Uniform wurtzite MnSe nanocrystals with surface-dependent magnetic behavior
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Manganese selenide (MnSe) possesses unique magnetic properties as an important magnetic semiconductor, but the synthesis and properties of MnSe nanocrystals are less developed compared to other semiconductor nanocrystals because of the inability to obtain high-quality MnSe, especially in the metastable wurtzite structure. Here, we have successfully fabricated wurtzite MnSe nanocrystals via a colloidal approach which affords uniform crystal sizes and tailored shapes. The selective binding strength of the amine surfactant is the determining factor in shape-control and shape-evolution. Bullet-shapes could be transformed into shuttle-shapes if part of the oleylamine in the reaction solution was replaced by trioctylamine, and tetrapod-shaped nanocrystals could be formed in trioctylamine systems. The three-dimensional (3D) structure of the bullet-shaped nanorods has been demonstrated by the advanced transmission electron microscope (TEM) 3D-tomography technology. High-resolution TEM (HRTEM) and electron energy-loss spectroscopy (EELS) show that planar-defect structures such as stacking faults and twinning along the [001] direction arise during the growth of bullet-shapes. On the basis of careful HRTEM observations, we propose a "quadra-twin core" growth mechanism for the formation of wurtzite MnSe nanotetrapods. Furthermore, the wurtzite MnSe nanocrystals show low-temperature surface spin-glass behavior due to their noncompensated surface spins and the blocking temperatures increase from 8.4 K to 18.5 K with increasing surface area/volume ratio of the nanocrystals. Our results provide a systematic study of wurtzite MnSe nanocrystals.
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Uniform wurtzite MnSe nanocrystals with surface-dependent magnetic behavior
)
Abstract
Manganese selenide (MnSe) possesses unique magnetic properties as an important magnetic semiconductor, but the synthesis and properties of MnSe nanocrystals are less developed compared to other semiconductor nanocrystals because of the inability to obtain high-quality MnSe, especially in the metastable wurtzite structure. Here, we have successfully fabricated wurtzite MnSe nanocrystals via a colloidal approach which affords uniform crystal sizes and tailored shapes. The selective binding strength of the amine surfactant is the determining factor in shape-control and shape-evolution. Bullet-shapes could be transformed into shuttle-shapes if part of the oleylamine in the reaction solution was replaced by trioctylamine, and tetrapod-shaped nanocrystals could be formed in trioctylamine systems. The three-dimensional (3D) structure of the bullet-shaped nanorods has been demonstrated by the advanced transmission electron microscope (TEM) 3D-tomography technology. High-resolution TEM (HRTEM) and electron energy-loss spectroscopy (EELS) show that planar-defect structures such as stacking faults and twinning along the [001] direction arise during the growth of bullet-shapes. On the basis of careful HRTEM observations, we propose a "quadra-twin core" growth mechanism for the formation of wurtzite MnSe nanotetrapods. Furthermore, the wurtzite MnSe nanocrystals show low-temperature surface spin-glass behavior due to their noncompensated surface spins and the blocking temperatures increase from 8.4 K to 18.5 K with increasing surface area/volume ratio of the nanocrystals. Our results provide a systematic study of wurtzite MnSe nanocrystals.
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Acknowledgements
This work was supported by the Ministry of Science and Technology of China (973 Project Nos. 2013CB932901 and 2009CB930803), and the National Natural Science Foundation of China (Nos. 11274066, 51172047, 50872145, and 51102050). The authors are grateful to the "Shu Guang" project supported by the Shanghai Municipal Education Commission and the Shanghai Education Development Foundation (09SG01).
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