Citation: Hantao Sun, Jianhui Liao, Shimin Hou. Single-Molecule Field-Effect Transistors with Graphene Electrodes and Covalent Pyrazine Linkers[J]. Acta Physico-Chimica Sinica, ;2021, 37(10): 190602. doi: 10.3866/PKU.WHXB201906027 shu

Single-Molecule Field-Effect Transistors with Graphene Electrodes and Covalent Pyrazine Linkers

Hantao Sun ^{1, 2} ,
Jianhui Liao ^1,, ,
Shimin Hou ^{1, 2,,}

1.
Key Laboratory for the Physics and Chemistry of Nanodevices, Department of Electronics, Peking University, Beijing 100871, China
2.
Centre for Nanoscale Science and Technology, Peking University, Beijing 100871, China

Corresponding author: Jianhui Liao, smhou@pku.edu.cn Shimin Hou, jianhui.liao@pku.edu.cn
Received Date: 5 June 2019
Revised Date: 18 June 2019
Accepted Date: 20 June 2019
Available Online: 1 July 2019
Fund Project: the National Natural Science Foundation of China 21573014the National Natural Science Foundation of China 61671021the National Natural Science Foundation of China 61621061the National Key R&D Program of China 2017YFA0204903the National Key R&D Program of China 2016YFA0201901

In single-molecule junctions, anchoring groups that connect the central molecule to the electrodes have profound effects on the mechanical and electrical properties of devices. The mechanical strength of the anchoring groups affects the device stability, while their electronic coupling strength influences the junction conductance and the conduction polarity. To design and fabricate high-performance single-molecule devices with graphene electrodes, it is highly desirable to explore robust anchoring groups that bond the central molecule to the graphene electrodes. Condensation of ortho-phenylenediamine terminated molecules with ortho-quinone moieties at the edges of graphene generates graphene-conjugated pyrazine units that can be employed as anchoring groups for the construction of molecular junctions with graphene electrodes. In this study, we investigated the fabrication and electrical characterization of single-molecule field-effect transistors (FETs) with graphene as the electrodes, pyrazine as the anchoring groups, and a heavily doped silicon substrate as the back-gate electrode. Graphene nano-gaps were fabricated by a high-speed feedback-controlled electro-burning method, and their edges were fully oxidized; thus, there were many ortho-quinone moieties at the edges. After the deposition of phenazine molecules with ortho-phenylenediamine terminals at both ends, a large current increase was observed, indicating that molecular junctions were formed with covalent pyrazine anchoring groups. The yield of the single-molecule devices was as high as 26%, demonstrating the feasibility of pyrazine as an effective anchoring group for graphene electrodes. Our electrical measurements show that the ten fabricated devices exhibited a distinct gating effect when a back-gate voltage was applied. However, the gate dependence of the conductance varied considerably from device to device, and three types of different gate modulation behaviors, including p-type, ambipolar, and n-type conduction, were observed. Our observations can be understood using a modified single-level model that takes into account the linear dispersion of graphene near the Dirac point; the unique band structure of graphene and the coupling strength of pyrazine with the graphene electrode both crucially affect the conduction polarity of single-molecule FETs. When the coupling strength of pyrazine with the graphene electrode is weak, the highest occupied molecular orbital (HOMO) of the central molecule dominates charge transport. Depending on the gating efficiencies of the HOMO level and the graphene states, devices can exhibit p-type or ambipolar conduction. In contrast, when the coupling is strong, the redistribution of electrons around the central molecule and the graphene electrodes leads to a realignment of the molecular levels, resulting in the lowest unoccupied molecular orbital (LUMO)-dominated n-type conduction. The high yield and versatility of the pyrazine anchoring groups are beneficial for the construction of single-molecule devices with graphene electrodes.
- Molecular electronics,
- Graphene electrode,
- Pyrazine anchoring group,
- Single-molecule field-effect transistor,
- Coupling strength
1. [1]
  Sun, L.; Diaz-Fernandez, Y. A.; Gschneidtner, T. A.; Westerlund, F.; Lara-Avila, S.; Moth-Poulsen, K. Chem. Soc. Rev. 2014, 43 (21), 7378. doi: 10.1039/C4CS00143E doi: 10.1039/C4CS00143E
2. [2]
  Su, T. A.; Neupane, M.; Steigerwald, M. L.; Venkataraman, L.; Nuckolls, C. Nat. Rev. Mater. 2016, 1, 16002. doi: 10.1038/natrevmats.2016.2 doi: 10.1038/natrevmats.2016.2
3. [3]
  Jia, C.; Guo, X. Chem. Soc. Rev. 2013, 42, 5642. doi: 10.1039/C3CS35527F doi: 10.1039/C3CS35527F
4. [4]
  Xin, N.; Guan, J.; Zhou, C.; Chen, X.; Gu, C.; Li, Y.; Ratner, M. A.; Nitzan, A.; Stoddart, J. F.; Guo, X. Nat. Rev. Phys. 2019, 1, 211. doi: 10.1038/s42254-019-0022-x doi: 10.1038/s42254-019-0022-x
5. [5]
  Metzger, R. M. Chem. Rev. 2015, 115, 5056. doi: 10.1021/cr500459d doi: 10.1021/cr500459d
6. [6]
  Xiang, D.; Wang, X.; Jia, C.; Lee, T.; Guo, X. Chem. Rev. 2016, 116, 4318. doi: 10.1021/acs.chemrev.5b00680 doi: 10.1021/acs.chemrev.5b00680
7. [7]
  Strachan, D. R.; Smith, D. E.; Fischbein, M. D.; Johnston, D. E.; Guiton, B. S.; Drndić, M.; Bonnell, D. A.; Johnson, A. T. Nano Lett. 2006, 6, 441. doi: 10.1021/nl052302a doi: 10.1021/nl052302a
8. [8]
  O'Neill, K.; Osorio, E. A.; van der Zant, H. S. J. Appl. Phys. Lett. 2007, 90, 133109. doi: 10.1063/1.2716989 doi: 10.1063/1.2716989
9. [9]
  Perrin, M. L.; Burzuri, E.; van der Zant, H. S. Chem. Soc. Rev. 2015, 44, 902. doi: 10.1039/C4CS00231H doi: 10.1039/C4CS00231H
10. [10]
  Jia, C.; Ma, B.; Xin, N.; Guo, X. Acc. Chem. Res. 2015, 48, 2565. doi: 10.1021/acs.accounts.5b00133 doi: 10.1021/acs.accounts.5b00133
11. [11]
  Prins, F.; Barreiro, A.; Ruitenberg, J. W.; Seldenthuis, J. S.; Aliaga-Alcalde, N.; Vandersypen, L. M.; van der Zant, H. S. Nano Lett. 2011, 11, 4607. doi: 10.1021/nl202065x doi: 10.1021/nl202065x
12. [12]
  Island, J. O.; Holovchenko, A.; Koole, M.; Alkemade, P. F.; Menelaou, M.; Aliaga-Alcalde, N.; Burzuri, E.; van der Zant, H. S. J. Phys.: Condens. Matter 201, 26, 474205. doi: 10.1088/0953-8984/26/47/474205 doi: 10.1088/0953-8984/26/47/474205
13. [13]
  Lau, C. S.; Mol, J. A.; Warner, J. H.; Briggs, G. A. Phys. Chem. Chem. Phys. 2014, 16, 20398. doi: 10.1039/C4CP03257H doi: 10.1039/C4CP03257H
14. [14]
  Sun, H.; Jiang, Z.; Xin, N.; Guo, X.; Hou, S.; Liao, J. ChemPhysChem 2018, 19, 2258. doi: 10.1002/cphc.201800220 doi: 10.1002/cphc.201800220
15. [15]
  Cao, Y.; Dong, S.; Liu, S.; He, L.; Gan, L.; Yu, X.; Steigerwald, M. L.; Wu, X.; Liu, Z.; Guo, X. Angew. Chem. Int. Ed. 2012, 124, 12394. doi: 10.1002/anie.201205607 doi: 10.1002/anie.201205607
16. [16]
  Mol, J. A.; Lau, C. S.; Lewis, W. J.; Sadeghi, H.; Roche, C.; Cnossen, A.; Warner, J. H.; Lambert, C. J.; Anderson, H. L.; Briggs, G. A. D. Nanoscale 2015, 7, 13181. doi: 10.1039/C5NR03294F doi: 10.1039/C5NR03294F
17. [17]
  Xu, Q.; Scuri, G.; Mathewson, C.; Kim, P.; Nuckolls, C.; Bouilly, D. Nano Lett. 2017, 17, 5335. doi: 10.1021/acs.nanolett.7b01745 doi: 10.1021/acs.nanolett.7b01745
18. [18]
  Xin, N.; Li, X.; Jia, C.; Gong, Y.; Li, M.; Wang, S.; Zhang, G.; Yang, J.; Guo, X. Angew. Chem. 2018, 130, 14222. doi: 10.1002/ange.201807465 doi: 10.1002/ange.201807465
19. [19]
  Sadeghi, H.; Sangtarash, S.; Lambert, C. Nano Lett. 2017, 17 (8), 4611. doi: 10.1021/acs.nanolett.7b01001 doi: 10.1021/acs.nanolett.7b01001
20. [20]
  Limburg, B.; Thomas, J. O.; Holloway, G.; Sadeghi, H.; Sangtarash, S.; Hou, I. C. Y.; Cremers, J.; Narita, A.; Müllen, K.; Lambert, C. J. Adv. Funct. Mater. 2018, 28, 1803629. doi: 10.1002/adfm.201803629 doi: 10.1002/adfm.201803629
21. [21]
  Guo, X.; Small, J. P.; Klare, J. E.; Wang, Y.; Purewal, M. S.; Tam, I. W.; Hong, B. H.; Caldwell, R.; Huang, L.; O'brien, S. Science 2006, 311, 356. doi: 10.1126/science.1120986 doi: 10.1126/science.1120986
22. [22]
  Cao, Y.; Dong, S.; Liu, S.; Liu, Z.; Guo, X. Angew. Chem. Int. Ed. 2013, 125, 3998. doi: 10.1002/anie.201208210 doi: 10.1002/anie.201208210
23. [23]
  Jia, C.; Migliore, A.; Xin, N.; Huang, S.; Wang, J.; Yang, Q.; Wang, S.; Chen, H.; Wang, D.; Feng, B. Science 2016, 352, 1443. doi: 10.1126/science.aaf6298 doi: 10.1126/science.aaf6298
24. [24]
  Lörtscher, E. Nat. Nanotech. 2013, 8, 381. doi: 10.1038/nnano.2013.105 doi: 10.1038/nnano.2013.105
25. [25]
  Ratner, M. Nat. Nanotech. 2013, 8, 378. doi: 10.1038/nnano.2013.110 doi: 10.1038/nnano.2013.110
26. [26]
  Fukushima, T.; Drisdell, W.; Yano, J.; Surendranath, Y. J. Am. Chem. Soc. 2015, 137, 10926. doi: 10.1021/jacs.5b06737 doi: 10.1021/jacs.5b06737
27. [27]
  Oh, S.; Gallagher, J. R.; Miller, J. T.; Surendranath, Y. J. Am. Chem. Soc. 2016, 138, 1820. doi: 10.1021/jacs.5b13080 doi: 10.1021/jacs.5b13080
28. [28]
  Ricke, N. D.; Murray, A. T.; Shepherd, J. J.; Welborn, M. G.; Fukushima, T.; Van Voorhis, T.; Surendranath, Y. ACS Catal. 2017, 7, 7680. doi: 10.1021/acscatal.7b03086 doi: 10.1021/acscatal.7b03086
29. [29]
  Jackson, M. N.; Oh, S.; Kaminsky, C. J.; Chu, S. B.; Zhang, G.; Miller, J. T.; Surendranath, Y. J. Am. Chem. Soc. 2018, 140, 1004. doi: 10.1021/jacs.7b10723 doi: 10.1021/jacs.7b10723
30. [30]
  Gajiwala, H.; Zand, R. Polymer 2000, 41, 2009. doi: 10.1016/S0032-3861(99)00371-7 doi: 10.1016/S0032-3861(99)00371-7
31. [31]
  Bindewald, E.; Lorenz, R.; Hübner, O.; Brox, D.; Herten, D.-P.; Kaifer, E.; Himmel, H. J. Dalt. Trans. 2015, 44, 3467. doi: 10.1039/C4DT03572K doi: 10.1039/C4DT03572K
32. [32]
  Sun, H.; Liu, X.; Su, Y.; Deng, B.; Peng, H.; Decurtins, S.; Sanvito, S.; Liu, S. X.; Hou, S.; Liao, J. Nanoscale 2019, doi: 10.1039/C9NR01551E doi: 10.1039/C9NR01551E
33. [33]
  Hihath, J.; Bruot, C.; Nakamura, H.; Asai, Y.; Díez-Pérez, I.; Lee, Y.; Yu, L.; Tao, N. ACS Nano 2011, 5, 8331. doi: 10.1021/nn2030644 doi: 10.1021/nn2030644
34. [34]
  Lörtscher, E.; Gotsmann, B.; Lee, Y.; Yu, L.; Rettner, C.; Riel, H. ACS Nano 2012, 6, 4931. doi: 10.1021/nn300438h doi: 10.1021/nn300438h
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