Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), UMR 7357 CNRS and Université de Strasbourg, 23 rue du Loess, BP 20 CR, F-67037 Strasbourg Cedex 2, France.
Phys Chem Chem Phys. 2019 Oct 2;21(38):21407-21417. doi: 10.1039/c9cp01993f.
SnO2 is a transparent large band gap semiconductor, particularly interesting for optoelectronic and photovoltaic devices, mainly because its conduction can be easily tuned by doping or by modulating the amount of oxygen vacancies. Besides, rare earth doping was successfully exploited for up conversion properties. Here we report on the functionalization of SnO2 nanoparticles with optically active Yb3+ ions using the sol-gel method, which allows UV to NIR spectral (down) conversion. As starting solutions we used stable non-alkoxide metal-organic compounds, which is rather uncommon. Transmission electron microscopy analysis demonstrated the formation of small well-crystallized nanoparticles while X-ray photoelectron spectroscopy measurements have revealed that the Yb is well inserted in the host matrix and has a 3+ valence state. All nanoparticles present large absorption in the UV-visible range (250 to 550 nm) and a band gap that decreases down to 2.72 eV upon doping. The UV energy converted into NIR on the basis of efficient energy transfer from SnO2 to the Yb3+ ions ranges between 250 and 400 nm. Reference undoped SnO2 nanoparticles with a mean size of 20 nm allow converting UV light into broad visible emission centered at 650 nm. The incorporation of up to 3.5 at% of Yb3+ ions into the SnO2 host matrix results in a spectacular decrease of the nanoparticle size down to 6.6 nm. This allowed also the shift of the photoluminescence to NIR in the 970-1050 nm range. The energy level structure of Yb3+ in SnO2 was successfully determined from the deconvolution of the Yb emission. This emission is significantly enhanced by increasing the doping level. All optical measurements suggest that these nanoparticles can be efficiently used as down-shifting converters.
SnO2 是一种透明的宽带隙半导体,对光电子和光伏器件特别有吸引力,主要是因为其导电性可以通过掺杂或调节氧空位的数量来轻松调节。此外,稀土掺杂成功地用于上转换性能。在这里,我们报告了使用溶胶-凝胶法将光学活性 Yb3+离子功能化到 SnO2 纳米粒子上,该方法允许在紫外到近红外光谱(向下)转换。作为起始溶液,我们使用了稳定的非醇盐金属有机化合物,这是相当罕见的。透射电子显微镜分析表明形成了小的结晶良好的纳米粒子,而 X 射线光电子能谱测量表明 Yb 很好地插入到主体基质中并且具有 3+价态。所有纳米粒子在紫外可见范围内(250 至 550nm)均具有较大的吸收,并且掺杂后带隙降低至 2.72eV。基于 SnO2 到 Yb3+离子的有效能量转移,将 UV 能量转换为 NIR 的范围在 250 至 400nm 之间。具有 20nm 平均尺寸的参考未掺杂 SnO2 纳米粒子允许将紫外光转换为中心在 650nm 的宽可见发射。将多达 3.5at%的 Yb3+离子掺入 SnO2 主体基质中会导致纳米粒子尺寸显着减小至 6.6nm。这也允许将光致发光转移到近红外970-1050nm 范围内。通过对 Yb 发射的分解,成功确定了 Yb3+在 SnO2 中的能级结构。通过增加掺杂水平,显著增强了这种发射。所有光学测量都表明这些纳米粒子可以有效地用作下转换转换器。