Structural, vibrational and electronic properties of α′-Ga<sub>2</sub>S<sub>3</sub> under compression

Gallego-Parra, Samuel; Vilaplana, R.; Gomis, O.; Silva, E. Lora da; Otero-de-la-Roza, Alberto; Rodríguez‐Hernández, P.; Múñoz, A.; González, J.; Sans, J. A.; Cuenca-Gotor, Vanesa P.; Ibáñez, J.; Popescu, Cătălin; Manjón, F. J.

doi:10.1039/d0cp06417c

Cited by 9 publications

(26 citation statements)

References 111 publications

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“…In general, there is a good agreement between the experimental and theoretical results on structural, vibrational, and optical properties as far as pressure-induced disorder is not crucial in the LP range. The excellent agreement of experimental and theoretical results allowed us to discuss the lattice dynamical properties of these semiconductors [8][9][10]12,13] in analogy with zincblende-type semiconductors (see Figure 2). The lack of agreement between the experimental and theoretical pressure dependence of the direct bandgap energy above certain pressure has allowed us to discuss the ranges of the pressure-induced disorder process that OVCs undergo prior to their transformation to the disorder rocksalt structure at HP (in analogy with zincblende-type semiconductors).…”

Section: Ordered-vacancy Compoundsmentioning

confidence: 74%

“…We have published some joint experimental and theoretical studies on structural, vibrational, and optical properties of adamantine OVCs under compression [7][8][9][10][11][12][13][14]. In general, there is a good agreement between the experimental and theoretical results on structural, vibrational, and optical properties as far as pressure-induced disorder is not crucial in the LP range.…”

Section: Ordered-vacancy Compoundsmentioning

confidence: 86%

“…The lack of agreement between the experimental and theoretical pressure dependence of the direct bandgap energy above certain pressure has allowed us to discuss the ranges of the pressure-induced disorder process that OVCs undergo prior to their transformation to the disorder rocksalt structure at HP (in analogy with zincblende-type semiconductors). However, the most striking results were the strong pressure dependence of the topmost valence band and the strong nonlinear pressure dependence of the direct bandgap [7,11,13,14], which is caused by the anticrossing between the two smallest conduction bands at HP at the Γ point. The first effect is a consequence of the strong compression of the anion LEP, which mainly contributes to the topmost valence band.…”

Section: Ordered-vacancy Compoundsmentioning

confidence: 99%

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Combined Experimental and Theoretical Studies: Lattice-Dynamical Studies at High Pressures with the Help of Ab Initio Calculations

et al. 2021

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Lattice dynamics studies are important for the proper characterization of materials, since these studies provide information on the structure and chemistry of materials via their vibrational properties. These studies are complementary to structural characterization, usually by means of electron, neutron, or X-ray diffraction measurements. In particular, Raman scattering and infrared absorption measurements are very powerful, and are the most common and easy techniques to obtain information on the vibrational modes at the Brillouin zone center. Unfortunately, many materials, like most minerals, cannot be obtained in a single crystal form, and one cannot play with the different scattering geometries in order to make a complete characterization of the Raman scattering tensor of the material. For this reason, the vibrational properties of many materials, some of them known for millennia, are poorly known even under room conditions. In this paper, we show that, although it seems contradictory, the combination of experimental and theoretical studies, like Raman scattering experiments conducted at high pressure and ab initio calculations, is of great help to obtain information on the vibrational properties of materials at different pressures, including at room pressure. The present paper does not include new experimental or computational results. Its focus is on stressing the importance of combined experimental and computational approaches to understand materials properties. For this purpose, we show examples of materials already studied in different fields, including some hot topic areas such as phase change materials, thermoelectric materials, topological insulators, and new subjects as metavalent bonding.

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Section: Ordered-vacancy Compoundsmentioning

confidence: 74%

Section: Ordered-vacancy Compoundsmentioning

confidence: 86%

Section: Ordered-vacancy Compoundsmentioning

confidence: 99%

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Combined Experimental and Theoretical Studies: Lattice-Dynamical Studies at High Pressures with the Help of Ab Initio Calculations

et al. 2021

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“…For the sake of clarity, only the most intense Raman mode, the A′(6), of α′-Ga 2 S 3 is marked in panel a. The reader is referred to our previous work (ref ) for further information about the pressure dependence of the Raman-active modes of α′-Ga 2 S 3 . All the observed Raman-active modes have been labeled in β′-Ga 2 S 3 and φ-Ga 2 S 3 .…”

Section: Resultsmentioning

confidence: 99%

“…X-ray diffraction (XRD) measurements under compression showed a PT to β-In 2 Se 3 -like ( R -3 m ) Ga 2 S 3 (hereinafter, β′-Ga 2 S 3 ) around 16 GPa, being the PT assisted by laser heating (LH) . However, a PT was found at similar pressures at RT in a study of the structural and vibrational properties of α′-Ga 2 S 3 at HP, i.e., without the need of LH . Similarly, Raman scattering (RS) measurements at RT observed a PT at 11.3 (17.2 GPa) with (and without) He as a pressure-transmitting medium (PTM) .…”

Section: Introductionmentioning

confidence: 99%

High-Pressure Synthesis of β- and α-In₂Se₃-Like Structures in Ga₂S₃

et al. 2022

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The synthesis of polymorphs of α′-Ga 2 S 3 at room temperature on compression/decompression is studied from a joint experimental and theoretical point of view to reveal the nature of their crystalline structures. The results of Raman scattering and X-ray diffraction measurements on these polymorphs have been analyzed supported by theoretical ab initio simulations. On compression, α′-Ga 2 S 3 undergoes a phase transition above 16 GPa to β′-Ga 2 S 3 with a tetradymite-like (R-3m) structure, isostructural with β-In 2 Se 3 . On decompression, β′-Ga 2 S 3 undergoes a phase transition below 9.0 GPa to φ-Ga 2 S 3 , which is isostructural with α-In 2 Se 3 (R3m). Raman signatures of symmetry breaking as well as clear structural differences between the pressure dependence of the unit-cell volume per formula unit, zero-pressure axial compressibilities, bulk modulus, and their first pressure derivative between β′-Ga 2 S 3 and φ-Ga 2 S 3 have allowed us to determine the R3m nature of φ-Ga 2 S 3 . The observation of the R3m phase is also supported by theoretical total energy ab initio simulations. This result unveils a pressure-induced paraelectricferroelectric R-3m-to-R3m transition, like the theoretically predicted temperature-induced transition in several III−VI B 2 X 3 compounds, which could find use in technological applications. Finally, φ-Ga 2 S 3 undergoes a phase transition below 1.0 GPa to γ-Ga 2 S 3 with a disordered zincblende (F-43m) phase, isostructural with α-Ga 2 Se 3 and remains metastable at room conditions. Since the disordered zincblende phase of Ga 2 X 3 chalcogenides has also been found upon decompression in AGa 2 X 4 chalcogenides, we discuss the relation between the pressure-induced phase transitions of both Ga 2 X 3 and AGa 2 X 4 compounds.

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Rigidity‐Driven Structural Isomers in the NaCl–Ga₂S₃ System: Implications for Energy Storage

Bokova,

Kassem,

Usuki

et al. 2024

Small Science

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Alternative energy sources require the search for innovative materials with promising functionalities. Systems with unusual chemical properties represent an insufficiently explored domain, concealing unexpected features. Using diffraction and Raman spectroscopy over a wide temperature range, supported by first‐principles simulations, a rare phenomenon is unveiled: phase‐dependent chemical interactions between binary components in the NaCl–Ga2S3 system. In this unique occurrence, previously intact binary crystalline species transform upon melting into mixed liquid structural isomers, forming bonds with new partners. The chemical combinatorics appears to be fully reversible for stable crystals and liquids. Despite this, rapidly frozen glasses out of thermodynamic equilibrium remain in a metastable isomeric state, offering remarkable properties, particularly a high room‐temperature Na+ conductivity, comparable to the best sodium halide superionic conductors and therefore encouraging for sodium solid‐state batteries and energy applications. A rigidity paradigm is responsible for the observed phenomenon, as the extremely constrained Ga2S3 crystal lattice does not survive viscous flow, breaking up at a short‐range level. The removal of rigidity constraints and dense packing leads to a significant increase in empty space, which is the origin of high sodium diffusivity. Broadly, the rigidity‐driven structural isomerism opens up an inspiring path to the discovery of atypical materials.

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Structural, vibrational and electronic properties of α′-Ga₂S₃ under compression

Cited by 9 publications

References 111 publications

Combined Experimental and Theoretical Studies: Lattice-Dynamical Studies at High Pressures with the Help of Ab Initio Calculations

Combined Experimental and Theoretical Studies: Lattice-Dynamical Studies at High Pressures with the Help of Ab Initio Calculations

High-Pressure Synthesis of β- and α-In₂Se₃-Like Structures in Ga₂S₃

Rigidity‐Driven Structural Isomers in the NaCl–Ga₂S₃ System: Implications for Energy Storage

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Structural, vibrational and electronic properties of α′-Ga2S3 under compression

Cited by 9 publications

References 111 publications

Combined Experimental and Theoretical Studies: Lattice-Dynamical Studies at High Pressures with the Help of Ab Initio Calculations

Combined Experimental and Theoretical Studies: Lattice-Dynamical Studies at High Pressures with the Help of Ab Initio Calculations

High-Pressure Synthesis of β- and α-In2Se3-Like Structures in Ga2S3

Rigidity‐Driven Structural Isomers in the NaCl–Ga2S3 System: Implications for Energy Storage

Contact Info

Product

Resources

About

Structural, vibrational and electronic properties of α′-Ga₂S₃ under compression

High-Pressure Synthesis of β- and α-In₂Se₃-Like Structures in Ga₂S₃

Rigidity‐Driven Structural Isomers in the NaCl–Ga₂S₃ System: Implications for Energy Storage