Black phosphorus (BP), a fascinating semiconductor with high mobility and a tunable direct bandgap, has emerged as a candidate beyond traditional silicon-based devices for next-generation electronics and optoelectronics. The ability to grow large-scale, high-quality BP films is a prerequisite for scalable integrated applications but has thus far remained a challenge due to unmanageable nucleation events. Here we develop a sustained feedstock release strategy to achieve subcentimetre-size single-crystal BP films by facilitating the lateral growth mode under a low nucleation rate. The as-grown single-crystal BP films exhibit high crystal quality, which brings excellent field-effect electrical properties and observation of pronounced Shubnikov–de Haas oscillations, with high mobilities up to ~6,500 cm² V⁻¹ s⁻¹ at low temperatures. We further extend this approach to the growth of single-crystal BP alloy films, which broaden the infrared emission regime of BP from 3.7 μm to 6.9 μm at room temperature. This work will greatly facilitate the development of high-performance electronics and optoelectronics based on BP family materials.

黑磷 (BP) 是一种迷人的半导体，具有高迁移率和可调直接带隙，已成为超越传统硅基器件的下一代电子和光电子器件的候选者。生长大规模、高质量 BP 薄膜的能力是可扩展集成应用的先决条件，但由于难以控制的成核事件，迄今为止仍然是一个挑战。在这里，我们开发了一种持续的原料释放策略，通过在低成核率下促进横向生长模式来实现亚厘米级单晶 BP 薄膜。生长的单晶 BP 薄膜具有高晶体质量，具有出色的场效应电性能和显着的 Shubnikov–de Haas 振荡观察结果，迁移率高达 ~6,500 cm ²  V^-1  s ^-1在低温下。我们进一步将这种方法扩展到单晶 BP 合金薄膜的生长，从而将 BP 在室温下的红外发射范围从 3.7 μm 扩大到 6.9 μm。这项工作将极大地促进基于BP族材料的高性能电子和光电子的发展。