To obtain semiconductor nanocrystals (NCs) with strong anodic electrochemiluminescence (ECL) remains a challenge due to their insufficiency to resist following corrosion upon holes injection to the NCs. Herein, we report strong and stable anodic ECL generated from 0.8 at% Mn²⁺ doped CdS NC films on indium tin oxide (ITO) electrode in the presence of coreactant triethanolamine (TEOA) under potential scan to +1.5 V vs. saturated calomel electrode (SCE), which is much more negative than the valence band potential of host NCs. The Mn²⁺ doping leads to an 8-fold enhancement in anodic ECL intensity in comparison with undoped CdS NC films due to efficient Mn excitation via nonradiative recombination energy transfer, i.e., exchange recombination. The efficiency is dependent on Mn²⁺ doping amount as well as applied potential for holes injection with the maximum obtained when the charge transfer to Mn dopants is possible and the energy gap between conduction band and applied potential matches with Mn excitation. This anodic ECL was used to detect dopamine, a model analyte, showing a wide linear range from 5 nM to 1 μM with a detection limit of 1 nM at S/N=3. This work provides a new insight into ECL generation in doped semiconductor NCs. The Mn²⁺ doped CdS NCs passivated by carboxylic groups display great potential in future development of biosensors.

获得具有强阳极电化学发光 (ECL) 的半导体纳米晶体 (NC) 仍然是一个挑战，因为它们不足以抵抗空穴注入到 NC 后的后续腐蚀。在此，我们报告了在共反应物三乙醇胺 (TEOA) 存在下，在氧化铟锡 (ITO) 电极上由 0.8 at% Mn ²⁺掺杂的 CdS NC 薄膜在 +1.5 V 与饱和甘汞电极的电位扫描下产生的强而稳定的阳极 ECL （SCE），这比宿主 NC 的价带电位更负。与未掺杂的CdS NC 薄膜相比， Mn ²⁺掺杂导致阳极ECL 强度提高8 倍，这是由于通过非辐射复合能量转移（即交换复合）进行的有效Mn 激发。效率取决于 Mn²⁺掺杂量以及空穴注入的施加电位，当电荷可能转移到 Mn 掺杂剂并且导带和施加电位之间的能隙与 Mn 激发匹配时获得最大值。该阳极 ECL 用于检测模型分析物多巴胺，其线性范围从 5 nM 到 1 μM，在 S/N=3 时检测限为 1 nM。这项工作为掺杂半导体 NC 中的 ECL 生成提供了新的见解。由羧基钝化的Mn ^{2+掺杂的CdS NCs在生物传感器的未来发展中显示出巨大的潜力。}