions to the superconducting state at 37-38.6 K with width of ~0.5 K. The high quality of the crystals allowed the accurate determination of magnetic, transport and optical properties as well as scanning tunnelling spectroscopy (STS) and decoration studies. Investigations of crystals with torque magnetometry show that Hc2//c is very low (24 kOe at 15 K), while Hc2//ab increases up to 140 kOe at 15 K. The upper critical field anisotropy gamma = Hc2//ab/ Hc2//c was found to be temperature dependent (decreasing from 6 at 15 K to 2.8 at 35 K). The effective anisotropy gamma_eff, as calculated from reversible torque data near Tc, is field dependent (increasing roughly linearly from 2 in zero field to 3.7 in 10 kOe). The temperature and field dependence of the anisotropy can be related to the double gap structure of MgB2 with a large two-dimensional gap and small three-dimensional gap, the latter being rapidly suppressed in a magnetic field. Torque magnetometry investigations show a pronounced peak effect, indicating an order-disorder transition of vortex matter. Decoration experiments and STS visualise a hexagonal vortex lattice. STS spectra evidence two gaps (3 meV/6 meV) with direction dependent weight. Magneto-optic investigations with H//c show a clear signature of the smaller of the two gaps, disappearing in fields higher than Hc2//c.
We present magneto-optical reflectivity results in the basal-plane of the hexagonal $MgB_2$. The data were collected on a mosaic of $MgB_2$ single crystals with $T_{c}=38 ~K$ from the ultraviolet down to the far infrared as a function of temperature and magnetic field oriented along the c-axis. In the far infrared there is a clear signature of the superconducting gap with a gap-ratio $2\Delta/k_{B}T_{c}\sim 1.2$, well below the weak-coupling value. The gap is suppressed in an external magnetic field, which is a function of temperature. We extract the upper critical field $H_{c2}$ along the c-axis. The temperature dependence of $H_{c2}$ is compatible with the Helfand-Werthamer behaviour.