Ultralow effective work function surfaces using diamondoid monolayers

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Electron emission is critical for a host of modern fabrication and analysis applications including mass spectrometry, electron imaging and nanopatterning. Here, we report that monolayers of diamondoids effectively confer dramatically enhanced field emission properties to metal surfaces. We attribute the improved emission to a significant reduction of the work function rather than a geometric enhancement. This effect depends on the particular diamondoid isomer, with [121]tetramantane-2-thiol reducing gold's work function from 5.1 eV to 1.60 ± 0.3 eV, corresponding to an increase in current by a factor of over 13,000. This reduction in work function is the largest reported for any organic species and also the largest for any air-stable compound1,2,3. This effect was not observed for sp3-hybridized alkanes, nor for smaller diamondoid molecules. The magnitude of the enhancement, molecule specificity and elimination of gold metal rearrangement precludes geometric factors as the dominant contribution. Instead, we attribute this effect to the stable radical cation of diamondoids. Our computed enhancement due to a positively charged radical cation was in agreement with the measured work functions to within ±0.3 eV, suggesting a new paradigm for low-work-function coatings based on the design of nanoparticles with stable radical cations.

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Figure 1: Field emission apparatus.
Figure 2: Diamondoid field emission.
Figure 3: Summary of the work functions obtained using the various experimental and computational techniques used in the present work.
Figure 4: Diamondoid radical cation mechanism.
Figure 5: Calculated field emission with radical cations.


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This work was supported by the Department of Energy Office of Basic Energy Sciences, Materials Sciences and Engineering Division (contract no. DE-AC02-76SF00515). The authors thank F. Wang and T. Carver for metal sputtering, S. Sun for assistance with UPS measurements and T. Deveraux and A. Sorini for discussions about the DFT model.

Author information

K.T.N., C.G., Z.S. and N.A.M. conceived and designed the electron emission experiments. J.E.D. and R.M.K.C. isolated and purified the unfunctionalized diamondoids. B.A.T., A.A.F. and P.R.S. designed and performed the thiol functionalization. K.T.N., C.G., J.D.F. and W.C. developed the attachment and monolayer UPS characterization. K.T.N., C.G. and N.A.M. performed the computations and analysed the emissions data. K.T.N., J.D.F. and N.A.M. performed the DFT calculations, and the paper was primarily written by K.T.N., C.G. and N.A.M., with edits by all authors.

Correspondence to Nicholas A. Melosh.

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Narasimha, K., Ge, C., Fabbri, J. et al. Ultralow effective work function surfaces using diamondoid monolayers. Nature Nanotech 11, 267–272 (2016) doi:10.1038/nnano.2015.277

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