Designing of metallic nanocrystals embedded in non-stoichiometric perovskite nanomaterial and its surface-electronic characteristics

Suriyaprakash, Jagadeesh; Xu, Yi‐Jun; Zhu, Yunlong; Yang, Lei; Tang, Yuguo; Wang, Y. J.; Li, S.; L., X.

doi:10.1038/s41598-017-09031-5

Cited by 16 publications

(9 citation statements)

References 61 publications

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“…Concerning the Ti 2 p XPS spectrum, the first component, around 458 eV, is attributed to the Ti 2 p 3/2 peak, whereas the second one around 463 eV is ascribed to the Ti 2 p 1/2 peak. The energy positions of both peaks coincide well with previous reports on different ferroelectric perovskites compounds 39,40 . The difference between Ti 2 p 3/2 and Ti 2 p 1/2 spin‐orbit splitting, which is around 5.5 eV, corresponds to Ti 4+ oxidation state.…”

Section: Resultssupporting

confidence: 89%

“…These peak positions correspond to Pb 2+ presents in the material lattice. 40 It is seen in Figure S3a,b that the binding energies of La 3d 5/2 are between 834.2 and 837.9 eV, confirming the existence of only La 3+ ions. 41 The energy difference between these peaks is about 4 eV, also in good agreement with the literature.…”

Section: Resultsmentioning

confidence: 63%

“…As shown in Figure a,b, the Pb 4 f XPS spectrum exhibits two components at approximately 137.9 and 142.8 eV, which are related to the Pb 4 f 7/2 and Pb 4 f 5/2 respectively. These peak positions correspond to Pb 2+ presents in the material lattice 40 . It is seen in Figure a,b that the binding energies of La 3 d 5/2 are between 834.2 and 837.9 eV, confirming the existence of only La 3+ ions 41 .…”

Section: Resultsmentioning

confidence: 64%

“…The energy positions of both peaks coincide well with previous reports on different ferroelectric perovskites compounds. 39,40 The difference between Ti 2p 3/2 and Ti 2p 1/2 spin-orbit splitting, which is around 5.5 eV, corresponds to Ti 4+ oxidation state. As shown in Figure S3a,b, the Pb 4f XPS spectrum exhibits two components at approximately 137.9 and 142.8 eV, which are related to the Pb 4f 7/2 and Pb 4f 5/2 respectively.…”

Section: Resultsmentioning

confidence: 99%

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Sintering‐driven effects on the band gap of (Pb,La)(Ti,Ni)O₃ photovoltaic ceramics

et al. 2021

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In this work, the influence of the sintering temperature on the physical properties of (Pb0.8La0.2)(Ti0.9Ni0.1)O3 (PLT‐Ni) ceramics is reported. The experimental data revealed that the energy band gap of PLT‐Ni ceramics could be tailored from approximately 2.7 to 2.0 eV by changing the sintering temperature from 1100°C to 1250°C. It is demonstrated that the simple substitution of Ti4+ by Ni2+ cations is effective to decrease the intrinsic band gap while increasing the tetragonality factor and the spontaneous polarization. However, the additional red‐shift observed in the absorption edge of the PLT‐Ni with increasing the sintering temperature was associated with a continuous increase in the oxygen vacancies (VO2‐) amount. It is believed that the impact of the creation of these thermally induced VO2‐ is manifold. The presence of VO2‐ and Ni2+ ions generate the Ni2+‐VO2‐ defect‐pairs that promoted both a decrease in the intrinsic band gap and an additional increase of the tetragonality factor, consequently, increasing the spontaneous polarization. The creation of Ni2+‐VO2‐ defects also changed the local symmetry of Ni2+ ions from octahedral to a square pyramid, thus lifting the degeneracy of the Ni2+ 3d orbitals. With the increase in the sintering temperature, lower‐energy absorbing intraband states were also formed due to an excess of VO2‐, being responsible for an add‐on shoulder in the absorption edge, extending the light absorption curve to longer wavelengths and leading to an additional absorption in “all investigated” spectrum as well.

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 63%

Section: Resultsmentioning

confidence: 64%

Section: Resultsmentioning

confidence: 99%

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Sintering‐driven effects on the band gap of (Pb,La)(Ti,Ni)O₃ photovoltaic ceramics

et al. 2021

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“…The ferroelectrics, PT and PZT, were selected owing to their large and stable ferroelectric polarization, and they have been investigated in several prior studies that demonstrated a strong polarization-dependent modulation of the Schottky barrier height with the surface Au nanoparticles. For example, the ferroelectric PT has been characterized as an n -type semiconductor with a bandgap of ~2.7 eV (Reddy and Parida, 2013) and an electron affinity χ of ~3.5 eV (Pintilie et al, 2008; Li et al, 2012; Suriyaprakash et al, 2017). When Au (work function Φ M = 5.1 eV) is in contact with a normal semiconductor with a similar electron affinity as that of PT, the semiconductor bands bend upward at their surface, leading to a low-energy Schottky barrier on the order of ~0.1–0.3 eV (Zhang and Yates, 2012; Pintilie et al, 2014).…”

Section: Experimental Investigations Of Schottky Barrier Heights and mentioning

confidence: 99%

Harnessing Plasmon-Induced Hot Carriers at the Interfaces With Ferroelectrics

et al. 2019

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This article reviews the scientific understanding and progress of interfacing plasmonic particles with ferroelectrics in order to facilitate the absorption of low-energy photons and their conversion to chemical fuels. The fundamental principles of hot carrier generation and charge injection are described for semiconductors interfaced with metallic nanoparticles and immersed in aqueous solutions, forming a synergistic juncture between the growing fields of plasmonically-driven photochemistry and semiconductor photocatalysis. The underlying mechanistic advantages of a metal-ferroelectric vs. metal-nonferroelectric interface are presented with respect to achieving a more optimal and efficient control over the Schottky barrier height and charge separation. Notable recent examples of using ferroelectric-interfaced plasmonic particles have demonstrated their roles in yielding significantly enhanced photocurrents as well as in the photon-driven production of molecular hydrogen. Notably, plasmonically-driven photocatalysis has been shown to occur for photon wavelengths in the infrared range, which is at lower energies than typically possible for conventional semiconductor photocatalysts. Recent results thus demonstrate that integrated ferroelectric-plasmonic systems represent a potentially transformative concept for use in the field of solar energy conversion.

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Rapid Plasma Exsolution from an A‐site Deficient Perovskite Oxide at Room Temperature

Khalid

Alessi

et al. 2022

Advanced Energy Materials

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and catalysis, capable of producing supported nanoparticles in a single synthesis step. [2][3][4][5][6][7] Exsolution was first observed on stoichiometric perovskite oxides where nanoparticles could be produced from transition metals present on the B-site of the perovskite oxide. This mechanism was initially referred to as solid-state recrystallization or self-regeneration. [8] Recently, however, the use of defect chemistry to synthesize the host oxides has revived the interest in exsolution because it allows a greater number of active cations, enhanced surface nucleation and nanoparticle growth and an overall faster and better controlled process. [3,9,10] Furthermore, the defect chemistry also allows for a structure that does not change when the reaction conditions change from oxidizing to reducing thus producing extremely controllable and stable catalysts. These advances have triggered fast growing research activities in the exsolution of nanoparticles and their application for environmental catalysis, solid oxide fuel cells, electrolysers, and chemical looping. [11][12][13][14][15][16][17][18][19] Exsolution is now an established term that refers to the growth of nanoparticles via the supply of metallic ionic species from an oxide host. This allows the formation of well anchored and partially embedded nanoparticles (socketed) on the support oxide, while also exhibiting crystallographic alignment. The application interest in exsolved nanoparticles High-performance nanoparticle platforms can drive catalysis progress to new horizons, delivering environmental and energy targets. Nanoparticle exsolution offers unprecedented opportunities that are limited by current demanding process conditions. Unraveling new exsolution pathways, particularly at low-temperatures, represents an important milestone that will enable improved sustainable synthetic route, more control of catalysis microstructure as well as new application opportunities. Herein it is demonstrated that plasma direct exsolution at room temperature represents just such a step change in the synthesis. Moreover, the factors that most affect the exsolution process are identified. It is shown that the surface defects produced initiate exsolution under a brief ion bombardment of an argon low-pressure and lowtemperature plasma. This results in controlled nanoparticles with diameters ≈19-22 nm with very high number densities thus creating a highly active catalytic material for CO oxidation which rivals traditionally created exsolved samples.

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Designing of metallic nanocrystals embedded in non-stoichiometric perovskite nanomaterial and its surface-electronic characteristics

Cited by 16 publications

References 61 publications

Sintering‐driven effects on the band gap of (Pb,La)(Ti,Ni)O₃ photovoltaic ceramics

Sintering‐driven effects on the band gap of (Pb,La)(Ti,Ni)O₃ photovoltaic ceramics

Harnessing Plasmon-Induced Hot Carriers at the Interfaces With Ferroelectrics

Rapid Plasma Exsolution from an A‐site Deficient Perovskite Oxide at Room Temperature

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Designing of metallic nanocrystals embedded in non-stoichiometric perovskite nanomaterial and its surface-electronic characteristics

Cited by 16 publications

References 61 publications

Sintering‐driven effects on the band gap of (Pb,La)(Ti,Ni)O3 photovoltaic ceramics

Sintering‐driven effects on the band gap of (Pb,La)(Ti,Ni)O3 photovoltaic ceramics

Harnessing Plasmon-Induced Hot Carriers at the Interfaces With Ferroelectrics

Rapid Plasma Exsolution from an A‐site Deficient Perovskite Oxide at Room Temperature

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Product

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Sintering‐driven effects on the band gap of (Pb,La)(Ti,Ni)O₃ photovoltaic ceramics

Sintering‐driven effects on the band gap of (Pb,La)(Ti,Ni)O₃ photovoltaic ceramics