Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, United States.
J Am Chem Soc. 2011 Oct 5;133(39):15475-86. doi: 10.1021/ja2039419. Epub 2011 Sep 14.
Eu(III)-doped Y(2)O(3) nanocrystals are prepared by microwave synthetic methods as spherical 6.4 ± 1.5 nm nanocrystals with a cubic crystal structure. The surface of the nanocrystal is passivated by acetylacetonate (acac) and HDA on the Y exposed facet of the nanocrystal. The presence of acac on the nanocrystal surface gives rise to a strong S(0) → S(1) (π → π*, acac) and acac → Ln(3+) ligand to metal charge transfer (LMCT) transitions at 270 and 370 nm, respectively, in the Eu:Y(2)O(3) nanocrystal. Excitation into the S(0) → S(1) (π → π*) or acac → Ln(3+) LMCT transition leads to the production of white light emission arising from efficient intramolecular energy transfer to the Y(2)O(3) oxygen vacancies and the Eu(III) Judd-Ofelt f-f transitions. The acac passivant is thermally stable below 400 °C, and its presence is evidenced by UV-vis absorption, FT-IR, and NMR measurements. The presence of the low-lying acac levels allows UV LED pumping of the solid phosphor, leading to high quantum efficiency (∼19%) when pumped at 370 nm, high-quality white light color rendering (CIE coordinates 0.33 and 0.35), a high scotopic-to-photopic ratio (S/P = 2.21), and thermal stability. In a LED lighting package luminosities of 100 lm W(-1) were obtained, which are competitive with current commercial lighting technology. The use of the passivant to funnel energy to the lanthanide emitter via a molecular antenna effect represents a new paradigm for designing phosphors for LED-pumped white light.
掺铕的 Y(2)O(3)纳米晶体通过微波合成方法制备,为具有立方晶体结构的 6.4 ± 1.5nm 球形纳米晶体。纳米晶体的表面由乙酰丙酮(acac)和 HDA 在纳米晶体暴露的 Y 面上钝化。纳米晶体表面上的 acac 分别在 270nm 和 370nm 处引起强 S(0) → S(1)(π → π*,acac)和 acac →Ln(3+)配体到金属电荷转移(LMCT)跃迁,在 Eu:Y(2)O(3)纳米晶体中。激发到 S(0) → S(1)(π → π*)或 acac →Ln(3+)LMCT 跃迁导致白光发射的产生,这是由于高效的分子内能量转移到 Y(2)O(3)氧空位和 Eu(III)Judd-Ofelt f-f 跃迁。acac 钝化剂在 400°C 以下热稳定,其存在通过紫外-可见吸收、FT-IR 和 NMR 测量得到证明。低 acac 能级的存在允许 UV LED 对固体荧光粉进行泵浦,当在 370nm 处泵浦时,可获得高光量子效率(约 19%)、高质量的白光显色指数(CIE 坐标为 0.33 和 0.35)、高光敏比(S/P = 2.21)和热稳定性。在 LED 照明封装中,获得了 100lmW(-1)的亮度,与当前的商业照明技术具有竞争力。使用钝化剂通过分子天线效应将能量传递给镧系元素发射体,代表了设计用于 LED 泵浦白光的荧光粉的新范例。