Effect of V5+/V4+ substitution on structural and magnetic orderings of SrFeO3-δ

IF 5.6 2区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Ceramics International Pub Date : 2025-09-01 DOI:10.1016/j.ceramint.2025.06.220

Rakhi Saha , Koyal Suman Samantaray , P. Maneesha , Suresh Chandra Baral , Sachindra Nath Sarangi , Rajashri Urkude , Biplab Ghosh , R. Mittal , Mayanak K. Gupta , Abdelkarim Mekki , Khalil Harrabi , Somaditya Sen

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Abstract

SrFeO_3-δ is a structurally versatile material, showing cubic (C) symmetry at δ = 0, which transitions to tetragonal (T) and then orthorhombic (Or) with increasing oxygen vacancies. These structural changes alter magnetic behavior through variations in bond angles and lengths, enabling both antiferromagnetic (AFM) and ferromagnetic (FM) interactions between Fe⁴⁺/Fe³⁺ ions and oxygen (or vacancies). While such tunable magnetic phases offer rich physics and potential applications, achieving room-temperature (RT) FM remains challenging. This study explores V⁵⁺/V⁴⁺ doping in SrFeO_3-δ (SrFe_1-xV_xO_3-δ; 0 ≤ x ≤ 0.03) to induce FM persisting up to RT and investigates its structural-magnetic correlation. Structural analysis from X-ray diffraction (XRD) and Raman spectroscopy, supported by phonon mode calculations, reveals that SrFeO_3-δ is in a mixed T-Or phase. At the same time, V-doped samples exhibit an emerging C-phase in a dominant T-lattice. Magnetic hysteresis (M − H) loops show notable FM behavior within the AFM matrix at low temperature ∼10K, with a FM and paramagnetic phase at room temperature. Temperature-dependent magnetization measurements indicate a T-phase related Néel temperature (T_N) shift from 70K to 55K in the doped samples as compared to the pure one. An increased magnetization difference between the field-cooled (FC) and zero-field-cooled (ZFC) data with increasing V-content suggests an increasing magnetic frustration due to competing FM/AFM exchange interactions. X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) analyses reveal a rise in Fe³⁺ and V⁵⁺ states, affecting oxygen vacancy distributions and corresponding structural shifts seen in XRD and Raman results. The multivalent Fe³⁺/Fe⁴⁺ and V⁴⁺/V⁵⁺ states enhance Double-Exchange (DE) interactions (Fe³⁺-O-Fe⁴⁺ and Fe³⁺-O-V⁵⁺), and V_O-mediated Fe³⁺-V_O-Fe³⁺ interaction, promoting ferromagnetism. Moreover, frequency-dependent magnetization studies display a subtle susceptibility peak shift, indicating spin-glass-like behavior in V-doped samples.

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V5+/V4+取代对SrFeO3-δ结构和磁序的影响

SrFeO3-δ是一种结构多样的材料，在δ = 0处呈现立方对称(C)，随着氧空位的增加，逐渐转变为四方对称(T)和正交对称（Or）。这些结构变化通过键角和长度的变化改变了磁性行为，使Fe4+/Fe3+离子与氧（或空位）之间的反铁磁（AFM）和铁磁（FM）相互作用成为可能。虽然这种可调谐磁相提供了丰富的物理和潜在的应用，但实现室温（RT） FM仍然具有挑战性。本研究探索在SrFeO3-δ (SrFe1-xVxO3-δ; 0≤x≤0.03)中掺杂V5+/V4+诱导FM持续至RT，并研究其结构-磁相关性。x射线衍射（XRD）和拉曼光谱的结构分析，以及声子模式计算的支持，表明SrFeO3-δ处于混合T-Or相。与此同时，v掺杂样品在主导t晶格中表现出新兴的c相。在低温~ 10K时，磁滞回圈（M−H）在AFM矩阵中表现出明显的调频行为，在室温下表现出调频和顺磁相。温度相关磁化测量表明，与纯样品相比，掺杂样品中t相相关的nsamel温度（TN）从70K转移到55K。场冷（FC）和零场冷（ZFC）数据之间的磁化差随着v含量的增加而增加，这表明由于FM/AFM交换相互作用的竞争，磁挫折增加。x射线光电子能谱（XPS）和x射线吸收近边结构（XANES）分析显示Fe3+和V5+态的增加，影响了XRD和Raman结果中氧空位分布和相应的结构位移。多价Fe3+/Fe4+和V4+/V5+态增强了双交换（DE）相互作用（Fe3+-O-Fe4+和Fe3+-O-V5+），以及vo介导的Fe3+-VO-Fe3+相互作用，促进了铁磁性。此外，频率相关磁化研究显示了微妙的磁化率峰移位，表明v掺杂样品具有自旋玻璃样行为。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Ceramics International 工程技术-材料科学：硅酸盐

CiteScore

9.40

自引率

15.40%

发文量

4558

审稿时长

25 days

期刊介绍： Ceramics International covers the science of advanced ceramic materials. The journal encourages contributions that demonstrate how an understanding of the basic chemical and physical phenomena may direct materials design and stimulate ideas for new or improved processing techniques, in order to obtain materials with desired structural features and properties. Ceramics International covers oxide and non-oxide ceramics, functional glasses, glass ceramics, amorphous inorganic non-metallic materials (and their combinations with metal and organic materials), in the form of particulates, dense or porous bodies, thin/thick films and laminated, graded and composite structures. Process related topics such as ceramic-ceramic joints or joining ceramics with dissimilar materials, as well as surface finishing and conditioning are also covered. Besides traditional processing techniques, manufacturing routes of interest include innovative procedures benefiting from externally applied stresses, electromagnetic fields and energetic beams, as well as top-down and self-assembly nanotechnology approaches. In addition, the journal welcomes submissions on bio-inspired and bio-enabled materials designs, experimentally validated multi scale modelling and simulation for materials design, and the use of the most advanced chemical and physical characterization techniques of structure, properties and behaviour. Technologically relevant low-dimensional systems are a particular focus of Ceramics International. These include 0, 1 and 2-D nanomaterials (also covering CNTs, graphene and related materials, and diamond-like carbons), their nanocomposites, as well as nano-hybrids and hierarchical multifunctional nanostructures that might integrate molecular, biological and electronic components.