Magnetic field effects in non-magnetic luminescent materials: from organic semiconductors to halide perovskites

Tao Cong; Wang Jing-Min; Niu Mei-Ling; Zhu Lin; Peng Qi-Ming; Wang Jian-Pu

doi:10.7498/aps.71.20211872

Abstract

Magnetic field effects (MFEs) are used to describe the changes of the photophysical properties (including photoluminescence, electroluminescence, injectedcurrent, photocurrent, etc.) when materials and devices are subjected to the external magnetic field. The MFEs in non-magnetic luminescent materials and devices were first observed in organic semiconductor. In the past two decades, the effects have been studied extensively as an emerging physical phenomenon, and also used as a unique experimental method to explore the processes such as charge transport, carrier recombination, and spin polarization in organic semiconductors. Recent studies have found that the MFEs can also be observed in metal halide perovskites with strong spin-orbital coupling. Besides, for expanding the research domain of MFEs, these findings can also be utilized to study the physical mechanism in metal halide perovskites, and then provide an insight into the improving of the performance of perovskite devices. In this review, we focus on the magnetic field effects on the electroluminescence and photoluminescence changes of organic semiconductors and halide perovskites. We review the mainstream of theoretical models and representative experimental phenomena which have been found to date, and comparatively analyze the luminescence behaviors of organic semiconductors and halide perovskites under magnetic fields. It is expected that this review can provide some ideas for the research on the MFEs of organic semiconductors and halideperovskites, and contribute to the research of luminescence in organic materials and halideperovskites.

Keywords:

Authors and contacts

Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University (NanjingTech), Nanjing 211816, China

Corresponding author: Peng Qi-Ming, iamqmpeng@njtech.edu.cn ; Wang Jian-Pu, iamjpwang@njtech.edu.cn

Funds: Projected supported by the National Natural Science Foundation-Outstanding Youth Foundation of China (Grant No. 62022040), the Young Scientists Fund of the National Natural Science Foundation of China (Grant No. 11804156), the National Natural Science Foundation of China (Grant No. 51972171), and the Postgraduate Research & Practice Innovation Program of Jiangsu Province, China (Grant Nos. KYCX21_1102, KYCX21_1089).

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References

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图 1 基于Alq₃的OLED (a)电致发光和(b)电流的磁场效应^[11]

Figure 1. Magnetic field effects on (a) electroluminescence and (b) current of Alq₃-based OLED^[11].

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图 2 Alq₃器件在不同电压下的(a) MC和(b) MEL^[13]; (c) Ru(bpy)₃器件在不同电压下的MEL^[12]; (d)不同长度一维结构器件的MR^[20]; 延迟荧光器件在不同温度下的(e) MC和(f) MEL^[21]

Figure 2. The (a) MC and (b) MEL of Alq₃-based OLED at different voltages^[13]; (c) the MEL of Ru(bpy)₃-based OLED at different voltages^[12]; (d) the MR in the device with one-dimensional structure^[20]; the (e) MC and (f) MEL of delayed fluorescence OLED at different temperatures ^[21] .

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图 3 OLED中载流子相互作用决定的激发态类型^[38]

Figure 3. Excited states in OLED determined by the interactions between carriers ^[38] .

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图 4 (a)自由载流子、电子-空穴对和激子的跃迁能级示意图及相关速率常数, 其中S和T分别表示单线态和三线态, G表示EHP的形成率, $ {k}_{\mathrm{d}}^{\mathrm{S}} $和$ {k}_{\mathrm{d}}^{\mathrm{T}} $分别代表单线态和三线态EHP的离解速率常数, $ {k}_{\mathrm{r}}^{\mathrm{S}} $和$ {k}_{\mathrm{r}}^{\mathrm{T}} $为单线态和三线态EHP的复合速率常数; (b)电子、空穴在磁场下以不同频率$ \omega $进动示意图

Figure 4. (a) Transition rate constants of free carriers, electron-hole pairs and excitons. S and T represent singlet and triplet states, respectively. G represents the formation rate of EHP. $ {k}_{\mathrm{d}}^{\mathrm{S}} $ and $ {k}_{\mathrm{d}}^{\mathrm{T}} $ represent the dissociation rate constants of singlet and triplet EHPs, respectively, $ {k}_{\mathrm{r}}^{\mathrm{S}} $ and $ {k}_{\mathrm{r}}^{\mathrm{T}} $ are the recombination rate constants of singlet and triplet EHPs. (b) The Larmor precession of electrons and holes with different frequency ω under a magnetic field.

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图 5 三线态-三线态淬灭(TTA)模型示意图^[66]

Figure 5. Schematic diagram of the triplet-triplet annihilation (TTA) model ^[66] .

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图 6 (a)双极化子的形成过程; (b)外磁场下双极化子形成概率减小; (c)利用双极化子模型拟合磁场效应^[44]

Figure 6. (a) Formation process of the bipolaron; (b) the probability of the bipolaron formation decreases under the external magnetic field; (c) fitting the magnetic field effect with the bipolaron model ^[44].

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图 7 (a)无外加磁场和(b)有外加磁场下三线态激子对自由载流子的散射作用^[38]

Figure 7. Scattering effects of triplet excitons on free carriers (a) without and (b) with an external magnetic field ^[38].

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图 8 (a)有机光电器件中的自旋极化效应, 其中绿线为外磁场方向^[3]; (b)自旋极化下荧光发射被强烈抑制而磷光发射增强^[43]

Figure 8. (a) Spin polarization in OLED, where the green line is the direction of the external magnetic field^[3] ; (b) the fluorescence is strongly suppressed while the phosphorescence is enhanced by TSP^[43] .

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图 9 金属卤化物钙钛矿的晶胞结构^[87]

Figure 9. Crystal structure of the metal halide perovskites^[87].

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图 10 (a)钙钛矿中不同自旋态的子能带偏离k空间的Γ点^[36]; (b)导带与价带表现出自旋极化方向相反的分裂^[94]

Figure 10. (a) Sub-bands with different spins states deviate from the Γ point in the k space of perovskites^[36]; (b) the conduction band and valence band show opposite spin splitting depending on the spin polarization direction^[94] .

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图 11 (a)电子-空穴对中Δg机制示意图; (b) 5 mA恒定电流下的MEL; (c)钙钛矿薄膜的MPL; (d) 0和5 T磁场下左右圆偏振旋光光谱; (e) 18 K温度下薄膜的圆偏振度与磁场的关系^[35]

Figure 11. (a) Schematic diagram of the Δg mechanism of electron-hole pairs; (b) the MEL at a constant current of 5 mA; (c) the MPL of the perovskite film; (d) the left and right circularly polarized optical rotation spectra at 0 and 5 T; (e) the relationship between the degree of circularly polarization and the magnetic field at 18 K ^[35] .

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图 12 (a)钙钛矿薄膜在不同激发光强下的MPL; (b)钙钛矿光伏器件在不同激发光强下的MC; (c)正MC和负MPL的线形特征; (d)钙钛矿中的电子-空穴对模型示意图^[33]

Figure 12. (a) MPL of the perovskite film with different excitation intensities at room temperature; (b) MC of the perovskite solar cell with different excitation intensities; (c) linear characteristics of positive MC and negative MPL; (d) schematic diagram of the electron-hole pair model in perovskites ^[33] .

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图 13 (a) (C₄H₉NH₃)₂PbBr₄的PL谱, 其中Γ₁和Γ₂为暗态, Γ₅为亮态; (b)自旋驰豫(左图)和自旋翻转(右图)示意图; (c) PL随磁场的变化^[32]

Figure 13. (a) PL spectra of (C₄H₉NH₃)₂PbBr₄, where Γ₁ and Γ₂ are dark states, and Γ₅ is bright state; (b) schematic diagram of the spin relaxation (left) and spin flip (right); (c) the PL changes under the magnetic fields^[32] .

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图 14 (a) 0 ℃下, CsPbBr₃薄膜有/无500 mT的PL光谱; (b)无磁场和(c)有磁场的瞬态PL光谱; (d)无磁场和(e)有磁场下515 nm处复合动力学轨迹^[34]

Figure 14. (a) The PL spectra of CsPbBr₃ film with/without a magnetic field of 500 mT at 0 ℃; the time resolved PL spectra in the obsence (b) and presence (c) of a magnetic field; the recombination kinetics extracted from the time resolved PLs in the obsence (d) and presence (e) of a magnetic field ^[34].

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表 1 光生载流子复合动力学常数^[34]

Table 1. Recombination kinetic constants of photogenerated carrier ^[34] .

Power/(mW· cm^–2)	Magnet OFF		Magnet ON
Power/(mW· cm^–2)	Fast decay/ps	Slow decay/ps	Fast decay/ps	Slow decay/ps
198	138$ \pm $9 (55%)	1038$ \pm $65 (45%)	104$ \pm $6 (63%)	959$ \pm $55 (37%)
305	138$ \pm $8 (55%)	1031$ \pm $31 (45%)	100$ \pm $4 (64%)	886$ \pm $25 (36%)
450	131$ \pm $5 (57%)	1000$ \pm $34 (43%)	101$ \pm $5 (65%)	892$ \pm $23 (35%)

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[1]	Sun D, Ehrenfreund E, Vardeny Z V 2014 Chem. Commun. 50 1781 Google Scholar
[2]	Sagar R U R, Zhang X, Wang J, Xiong C 2014 J. Appl. Phys. 115 123708 Google Scholar
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