Recent Development of the Transformation from Amorphous Carbon to Graphene Method via Metal Catalyst

doi:10.15541/jim20170527

Abstract

Abstract:

Graphene has drawn wide attention owing to its excellent properties since the discovery in 2004. There are many methods to produce graphene so far but many challenges still exist in producing scalable and high quality graphene. Thus, preparation of graphene should be further explored. Amorphous carbon and graphene are two allotropes of carbon. As one kind of solid carbon source, amorphous carbon could also be used to produce graphene. The preparation of graphene from amorphous carbon via metal catalyst has aroused much interest. Here, the advantages of using amorphous carbon as solid carbon source, to get high quality and large size graphene via metal catalyst in recent years are summarized. Several influence factors, such as metal sort, annealing temperature, the ratio of amorphous carbon to metal, have been discussed elaborately. Meanwhile, transformation mechanism from amorphous carbon to graphene has been reviewed and summarized simultaneously. Finally, the prospect of this novel fabrication method for graphene was put forward.

Key words: amorphous carbon, graphene, solid carbon source, metal catalyst

CLC Number:

TQ127

LI Han-Chao, LIU Pan-Pan, SUN Li-Li, KE Pei-Ling, CUI Ping, WANG Ai-Ying. Recent Development of the Transformation from Amorphous Carbon to Graphene Method via Metal Catalyst[J]. Journal of Inorganic Materials, 2018, 33(6): 587-595.

Figures/Tables 12

Fig. 1 Schematic of graphene synthesis mechanism[30](a) Local annealing of the Ni layer by laser irradiation; (b) Dissolution of a-C in the Ni layer; (c) Aggregation and retraction of the Ni layer; (d) Direct graphene synthesis on a SiO2 surface

Fig. 2 Raman spectrum for a sample irradiated with a laser in H2 atmosphere at a substrate temperature of 200℃[30]

Fig. 3 Process schematic for the metal-catalyzed crystallization of a-C to graphene by thermal annealing[31]

Fig. 4 Schematic illumination of the graphene growth method[32]

Fig. 5 Raman spectra of (a) a-C (40 nm) and (b) the resulting graphene layer after Ni-catalyzed crystallization (Ni thickness ~300 nm) with excitation laser wavelength 632.8 nm[31]

Table 1 Parameters and results of thermal annealing for the experiment of transformation of a-C to graphene

a-C method	T/℃	Annealing time/min	Gas	Catalyst	Pressure/Pa	Graphene morphology	Raman		Ref.
a-C method	T/℃	Annealing time/min	Gas	Catalyst	Pressure/Pa	Graphene morphology	I_D/I_G	I_2D/I_G	Ref.
EBE	650-950	15	Ar	Ni, Co	226	Single, double layer	0.09	-	[31]
FVAD	600-1000	5	-	Ni	-	Few layer	-	-	[32]
PAPD	700-1000	5	N₂	Co, Ni	-	Multilayer	0.59	1	[35]
LA	1000	30	-	Ga	1.33×10^-2	Few layer	-	-	[36]
FIB-CVD	900-1100	30, 60	-	Ga	-	Three, four layer	-	0.84	[37]
PLD	800	5	Ar	Co	0.1	Single, double layer	2.5	0.67-1.43	[39]
MS	750-800	5-10	-	Co, Ni	3.0×10^-4	Single, double layer	-	1.43	[40]
DCMS	1100	2	Ar	Ni	0.266	Single, double layer	-	2.5	[46]
PAPD	900	5	N₂	Ni	-	Multilayer	-	-	[42]
DCMS	900	30	-	Ni	2.66×10^-4	Single, double layer	0.03	4.8	[52]

Fig. 6 Raman spectroscopic analysis of graphene from different growth conditions[33](a) Raman spectra of graphene on the top of the nickel layer before and after UV-ozone exposure, and graphene on the substrate after UV-ozone exposure and nickel removal; (b) Raman spectra of PMMA-derived graphene by different metal catalysts

Fig. 7 Contour maps of in situ XRD results showing the 002 graphite peak in Si/SiO2/a-C/Ni (100 nm) samples heated to and cooled from 1000℃ in He at a ramp rate of 3℃/s for a-C thicknesses of (a) 3 nm, (b) 10 nm, and (c) 30 nm. The contour lines have a linear intensity spacing that is different for each a-C thickness[41]

Fig. 8 (a) AFM image of a transferred graphene sheet on Si/SiO2 substrate; (b) Graphene (and graphite) thickness vs initial a-C thickness[31] Samples were annealed at 800?℃ for 15 min with a 300 nm Ni catalyst layer

Fig. 9 Influence of Ni and C film thicknesses on graphene growth[46](a) Raman spectra of RTP graphene grown with a 5 nm C film covered with a Ni film of different thicknesses; (b) ID/IG and I2D/IG Raman peak ratios of the RTP graphene as functions of Ni film thickness; (c) Raman spectra of RTP graphene grown with a 65 nm Ni film on top of a C film with different thicknesses; (d) ID/IG and I2D/IG Raman peak ratios of the RTP graphene as functions of C film thickness

Fig. 10 Plan-view scanning transmission electron microscopy (STEM) dark-field images of Ni crystals on an amorphous carbon film at 400℃ (a), 600℃ (b) and 720℃ (c) [25](a) At 400℃, the coherent polycrystalline Ni film (bright) covers the C substrate entirely; holes in the C film appear black; (b) At 600℃, ripening of the metal crystals starts and uncovers areas of the amorphous carbon film (light gray contrast); (c) At 720℃, ripening continues and graphene areas appear (dark, marked with arrows)

Fig. 11 Schematic illustration of graphene formation via C dissolution-precipitation

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