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. 2020 Nov 6;6(45):eabb5381.
doi: 10.1126/sciadv.abb5381. Print 2020 Nov.

Magnetizing lead-free halide double perovskites

Weihua Ning  1 , Jinke Bao  2 , Yuttapoom Puttisong  1 , Fabrizo Moro  1 , Libor Kobera  3 , Seiya Shimono  4 , Linqin Wang  5 , Fuxiang Ji  1 , Maria Cuartero  5 , Shogo Kawaguchi  6 , Sabina Abbrent  3 , Hiroki Ishibashi  7 , Roland De Marco  8 , Irina A Bouianova  1 , Gaston A Crespo  5 , Yoshiki Kubota  7 , Jiri Brus  3 , Duck Young Chung  2 , Licheng Sun  5   9 , Weimin M Chen  1 , Mercouri G Kanatzidis  2   10 , Feng Gao  11
Affiliations

Magnetizing lead-free halide double perovskites

Weihua Ning et al. Sci Adv. .

Abstract

Spintronics holds great potential for next-generation high-speed and low-power consumption information technology. Recently, lead halide perovskites (LHPs), which have gained great success in optoelectronics, also show interesting magnetic properties. However, the spin-related properties in LHPs originate from the spin-orbit coupling of Pb, limiting further development of these materials in spintronics. Here, we demonstrate a new generation of halide perovskites, by alloying magnetic elements into optoelectronic double perovskites, which provide rich chemical and structural diversities to host different magnetic elements. In our iron-alloyed double perovskite, Cs2Ag(Bi:Fe)Br6, Fe3+ replaces Bi3+ and forms FeBr6 clusters that homogenously distribute throughout the double perovskite crystals. We observe a strong temperature-dependent magnetic response at temperatures below 30 K, which is tentatively attributed to a weak ferromagnetic or antiferromagnetic response from localized regions. We anticipate that this work will stimulate future efforts in exploring this simple yet efficient approach to develop new spintronic materials based on lead-free double perovskites.

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Figures

Fig. 1
Fig. 1. Basic characterizations of the double perovskite Cs2Ag(Bi:Fe)Br6.
(A) Photographs and crystal structures of double perovskites Cs2AgBiBr6 and Cs2Ag(Bi:Fe)Br6. (B) ESR signals from Cs2AgBiBr6 and Cs2Ag(Bi:Fe)Br6 at room temperature (RT). a.u., arbitrary units. (C) Powder XRD patterns for Cs2AgBiBr6 and Cs2Ag(Bi:Fe)Br6, and the simulated XRD pattern of Cs2AgBiBr6 as reference, an expansion of highly intense reflections (220) (D) and (400) (E), illustrating shift toward higher 2θ angles and the symmetric to asymmetric transformation after Fe3+ alloying. (F) NEXAFS Fe 2p3/2 edge spectrum for Cs2Ag(Bi:Fe)Br6, in which the baseline has been corrected.
Fig. 2
Fig. 2. Temperature-dependent specific heat capacity and SPD.
Specific heat capacity (A) and SPD patterns (B) of Cs2Ag(Bi:Fe)Br6 at different temperatures. The lattice constant (C) and rotation angle (D) in 293 to 30 K for Cs2Ag(Bi:Fe)Br6. The crystal structures of Cs2Ag(Bi:Fe)Br6 at high temperature (HT, 300 K) (E) and low temperature (LT, 30 K) (F), red lines representing unit cells. Inset plot in (A) represents a magnification of the Cp peak at 120 K.
Fig. 3
Fig. 3. ssNMR of Cs2AgBiBr6 and Cs2Ag(Bi:Fe)Br6.
133Cs-133Cs SD/MAS NMR and 133Cs Hahn-echo MAS NMR spectra of Cs2AgBiBr6 (A) and Cs2Ag(Bi:Fe)Br6 (B). 133Cs T1 saturation recovery buildup curves of Cs2AgBiBr6 (C) and Cs2Ag(Bi:Fe)Br6 (D). (E) 209Bi ssNMR of Cs2AgBiBr6 and Cs2Ag(Bi:Fe)Br6 conducted at static conditions. (F) Schematic representation of possible scenarios for Fe3+ distribution inside the perovskite lattice: parent perovskite lattice, isolated Fe3+ ions, small Fe3+ clusters, and large Fe3+ clusters. The percentages are the ideally calculated values for Cs+ exhibiting fast relaxation in different scenarios.
Fig. 4
Fig. 4. Magnetic characterizations of Cs2Ag(Bi:Fe)Br6.
(A) Temperature-dependent magnetic susceptibility of Cs2Ag(Bi:Fe)Br6 under zero-field-cooled (ZFC) and field-cooled (FC) procedures with a magnetic field H = 1000 Oe. (B) Isothermal field-dependent magnetization of Cs2Ag(Bi:Fe)Br6. The inset plot presents the low–magnetic field magnetization from −0.1 to 0.1 T. (C) ESR spectrum from Cs2AgBiBr6 (the gray curves) and Cs2Ag(Bi:Fe)Br6 (the red curves) crystal powder, measured at 7.2 and 40 K, respectively. The simulated ESR spectra (the blue curves) are obtained from a spin Hamiltonian analysis, which consist of the contributions from Fe3+, with S = 5/2 and g = 2.032, and a defect center of unknown origin, with S = 1/2 and g = 2.032. The discrepancy between the simulated and experimental ESR spectra indicates the existence of a third ESR signal—a broad background signal, which becomes more pronounced at low temperatures. (D) Temperature dependence of total microwave absorption (the black spheres), together with the contributions from the three individual ESR components revealed from the spin Hamiltonian analysis.
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