Valence State of Pb in Transition Metal Perovskites PbTMO3 (TM = Ti, Ni) Determined From X-Ray Absorption Near-Edge Spectroscopy

Kai Chen; Yimin Mijiti; Stefano Agrestini; Sheng Chieh Liao; Xiang Li; Jianshi Zhou; Andrea Di Cicco; Francois Baudelet; Liu Hao Tjeng; Zhiwei Hu

doi:10.1002/pssb.201800014

Valence State of Pb in Transition Metal Perovskites PbTMO₃ (TM = Ti, Ni) Determined From X-Ray Absorption Near-Edge Spectroscopy

Kai Chen, Yimin Mijiti, Stefano Agrestini, Sheng Chieh Liao, Xiang Li, Jianshi Zhou, Andrea Di Cicco, Francois Baudelet, Liu Hao Tjeng, Zhiwei Hu^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

11 Citations (Scopus)

Abstract

We present a combined experimental and theoretical Pb-L₃ X-ray absorption near-edge spectroscopy (XANES) to investigate the chemical state of Pb in transition metal perovskites PbTMO₃ (TM = Ti, Ni). A pre-edge feature originated from the excitation of a 2p core electron to the 6s orbital is only observed in PbNiO₃, from which the valence of Pb is determined to be Pb⁴⁺ with two 6s holes. However, no such 2p–6s related excitation was observed in PbTiO₃, indicating the formation of Pb²⁺ with fully occupied 6s² state in this materials. Our results demonstrate that this pre-edge peak from dipole allowed 2p–6s transition is a sensitive finger-print of the Pb valence state in solid state materials.

Original language	English
Article number	1800014
Journal	Physica Status Solidi (B): Basic Research
Volume	255
Issue number	6
DOIs	https://doi.org/10.1002/pssb.201800014
Publication status	Published - Jun 2018
Externally published	Yes

Keywords

X-ray absorption near-edge spectroscopy
perovskites
valence states

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10.1002/pssb.201800014

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Chen, K., Mijiti, Y., Agrestini, S., Liao, S. C., Li, X., Zhou, J., Di Cicco, A., Baudelet, F., Tjeng, L. H., & Hu, Z. (2018). Valence State of Pb in Transition Metal Perovskites PbTMO₃ (TM = Ti, Ni) Determined From X-Ray Absorption Near-Edge Spectroscopy. Physica Status Solidi (B): Basic Research, 255(6), Article 1800014. https://doi.org/10.1002/pssb.201800014

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title = "Valence State of Pb in Transition Metal Perovskites PbTMO3 (TM = Ti, Ni) Determined From X-Ray Absorption Near-Edge Spectroscopy",

abstract = "We present a combined experimental and theoretical Pb-L3 X-ray absorption near-edge spectroscopy (XANES) to investigate the chemical state of Pb in transition metal perovskites PbTMO3 (TM = Ti, Ni). A pre-edge feature originated from the excitation of a 2p core electron to the 6s orbital is only observed in PbNiO3, from which the valence of Pb is determined to be Pb4+ with two 6s holes. However, no such 2p–6s related excitation was observed in PbTiO3, indicating the formation of Pb2+ with fully occupied 6s2 state in this materials. Our results demonstrate that this pre-edge peak from dipole allowed 2p–6s transition is a sensitive finger-print of the Pb valence state in solid state materials.",

keywords = "X-ray absorption near-edge spectroscopy, perovskites, valence states",

author = "Kai Chen and Yimin Mijiti and Stefano Agrestini and Liao, {Sheng Chieh} and Xiang Li and Jianshi Zhou and {Di Cicco}, Andrea and Francois Baudelet and Tjeng, {Liu Hao} and Zhiwei Hu",

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year = "2018",

month = jun,

doi = "10.1002/pssb.201800014",

language = "English",

volume = "255",

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T1 - Valence State of Pb in Transition Metal Perovskites PbTMO3 (TM = Ti, Ni) Determined From X-Ray Absorption Near-Edge Spectroscopy

AU - Chen, Kai

AU - Mijiti, Yimin

AU - Agrestini, Stefano

AU - Liao, Sheng Chieh

AU - Li, Xiang

AU - Zhou, Jianshi

AU - Di Cicco, Andrea

AU - Baudelet, Francois

AU - Tjeng, Liu Hao

AU - Hu, Zhiwei

PY - 2018/6

Y1 - 2018/6

N2 - We present a combined experimental and theoretical Pb-L3 X-ray absorption near-edge spectroscopy (XANES) to investigate the chemical state of Pb in transition metal perovskites PbTMO3 (TM = Ti, Ni). A pre-edge feature originated from the excitation of a 2p core electron to the 6s orbital is only observed in PbNiO3, from which the valence of Pb is determined to be Pb4+ with two 6s holes. However, no such 2p–6s related excitation was observed in PbTiO3, indicating the formation of Pb2+ with fully occupied 6s2 state in this materials. Our results demonstrate that this pre-edge peak from dipole allowed 2p–6s transition is a sensitive finger-print of the Pb valence state in solid state materials.

AB - We present a combined experimental and theoretical Pb-L3 X-ray absorption near-edge spectroscopy (XANES) to investigate the chemical state of Pb in transition metal perovskites PbTMO3 (TM = Ti, Ni). A pre-edge feature originated from the excitation of a 2p core electron to the 6s orbital is only observed in PbNiO3, from which the valence of Pb is determined to be Pb4+ with two 6s holes. However, no such 2p–6s related excitation was observed in PbTiO3, indicating the formation of Pb2+ with fully occupied 6s2 state in this materials. Our results demonstrate that this pre-edge peak from dipole allowed 2p–6s transition is a sensitive finger-print of the Pb valence state in solid state materials.

KW - X-ray absorption near-edge spectroscopy

KW - perovskites

KW - valence states

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U2 - 10.1002/pssb.201800014

DO - 10.1002/pssb.201800014

M3 - Article

AN - SCOPUS:85041663274

SN - 0370-1972

VL - 255

JO - Physica Status Solidi (B): Basic Research

JF - Physica Status Solidi (B): Basic Research

IS - 6

M1 - 1800014

ER -

Valence State of Pb in Transition Metal Perovskites PbTMO₃ (TM = Ti, Ni) Determined From X-Ray Absorption Near-Edge Spectroscopy

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