Wpływ substytucji kationowej na strukturalne i magnetyczne właściwości wybranych chromitów selenowych

Jendrzejewska, I.

Artykuł - szczegóły

Tytuł artykułu

Wpływ substytucji kationowej na strukturalne i magnetyczne właściwości wybranych chromitów selenowych

Autorzy

Jendrzejewska I.

Wybrane pełne teksty z tego czasopisma

Identyfikatory

Warianty tytułu

Influence of cation substitution on structural and magnetic properties of selected chromium selenides

Języki publikacji

Abstrakty

Selenospinels with general formula ACr₂Se₄ (A = Zn, Cu, Cd) were doped with nickel and tin ions. The chemical synthesis was carried out based on solid phase reactions. To estimate the chemical composition of the mono- and polycrystalline compounds, the following methods were applied: JEOL scanning microscope and ICP-AES (Inductively Coupled Plasma - Atomic Emission Spectrometry). For the obtained polycrystalline compounds, their structural parameters were defined using X-ray diffraction analysis and Rietveld method. Definition of structure of the monocrystals was carried out using KM4 four-circle diffractometer and SHELX software. Magnetic properties were investigated with strong stationary magnetic fields up to 14 T in the temperature range of 4.2-300 K using an induction magnetometer and with stationary magnetic fields up to 0.5 T in the temperature range of 1.8-300 K using a SQUID superconducting magnetometer. In the systems doped with nickel, depending on the reaction stoichiometry, nickel ions were directed to tetrahedral or octahedral positions. When the octahedral positions are fully occupied by chromium ions, small amounts of nickel directed to tetrahedral positions are able to occupy them. The increasing amount of Ni^2- ions tends to occupy the octahedral positions in accordance with preference energy, leading to change in structure from cubic to monoclinic one [19, 37, 38]. Nickel ions present in the spinel crystal lattice influence the magnetic properties of these compounds. For ZnCr_2-xNi_x_{Se₄ system, an increase in values of effective magnetic moment and saturation magnetic moment accompanying the increase in nickel ions concentration was ascertained. It was caused by the presence of another magnetic ions in ZnCr₂Se₄ crystal lattice. The values of paramagnetic Curie-Weiss point and Néel point decrease with the increase in nickel concentration. It is associated with an increase in antiferromagnetic interactions in the system caused by nickel ions [39-41]. Like in the Cd_1–xNi_xCr₂Se₄system, saturation magnetic moment does not depend on the amount of nickel built-in, and the crystals exhibit strong ferromagnetic interactions. Lack of a change in saturation indicates that nickel is built in with compensated magnetic moment, or in a low-spin state (S = 0). Cadmium and nickel ions occupy tetrahedral positions and chromium ions - octahedral ones [42]. In the systems doped with tin, the reactions carried out in the solid phase were aimed to build in tin ions in tetra-and octahedral positions. X-ray diffraction studies confirmed the presence of tin ions in selected chromites. Mössbauer spectroscopy applied for the complex system Zn_1–xSn_xCr₂Se₄ confirmed the presence of tin ions in two inequivalent positions: in tetrahedral and in octahedral environments. Based on theses considerations, the general formula of these compounds may be as follows: Zn_xSn_δCr_ySn_ηSe₄, where δ – parameter describing the share of tin ions in tetrahedral sublattice, η – parameter describing the share of tin ions in octahedral sublattice [43]. Although tin ions does not contribute to a magnetic share, their presence in the crystal lattice promotes an increase in antiferromagnetic interactions in the studied compounds. Under the influence of tin ions, conductance changes from p-type (hole conduction) occurring in pure ZnCr₂Se₄to n-type (electron conduction) [44, 45]. In CuCr_2-xSn_xSe₄ system, magnetic properties change from ferromagnetic for nominal value x = 0.2 to antiferromagnetic for nominal value x = 1.0. These changes are caused by the presence of Sn⁴⁺ ions in the system, generating Cr²⁺ ions. The observed change in structure is caused by Jahn-Teller effect, occurring in the presence of Cu²⁺ and Cr²⁺ ions [46].}

Słowa kluczowe

struktura krystaliczna dyfrakcja rentgenowska ferromagnetyzm antyferromagnetyzm

crystal structure X-ray diffraction ferromagnetism antiferromagnetism

Wydawca

Polskie Towarzystwo Chemiczne

Czasopismo

Wiadomości Chemiczne

Rocznik

2010

Tom

[Z] 64, 9-10

Strony

859--898

Opis fizyczny

Bibliogr. 52 poz., tab., wykr.

Twórcy

autor

Jendrzejewska I.

Instytut Chemii, Uniwersytet Śląski ul. Szkolna 9, 40-006 Katowice, izajen@poczta.wp.pl

Bibliografia

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Bibliografia

Identyfikator YADDA

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