Andrea Sanson

Tunable thermal expansion in framework materials through redox intercalation

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework-type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF3, doped with 10% Fe to enable reduction. The small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. Redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion.

High‐Curie‐Temperature Ferromagnetism in (Sc,Fe)F3 Fluorides and its Dependence on Chemical Valence

A magnetic metal-fluoride system is shown for the first time to have a high Curie temperature (≈545 K). The magnetism correlates intimately with the Fe(2+)/Fe(3+) ratio. As the ratio increases, the weak magnetism displayed by unordered magnetic moments intensifies, and these magnetic moments align in parallel. Simultaneously, a magneto-volume effect is also shown to increase the lattice volume.

Pectins, Hemicelluloses and Celluloses Show Specific Dynamics in the Internal and External Surfaces of Grape Berry Skin During Ripening

Grapevine berry skin is a complex structure that contributes to the final size and shape of the fruit and affects its quality traits. The organization of cell wall polysaccharides in situ and their modification during ripening are largely uncharacterized. The polymer structure of Corvina berry skin, its evolution during ripening and related modifying genes were determined by combing mid-infrared micro-spectroscopy and multivariate statistical analysis with transcript profiling and immunohistochemistry. Spectra were acquired in situ using a surface-sensitive technique on internal and external sides of the skin without previous sample pre-treatment, allowing comparison of the related cell wall polymer dynamics. The external surface featured cuticle-related bands; the internal surface showed more adsorbed water. Application of surface-specific normalization revealed the major molecular changes related to hemicelluloses and pectins in the internal surface and to cellulose and pectins in the external surface and that they occur between mid-ripening and full ripening in both sides of the skin. Transcript profiling of cell wall-modifying genes indicated a general suppression of cell wall metabolism during ripening. Genes related to pectin metabolism-a β-galactosidase, a pectin(methyl)esterase and a pectate lyase-and a xyloglucan endotransglucosylase/hydrolase, involved in hemicellulose modification, showed enhanced expression. In agreement with Fourier transform infrared spectroscopy, patterns due to pectin methyl esterification provided new insights into the relationship between pectin modifications and the associated transcript profile during skin ripening. This study proposes an original description of polymer dynamics in grape berries during ripening, highlighting differences between the internal and external sides of the skin.

Switching Between Giant Positive and Negative Thermal Expansions of a YFe(CN)6-Based Prussian Blue Analogue Induced by Guest Species

The control of thermal expansion of solid compounds is intriguing but remains challenging. The effect of guests on the thermal expansion of open-framework structures was investigated. Notably, the presence of guest ions (K+ ) and molecules (H2 O) can substantially switch thermal expansion of YFe(CN)6 from negative (αv =-33.67×10-6  K-1 ) to positive (αv =+42.72×10-6  K-1 )-a range that covers the thermal expansion of most inorganic compounds. The mechanism of such substantial thermal expansion switching is revealed by joint studies with synchrotron X-ray diffraction, X-ray absorption fine structure, neutron powder diffraction, and density functional theory calculations. The presence of guest ions or molecules plays a critical damping effect on transverse vibrations, thus inhibiting negative thermal expansion. An effective method is demonstrated to control the thermal expansion in open-framework materials by adjusting the presence of guests.

Non-Conventional Characterization of Electrically Active Dopant Profiles in Al-Implanted Ge by Depth-Resolved Micro-Raman Spectroscopy

Al-implanted Ge samples were investigated by micro-Raman spectroscopy combined with a small angle beveling technique. By means of a reverse Monte Carlo procedure, the concentration profiles of the electrically active dopant ions were determined from the Raman peak observed at ~370 cm-1 related to substitutional Al atoms. Furthermore, a clear relationship between the Ge–Ge Raman peak at ~300 cm-1 and the active dopant concentration was also observed. This work shows that micro-Raman spectroscopy could be adopted for quantitative characterizations of the carrier concentration profiles in extrinsic semiconductors.

Bond thermal expansion and effective pair potential in crystals: the case of cadmium selenide

The local dynamics of cadmium selenide (CdSe) with wurtzite structure has been investigated by molecular dynamics simulations, using a many-body Tersoff potential. The radial distribution functions (i.e., the effective pair potentials) of the first seven coordination shells have been determined as a function of temperature, as well as their parallel and perpendicular mean-square relative atomic displacements. The bond thermal expansion of the first coordination shell is mainly due to the asymmetry of the effective pair potential. In contrast, the bond thermal expansion of the outer shells is mostly due to a rigid shift of the effective pair potential. This behavior, recently observed also in simple cubic monoatomic crystals, can be generalized and related to the correlation of atomic motion. Finally, a shift toward lower values of the first Se-Cd effective pair potential has been observed when increasing the temperature, confirming previous findings by extended x-ray absorption fine-structure measurements. Differently from superionic conductors like AgI and CuBr, in which this anomalous negative shift was tentatively explained by cluster distortion and cation diffusion, the negative shift of CdSe is related to the peculiar properties of the crystalline potential.

Isotropic Zero Thermal Expansion and Local Vibrational Dynamics in (Sc,Fe)F3

Scandium fluoride (ScF3) exhibits a pronounced negative thermal expansion (NTE), which can be suppressed and ultimately transformed into an isotropic zero thermal expansion (ZTE) by partially substituting Sc with Fe in (Sc0.8Fe0.2)F3 (Fe20). The latter displays a rather small coefficient of thermal expansion of -0.17 × 10-6/K from 300 to 700 K. Synchrotron X-ray and neutron pair distribution functions confirm that the Sc/Fe-F bond has positive thermal expansion (PTE). Local vibrational dynamics based on extended X-ray absorption fine structure indicates a decreased anisotropy of relative vibration in the Sc/Fe-F bond. Combined analysis proposes a delicate balance between the counteracting effects of the chemical bond PTE and NTE from transverse vibration. The present study extends the scope of isotropic ZTE compounds and, more significantly, provides a complete local vibrational dynamics to shed light on the ZTE mechanism in chemically tailored NTE compounds.

Thermal and magnetic anomalies of α-iron: an exploration by extended x-ray absorption fine structure spectroscopy and synchrotron x-ray diffraction

The local structure and dynamics of α-iron have been investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy and x-ray diffraction (XRD) in order to shed light on some thermal and magnetic anomalies observed in the last decades. The quantitative EXAFS analysis of the first two coordination shells reveals a peculiar local vibrational dynamics of α-iron: the second neighbor distance exhibits anharmonicity and vibrational anisotropy larger than the first neighbor distance. We search for possible distortions of the bcc structure to justify the unexplained magnetostriction anomalies of α-iron and provide a value for the maximum dislocation of the central Fe atom. No thermal anomalies have been detected from the current XRD data. On the contrary, an intriguing thermal anomaly at about 150 K, ascribed to a stiffening of the Fe-Fe bonds, was found by EXAFS.

Localized Symmetry Breaking for Tuning Thermal Expansion in ScF3 Nanoscale Frameworks

The local symmetry, beyond the averaged crystallographic structure, tends to bring unusual performances. Negative thermal expansion is a peculiar physical property of solids. Here, we report the delicate design of the localized symmetry breaking to achieve controllable thermal expansion in ScF3 nanoscale frameworks. Intriguingly, an isotropic zero thermal expansion is concurrently engineered by localized symmetry breaking, with a remarkably low coefficient of thermal expansion of about +4.0 × 10-8/K up to 675 K. This mechanism is investigated by the joint analysis of atomic pair distribution function of synchrotron X-ray total scattering and extended X-ray absorption fine structure spectra. A localized rhombohedral distortion presumably plays a critical role in stiffening ScF3 nanoscale frameworks and concomitantly suppressing transverse thermal vibrations of fluorine atoms. This physical scenario is also theoretically corroborated by the extinction of phonon modes with negative Grüneisen parameters in rhombohedral ScF3. The present work opens an untraditional chemical modification route to achieve controllable thermal expansion by breaking local symmetries in materials.

Vibrational dynamics of rutile-type GeO2 from micro-Raman spectroscopy experiments and first-principles calculations

The vibrational dynamics of germanium dioxide in the rutile structure has been investigated by using polarized micro-Raman scattering spectroscopy coupled with first-principles calculations. Raman spectra were carried out in backscattering geometry at room temperature from micro-crystalline samples either unoriented or oriented by means of a micromanipulator, which enabled successful detection and identification of all the Raman active modes expected on the basis of the group theory. In particular, the Eg mode, incorrectly assigned or not detected in the literature, has been definitively observed by us and unambiguously identified at under excitation by certain laser lines, thus revealing an unusual resonance phenomenon. First-principles calculations within the framework of the density functional theory allow quantifying both wave number and intensity of the Raman vibrational spectra. The excellent agreement between calculated and experimental data corroborates the reliability of our findings.