van Druenen Maart, Davitt Fionán, Collins Timothy, Glynn Colm, O'Dwyer Colm, Holmes Justin D, Collins Gillian
School of Chemistry, ERI & Tyndall National Institute , University College Cork , Cork T12 YN60 , Ireland.
AMBER@CRANN, Trinity College Dublin , Dublin 2 , Ireland.
Langmuir. 2019 Feb 12;35(6):2172-2178. doi: 10.1021/acs.langmuir.8b04190. Epub 2019 Jan 28.
Black phosphorus (BP) is emerging as a promising candidate for electronic, optical, and energy storage applications. However, its poor ambient stability remains a critical challenge. Evaluation of few-layer liquid-exfoliated BP during ambient exposure using X-ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared spectroscopy allows its surface chemistry to be investigated. Oxidation of liquid-exfoliated few-layer BP initially occurs through nonbridging oxide species, which convert to bridging oxide species after ambient exposure. We demonstrate the instability of these bridging oxide species, which undergo hydrolysis to form volatile phosphorus oxides and evaporate from the BP surface. FTIR spectroscopy, scanning transmission electron microscopy, and atomic force microscopy were used to confirm the formation of liquid oxides through a continuous oxidation cycle that results in the decomposition of BP. Furthermore, we show that the instability of few-layer BP originates from the formation of bridging oxide species.
黑磷（BP）正成为电子、光学和储能应用中一个有前景的候选材料。然而，其在环境中的稳定性较差仍然是一个关键挑战。使用X射线光电子能谱和衰减全反射傅里叶变换红外光谱对环境暴露期间的少层液体剥离BP进行评估，能够研究其表面化学性质。液体剥离的少层BP的氧化最初通过非桥连氧化物物种发生，在环境暴露后这些物种会转化为桥连氧化物物种。我们证明了这些桥连氧化物物种的不稳定性，它们会发生水解形成挥发性磷氧化物并从BP表面蒸发。利用傅里叶变换红外光谱、扫描透射电子显微镜和原子力显微镜通过一个导致BP分解的连续氧化循环来确认液体氧化物的形成。此外，我们表明少层BP的不稳定性源于桥连氧化物物种的形成。
