Mukhina Maria V, Tresback Jason, Ondry Justin C, Akey Austin, Alivisatos A Paul, Kleckner Nancy
Department of Molecular and Cellular Biology, Harvard University, 52 Oxford Street, Cambridge, Massachusetts 02138,United States.
Center for Nanoscale Systems, Harvard University, 11 Oxford Street, Cambridge, Massachusetts 02138, United States.
ACS Nano. 2021 Mar 23;15(3):4115-4133. doi: 10.1021/acsnano.0c08890. Epub 2021 Feb 17.
Mechanoluminescent materials, which emit light in response to elastic deformation, are demanded for use as stress sensors. ZnS doped with Mn is known to exhibit one of the lowest reported thresholds for appearance of mechanoluminescence, with repeatable light emission under contact pressure <10 MPa. The physical basis for such behavior remains as yet unclear. Here, reliable microscopic detection of mechanoluminescence of single ZnS:Mn microparticles, in combination with nanoscale structural characterization, provides evidence that the mechanoluminescent properties of these particles result from interplay between a non-centrosymmetric crystal lattice and its defects, ., dislocations and stacking faults. Statistical analysis of the distributions of mechanoluminescence energy release trajectories reveals two distinct mechanisms of excitation: one attributable to a piezo-phototronic effect and the other due to dislocation motion. At pressures below 8.1 MPa, both mechanisms contribute to mechanoluminescent output, with a dominant contribution from the piezo-phototronic mechanism. In contrast, above 8.1 MPa, dislocation motion is the primary excitation source. For the piezo-phototronic mechanism, we propose a specific model that accounts for elastic ZnS:Mn mechanoluminescence under very low pressure. The charged interfaces in stacking faults lead to the presence of filled traps, which otherwise would be empty in the absence of the built-in electric field. Upon application of external stress, local enhancement of the piezoelectric field at the stacking faults' interfaces facilitates release of the trapped carriers and subsequent luminescence. This field enhancement explains how <10 MPa pressure produces thousands of photons.
机械发光材料可在弹性变形时发光,作为应力传感器有很大需求。已知掺杂锰的硫化锌表现出已报道的最低机械发光阈值之一,在接触压力<10兆帕时能实现可重复发光。这种现象的物理基础尚不清楚。在此,对单个硫化锌:锰微粒的机械发光进行可靠的微观检测,并结合纳米级结构表征,提供了证据表明这些微粒的机械发光特性源于非中心对称晶格与其缺陷(即位错和堆垛层错)之间的相互作用。对机械发光能量释放轨迹分布的统计分析揭示了两种不同的激发机制:一种归因于压光电效应,另一种归因于位错运动。在压力低于8.1兆帕时,两种机制都对机械发光输出有贡献,其中压光电机制起主要作用。相比之下,在8.1兆帕以上,位错运动是主要的激发源。对于压光电机制,我们提出了一个特定模型来解释极低压力下弹性硫化锌:锰的机械发光。堆垛层错中的带电界面导致存在填充陷阱,否则在没有内建电场的情况下这些陷阱是空的。施加外部应力时,堆垛层错界面处压电场的局部增强促进了捕获载流子的释放及随后的发光。这种场增强解释了<10兆帕的压力如何产生数千个光子。