Prediction and observation of defect-induced room-temperature ferromagnetism in halide perovskites

Abstract: The possibility to induce a macroscopic magnetic moment in lead halide perovskites (LHPs), combined with their excellent optoelectronic properties, is of fundamental interest and has promising spintronic applications. However, these possibilities remain an open question in both theory and experiment. Here, theoretical and experimental studies are performed to explore ferromagnetic states in LHPs originated from lattice defects. First-principle calculations reveal that shallow-level Br vacancies in defective CsPbBr₃ can produce spin-splitting states and the coupling between them leads to a ferromagnetic ground state. Experimentally, ferromagnetism at 300 K is observed in room-temperature synthesized CsPbBr₃ nanocrystals, but is not observed in hot-injection prepared CsPbBr₃ quantum dots and in CsPbBr₃ single crystals, highlighting the significance played by vacancy defects. Furthermore, the ferromagnetism in the CsPbBr₃ nanocrystals can be enhanced fourfold with Ni²⁺ ion dopants, due to enhancement of the exchange coupling between magnetic polarons. Room-temperature ferromagnetism is also observed in other LHPs, which suggests that vacancy-induced ferromagnetism may be a universal feature of solution-processed LHPs, which is useful for future spintronic devices.

Key words: lead halide perovskites, magnetic nanocrystals, halogen vacancy defects, DFT calculations, magnetic polarons

References:

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[1]	Žutić I, Fabian J, Das Sarma S. Spintronics: Fundamentals and applications. Rev Mod Phys, 2004, 76, 323
[2]	Qi B, Ólafsson S, Gíslason H P. Vacancy defect-induced d0 ferromagnetism in undoped ZnO nanostructures: Controversial origin and challenges. Prog Mater Sci, 2017, 90, 45
[3]	Matsumoto Y, Murakami M, Shono T, et al. Room-temperature ferromagnetism in transparent transition metal-doped titanium dioxide. Science, 2001, 291, 854
[4]	Sharma P, Gupta A, Rao K V, et al. Ferromagnetism above room temperature in bulk and transparent thin films of Mn-doped ZnO. Nat Mater, 2003, 2, 673
[5]	Ogale S B, Choudhary R J, Buban J, et al. High temperature ferromagnetism with a giant magnetic moment in transparent Co-doped SnO_{2− δ}. Phys Rev Lett, 2003, 91, 077205
[6]	Fernandes V, Klein J J, Mattoso N, et al. Room temperature ferromagnetism in Co-doped CeO₂ films on Si(001). Phys Rev B, 2007, 75, 121304(R
[7]	Reed M L, El-Masry N A, Stadelmaier H H, et al. Room temperature ferromagnetic properties of (Ga, Mn)N. Appl Phys Lett, 2001, 79, 3473
[8]	Coey J M D. d⁰ Ferromagnetism. Solid State Sci, 2005, 7, 660
[9]	Sundaresan A, Bhargavi R, Rangarajan N, et al. Ferromagnetism as a universal feature of nanoparticles of the otherwise nonmagnetic oxides. Phys Rev B, 2006, 74, 161306
[10]	Rumaiz A K, Ali B, Ceylan A, et al. Experimental studies on vacancy induced ferromagnetism in undoped TiO₂. Solid State Commun, 2007, 144, 334
[11]	Zhan P, Wang W P, Liu C, et al. Oxygen vacancy–induced ferromagnetism in un-doped ZnO thin films. J Appl Phys, 2012, 111, 033501
[12]	Niu G, Hildebrandt E, Schubert M A, et al. Oxygen vacancy induced room temperature ferromagnetism in Pr-doped CeO₂ thin films on silicon. ACS Appl Mater Interfaces, 2014, 6, 17496
[13]	Roul B, Rajpalke M K, Bhat T N, et al. Experimental evidence of Ga-vacancy induced room temperature ferromagnetic behavior in GaN films. Appl Phys Lett, 2011, 99, 162512
[14]	Wang H X, Zong Z C, Yan Y. Mechanism of multi-defect induced ferromagnetism in undoped rutile TiO₂. J Appl Phys, 2014, 115, 233909
[15]	Han X P, Lee J, Yoo H I. Oxygen-vacancy-induced ferromagnetism in CeO₂ from first principles. Phys Rev B, 2009, 79, 100403
[16]	Dev P, Xue Y, Zhang P H. Defect-Induced intrinsic magnetism in wide-gap III nitrides. Phys Rev Lett, 2008, 100, 117204
[17]	Wang Y R, Piao J Y, Xing G Z, et al. Zn vacancy induced ferromagnetism in K doped ZnO. J Mater Chem C, 2015, 3, 11953
[18]	Ahn C H, Kim Y Y, Kim D C, et al. Erratum: “A comparative analysis of deep level emission in ZnO layers deposited by various methods ” [J. Appl. Phys. 105, 013502 (2009)]. J Appl Phys, 2009, 105, 089902
[19]	Fabbri F, Villani M, Catellani A, et al. Zn vacancy induced green luminescence on non-polar surfaces in ZnO nanostructures. Sci Rep, 2014, 4, 5158
[20]	Morgan B J, Watson G W. Polaronic trapping of electrons and holes by native defects in anatase TiO₂. Phys Rev B, 2009, 80, 233102
[21]	Lyons J L, van de Walle C G. Computationally predicted energies and properties of defects in GaN. npj Comput Mater, 2017, 3, 12
[22]	Akkerman Q A, Rainò G, Kovalenko M V, et al. Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals. Nat Mater, 2018, 17, 394
[23]	Walsh A, Scanlon D O, Chen S Y, et al. Self-regulation mechanism for charged point defects in hybrid halide perovskites. Angew Chem Int Ed, 2015, 54, 1791
[24]	Dong Q F, Fang Y J, Shao Y C, et al. Solar cells. Electron-hole diffusion lengths > 175 μm in solution-grown CH₃NH₃PbI₃ single crystals. Science, 2015, 347, 967
[25]	Dutta A, Behera R K, Pal P, et al. Near-unity photoluminescence quantum efficiency for all CsPbX₃ (X = Cl, Br, and I) perovskite nanocrystals: A generic synthesis approach. Angew Chem Int Ed, 2019, 58, 5552
[26]	Jeon N J, Na H, Jung E H, et al. A fluorene-terminated hole-transporting material for highly efficient and stable perovskite solar cells. Nat Energy, 2018, 3, 682
[27]	Lin K, Xing J, Quan L N, et al. Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent. Nature, 2018, 562, 245
[28]	Cao Y, Wang N N, Tian H, et al. Perovskite light-emitting diodes based on spontaneously formed submicrometre-scale structures. Nature, 2018, 562, 249
[29]	Yin W J, Shi T T, Yan Y F. Unusual defect physics in CH₃NH₃PbI₃ perovskite solar cell absorber. Appl Phys Lett, 2014, 104, 063903
[30]	Kang J, Wang L W. High defect tolerance in lead halide perovskite CsPbBr₃. J Phys Chem Lett, 2017, 8, 489
[31]	Zhai Y X, Baniya S, Zhang C, et al. Giant Rashba splitting in 2D organic-inorganic halide perovskites measured by transient spectroscopies. Sci Adv, 2017, 3, e1700704
[32]	Zhang C, Sun D L, Yu Z G, et al. Field-induced spin splitting and anomalous photoluminescence circular polarization in CH₃NH₃PbI₃ films at high magnetic field. Phys Rev B, 2018, 97, 134412
[33]	Sun D L, Zhang C, Kavand M, et al. Surface-enhanced spin current to charge current conversion efficiency in CH₃NH₃PbBr₃-based devices. J Chem Phys, 2019, 151, 174709
[34]	Wang J, Zhang C, Liu H, et al. Spin-optoelectronic devices based on hybrid organic-inorganic trihalide perovskites. Nat Commun, 2019, 10, 129
[35]	Kresse, Furthmüller. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B, 1996, 54, 11169
[36]	Perdew J P, Ruzsinszky A, Csonka G I, et al. Restoring the density-gradient expansion for exchange in solids and surfaces. Phys Rev Lett, 2008, 100, 136406
[37]	Jakes P, Zimmermann J, von Seggern H, et al. Eu²⁺-doped CsBr photostimulable X-ray storage phosphors: Analysis of defect structure by high-frequency EPR. Funct Mater Lett, 2014, 7, 1350073
[38]	Coey M, Ackland K, Venkatesan M, et al. Collective magnetic response of CeO₂ nanoparticles. Nat Phys, 2016, 12, 694
[39]	Coey J M D. Magnetism in d⁰ oxides. Nat Mater, 2019, 18, 652
[40]	Yuan Y B, Huang J S. Ion migration in organometal trihalide perovskite and its impact on photovoltaic efficiency and stability. Acc Chem Res, 2016, 49, 286
[41]	Yong Z J, Guo S Q, Ma J P, et al. Doping-enhanced short-range order of perovskite nanocrystals for near-unity violet luminescence quantum yield. J Am Chem Soc, 2018, 140, 9942
[42]	Kaminski A, Das Sarma S. Polaron percolation in diluted magnetic semiconductors. Phys Rev Lett, 2002, 88, 247202
[43]	Coey J M D, Venkatesan M, Fitzgerald C B. Donor impurity band exchange in dilute ferromagnetic oxides. Nat Mater, 2005, 4, 173
[44]	Kang Y, Han S. Intrinsic carrier mobility of cesium lead halide perovskites. Phys Rev Appl, 2018, 10, 044013
[45]	Pan F, Song C, Liu X J, et al. Ferromagnetism and possible application in spintronics of transition-metal-doped ZnO films. Mater Sci Eng R, 2008, 62, 1

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Prediction and observation of defect-induced room-temperature ferromagnetism in halide perovskites

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