Adopting black phosphorus (BP) as a material in electronic and optoelectronic device manufacturing requires the development and understanding of a large-scale synthesis technique. To that end, high-energy planetary ball milling is demonstrated as a scalable synthesis route, and the mechanisms and conversion kinetics of the BP phase transformation are investigated. During the milling process, media collisions rapidly compress amorphous red phosphorus (RP) into crystalline, orthorhombic BP flakes, resulting in a conversion yield of ≈90% for ≈5 g of bulk BP powder. Milling conversion kinetics, monitored via ex situ x-ray diffraction, manifest a sigmoidal behavior best described by the Avrami rate model with each impact of sufficient energy (>25 mJ) producing BP nuclei; the process appears to be limited by grain growth. Using a kinematic model for ball trajectories and impact energies, the optimum milling condition is determined to be an impact energy near ≈25 mJ and a milling dose near ≈100 kJ/gram. Photoexcitation of exfoliated BP flakes reveals emission in the near-infrared, indicating the formation of few-layer BP, a promising advance for optoelectronic device applications.

在电子和光电设备制造中采用黑磷（BP）作为材料需要开发和理解大规模合成技术。为此，高能行星球磨被证明是可扩展的合成路线，并且研究了BP相变的机理和转化动力学。在研磨过程中，介质碰撞迅速将无定形的红磷（RP）压缩成晶体，正交晶的BP薄片，对于≈5g的BP大块粉末，转化率约为≈90％。通过异位X射线衍射监测的铣削转化动力学表明，Avrami速率模型最好地描述了S型行为，每一次产生足够能量（> 25 mJ）的BP核都会产生冲击。该过程似乎受谷物生长的限制。使用运动学模型计算球的轨迹和冲击能量，确定最佳研磨条件为：≈25mJ附近的冲击能和≈100kJ / g附近的研磨剂量。剥落的BP薄片的光激发揭示了近红外光的发射，表明形成了几层BP，这对于光电器件应用来说是一个有希望的进步。