Imaging the aftermath of hot electron dynamics with molecular nanoprobe experiments

Session

Atomic and Molecular Resolution Phenomena via AFM, STM and Scanning Probes

Authors

Dr Peter Sloan (1, 3), Pieter Keenan (2, 1, 3), Dr Kristina Rusimova (2, 1, 3)

Affiliations

1. Centre for Nanoscience and Nanotechnology, University of Bath
2. Centre for Photonics and Photonic Materials, University of Bath
3. Department of Physics, University of Bath

Keywords

hot electrons, STM, nanoprobe, transport, single molecules

Abstract text

Understanding the ultra-fast transport properties of hot charge carriers is of significant importance both fundamentally and technically in applications like solar cells and transistors. However, direct measurement of charge transport at the relevant nanometre length scales is challenging with only a few experimental methods demonstrated to date. Here we report on molecular nanoprobe experiments on the Si(111)-7×7 at room temperature where charge injected from the tip of a scanning tunnelling microscope (STM) travels laterally across a surface and induces single adsorbate toluene molecules to react over length scales of tens of nanometres (see Fig. 1) (1-3). A simple model is developed for the fraction of the tunnelling current captured into each of the surface electronic bands with input from only high-resolution scanning tunnelling spectroscopy (STS) of the clean Si(111)-7×7 surface. This model is quantitatively linked to the voltage dependence of the molecular nanoprobe experiments through a single manipulation probability (i.e. fitting parameter) per state. This model fits the measured data and gives explanation to the measured voltage onsets, exponential increase in the measured manipulation probabilities and plateau at higher voltages. It also confirms an ultrafast relaxation to the bottom of a surface band for the injected charge after injection, but before the nonlocal spread across the surface (4).

Fig. 1 Nonlocal molecular manipulation induced by charge injection from an STM tip. a and b 50 nm×50 nm images (+1 V, 100 pA) of Si(111) − 7 × 7 partially covered with toluene molecules (dark-spots) before (a) and after (b) hole injection (−1.4 V, 250 pA, 20 s) into the white ×. Circles indicate the extents of ballistic (red) and diffusive (pink) hot-electron transport.

References

(1) Lock, D., Rusimova, K. R., Pan, T. L., Palmer, R. E. and Sloan, P. A., Nat Comms, 6, 8365 (2015).

(2) Rusimova, K. R., Bannister, N., Harrison, P., Lock, D., Crampin, S., Palmer, R. E., Sloan, P. A., Nat Comms, 7, 12839 (2016).

(3) Rusimova, K. R., Purkiss, R. M., Howes, R., Lee, F., Crampin, S., Sloan, P. A., Science, 361 (6406), 1012-1016 (2018).

(4) Sloan, P. A. and Rusimova, K. R., Nanoscale Advances, 4(22), 4880-4885 (2022).