Surface vacancy engineering played a significant role in tailoring the structure and improving the performance of semiconductor nanocrystals (SNCs). Developing controllable vacancy engineering strategies to overcome kinetic energy barriers in multi-step reactions is anticipated to explore further synthesis mechanisms and functional nanomaterials. Herein, we exploited an effective surface-vacancy-engineering-initialized cation exchange (SVEICE) strategy to realize energy-unfavored cation exchange reactions from ternary CuInX₂ (X = S, Se) to Cu, In dual-doped binary CdX, or ZnX SNCs, unprecedentedly. The sequential and selective creation of Cu and In vacancies on multi-component SNC surface is critical to break through kinetic energy barriers. The emission of dual-doped CdS:Cu/In SNCs crossed visible-NIR region due to the radiative transition from doped In level to Cu-doped e- or t-level, and the radiative recombination process could also be tailored by this strategy. Further energy analysis and experiments confirmed its versatility.

表面空位工程在调整结构和改善半导体纳米晶体（SNC）的性能方面起着重要作用。预期开发可控的空位工程策略以克服多步反应中的动能壁垒，以探索进一步的合成机理和功能性纳米材料。本文中，我们利用有效的表面空位工程初始化阳离子交换（SVEICE）策略来实现三元CuInX _2的能量不利阳离子交换反应（X = S，Se）到Cu，在双掺杂二元CdX或ZnX SNC中是前所未有的。在多组分SNC表面上顺序和选择性地生成Cu和In空位对于突破动能垒至关重要。由于从掺杂的In能级到Cu掺杂的e或t能级的辐射跃迁，双掺杂CdS：Cu / In SNC的发射越过可见NIR区域，并且该策略也可以调整辐射复合过程。进一步的能量分析和实验证实了它的多功能性。