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A molecular shift register made using tunable charge patterns in one-dimensional molecular arrays on graphene

Abstract

The ability to tune the electronic properties of molecular arrays is an important step in the development of molecule-scale electronic devices. However, control over internal device charge distributions by tuning interactions between molecules has proved challenging. Here, we show that gate-tunable charge patterning can occur in one-dimensional molecular arrays on graphene field-effect transistors. One-dimensional molecular arrays are fabricated using an edge-templated self-assembly process that allows organic molecules (F4TCNQ) to be precisely positioned on graphene devices. The charge configurations of the molecular arrays can be reversibly switched between different collective charge states by tuning the graphene Fermi level via a back-gate electrode. Charge pinning at the ends of the molecular arrays allows the charge state of the entire array to be controlled by adding or removing an edge molecule and changing the total number of molecules in an array between odd and even integers. Charge patterns altered in this way propagate down the array in a cascade effect, allowing the array to function as a charge-based molecular shift register. An extended multi-site Anderson impurity model is used to quantitatively explain this behaviour.

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Fig. 1: Scanned probe images of a 1D F4TCNQ molecular array.
Fig. 2: Gate-tunable charge patterns in a 1D molecular array.
Fig. 3: Molecular orbital energy in a 1D array.
Fig. 4: 1D array charge pattern control via molecular manipulation.

Data availability

The data that support the findings of this study are available from the corresponding author on reasonable request.

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Acknowledgements

This work was funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under contract no. DE-AC02-05-CH11231 (Nanomachine program KC1203; STM imaging and spectroscopy and theory). Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05-CH11231 (graphene growth and growth characterization). Device fabrication was supported by National Science Foundation grant no. DMR-1807233. The GW calculations were supported by the National Science Foundation grant no. DMR-1926004. K.W. and T.T. acknowledges support from MEXT Japan grant no. JPMXP0112101001 (characterization of BN crystals) and CREST, JST no. JPMJCR15F3 (growth of BN crystals). A.A.O. acknowledges support from the Swiss National Science Foundation (SNSF) Postdoctoral Research Fellowship under grant no. P2ELP2-151852. J. Lischner acknowledges support from ARCHER UK National Supercomputing Service under EPSRC EP/L000202 and EP/R029431 (simulations). J. Lu acknowledges support from the Singapore Ministry of Education grant no. R-143-000-A06-112 (data analysis). H.-Z.T. acknowledges postdoctoral fellowship support from the Shenzhen Peacock Plan (grant nos. KQJSCX20170727100802505 and KQTD2016053112042971).

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Contributions

H.-Z.T. and J. Lu designed and performed the experiments and analysed the data. J. Lischner performed the theoretical modelling through a multi-site Anderson impurity model. A.A.O., F.L., A.S.A., S.W., C.K., C.S. and A.R. helped with the experiments and gave technical support and conceptual advice. A.Z., K.C.N., J.C. and W.-W.C. facilitated sample fabrication. K.W. and T.T. gave technical support and grew h-BN for the device. S.G.L. supervised the theoretical calculations. M.F.C. supervised the experiments and data analysis. H.-Z.T., J. Lischner, J. Lu and M.F.C. wrote the manuscript.

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Correspondence to Michael F. Crommie.

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Supplementary Figs. 1–5 and note.

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Tsai, HZ., Lischner, J., Omrani, A.A. et al. A molecular shift register made using tunable charge patterns in one-dimensional molecular arrays on graphene. Nat Electron 3, 598–603 (2020). https://doi.org/10.1038/s41928-020-00479-4

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