Covalent Functionalization of Few-Layer Black Phosphorus Using Iodonium Salts and Comparison to Diazonium Modified Black Phosphorus,Chemistry of Materials

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Covalent Functionalization of Few-Layer Black Phosphorus Using Iodonium Salts and Comparison to Diazonium Modified Black Phosphorus
Chemistry of Materials ( IF 7.2 ) Pub Date : 2018-06-22 00:00:00 , DOI: 10.1021/acs.chemmater.8b01306
Maart van Druenen _{1,

2} , Fionán Davitt _{1,

2} , Timothy Collins ₁ , Colm Glynn ₁ , Colm O’Dwyer ₁ , Justin D. Holmes _{1,

2} , Gillian Collins _{1,

2}

Affiliation

Since the isolation of two-dimensional (2D) phosphorene, black phosphorus (BP) has gained popularity due to its high carrier mobility and tunable bandgap. Poor ambient stability of BP remains a key issue and impedes its use in electronic applications. Here we report a new stabilization strategy based on covalent functionalization of liquid exfoliated few-layer BP using aryl iodonium salts. Arylation of BP using iodonium salts enables covalent modification without inducing oxidation and alters the degradation chemistry of BP by inhibiting bridged oxygen formation through attachment to surface oxygen sites. In comparison, functionalization using aryl diazonium salts results in oxidation and aryl multilayer formation and does not adequately disrupt noncovalent solvent passivation. Aryl functionalization of BP using iodonium salts displays superior ambient stability compared to arylation using diazonium salts associated with greater covalent functionalization as characterized using X-ray photoelectron spectroscopy, scanning transmission electron microscopy, photoluminescence, and attenuated total reflectance infrared spectroscopy.

中文翻译：

使用碘鎓盐共生几层黑色磷的共价官能化及其与重氮修饰的黑色磷的比较

自从隔离二维（2D）磷烯以来，黑磷（BP）由于其高的载流子迁移率和可调节的带隙而受到欢迎。BP的环境稳定性差仍然是关键问题，并阻碍了其在电子应用中的使用。在这里，我们报告了一种新的稳定化策略，该策略基于使用芳基碘鎓盐对液体剥落的多层BP进行共价官能化。使用碘鎓盐对BP进行芳基化可实现共价修饰而不会引起氧化，并通过抑制通过连接至表面氧位而形成的桥接氧来改变BP的降解化学。相比之下，使用芳基重氮盐进行官能化会导致氧化和形成芳基多层膜，并且不会充分破坏非共价溶剂的钝化作用。

更新日期：2018-06-22

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