International Laboratory of Glass-Based Functional Materials, Mendeleev University of Chemical Technology of Russia, Moscow, Russia.
Nanotechnology. 2012 Jan 13;23(1):015708. doi: 10.1088/0957-4484/23/1/015708. Epub 2011 Dec 8.
The target of taking advantage of the near-infrared light-emission properties of nickel ions in crystals for the design of novel broadband optical amplifiers requires the identification of suitable nanostructured glasses able to embed Ni-doped nanocrystals and to preserve the workability of a glass. Here we show that Ni doping of Li(2)O-Na(2)O-Ga(2)O(3)-GeO(2)-SiO(2) glass (with composition 7.5:2.5:20:35:35 and melting temperature 1480 °C, sensibly lower than in Ge-free silicates) enables the selective embedding of nickel ions in thermally grown nanocrystals of spinel-like gallium oxide. The analysis of transmission electron microscopy and x-ray diffraction data as a function of Ni-content (from 0.01 to 1 mol%) indicates that Ni ions promote the nanophase crystallization without affecting nanoparticle size (6 nm) and concentration (4 × 10(18) cm(-3)). Importantly, as shown by optical absorption spectra, all nickel ions enter into the nanophase, with a number of ions per nanocrystal that depends on the nanocrystal concentration and ranges from 1 to 10(2). Photoluminescence data indicate that fast non-radiative decay processes become relevant only at mean ion-ion distances shorter than 1.4 nm, which enables the incorporation of a few Ni ions per nanoparticle without too large a worsening of the light-emission efficiency. Indeed, at 0.1 mol% nickel, the room temperature quantum yield is 9%, with an effective bandwidth of 320 nm.
利用晶体中镍离子的近红外发光特性来设计新型宽带光学放大器的目标,需要识别合适的纳米结构玻璃,以嵌入掺镍纳米晶体并保持玻璃的可加工性。在这里,我们表明,在 Li(2)O-Na(2)O-Ga(2)O(3)-GeO(2)-SiO(2)玻璃(组成 7.5:2.5:20:35:35,熔点 1480°C,明显低于无锗硅酸盐)中掺杂 Ni,可以选择性地将镍离子嵌入尖晶石状氧化镓的热生长纳米晶体中。随着 Ni 含量(从 0.01 到 1 mol%)的透射电子显微镜和 X 射线衍射数据分析表明,Ni 离子促进了纳米相结晶,而不影响纳米颗粒的尺寸(6nm)和浓度(4×10(18)cm(-3))。重要的是,正如光吸收光谱所示,所有的镍离子都进入了纳米相,每个纳米晶体中的离子数取决于纳米晶体的浓度,范围从 1 到 10(2)。磷光数据表明,只有当平均离子-离子距离小于 1.4nm 时,快速非辐射衰减过程才变得相关,这使得每个纳米颗粒可以掺入少量的 Ni 离子,而不会对发光效率造成太大的恶化。事实上,在 0.1mol%镍的情况下,室温量子产率为 9%,有效带宽为 320nm。