Department of Chemistry, University of Alberta , 11421 Saskatchewan Dr., Edmonton, Alberta T6G 2M9, Canada.
National Institute for Nanotechnology , 11421 Saskatchewan Dr., Edmonton, Alberta T6G 2M9, Canada.
J Am Chem Soc. 2016 Jan 27;138(3):722-5. doi: 10.1021/jacs.5b10018. Epub 2016 Jan 14.
Visible light emission was observed for molecular junctions containing 5-19 nm thick layers of aromatic molecules between carbon contacts and correlated with their current-voltage behaviors. Their emission was compared to that from Al/AlOx/Au tunnel junctions, which has been previously attributed to transport of carriers across the AlOx layer to yield "hot carriers" which emit light as they relax within the Au contact. The maximum emitted photon energy is equal to the applied bias for the case of coherent tunneling, and such behavior was observed for light emission from AlOx and thin (<5 nm) molecular junctions. For thicker films, the highest energy observed for emitted photons is less than eVapp and exhibits an energy loss that is strongly dependent on molecular layer structure and thickness. For the case of nitroazobenzene junctions, the energy loss is linear with the molecular layer thickness, with a slope of 0.31 eV/nm. Energy loss rules out coherent tunneling as a transport mechanism in the thicker films and provides a direct measure of the electron energy after it traverses the molecular layer. The transition from elastic transport in thin films to "lossy" transport in thick films confirms that electron hopping is involved in transport and may provide a means to distinguish between various hopping mechanisms, such as activated electron transport, variable range hopping, and Poole Frankel transport.
观察到含有 5-19nm 厚芳香族分子层的分子结在碳接触之间具有可见光发射,并与它们的电流-电压行为相关联。将它们的发射与之前归因于载流子穿过 AlOx 层传输以产生“热载流子”的 Al/AlOx/Au 隧道结的发射进行了比较,“热载流子”在 Au 接触中弛豫时会发光。对于相干隧道的情况,最大发射光子能量等于施加的偏压,并且在 AlOx 和薄(<5nm)分子结的光发射中观察到这种行为。对于较厚的薄膜,观察到的发射光子的最高能量小于 eVapp,并表现出强烈依赖于分子层结构和厚度的能量损失。对于硝基偶氮苯结的情况,能量损失与分子层厚度呈线性关系,斜率为 0.31eV/nm。能量损失排除了相干隧道作为较厚薄膜中传输机制的可能性,并提供了电子穿过分子层后的能量的直接测量。从薄膜中的弹性传输到厚膜中的“损耗”传输的转变证实了电子跳跃参与了传输,并且可能提供了一种区分各种跳跃机制(例如激活电子传输、变程跳跃和 Poole Frankel 传输)的手段。