Blown Bubble Assembly and in situ Fabrication of Sausage-Like ...
Blown Bubble Assembly and in situ Fabrication of Sausage-Like Graphene Nanotubes Containing Copper Nano-Blocks Shiting Wu,1 Long Yang,2 Mingchu Zou,1 Yanbing Yang,3 Mingde Du,2 Wenjing Xu,1 Liusi Yang,1 Ying Fang,2 Anyuan Cao1* 1
Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871, P.
R. China 2
National Center for Nanoscience and Technology, 11 Beiyitiao Street, Zhongguancun, Beijing 100190, P. R.
China 3
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China
* Corresponding author: [email protected]
Supporting Information Figure S1 Figure S2 Figure S3 Figure S4 Figure S5 Figure S6 Figure S7 Table S1 Figure S8 Figure S9 Figure S10 Figure S11
1
Figure S1. Characterization of Cu nanowires synthesized through hydrothermal method. (a) SEM image of the as-synthesized Cu nanowires. (b) Histogram of the Cu nanowire length distribution. Most nanowires have length in the range of 20-30 m. (c) XRD pattern of the single-crystalline Cu naowires with lattice faces labeled; (d) TEM image of an individual Cu nanowire. (e) High-resolution TEM image of the Cu nanowire. Inset is histogram of the nanowire diameter distribution, and the average diameter of the nanowire is about 150 nm. (f) Selected area electron diffraction pattern of Cu nanowires.
Figure S2. Cu nanowire arrays and assembled sausage-like GNT@CuNB nanostructures. (a) Optical image of Cu nanowire arrays embedded in PMMA bubble film. (b) Optical image and (c) SEM image of the assembled sausages by thermal annealing process. Those assembled GNT@CuNB sausages were fabricated in the same location of Cu nanowire arrays with similar density. (d) Optical image of crossed Cu nanowires. Inset is the enlarged image of (d). 2
Figure S3. Diameter distribution histogram of (a) the initial Cu nanowires, (b) the CuNBs within GNTs synthesized by being heated at 900 oC for 15 minutes, and (c) for 30 minutes.
Figure S4. Optical transmittances of the 2-layer/4-layer Cu nanowire and GNT@CuNB networks. Inset is photo of the samples transferred on quartz.
Figure S5. Characterization of the outer graphene layer in the GNT@CuNB nanostructure. (a) Raman spectra of the outer GNT synthesized under different annealing temperatures (from 700 to 1000 oC). (b) High resolution TEM image of the hollow GNT by dissolving the inner CuNBs, showing 6 to 7 graphene layers. (c) High resolution TEM image of the hollow GNT where the elected area diffraction pattern (inset) is recorded. 3
Figure S6. Formation of the sausage-like GNTs@CuNB nanostructures. (a) Illustration of the formation process. (b-e) SEM images of the four stages in the formation process: (b) nanonecklace; (c) nanobottle; (d) nanocoreshell; (e) nanosphere. SEM images of (f) tube-like graphene, (g) GNT with crack and (h) unzipped GNT.
Figure S7. (a) SEM image of the G-Cu-(G)-Cu device containing one-side filled channel (Cu-G) on the left and two-side filled channel (Cu-(G)-Cu) on the right. (b) I-V curves of the two channels.
4
Table S1 Relation between the filling ratio of CuNB in the GNT sausage and the linear resistance of the sausage. Length of Cu NB (L1, μm)
Distance between two electrodes (L2, μm)
Filling ratio L1/L2 (%)
Line resistance (RL, k/μm)
Cu-Cu channel in the Cu-Cu(G)-G device
2.8
2.8
100
6.99
Cu-G channel in the G-Cu-(G)-Cu device
10.13
13.91
72.83
27.71
Cu-G channel in the G-G-Cu device
4.85
7.82
62.02
29.08
Cu-(G)-Cu channel in the G-Cu-(G)-Cu device
2.52
7.72
32.64
44.05
Figure S8. Relation between the filling ratio of CuNB in the GNT sausage and the linear resistance of the sausage. If there is at least one electrode placed on the part of GNT@CuNB, the more CuNB is encapsulated in, the lower is the linear resistance of the GNT sausage.
5
Figure S9. Drain current-gate voltage curves of (a) the Cu-G channel and (b) the G-G channel in the G-G-Cu device; (c) the Cu-Cu channel and (d) the G-G channel in the Cu-Cu(G)-G device; (e) the Cu-(G)-Cu channel and (f) the Cu-G channel in the G-Cu-(G)-Cu device; (g-i) B-C, A-C and A-B in the GNT-GNT crossed configuration at bias drain voltage=1V, 2V, 3V, 4V and 5V, respectively.
Figure S10. (a) SEM image, (b) optical image and (c) I-V curves of the GNT-CuNB crossed sausages. (d-f) Drain current-gate voltage curves between A-C, A-B and B-C at bias drain voltage=1V, 2V, 3V, 4V and 5V, respectively. (g-i) I-V curves of the GNT-CuNB crossed sausages measured after 165 days between A-C, A-B and B-C. 6
Figure S11. (a) SEM image of the CuNB-CuNB crossed sausages. (b) I-V curves of the junction measured at different electrodes (A, B, C). Inset is the optical image of the CuNB-CuNB crossed sausages.
7
Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871, P.
R. China 2
National Center for Nanoscience and Technology, 11 Beiyitiao Street, Zhongguancun, Beijing 100190, P. R.
China 3
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China
* Corresponding author: [email protected]
Supporting Information Figure S1 Figure S2 Figure S3 Figure S4 Figure S5 Figure S6 Figure S7 Table S1 Figure S8 Figure S9 Figure S10 Figure S11
1
Figure S1. Characterization of Cu nanowires synthesized through hydrothermal method. (a) SEM image of the as-synthesized Cu nanowires. (b) Histogram of the Cu nanowire length distribution. Most nanowires have length in the range of 20-30 m. (c) XRD pattern of the single-crystalline Cu naowires with lattice faces labeled; (d) TEM image of an individual Cu nanowire. (e) High-resolution TEM image of the Cu nanowire. Inset is histogram of the nanowire diameter distribution, and the average diameter of the nanowire is about 150 nm. (f) Selected area electron diffraction pattern of Cu nanowires.
Figure S2. Cu nanowire arrays and assembled sausage-like GNT@CuNB nanostructures. (a) Optical image of Cu nanowire arrays embedded in PMMA bubble film. (b) Optical image and (c) SEM image of the assembled sausages by thermal annealing process. Those assembled GNT@CuNB sausages were fabricated in the same location of Cu nanowire arrays with similar density. (d) Optical image of crossed Cu nanowires. Inset is the enlarged image of (d). 2
Figure S3. Diameter distribution histogram of (a) the initial Cu nanowires, (b) the CuNBs within GNTs synthesized by being heated at 900 oC for 15 minutes, and (c) for 30 minutes.
Figure S4. Optical transmittances of the 2-layer/4-layer Cu nanowire and GNT@CuNB networks. Inset is photo of the samples transferred on quartz.
Figure S5. Characterization of the outer graphene layer in the GNT@CuNB nanostructure. (a) Raman spectra of the outer GNT synthesized under different annealing temperatures (from 700 to 1000 oC). (b) High resolution TEM image of the hollow GNT by dissolving the inner CuNBs, showing 6 to 7 graphene layers. (c) High resolution TEM image of the hollow GNT where the elected area diffraction pattern (inset) is recorded. 3
Figure S6. Formation of the sausage-like GNTs@CuNB nanostructures. (a) Illustration of the formation process. (b-e) SEM images of the four stages in the formation process: (b) nanonecklace; (c) nanobottle; (d) nanocoreshell; (e) nanosphere. SEM images of (f) tube-like graphene, (g) GNT with crack and (h) unzipped GNT.
Figure S7. (a) SEM image of the G-Cu-(G)-Cu device containing one-side filled channel (Cu-G) on the left and two-side filled channel (Cu-(G)-Cu) on the right. (b) I-V curves of the two channels.
4
Table S1 Relation between the filling ratio of CuNB in the GNT sausage and the linear resistance of the sausage. Length of Cu NB (L1, μm)
Distance between two electrodes (L2, μm)
Filling ratio L1/L2 (%)
Line resistance (RL, k/μm)
Cu-Cu channel in the Cu-Cu(G)-G device
2.8
2.8
100
6.99
Cu-G channel in the G-Cu-(G)-Cu device
10.13
13.91
72.83
27.71
Cu-G channel in the G-G-Cu device
4.85
7.82
62.02
29.08
Cu-(G)-Cu channel in the G-Cu-(G)-Cu device
2.52
7.72
32.64
44.05
Figure S8. Relation between the filling ratio of CuNB in the GNT sausage and the linear resistance of the sausage. If there is at least one electrode placed on the part of GNT@CuNB, the more CuNB is encapsulated in, the lower is the linear resistance of the GNT sausage.
5
Figure S9. Drain current-gate voltage curves of (a) the Cu-G channel and (b) the G-G channel in the G-G-Cu device; (c) the Cu-Cu channel and (d) the G-G channel in the Cu-Cu(G)-G device; (e) the Cu-(G)-Cu channel and (f) the Cu-G channel in the G-Cu-(G)-Cu device; (g-i) B-C, A-C and A-B in the GNT-GNT crossed configuration at bias drain voltage=1V, 2V, 3V, 4V and 5V, respectively.
Figure S10. (a) SEM image, (b) optical image and (c) I-V curves of the GNT-CuNB crossed sausages. (d-f) Drain current-gate voltage curves between A-C, A-B and B-C at bias drain voltage=1V, 2V, 3V, 4V and 5V, respectively. (g-i) I-V curves of the GNT-CuNB crossed sausages measured after 165 days between A-C, A-B and B-C. 6
Figure S11. (a) SEM image of the CuNB-CuNB crossed sausages. (b) I-V curves of the junction measured at different electrodes (A, B, C). Inset is the optical image of the CuNB-CuNB crossed sausages.
7
