Black phosphorus (BP) has received growing attention due to its suitable carrier mobility and switching ratio, tunable direct band gap, and strong in-plane anisotropy. In recent years, the applied research of both bulk and few-layer BP has yielded continuous breakthroughs, while the device applications with stable performance have lagged due to their poor environmental stability. Additionally, fabricating high-quality doped BP by a desirable chemical vapor transport (CVT) method has been challenging. Herein, the CVT approach with a constant temperature was employed to fabricate Sb-doped BP (Sb−BP) and Bi-doped BP (Bi−BP) to enhance the performance of pristine BP. The characterizations, including Raman, transmission electron microscopy, atomic force microscopy, and so forth, were employed to study the phase structure and properties of the as-grown crystals. The results suggest that BP and doped BP belong to an orthorhombic structure and show good crystallinity. Distinct from pristine BP, the light absorption and electrochemical properties of orthorhombic BP were improved by doping. Furthermore, the storage time of Sb−BP exceeds 65 days, while the degradation of pristine BP occurs within 38 days in ambient condition. The degradation rate of Sb−BP was slower than that of pristine BP even in the harsh environment, which indicates that the antioxidation of Sb−BP is outstanding. Hence, doping is a viable method to modify the properties of BP. This work provides useful guidance for preparing other doped BP and BP compounds, broadening the application field of the phosphorus family.

摘 要: 黑磷(Black phosphorus, BP)以其优异而独特的物理化学性质在能源储存与转换、微纳器件、光/电催化和生 物医药等领域展现出良好的应用前景。高质量正交 BP 前体的制备是实现二维 BP 和零维 BP 量子点应用的关键。 本工作采用无温度梯度的化学气相运输(CVT)法研究了矿化剂组分和比例对 BP 生长的影响，并利用 XRD、XPS 和 TEM 等对 BP 晶体的物相结构和形貌进行了表征。结果表明，只有锡(或铅)和碘共存且比例合适时才能制备出正交 BP；生长 BP 所需的锡碘比例(Sn/I2)范围较宽，其中 Sn/I2=0.47 时制得的 BP 尺寸为 1.2 cm，且产率高、晶体质量 较优。结合 BP 的成核生长机理可知，锡和碘对 BP 的成核生长具有重要作用；碘的矿化效果较锡明显，而足量的 锡则有利于无温度梯度条件下大尺寸块体 BP 晶体的合成。Sn/I2=0.47 为本工作中制备 BP 的最佳参数。