博彩平台

Atomically Precise Doping of Monomanganese Ion into Coreless Supertetrahedral Chalcogenide Nanocluster Inducing Unusual Red Shift in Mn²⁺ Emission

Jian Lin †, Qian Zhang †, Le Wang †, Xiaochun Liu †, Wenbo Yan †, Tao Wu *†(吴涛), Xianhui Bu *‡（卜贤辉）, and Pingyun Feng *§（冯萍云）

^† College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu 215123, China

^‡ Department of Chemistry and Biochemistry, California State University, 1250 Bellflower Blvd., Long Beach, California 90840, United States

^§ Department of Chemistry, University of California, Riverside, California 92521, United States

J. Am. Chem. Soc. 2014, 136, 4769–4779.

We report a simple and yet effective method to introduce Mn²⁺ ions into semiconducting nanoclusters with atomically precise control. Our method utilizes one type of micrometer-sized crystals, composed of well-defined isolated supertetrahedral chalcogenide nanoclusters ( 2 nm, [Cd₆In₂₈S₅₂(SH)₄]) whose core metal site is unoccupied in as-synthesized pristine form. This unique model structure with vacant core site makes it possible to achieve ordered distribution of Mn²⁺ dopants, and at the same time effectively preclude the formation of Mn²⁺ clusters in the host matrix. A two-step synthesis strategy is applied to realize an atomically precise doping of Mn²⁺ ion into the core site of the nanoclusters, and to achieve uniform distribution of Mn²⁺ dopants in the crystal lattice. The PL, X-ray photoelectron (XPS), as well as the electron paramagnetic resonance (EPR) spectra reveal the successful incorporation of Mn²⁺ ion into the core site of the nanocluster. Different from the pristine host material with weak green emission ( 490 nm), the Mn²⁺-doped material shows a strong red emission (630 nm at room temperature and 654 nm at 30 K), which is significantly red-shifted relative to the orange emission ( 585 nm) observed in traditional Mn²⁺-doped II–VI semiconductors. Various experiments including extensive synthetic variations and PL dynamics have been performed to probe the mechanistic aspects of synthesis process and resultant unusual structural and PL properties. The quaternary semiconductor material reported here extends the emission window of Mn²⁺-doped II–VI semiconductor from yellow-orange to red, opening up new opportunities in applications involving photonic devices and bioimaging.

链接： //pubs.acs.org/doi/abs/10.1021/ja501288x