Department of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2L 3G1, Canada.
J Am Chem Soc. 2011 May 4;133(17):6711-9. doi: 10.1021/ja111514u. Epub 2011 Apr 8.
We demonstrate compositionally tunable photoluminescence in complex transparent conducting oxide nanocrystals. Alloyed gallium indium oxide (GIO) nanocrystals with variable crystal structures are prepared by a colloidal method throughout the full composition range and studied by different structural and spectroscopic methods, including photoluminescence and X-ray absorption. The structures and sizes of the GIO nanocrystals can be simultaneously controlled, owing to the difference in the growth kinetics of In(2)O(3) and Ga(2)O(3) nanocrystals and the polymorphic nature of both materials. Using the synthesized nanocrystal series, we demonstrate the structural and compositional dependences of the photoluminescence of GIO nanocrystals. These dependences, induced by the interactions between specific defect sites acting as electron donors and acceptors, are used to achieve broad emission tunability in the visible spectral range at room temperature. The nature of the photoluminescence is identified as donor-acceptor pair recombination and changes with increasing indium content owing to the changes in the energy states of, and interactions between, donors and acceptors. Structural analysis of GIO nanocrystals by extended X-ray absorption fine structure spectroscopy reveals that In(3+) occupies only octahedral, rather than tetrahedral, sites in the spinel-type γ-Ga(2)O(3) nanocrystal host lattice, until reaching the substitutional incorporation limit of ca. 25%. The emission decay dynamics is also strongly influenced by the nanocrystal structure and composition. The oxygen vacancy defects, responsible for the observed photoluminescence properties, are also implicated in other functional properties, particularly conductivity, enabling the application of colloidal GIO nanocrystals as integrated optoelectronic materials.
我们展示了在复杂透明导电氧化物纳米晶体中具有组成可调的光致发光。通过胶体方法制备了具有可变晶体结构的合金化镓铟氧化物(GIO)纳米晶体,并通过不同的结构和光谱方法进行了研究,包括光致发光和 X 射线吸收。由于 In(2)O(3)和 Ga(2)O(3)纳米晶体的生长动力学差异以及两种材料的多晶型性质,可以同时控制 GIO 纳米晶体的结构和尺寸。利用合成的纳米晶体系列,我们证明了 GIO 纳米晶体的光致发光的结构和组成依赖性。这些依赖性是由作为电子供体和受体的特定缺陷位点之间的相互作用引起的,可用于在室温下实现可见光范围内的宽发射可调谐性。光致发光的性质被确定为施主-受主对复合,并随着铟含量的增加而变化,这是由于施主和受体的能量状态和相互作用的变化所致。通过扩展 X 射线吸收精细结构光谱对 GIO 纳米晶体的结构分析表明,In(3+)仅占据尖晶石型 γ-Ga(2)O(3)纳米晶主体晶格中的八面体而不是四面体位置,直到达到约 25%的替代掺入极限。发射衰减动力学也受到纳米晶体结构和组成的强烈影响。负责观察到的光致发光性质的氧空位缺陷也与其他功能性质有关,特别是导电性,使胶体 GIO 纳米晶体能够作为集成光电材料应用。