State Key Laboratory of Extreme Photonics and Instrumentation, College of Optical Science and Engineering, International Research Center for Advanced Photonics, Zhejiang University, Hangzhou, China.
ZJU-Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University, Hangzhou, China.
Nature. 2024 Sep;633(8029):344-350. doi: 10.1038/s41586-024-07792-4. Epub 2024 Sep 11.
Reliable control of the conductivity and its polarity in semiconductors is at the heart of modern electronics, and has led to key inventions including diodes, transistors, solar cells, photodetectors, light-emitting diodes and semiconductor lasers. For archetypal semiconductors such as Si and GaN, positive (p)- and negative (n)-type conductivities are achieved through the doping of electron-accepting and electron-donating elements into the crystal lattices, respectively. For halide perovskites, which are an emerging class of semiconductors, mechanisms for reliably controlling charge conduction behaviours while maintaining high optoelectronic qualities are yet to be discovered. Here we report that the p- and n-type characteristics in a wide-bandgap perovskite semiconductor can be adjusted by incorporating a phosphonic acid molecular dopant with strong electron-withdrawing abilities. The resultant carrier concentrations were more than 10 cm for the p- and n-type samples, with Hall coefficients ranging from -0.5 m C (n-type) to 0.6 m C (p-type). A shift of the Fermi level across the bandgap was observed. Importantly, the transition from n- to p-type conductivity was achieved while retaining high photoluminescence quantum yields of 70-85%. The controllable doping in the emissive perovskite semiconductor enabled the demonstration of ultrahigh brightness (more than 1.1 × 10 cd m) and exceptional external quantum efficiency (28.4%) in perovskite light-emitting diodes with a simple architecture.
可靠地控制半导体的电导率及其极性是现代电子学的核心,这导致了关键发明的出现,包括二极管、晶体管、太阳能电池、光电探测器、发光二极管和半导体激光器。对于典型的半导体,如硅和氮化镓,通过将电子受体和电子供体元素掺杂到晶格中,可以分别实现正(p)型和负(n)型电导率。对于卤化物钙钛矿,它是一类新兴的半导体,在保持高光电子质量的同时,仍需要发现可靠地控制电荷传导行为的机制。在这里,我们报告说,通过掺入具有强电子吸电子能力的膦酸分子掺杂剂,可以调整宽带隙钙钛矿半导体的 p 型和 n 型特性。所得的载流子浓度对于 p 型和 n 型样品超过 10^17 cm,霍尔系数范围从 -0.5 mC(n 型)到 0.6 mC(p 型)。观察到费米能级在能带隙中的移动。重要的是,在保持高的光致发光量子产率(70-85%)的同时,实现了从 n 型到 p 型电导率的转变。在发射钙钛矿半导体中的可控制掺杂使得能够在具有简单结构的钙钛矿发光二极管中展示超高亮度(超过 1.1×10^7 cd/m)和卓越的外量子效率(28.4%)。