J. Mater. Sci. Technol. ›› 2018, Vol. 34 ›› Issue (12): 2398-2406.DOI: 10.1016/j.jmst.2018.04.021
• Orginal Article • Previous Articles Next Articles
Xinyi Jiaab, Nan Huanga, Yuning Guoc, Lusheng Liua, Peng Lia, Zhaofeng Zhaiab, Bing Yanga, Ziyao Yuanab, Dan Shiab, Xin Jiangac*()
Received:
2018-02-12
Revised:
2018-04-11
Accepted:
2018-04-12
Online:
2018-12-20
Published:
2018-11-15
Contact:
Jiang Xin
Xinyi Jia, Nan Huang, Yuning Guo, Lusheng Liu, Peng Li, Zhaofeng Zhai, Bing Yang, Ziyao Yuan, Dan Shi, Xin Jiang. Growth behavior of CVD diamond films with enhanced electron field emission properties over a wide range of experimental parameters[J]. J. Mater. Sci. Technol., 2018, 34(12): 2398-2406.
Fig. 1. XRD patterns of diamond films deposited at microwave power of (a) 4 kW, (b) 6 kW, (c) 8 kW and (d)10 kW with different CH4/H2 ratios. The red lines at the bottom of each image are the standard diamond peaks (JCPDS: 06-0675).
4 kW | 6 kW | 8 kW | 10 kW | |
---|---|---|---|---|
1 vol.% | (111) | (111) | (111) | Random |
3 vol.% | (111) | (110) | (110) | (110) |
5 vol.% | (111) | (110) | (110) | (110) |
7 vol.% | (111) | (110) | (100) | (110) |
9 vol.% | (111) | (100) | Nano-diamond | Diamond/graphite nanostructures |
Table 1 Preferential orientation of various samples.
4 kW | 6 kW | 8 kW | 10 kW | |
---|---|---|---|---|
1 vol.% | (111) | (111) | (111) | Random |
3 vol.% | (111) | (110) | (110) | (110) |
5 vol.% | (111) | (110) | (110) | (110) |
7 vol.% | (111) | (110) | (100) | (110) |
9 vol.% | (111) | (100) | Nano-diamond | Diamond/graphite nanostructures |
H2 flow (sccm) | Gas pressure (Torr) | Microwave power (kW) | CH4/H2 radio (vol.%) | Growth rate (nm/h) | Thickness (nm) | Morphology |
---|---|---|---|---|---|---|
400 | 60 | 4 | 1 | 173 | 518 ± 25 | Random |
3 | 233 | 701 ± 31 | ||||
5 | 333 | 1000 ± 37 | ||||
7 | 473 | 1419 ± 32 | ||||
9 | 576 | 1726 ± 24 | ||||
6 | 1 | 203 | 610 ± 54 | Random | ||
3 | 484 | 1452 ± 25 | Triquetrous | |||
5 | 880 | 2642 ± 22 | Triquetrous | |||
7 | 1233 | 3700 ± 16 | Square | |||
9 | 1367 | 4110 ± 8 | Square | |||
8 | 1 | 200 | 600 ± 47 | Random | ||
3 | 620 | 1241 ± 28 | Triquetrous | |||
5 | 1088 | 3264 ± 23 | Triquetrous | |||
7 | 1410 | 4232 ± 14 | Square | |||
9 | 1411 | 4235 ± 7 | Nano-diamond | |||
10 | 1 | 200 | 599 ± 35 | Random | ||
3 | 533 | 1600 ± 26 | Triquetrous | |||
5 | 1216 | 3648 ± 18 | Triquetrous | |||
7 | 1366 | 4098 ± 11 | Nano-diamond | |||
9 | 1110 | 3332 ± 13 | Diamond/graphite nanostructures |
Table 2 Effects of microwave power and CH4/H2 radio on the growth of diamond films.
H2 flow (sccm) | Gas pressure (Torr) | Microwave power (kW) | CH4/H2 radio (vol.%) | Growth rate (nm/h) | Thickness (nm) | Morphology |
---|---|---|---|---|---|---|
400 | 60 | 4 | 1 | 173 | 518 ± 25 | Random |
3 | 233 | 701 ± 31 | ||||
5 | 333 | 1000 ± 37 | ||||
7 | 473 | 1419 ± 32 | ||||
9 | 576 | 1726 ± 24 | ||||
6 | 1 | 203 | 610 ± 54 | Random | ||
3 | 484 | 1452 ± 25 | Triquetrous | |||
5 | 880 | 2642 ± 22 | Triquetrous | |||
7 | 1233 | 3700 ± 16 | Square | |||
9 | 1367 | 4110 ± 8 | Square | |||
8 | 1 | 200 | 600 ± 47 | Random | ||
3 | 620 | 1241 ± 28 | Triquetrous | |||
5 | 1088 | 3264 ± 23 | Triquetrous | |||
7 | 1410 | 4232 ± 14 | Square | |||
9 | 1411 | 4235 ± 7 | Nano-diamond | |||
10 | 1 | 200 | 599 ± 35 | Random | ||
3 | 533 | 1600 ± 26 | Triquetrous | |||
5 | 1216 | 3648 ± 18 | Triquetrous | |||
7 | 1366 | 4098 ± 11 | Nano-diamond | |||
9 | 1110 | 3332 ± 13 | Diamond/graphite nanostructures |
Fig. 5. Effects of gas pressure on the morphology and growth rate of diamond films. The films are grown at a microwave power of 6 kW and 3% CH4 concentration and gas pressures are (a) and (f) 40 mbar, (b) and (g) 50 mbar, (c)and (h) 60 mbar, (d)and (i) 80 mbar and (e) and (j)90 mbar, respectively.
Microwave power (kW) | H2 flow (sccm) | CH4/H2 radio (vol.%) | Gas pressure (mbar) | Growth rate (nm/h) | Thickness (nm) | Morphology |
---|---|---|---|---|---|---|
6 | 400 | 3 | 40 | 190 | 570 ± 46 | Triquetrous |
50 | 297 | 892 ± 33 | ||||
60 | 418 | 1254 ± 19 | ||||
80 | 677 | 2030 ± 23 | ||||
90 | 823 | 2468 ± 14 | Square |
Table 3 Effect of gas pressure on the growth of diamond films.
Microwave power (kW) | H2 flow (sccm) | CH4/H2 radio (vol.%) | Gas pressure (mbar) | Growth rate (nm/h) | Thickness (nm) | Morphology |
---|---|---|---|---|---|---|
6 | 400 | 3 | 40 | 190 | 570 ± 46 | Triquetrous |
50 | 297 | 892 ± 33 | ||||
60 | 418 | 1254 ± 19 | ||||
80 | 677 | 2030 ± 23 | ||||
90 | 823 | 2468 ± 14 | Square |
Fig. 7. C1 s XPS spectroscopy of (a) microcrystalline diamond films (10 kW, 3 vol.%), (b) nanocrystalline diamond films (10 kW, 7 vol.%), (c) diamond/graphite hybrid nanostructure (10 kW, 9 vol.%). The fitting of the composite interlayers C1 s peaks was carried out by using Lorentzian peaks at binding energies of 284.2 eV and 285.1 eV, which are attributed to the sp2 C=C and sp3 C—C, respectively.
Fig. 8. (a) SEM image of the diamond/graphite hybrid nanostructure; (b) HRTEM image of the diamond/graphite hybrid nanostructure; (c) Field electron emission current density (Je) as a function of applied field (E) of diamond/graphite hybrid nanostructures emitters; (d) the corresponding F-N plots, i.e., ln (Je/E2) - 1/E plots.
Field-emitting materials | E0 (V/μm) | Je (mA/cm2) | β |
---|---|---|---|
Ultrathin diamond nanorods [ | 1.3 | 10.0@(2.9 V/μm) | - |
UNCD nanopillars [ | 11.6 | 3.95@(3 V/μm) | 3041 |
MCD nanocones [ | 35 | 0.91@(200 V/μm) | 259 |
Few layer graphene- diamond nanorods [ | 4.21 | 2.24@(10 V/μm) | 3480 |
Diamond- graphite hybrid nanorod arrays[ | 5.26 | 1.0@(10.55 V/μm) | 3270 |
Diamond/carbon nanosheet composite films[ | 2.91 | 3.21@(7.2 V/μm) | - |
MCD-UNCD composed film[ | 6.5 | 1.0@(30 V/μm) | - |
Au ion implanted UNCD films[ | 4.88 | 6.52@(8 V/μm) | - |
N2-UNCD nanorods[ | 0.21 | 7.06@(3.05 V/μm) | 1945 |
NCD-coated CNTs[ | 2.19 | 2.33@(4.76 V/μm) | 2566 |
Diamond/graphite hybrid nanostructures | 2.17 | 4.32@(1.05 V/μm) | 3160 |
Table 4 Comparison of electron field emission properties for various field-emitting materials.
Field-emitting materials | E0 (V/μm) | Je (mA/cm2) | β |
---|---|---|---|
Ultrathin diamond nanorods [ | 1.3 | 10.0@(2.9 V/μm) | - |
UNCD nanopillars [ | 11.6 | 3.95@(3 V/μm) | 3041 |
MCD nanocones [ | 35 | 0.91@(200 V/μm) | 259 |
Few layer graphene- diamond nanorods [ | 4.21 | 2.24@(10 V/μm) | 3480 |
Diamond- graphite hybrid nanorod arrays[ | 5.26 | 1.0@(10.55 V/μm) | 3270 |
Diamond/carbon nanosheet composite films[ | 2.91 | 3.21@(7.2 V/μm) | - |
MCD-UNCD composed film[ | 6.5 | 1.0@(30 V/μm) | - |
Au ion implanted UNCD films[ | 4.88 | 6.52@(8 V/μm) | - |
N2-UNCD nanorods[ | 0.21 | 7.06@(3.05 V/μm) | 1945 |
NCD-coated CNTs[ | 2.19 | 2.33@(4.76 V/μm) | 2566 |
Diamond/graphite hybrid nanostructures | 2.17 | 4.32@(1.05 V/μm) | 3160 |
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