Determination of standard thermodynamic properties of Sb 2 O 3 by a solid-oxide electrolyte EMF technique

Aspiala, Markus; Sukhomlinov, Dmitry; Taskinen, Pekka

doi:10.1016/j.ssi.2014.07.016

Cited by 10 publications

(4 citation statements)

References 15 publications

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“…The Te atoms are situated at the very surface. The Te−O bond formation is more beneficial than that of Bi−O (−283.7 kJ/ mol), 39 and this fact explains the Te oxidation and, finally, the congruent oxidation of the first QL (step I in Figure 4i). Mobility of the Te 2− ions in Bi 2 Te 3 is hardly possible due to their large size.…”

Section: Resultsmentioning

confidence: 98%

“…All in all, the Sb 2 Te 3 reactivity is determined by the energy benefit of the Sb–O bond formation. The Sb–O standard formation enthalpy comprises −355 kJ/mol versus −319–321 kJ/mol for Te–O. , We suppose that the reaction centers are antisite defects, i.e., Sb atoms in the very surface Te layer. This speculation is supported by the fact that according to the STEM images in Figure d the Sb 2 O 3 layer is nonplanar, and highly oxidized regions are about 12 nm apart, which corresponds to the Sb excess of ∼1 atom % typical for our crystals.…”

Section: Resultsmentioning

confidence: 99%

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Mechanistic Studies of Gas Reactions with Multicomponent Solids: What Can We Learn By Combining NAP XPS and Atomic Resolution STEM/EDX?

et al. 2019

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Rapid development of experimental techniques has enabled real time studies of solid−gas reactions at the level reaching the atomic scale. In the present paper, we focus on a combination of atomic resolution STEM/EDX, which visualizes the reaction zone, and near ambient pressure (NAP) XPS, which collects information for a surface layer of variable thickness under reaction conditions. We compare the behavior of two affined topological insulators, Bi 2 Te 3 and Sb 2 Te 3 . We used a simple reaction with molecular oxygen occurring at 298 K, which is of practical importance to avoid material degradation. Despite certain limitations, a combination of in situ XPS and ex situ cross-sectional STEM/EDX allowed us to obtain a self-consistent picture of the solid−gas reaction mechanism for oxidation of Sb 2 Te 3 and Bi 2 Te 3 crystals, which includes component redistribution between the oxide and the subsurface layer and Te segregation with formation of a thin ordered layer at the interface. The process is multistep in case of both compounds. At the very beginning of the oxidation process the reactivity is determined by the energy benefit of the corresponding element−oxygen bond formation. Further in the oxidation process, the behavior of these two compounds becomes similar and features component redistribution between the oxide and the subsurface layer.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Mechanistic Studies of Gas Reactions with Multicomponent Solids: What Can We Learn By Combining NAP XPS and Atomic Resolution STEM/EDX?

et al. 2019

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“…−709.74 kJ mol −1 (Aspiala et al, 2014) and showed that most available values in the literature cluster tightly between −708 and −710 kJ mol −1 .…”

Section: Consistency Of the Formation Enthalpies Of Antimony Oxidesmentioning

confidence: 83%

Chapmanite [Fe2Sb(Si2O5)O3(OH)]: thermodynamic properties and formation in low-temperature environments

et al. 2021

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Abstract. In this work, we have determined or evaluated thermodynamic properties of synthetic Sb2O5, MgSb2O6 (analogue of the mineral byströmite), Mg[Sb(OH)6]2⋅6H2O (brandholzite), and natural chapmanite [(Fe1.88Al0.12)Sb(Si2O5)O3(OH)]. Enthalpies of reactions, including formation enthalpies, were evaluated using reference compounds Sb, Sb2O3, Sb2O5, and other phases, with high-temperature oxide melt solution calorimetry in lead borate and sodium molybdate solvents. Heat capacity and entropy were determined by relaxation and differential scanning calorimetry. The best set of ΔfHo (kJ mol−1) and So (J mol−1 K−1) is byströmite -1733.0±3.6, 139.3±1.0; brandholzite -5243.1±3.6, 571.0±4.0; and chapmanite -3164.9±4.7, 305.1±2.1. The data for chapmanite give ΔfGo of -2973.6±4.7 kJ mol−1 and log⁡K=-17.10 for the dissolution reaction (Fe1.88Al0.12)Sb(Si2O5)O3(OH) + 6H+→ 1.88Fe3+ + 0.12Al3+ + 2SiO20 + Sb(OH)30 + 2H2O. Analysis of the data showed that chapmanite is finely balanced in terms of its stability with schafarzikite (FeSb2O4) and tripuhyite (FeSbO4) under a specific, narrow range of conditions when both aqueous Fe(III) and Sb(III) are abundant. In such a model, chapmanite is metastable by a narrow margin but could be stabilized by high SiO20(aq) activities. Natural assemblages of chapmanite commonly contain abundant amorphous silica, suggesting that this mechanism may be indeed responsible for the formation of chapmanite. Chapmanite probably forms during low-temperature hydrothermal overprint of pre-existing Sb ores under moderately reducing conditions; the slightly elevated temperatures may help to overcome the kinetic barrier for its crystallization. During weathering, sheet silicates may adsorb Sb3+ in tridentate hexanuclear fashion, thus exposing their chapmanite-like surfaces to the surrounding aqueous environment. Formation of chapmanite, as many other sheet silicates, under ambient conditions, is unlikely.

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“…Consequently, the remaining Sb atoms are expected to gather oxygen to form Sb─O bonds even if they are briefly exposed to air because the formation enthalpy of Sb 2 O 3 (−709.74 kJ mol −1 ) is lower than that of Sb 2 Se 3 (−144.25 kJ mol −1 ). [28,29] This surface oxidation of Sb 2 Se 3 can contribute to the stability of devices under moisture and oxygen ambient. [16] Besides, the integrated area of excess Se (Se 0 ) from Se 3d as a function of annealing temper- ature (Figure 2d) supports the breakage of the Sb─Se bonds.…”

Section: Resultsmentioning

confidence: 99%

Realization of High‐Performance Photoresponsivity of Sb₂Se₃‐Based Phototransistors by Using Hybrid Structure and Optimizing Annealing Temperature

Kim,

You,

Seong

2023

Adv Materials Technologies

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Antimony selenide (Sb2Se3) is attracting attention as a candidate material with a high potential for photodetection due to its high absorption coefficient and excellent stability compared to other light‐absorbing materials. However, Sb2Se3‐based photodetectors are found to yield rather low responsivity in the visible and near‐infrared regions. Herein, the hybrid structure of ZnON/Sb2Se3 is for the first time adopted to increase the performance of Sb2Se3‐based phototransistors. It is shown that ZnON with high mobility enhances the photoresponse by promoting the recirculation of photocarriers. The (Sb4Se6)n ribbons of Sb2Se3 are found to be vertically oriented when annealed at 200 °C, inducing photocarriers to ZnON more easily than laterally oriented ribbons. The 200 °C‐annealed phototransistors give high responsivity of 2.14 × 104 A/W−1 (650 nm) and 2.47 × 104 A/W (905 nm), the latter being the highest among Sb2Se3‐based photodetectors. Further, the 200 °C‐annealed phototransistors exhibit superb stability, showing over 92% of the initial responsivity and over 81% detectivity even after being exposed to air for 5 weeks without passivation. It is further shown that the optimal devices reveal remarkably stable detectivity of 4.76 × 1013 Jones and 5.95 × 1013 Jones for 650 nm and 905 nm light, respectively.

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Determination of standard thermodynamic properties of Sb 2 O 3 by a solid-oxide electrolyte EMF technique

Cited by 10 publications

References 15 publications

Mechanistic Studies of Gas Reactions with Multicomponent Solids: What Can We Learn By Combining NAP XPS and Atomic Resolution STEM/EDX?

Mechanistic Studies of Gas Reactions with Multicomponent Solids: What Can We Learn By Combining NAP XPS and Atomic Resolution STEM/EDX?

Chapmanite [Fe<sub>2</sub>Sb(Si<sub>2</sub>O<sub>5</sub>)O<sub>3</sub>(OH)]: thermodynamic properties and formation in low-temperature environments

Realization of High‐Performance Photoresponsivity of Sb₂Se₃‐Based Phototransistors by Using Hybrid Structure and Optimizing Annealing Temperature

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Determination of standard thermodynamic properties of Sb 2 O 3 by a solid-oxide electrolyte EMF technique

Cited by 10 publications

References 15 publications

Mechanistic Studies of Gas Reactions with Multicomponent Solids: What Can We Learn By Combining NAP XPS and Atomic Resolution STEM/EDX?

Mechanistic Studies of Gas Reactions with Multicomponent Solids: What Can We Learn By Combining NAP XPS and Atomic Resolution STEM/EDX?

Chapmanite [Fe&lt;sub&gt;2&lt;/sub&gt;Sb(Si&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;)O&lt;sub&gt;3&lt;/sub&gt;(OH)]: thermodynamic properties and formation in low-temperature environments

Realization of High‐Performance Photoresponsivity of Sb2Se3‐Based Phototransistors by Using Hybrid Structure and Optimizing Annealing Temperature

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Chapmanite [Fe<sub>2</sub>Sb(Si<sub>2</sub>O<sub>5</sub>)O<sub>3</sub>(OH)]: thermodynamic properties and formation in low-temperature environments

Realization of High‐Performance Photoresponsivity of Sb₂Se₃‐Based Phototransistors by Using Hybrid Structure and Optimizing Annealing Temperature