P. Echegut

Phase transformations of crystalline SiO2 versus dynamic disorder between room temperature and liquid state

The sequence of phase transitions of crystalline silica has been probed by infrared emission spectroscopy. The lattice dynamics, deeply impacted by the low frequency dynamic disorder, exhibit with increasing temperature signs of inhomogeneous broadening of the symmetry allowed normal modes. High frequency supplementary components are also activated. The analysis with a causal Voigt dielectric function model within the framework of hard mode spectroscopy allowed a fine characterization of solid–solid phase transitions. We also report experimental evidence showing that the occurrence of the intermediate ill-defined region above 1300 K is concomitant with the reactivation of the low frequency dynamic disorder; a behavior change that on the way explains the appearance of the negative thermal expansion regime.

Infrared optical properties of α-alumina with the approach to melting: γ-like tetrahedral structure and small polaron conduction

The normal spectral emittance of α-Al2O3 single crystal has been measured from room temperature up to the liquid state and from 20 cm−1 up to 10 000 cm−1, in two polarization configurations. The spectra were fitted with a semi-quantum dielectric function model. AlO4 structure units are revealed within the phonon spectral range more than a hundred degrees below the melting point when heating from the solid state. In parallel, the anomalous increase of emittance observed within the transparency spectral range with the approach to melting appears strongly correlated. Implications on the electronic structure are discussed: the existence of small polaron conduction is suggested which has never been mentioned before.

Tuning the spectral emittance of α-SiC open-cell foams up to 1300 K with their macro porosity

A simple and robust analytical model is used to finely predict the spectral emittance under air up to 1300 K of α-SiC open-cell foams constituted of optically thick struts. The model integrates both the chemical composition and the macro-porosity and is valid only if foams have volumes higher than their Representative Elementary Volumes required for determining their emittance. Infrared emission spectroscopy carried out on a doped silicon carbide single crystal associated to homemade numerical tools based on 3D meshed images (Monte Carlo Ray Tracing code, foam generator) make possible to understand the exact role of the cell network in emittance. Finally, one can tune the spectral emittance of α-SiC foams up to 1300 K by simply changing their porosity.

Optical indices and transport scattering coefficient of pyrolytic boron nitride: a natural thermal barrier coating for solar shields

Absorption and scattering properties of pyrolytic boron nitride (pBN) have been characterized by infrared spectroscopy. The strong dielectric anisotropy predicted by first principles calculations is confirmed by measurements performed on a highly oriented pBN sample. Optical properties of textured samples elaborated by chemical vapor deposition were identified from normal hemispherical reflectance and transmittance spectra by applying modified two-flux and four-flux transport models. It is also shown that coating carbon–carbon composites used to build solar shields with a pBN layer having an optimal thickness could improve the protection performance.

Paramagnetic collective electronic mode and low temperature hybrid modes in the far infrared dynamics of orthorhombic NdMnO3

We report on the far- and mid-infrared reflectivity of NdMnO3 from 4 to 300 K. Two main features are distinguished in the infrared spectra: active phonons in agreement with expectations for the orthorhombic [Formula: see text]-Pbnm (Z = 4) space group remaining constant down to 4 K and a well defined collective excitation in the THz region due to eg electrons in a d-orbital fluctuating environment. We trace its origin to the NdMnO3 high-temperature orbital disordered intermediate phase not being totally dynamically quenched at lower temperatures. This results in minute orbital misalignments that translate into randomized non-static eg electrons within orbitals yielding a room-temperature collective excitation. Below TN ∼ 78 K, electrons gradually localize, inducing long-range magnetic order as the THz band condenses into two modes that emerge pinned to the A-type antiferromagnetic order. They harden simultaneously down to 4 K, obeying power laws with TN as the critical temperature and exponents β ∼ 0.25 and β ∼ 0.53, as for a tri-critical point and Landau magnetic ordering, respectively. At 4 K they match known zone center spin wave modes. The power law dependence is concomitant with a second order transition in which spin modes modulate orbital instabilities in a magnetoelectric hybridized orbital-charge-spin-lattice scenario. We also found that phonon profiles also undergo strong changes at TN ∼ 78 K due to magnetoelasticity.

Identification of spin wave resonances and crystal field levels in simple chromites RCrO3 (R = Pr, Sm, Er) at low temperatures in the THz spectral region

Abstract We report on THz absorption spectroscopy combined with high magnetic fields of polycrystalline RCrO3 (R = Pr, Sm, Er) aiming understanding spin wave resonances at their low temperature magnetic phases. Our measurements show that the temperature, and the implicit anisotropies at which the Cr3+ spin reorientation at TSR takes place, are determinant on the ferromagnetic-like (FM) and the antiferromagnetic-like (AFM) spin modes being optically active. It is found that they are dependent on Rare Earth 4f moment and ion size. We also studied temperature and field dependence of crystal field levels in the same spectroscopic region. Pr3+ non-Kramers emerges at 100 K and Zeeman splits. An observed absence of spin wave resonances in PrCrO3 is attributed to Pr3+ remaining paramagnetic. In SmCrO3 near cancelation of the spin and orbital moments is proposed as the possible reason for not detecting Sm3+ ground state transitions. Here, the FM and AFM resonant modes harden when the temperature decreases and split linearly under applied fields at 5 K and below. In ErCrO3 the Er3+ Kramers doublet becomes active at about the TSR onset. Each line further experiences Zeeman splitting under magnetic fields while an spin reversal induced by a ∼2.5 T field, back to the Γ4 (Fz) from the Γ1 phase at 2 K, produces a secondary splitting. The 5 K AFM and FM excitations in ErCrO3 have a concerted frequency-intensity temperature dependence and a shoulder pointing to the Er3+ smaller ion size also disrupting the two magnetic sublattice approximation. Both resonances reduce to one when the temperature is lowered to 2 K in the Γ1 representation. Our findings have important implications on the complex interplay in the magneto-electrodynamics associated with the Rare-Earth 4f – 3d transition metal spin coupling and the structural A site instabilities in perovskite multiferroics.

Atom probing of thermally populated surface polaritons

Thermal emission has been the historic paradigm to understand quantization of energy, for light and matter. However, the universal far field blackbody radiation is not sufficient to account for the near field effects of the thermal emission [1]. When matter is heated up, surface polaritons at its boundary become thermally excited, and intense electromagnetic fields evanescently decay away from the surface. For a given material, with a well-defined shape, the population of these surface modes obeys a thermodynamic distribution, according to the local density of states in vacuum near the interface. In addition, rising up the temperature is susceptible to induce phenomenological changes of the surface mode resonances, such as broadening or shift.

Phonons and hybrid modes in the high and low temperature far infrared dynamics of hexagonal TmMnO3

We report on temperature dependent TmMnO3 far infrared emissivity and reflectivity spectra from 1910 K to 4 K. At the highest temperature the number of infrared bands is lower than that predicted for centrosymmetric P63/mmc (D(4)(6h)) (Z = 2) space group due to high temperature anharmonicity and possible defect induced bitetrahedra misalignments. On cooling, at ~1600 ± 40 K, TmMnO3 goes from non-polar to an antiferroelectric-ferroelectric polar phase reaching the ferroelectric onset at ~700 K. Room temperature reflectivity is fitted using 19 oscillators and this number of phonons is maintained down to 4 K. A weak phonon anomaly in the band profile at 217 cm(-1) (4 K) suggests subtle Rare Earth magneto-electric couplings at ~TN and below. A low energy collective excitation is identified as a THz instability associated with room temperature eg electrons in a d-orbital fluctuating environment. It condenses into two modes that emerge pinned to the E-type antiferromagnetic order hardening simultaneously down to 4 K. They obey power laws with TN as the critical temperature and match known zone center magnons. The one peaking at 26 cm(-1), with critical exponent β=0.42 as for antiferromagnetic order in a hexagonal lattice, is dependent on the Rare Earth ion. The higher frequency companion at ~50 cm(-1), with β=0.25, splits at ~TN into two peaks. The weaker band of the two is assimilated to the upper branch of the gap opening in the transverse acoustical (TA) phonon branch crossing the magnetic dispersion found in YMnO3. (Petit et al 2007 Phys. Rev. Lett. 99 266604). The stronger second band at ~36 cm(-1) corresponds to the lower branch of the TA gap. We assign both excitations as zone center magneto-electric hybrid quasiparticles, concluding that in NdMnO3 perovskite the equivalent picture corresponds to an instability which may be driven by an external field to transform NdMnO3 into a multiferroic compound by perturbation enhancing the TA phonon-magnetic correlation.