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Title: Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor

Abstract

The rational bottom-up synthesis of atomically defined graphene nanoribbon (GNR) heterojunctions represents an enabling technology for the design of nanoscale electronic devices. Synthetic strategies used thus far have relied on the random copolymerization of two electronically distinct molecular precursors to yield GNR heterojunctions. In this paper we report the fabrication and electronic characterization of atomically precise GNR heterojunctions prepared through late-stage functionalization of chevron GNRs obtained from a single precursor. Post-growth excitation of fully cyclized GNRs induces cleavage of sacrificial carbonyl groups, resulting in atomically well-defined heterojunctions within a single GNR. The GNR heterojunction structure was characterized using bond-resolved scanning tunnelling microscopy, which enables chemical bond imaging at T = 4.5 K. Scanning tunnelling spectroscopy reveals that band alignment across the heterojunction interface yields a type II heterojunction, in agreement with first-principles calculations. Finally, GNR heterojunction band realignment proceeds over a distance less than 1 nm, leading to extremely large effective fields.

Authors:
 [1];  [1];  [1];  [2];  [3];  [1];  [1];  [2];  [2];  [4];  [1];  [1];  [4];  [3];  [5];  [6]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States). Dept. of Physics
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  3. Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  4. Univ. of Texas, Austin, TX (United States). Center for Computational Materials. Inst. for Computational Engineering and Sciences. Dept. of Physics. Dept. of Chemical Engineering
  5. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division. Kavli Energy NanoSciences Inst.
  6. Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division. Kavli Energy NanoSciences Inst.
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR); Defense Advanced Research Projects Agency (DARPA); US Army Research Laboratory (USARL); Army Research Office (ARO); National Science Foundation (NSF); Welch Foundation; Swiss National Science Foundation (SNSF)
OSTI Identifier:
1461121
Grant/Contract Number:  
AC02-05CH11231; SC0010409; FG02-06ER46286; W911NF-15-1-0237; DMR-1508412; F-1837; P2ELP2-151852
Resource Type:
Accepted Manuscript
Journal Name:
Nature Nanotechnology
Additional Journal Information:
Journal Volume: 12; Journal Issue: 11; Journal ID: ISSN 1748-3387
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; electronic properties and devices; electronic properties and materials

Citation Formats

Nguyen, Giang D., Tsai, Hsin-Zon, Omrani, Arash A., Marangoni, Tomas, Wu, Meng, Rizzo, Daniel J., Rodgers, Griffin F., Cloke, Ryan R., Durr, Rebecca A., Sakai, Yuki, Liou, Franklin, Aikawa, Andrew S., Chelikowsky, James R., Louie, Steven G., Fischer, Felix R., and Crommie, Michael F. Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor. United States: N. p., 2017. Web. doi:10.1038/nnano.2017.155.
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Nguyen, Giang D., Tsai, Hsin-Zon, Omrani, Arash A., Marangoni, Tomas, Wu, Meng, Rizzo, Daniel J., Rodgers, Griffin F., Cloke, Ryan R., Durr, Rebecca A., Sakai, Yuki, Liou, Franklin, Aikawa, Andrew S., Chelikowsky, James R., Louie, Steven G., Fischer, Felix R., & Crommie, Michael F. Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor. United States. https://doi.org/10.1038/nnano.2017.155
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Nguyen, Giang D., Tsai, Hsin-Zon, Omrani, Arash A., Marangoni, Tomas, Wu, Meng, Rizzo, Daniel J., Rodgers, Griffin F., Cloke, Ryan R., Durr, Rebecca A., Sakai, Yuki, Liou, Franklin, Aikawa, Andrew S., Chelikowsky, James R., Louie, Steven G., Fischer, Felix R., and Crommie, Michael F. Mon . "Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor". United States. https://doi.org/10.1038/nnano.2017.155. https://www.osti.gov/servlets/purl/1461121.
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@article{osti_1461121,
title = {Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor},
author = {Nguyen, Giang D. and Tsai, Hsin-Zon and Omrani, Arash A. and Marangoni, Tomas and Wu, Meng and Rizzo, Daniel J. and Rodgers, Griffin F. and Cloke, Ryan R. and Durr, Rebecca A. and Sakai, Yuki and Liou, Franklin and Aikawa, Andrew S. and Chelikowsky, James R. and Louie, Steven G. and Fischer, Felix R. and Crommie, Michael F.},
abstractNote = {The rational bottom-up synthesis of atomically defined graphene nanoribbon (GNR) heterojunctions represents an enabling technology for the design of nanoscale electronic devices. Synthetic strategies used thus far have relied on the random copolymerization of two electronically distinct molecular precursors to yield GNR heterojunctions. In this paper we report the fabrication and electronic characterization of atomically precise GNR heterojunctions prepared through late-stage functionalization of chevron GNRs obtained from a single precursor. Post-growth excitation of fully cyclized GNRs induces cleavage of sacrificial carbonyl groups, resulting in atomically well-defined heterojunctions within a single GNR. The GNR heterojunction structure was characterized using bond-resolved scanning tunnelling microscopy, which enables chemical bond imaging at T = 4.5 K. Scanning tunnelling spectroscopy reveals that band alignment across the heterojunction interface yields a type II heterojunction, in agreement with first-principles calculations. Finally, GNR heterojunction band realignment proceeds over a distance less than 1 nm, leading to extremely large effective fields.},
doi = {10.1038/nnano.2017.155},
journal = {Nature Nanotechnology},
number = 11,
volume = 12,
place = {United States},
year = {Mon Sep 25 00:00:00 EDT 2017},
month = {Mon Sep 25 00:00:00 EDT 2017}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1038/nnano.2017.155
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Cited by: 135 works
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Figures / Tables:

Figure 1 Figure 1: Bottom-up fabrication of fluorenone GNRs. a, Schematic representation of the synthesis of fluorenone GNRs from molecular precursor 1. b, Representative STM topographic image of a fluorenone GNR (CO functionalized tip, Vs = −1.0 V, It = 10 pA). c, BRSTM image of the same fluorenone GNR as inmore » b. The covalent bond network within the GNR is clearly resolved (Vs = 40 mV, It = 10 pA, Vac = 20 mV, f = 401 Hz).« less
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