Parametric Study of Methanol Chemical Vapor Deposition Growth for Graphene
Parametric Study of Methanol Chemical Vapor Deposition Growth for Graphene
Carbon letters. 2012. Oct, 13(4): 205-211
Copyright ©2012, Korean Carbon Society
This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License ( by-nc/3.0/) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
  • Received : August 01, 2012
  • Accepted : September 11, 2012
  • Published : October 31, 2012
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About the Authors
Hyunjin, Cho
Department of Organic Materials and Fiber Engineering, Chonbuk National University, Jeonju 561-756, Korea
Changhyup, Lee
Soft Innovative Materials Research Center, Korea Institute of Science and Technology, Jeonbuk 565-905, Korea
In Seoup, Oh
Soft Innovative Materials Research Center, Korea Institute of Science and Technology, Jeonbuk 565-905, Korea
Sungchan, Park
Department of Materials Science and Engineering, Chonbuk National University, Jeonju 561-756, Korea
Hwan Chul, Kim
Department of Organic Materials and Fiber Engineering, Chonbuk National University, Jeonju 561-756, Korea
Myung Jong, Kim
Soft Innovative Materials Research Center, Korea Institute of Science and Technology, Jeonbuk 565-905, Korea

Methanol as a carbon source in chemical vapor deposition (CVD) graphene has an advantage over methane and hydrogen in that we can avoid optimizing an etching reagent condition. Since methanol itself can easily decompose into hydrocarbon and water (an etching reagent) at high temperatures [1] , the pressure and the temperature of methanol are the only parameters we have to handle. In this study, synthetic conditions for highly crystalline and large area graphene have been optimized by adjusting pressure and temperature; the effect of each parameter was analyzed systematically by Raman, scanning electron microscope, transmission electron microscope, atomic force microscope, four-point-probe measurement, and UV-Vis. Defect density of graphene, represented by D/G ratio in Raman, decreased with increasing temperature and decreasing pressure; it negatively affected electrical conductivity. From our process and various analyses, methanol CVD growth for graphene has been found to be a safe, cheap, easy, and simple method to produce high quality, large area, and continuous graphene films.
1. Introduction
After Geim and Novoselov’s research in 2004 [2] , graphene has come to be regarded as a highly promising material in a variety of areas on account of its mechanical, optical, electrical, physical, thermal, and chemical properties. Graphene is known to consist of carbon atoms with a two-dimension and hexagonal phase in a crystal lattice; it is classified as a carbon allotrope with zero-dimension fullerenes, one-dimension nanotubes, and three-dimension graphite [3] . Like a synthetic fiber, graphene has led to research trends in a lot of research groups and many researchers has carried out considerable studies regarding not only fundamental experiments but also commercial applications [4] . Consequently, graphene synthesis techniques, such as the mechanical exfoliation technique [5] , chemical vapor deposition (CVD) growth [6 , 7] , chemical exfoliation of graphite [8] , and epitaxial growth on SiC [9] have been investigated systematically. For electrical and chemical applications in particular, CVD growth is mainly employed; this synthesis technique produces high quality, large area, and continuous graphene films as compared with other techniques. Moreover, graphene has been introduced into multifarious applications in various fields, such as transparent electrodes [10] , flexible and stretchable electronics [11 , 12] , heat transport [13] , super-capacitors [14] , sensors [15] , barriers [16] , field effect transistors [17] , and composites [18] .
CVD graphene utilizes various gases as carbon sources, such as methane, ethylene, and acetylene; hydrogen is used as an etching reagent, one that can reduce defective structures by regulating the growth rate. Recently, CVD graphene using liquid precursors has been reported and found to have advantages due to its low cost and easy, simple, and safe handling. Miyata et al. [19] studied graphene synthesis using ethanol on nickel foil under atmospheric pressure with Ar; a mono layer and a few layers of graphene using nhexane were also prepared under low pressure with Ar/H 2 [20] . Besides this, CVD graphene growth processes using ethanol and pentane under atmospheric pressure on copper foil [21] , and using methanol, ethanol, and propanol under low pressure [22] have been reported. However, most of the studies mentioned above reported only restrictively about the growth method and electrical devices, without detailed study of the synthesis.
Herein, we report on a parametric study of CVD graphene growth using methanol as a carbon source under low pressure. Since methanol is the only precursor, it was possible to optimize the growth conditions of the graphene by controlling only two parameters, such as pressure and temperature at high temperature; methanol is easily decomposed into hydrocarbon and water (etching reagent) [1] , so an additional etching reagent is not necessary. The D/G ratio, which is related to the defect density of graphene, is found to decrease with increasing temperature and decreasing pressure. The electrical conductivity of graphene, on the other hand, is found to increase with increasing temperature and pressure. Also, we found that the crystallinity of graphene and the number of layers were affected by growth temperature and pressure. The optical transmittance of graphene was also investigated at various temperature conditions (700℃ through 1000℃) in order to approximately calculate the number of graphene layers [23] . In order to accurately estimate the number of graphene layers, transmission electron microscope (TEM) analysis was performed for the same samples.
2. Experimental
- 2.1. Graphene synthesis method
The CVD system for graphene growth was kept under low pressure CVD (LPCVD). The methanol solution was used as a carbon source. A thin copper foil (25 μm thick) provided from Alfa Aesar was used as a transition metal catalyst substrate. The thin copper foil was located at the middle position in a 2 inch quartz tube in the CVD device; we operated a rotary vacuum pump that was used in order to maintain low pressure. The temperature of the CVD furnace was increased to 1000℃ for approximately 45 min. The pressure of the hydrogen was 53 mtorr and the flow rate was 10 sccm. Subsequently, in order to develop larger grain boundaries and a smooth surface, the sample was annealed at 1000℃ for 30 min under the same hydrogen atmosphere. Then, a carbon source was introduced into the quartz tube furnace for the nucleation and growth of graphene. The amount of carbon source was controlled using a mass flow controller (MFC) connected to a methanol containing glass component. During the synthesis, hydrogen gas was completely stopped, and the pressure was approximately 150-155 mtorr. The temperature was changed from 700℃ to 1000℃ in order to investigate the effect of temperature on the graphene quality. After the synthesis, the carbon source was completely stopped and the quartz tube was cooled down using 10 sccm of hydrogen gas.
- 2.2. Transfer
Graphene on the thin copper foil was transferred to various substrates for Raman spectroscope and atomic force microscope (AFM) analysis; it was transferred to TEM grids for TEM analysis. The spin coating using poly methyl methacrylate (PMMA) on graphene/thin copper foil was carried out at 4200 rpm for 40 s, followed by heating of the graphene/thin copper foil at 180℃ for 1 min. Then, ammonium persulfate [(NH 4 ) 2 S 2 O 8 ] dissolved in water was used in order to separate and remove the thin copper foil. The film of PMMA/graphene was rinsed at least three times using deionized water for 20 min. Subsequently, the PMMA/graphene film was transferred onto a 300 nm SiO 2 /Si substrate and glass substrate. PMMA on graphene was then removed with acetone.
- 2.3. Characterization
As-grown graphene films on the thin copper foil were analyzed using a scanning electron microscope (SEM) instrument (S-4700, Hitachi); the transferred graphene on the 300 nm SiO2/ Si substrate was analyzed by Raman spectroscopy (Horiba) and AFM (Veeco Dimension 3100). The optical transmittance was measured with UV-Vis spectroscopy (Jasco V-670). The sheet resistivity was measured using a four-point-probe resistivity meter (FPP-RS, DASOL ENG). TEM (JEM-2200FS), equipped with beam electron diffraction, was used to analyze the structure and the number of graphene layers.
3. Results and Discussion
Fig. 1 a provides a schematic diagram of the LPCVD. Methanol as a liquid carbon source was stored in a glass component in which the temperature was maintained at 30℃ water and methanol vapor was introduced into a quartz tube furnace using the MFC, which allows a precise control of a carbon source. Thin copper foil was used as a catalyst substrate due to the low solubility of carbon atoms [7] ; thus, nucleation and growth of graphene can occur via surface adsorption of carbon atoms [24] . After the graphene growth, the graphene/copper foil was transferred, using a typical method [25] , to various substrates, such as a 300 nm SiO 2 /Si substrate and a glass substrate, as shown in Fig. 1 c. The optical transmittance of graphene is too high to be clearly observed at the location of graphene on the substrates, as shown in Fig. 1 c. Considering the good optical and electronic properties of graphene, CVD graphene films can be used in transparent and flexible electrodes [10] .
Fig. 2 shows a data set collected from the methanol CVD graphene films under the optimized conditions. An SEM image of the as-grown graphene film is shown in Fig. 2 a; graphene covered a large area of the thin copper foil over grain boundaries. Besides this, wrinkles and ripples of graphene can be identified on the copper surface due to the different thermal expansion coefficients between the copper and the graphene [26] . Some particle-like impurities were also found to exist on the graphene surface because evaporated copper re-deposited at the growth temperature.
The inset in Fig. 2 a shows an optical image of a graphene
Lager Image
(a) Schematic diagram of the chemical vapor deposition (CVD) setup for graphene growth using methanol as a liquid carbon source in a glass component, (b) the experimental procedure with parameters (time, temperature, pressure, and gas flow rate), (c) an image showing that methanol CVD graphene films, with size of more than 1.5 × 1.5 cm2, were transferred to other substrates, such as a 300 nm SiO2/Si or glass substrate.
Lager Image
Characterization of methanol chemical vapor deposition (CVD) graphene films under the optimized conditions. (a) Scanning electron microscope image of an as-grown graphene film on 25 μm copper foil, with an optical image of graphene on a 300 nm SiO2/Si substrate in the inset (bar : 2.5 μm), (b) transmission electron microscope image and selected area electron diffraction data (inset) of CVD graphene films, (c) atomic force microscope analysis data, and (d) Raman spectra of a transferred graphene film on a 300 nm SiO2/Si substrate.
film transferred to a 300 nm SiO 2 /Si substrate; the scale bar in the image is 2.5 μm. A large area of the graphene was easily transferred to other substrates without causing serious damage.
A monolayer of graphene film can be seen in the TEM image in Fig. 2 b. The inset in Fig. 2 b shows selected area electron diffraction (SAED) data, which indicate that the methanol CVD
Lager Image
(a) Raman spectra and (b) the D/G ratio of graphene films synthesized at pressures of 150 mtorr, 300 mtorr, 450 mtorr, and 600 mtorr. The data were collected from the graphene transferred onto a 300 nm SiO2/Si substrate.
Lager Image
(a) Raman spectra and (b) the D/G ratio of graphene films synthesized at different temperatures (700℃ , 800℃ , 900℃ , and 1000℃ ) under constant pressure (150 mtorr). Relation between the D/G ratio and the electrical conductivity of graphene is presented in Fig. 4b.
graphene films have good crystallinity, showing clear hexagonal structures. AFM was used to analyze the thickness and the morphology of graphene films. The vertical distances were 1.073 nm and 1.376 nm at the two different spots. These values correspond to 1-2 layers, considering AFM measurement errors and the fact that the interspace between graphite layers is approximately 0.4 nm.
Fig. 2 d shows the Raman spectrum of the graphene films. In the Raman spectrum, the D peak represents defects or disorder in the structure; the G peak represents the tangential mode of the graphitic structures [27] . The intensity of the G' peak represents the second order of the zone-boundary phonons [28] . These peaks can be seen at 1344 cm -1 (D), 1585.7 cm -1 (G), and 2687.9 cm -1 (G'). Graphene quality and number of layers can be estimated from the D/G and G′/G (2D/G) ratios of the Raman spectrum. Ferrari et al. [29] reported that the G′/G (2D/G) ratio of monolayer graphene obtained using the procedure of micromechanical cleavage of graphite showed a figure of roughly 4; also, the full width at half maximum (FWHM) was about 25 cm -1 . However, the G′/G (2D/G) ratio of monolayer CVD graphene showed a value of more than 2; the FWHM was 33 cm -1 [7] . In this experiment, the D/G ratio and G′/G ratio of the methanol CVD graphene were 0.04 and 2.95, respectively; the FWHM was 30.4 cm -1 . Considering the TEM, Raman, SEM, and AFM data collected from the methanol CVD graphene, it seems that methanol as a carbon source can be effectively transformed to large area and high quality graphene films without using an etching reagent because methanol itself can be decomposed promptly to hydrocarbon and water (etching reagent) at high temperatures [1] . Thus, in comparison with methane CVD gra-phene [7] and mechanically exfoliated graphene [29] , methanol CVD graphene showed competitive characteristics.
In order to investigate the effect of pressure on the crystallinity and the quality of graphene, the pressure of CVD synthesis was changed from 150 mtorr to 600 mtorr with 150 mtorr. The grown graphene films were analyzed using Raman spectroscopy after transfer of the graphene films onto a SiO 2 /Si substrate. As shown in Fig. 3 a and b, the D/G ratio tended to increase with the increasing pressure. Li et al. [30] reported that the nucleation density of graphene under low pressure was lower than that of graphene under high pressure, and thus the lower nucleation density of graphene led to a significant increase in the size of the single crystalline domain in methane CVD growth. It appears that the tendency of the D/G ratio observed in our samples was similar to that in the previous study. The higher nucleation density at a higher pressure led to frequent formation of domain boundaries, which formed defects in hexagonal structures. The other reason for the high nucleation density could be amorphous carbon formation in the graphene structures due to the limited catalytic activity of the Cu foil with the increased methanol flux. Our results confirmed that methanol CVD graphene films grown under the lowest pressure had good quality and crystallinity with a minimal degree of defects or disorder.
Defects and disorder in graphene could be affected not only by the pressure but also by the temperature. In order to investigate the temperature effect, the pressure was kept at 150 mtorr for all the synthesis experiments; the synthesis temperature was varied from 700℃ to 1000℃ at intervals 100℃ . As illustrated in Fig. 4 a and b, the intensity of the D peak increased with decreasing temperature. Accordingly, both the D/G ratio and the
Lager Image
(a) UV-Vis spectra and (b) the calculated number of layers of graphene synthesized at different temperatures (700℃ , 800℃ , 900℃ , and 1000℃ ) under constant pressure (150 mtorr). The optical transmittance of a transferred graphene film on a glass substrate increased with increasing temperatures. The calculated layers decreased proportionally with increasing temperatures.
Lager Image
High-resolution transmission electron microscope images and selected area electron diffraction data of graphene grown at various temperatures. The synthesis temperatures were (a) 700℃ , (b) 800℃ , (c) 900℃ , and (d) 1000℃ .
electrical conductivity of methanol CVD graphene decreased with decreasing temperature. The defects and disorder in the crystalline lattices negatively affected the conductivity. Thus, these results prove that the temperature was one of the most important parameters for the growth of highly crystalline and good quality methanol CVD graphene films.
We further investigated the UV-Vis spectra of methanol CVD graphene film grown under various temperature conditions. As shown in Fig. 5 a, the optical transmittance was measured in order to determine the number of layers. The number of graphene layers was calculated by considering that 2.3% absorption corresponded to one layer [23] . In other words, 95.3% of the optical transmittance shown in Fig. 5 b could be calculated as representing approximately 2 layers of the methanol CVD graphene.
High resolution TEM (HR-TEM) images were collected in order to precisely estimate the number of layers and to compare that estimation with the optical transmittance data. The number of graphene layers was commonly counted at the folded edge of the graphene. As shown in Fig. 6 d, monolayer graphene films were frequently observed at 1000℃, which is the highest temperature in our experiments. In addition, SAED, as can be seen in Fig. 6 d, showed hexagonal patterns that represent a highly crystalline structure. On the other hand, the HR-TEM images in Figs. 6 a-c show that double-, triple-, or multi-layers of methanol CVD graphene were grown under those conditions. These results correspond with the optical transmittance data, shown in Fig. 5 b. This tendency was also observed in carbon nanotube CVD growth, such that high quality single-walled carbon nanotubes were grown at the higher temperatures while defective multi-walled carbon nanotubes were grown at the lower temperatures [31] .
4. Conclusions
Graphene growth using a methanol CVD method was parametrically studied. The optimized conditions were reached when graphene films were grown under 150 mtorr pressure and at a temperature of 1000℃ for a fixed growth time. Hydrocarbon and water decomposed from the methanol at high temperatures were used as a carbon source and as an etching reagent for graphene growth. The D/G ratio of the methanol CVD graphene decreased in accordance with increasing temperature and decreasing pressure. On the contrary, the electrical conductivity of the methanol CVD graphene increased proportionally with increasing temperature and decreasing pressure. The pressure and temperature for graphene growth affected the number of layers and the crystallinity of the graphene. Considering the various results collected from SEM, Raman, AFM, TEM, UV-Vis, and four-point-probe measurement, the quality of methanol CVD graphene was found to be comparable to that of methane CVD graphene and graphene formed under mechanical exfoliation. Thus, the methanol CVD graphene growth described here was a cheap, safe, easy, and simple method for continuous, high quality, and large area graphene synthesis.
This work was supported by a grant from the Korea Institute of Science and Technology (KIST) institutional program, the Converging Research Center program, funded by the Ministry of Education, Science and Technology (2012K001429), and by the fundamental R&D program for Core Technology of Materials, funded by the Ministry of Knowledge Economy.
Oshima H , Suzuki Y , Shimazu T , Maruyama S (2008) Novel and simple synthesis method for submillimeter long vertically aligned singlewalled carbon nanotubes by no-flow alcohol catalytic chemical vapor deposition Jpn J Appl Phys 47 1982 -    DOI : 10.1143/JJAP.47.1982
Novoselov KS , Geim AK , Morozov SV , Jiang D , Zhang Y , Dubonos SV , Grigorieva IV , Firsov AA (2004) Electric field effect in atomically thin carbon films Science 306 666 -    DOI : 10.1126/science.1102896
Gaim AK , Novoselov KS (2007) The rise of graphene Nat Mater 6 183 -    DOI : 10.1038/nmat1849
Rocha CG , Rummeli MH , Ibrahim I , Sevincli H , Borrnert F , Kunstmamn J , Bachmatiuk A , Potschke M , Li W , Makharza SAM , Roche S , Buchner B , Cuniberti G (2012) Tailoring the physical properties of graphene. In: Choi W, Lee JW, eds. Graphene: synthesis and applications. Nanomaterials and their applications CRC Press Boca Raton 1 -
Hernandez Y , Nicolosi V , Lotya M , Blighe FM , Sun Z , De S , Mc-Govern IT , Holland B , Byrne M , Gun’Ko YK , Boland JJ , Niraj P , Duesberg G , Krishnamurthy S , Goodhue R , Hutchison J , Scardaci V , Ferrari AC , Coleman JN (2008) High-yield production of graphene by liquid-phase exfoliation of graphite Nat Nanotechnol 3 563 -    DOI : 10.1038/nnano.2008.215
Kim KS , Zhao Y , Jang H , Lee SY , Kim JM , Kim KS , Ahn JH , Kim P , Choi JY , Hong BH (2009) Large-scale pattern growth of graphene films for stretchable transparent electrodes Nature 457 706 -    DOI : 10.1038/nature07719
Li X , Cai W , An J , Kim S , Nah J , Yang D , Piner R , Velamakanni A , Jung I , Tutuc E , Banerjee SK , Colombo L , Ruoff RS (2009) Large-area synthesis of high quality and uniform graphene films on copper foils Science 324 1312 -    DOI : 10.1126/science.1171245
Lu X , Yu M , Huang H , Rouff RS (1999) Tailoring graphite with the goal of achieving single sheets Nanotechnology 10 269 -    DOI : 10.1088/0957-4484/10/3/308
Berger C , Song Z , Li T , Li X , Ogbazghi AY , Feng R , Dai Z , Marchenokov AN , Conrad EH , First PN , de Heer WA (2004) Ultrathin epitaxial graphite: 2D electron gas properties and a route toward graphene based nanoelectronics J Phys Chem B 108 19912 -    DOI : 10.1021/jp040650f
Bae S , Kim H , Lee Y , Xu X , Park JS , Zheng Y , Balakrishnan J , Lei T , Kim HR , Song YI , Kim YJ , Kim KS , Ozyilmaz B , Ahn JH , Hong BH , Iijima S (2010) Roll-to-roll production of 30-inch graphene films for transparent electrodes Nat Nanotechnol 5 574 -    DOI : 10.1038/nnano.2010.132
Lee SK , Kim BJ , Jang H , Yoon SC , Lee C , Hong BH , Rogers JA , Cho JH , Ahn JH (2011) Stretchable graphene transistors with printed dielectrics and gate electrodes Nano Lett 11 4642 -    DOI : 10.1021/nl202134z
Kim RH , Bae MH , Kim DG , Cheng H , Kim BH , Kim DH , Li M , Wu J , Du F , Kim HS , Kim S , Estrada D , Hong SW , Huang Y , Pop E , Rogers JA (2011) Stretchable, transparent graphene interconnects for arrays of microscale inorganic light emitting diodes on rubber substrates Nano Lett 11 3881 -    DOI : 10.1021/nl202000u
Kang J , Kim H , Kim KK , Lee SK , Bae S , Ahn JH , Kim YJ , Choi JB , Hong BH (2011) High-performance graphene-based transparent flexible heaters Nano Lett 11 5154 -    DOI : 10.1021/nl202311v
Yoo JJ , Balakrishnan K , Huang J , Meunier V , Sumpter BG , Srivastava A , Conway M , Mohana Reddy AL , Yu J , Vajtai R , Ajayan PM (2011) Ultrathin planar graphene supercapacitors Nano Lett 11 1423 -    DOI : 10.1021/nl200225j
Wang Y , Yang R , Shi Z , Zhang L , Shi D , Wang E , Zhang G (2011) Superelastic graphene ripples for flexible strain sensors ACS Nano 5 3645 -    DOI : 10.1021/nn103523t
Bunch JS , Verbridge SS , Alden JS , van der Zande AM , Parpia JM , Craighead HG , McEuen PL (2008) Impermeable atomic membranes from graphene sheets Nano Lett 8 2458 -    DOI : 10.1021/nl801457b
Wang Z , Zhang Z , Xu H , Ding L , Wang S , Peng LM (2010) A high performance top-gate graphene field-effect transistor based frequency doubler Appl Phys Lett 96 173104 -    DOI : 10.1063/1.3413959
Jang BZ , Zhamu A (2008) Processing of nanographene platelets (NGPs) and NGP nanocomposites: a review J Mater Sci 43 5092 -    DOI : 10.1007/s10853-008-2755-2
Miyata Y , Kamon K , Ohashi K , Kitaura R , Yoshimura M , Shinohara H (2010) A simple alcohol-chemical vapor deposition synthesis of single-layer graphenes using flash cooling Appl Phys Lett 96 263105 -    DOI : 10.1063/1.3458797
Srivastava A , Galande C , Ci L , Song L , Rai C , Jariwala D , Kelly KF , Ajayan PM (2010) Novel liquid precursor-based facile synthesis of large-area continuous, single and few-layer graphene films Chem Mater 22 3457 -    DOI : 10.1021/cm101027c
Dong X , Wang P , Fang W , Su CY , Chen YH , Li LJ , Huang W , Chen P (2011) Growth of large-sized graphene thin-films by liquid precursor- based chemical vapor deposition under atmospheric pressure Carbon 49 3672 -    DOI : 10.1016/j.carbon.2011.04.069
Guermoune A , Chari T , Popescu F , Sabri SS , Guillemette J , Skulason HS , Szkopek T , Siaj M (2011) Chemical vapor deposition synthesis of graphene on copper with methanol, ethanol, and propanol precursors Carbon 49 4204 -    DOI : 10.1016/j.carbon.2011.05.054
Nair RR , Blake P , Grigorenko AN , Noboselov KS , Booth TJ , Stauber T , Peres NMR , Geim AK (2008) Fine structure constant defines visual transparency of graphene Science 320 1308 -    DOI : 10.1126/science.1156965
Li X , Cai W , Colombo L , Rouff RS (2009) Evolution of graphene growth on Ni and Cu by carbon isotope labeling Nano Lett 9 4268 -    DOI : 10.1021/nl902515k
Li X , Zhu Y , Cai W , Borysiak M , Han B , Chen D , Piner RD , Colombo L , Ruoff RS (2009) Transfer of large-area graphene films for highperformance transparent conductive electrodes Nano Lett 9 4359 -    DOI : 10.1021/nl902623y
Zhang Y , Gao T , Gao Y , Xie S , Ji Q , Yan K , Peng H , Liu Z (2011) Defectlike structures of graphene on copper foils for strain relief investigated by high-resolution scanning tunneling microscopy ACS Nano 5 4014 -    DOI : 10.1021/nn200573v
Tuinstra F , Koenig JL (1970) Raman spectrum of graphite J Chem Phys 53 1126 -    DOI : 10.1063/1.1674108
Nemanich RJ , Solin SA (1979) First- and second-order Raman scattering from finite-size crystals of graphite Phys Rev B 20 2 -    DOI : 10.1103/PhysRevB.20.392
Ferrari AC , Meyer JC , Scardaci V , Casiraghi C , Lazzeri M , Mauri F , Piscanec S , Jiang D , Novoselov KS , Roth S , Geim AK (2006) Raman spectrum of graphene and graphene layers Phys Rev Lett 97 187401 -    DOI : 10.1103/PhysRevLett.97.187401
Li X , Magnuson CW , Venugopal A , Tromp RM , Hannon JB , Vogel EM , Colombo L , Ruoff RS (2011) Large-area graphene single crystals grown by low-pressure chemical vapor deposition of methane on copper J Am Chem Soc 133 2816 -    DOI : 10.1021/ja109793s
Dai H (2001) Nanotube growth and characterization. In: Dresselhaus MS, Dresselhaus G, Avouris P, eds. Carbon nanotubes: synthesis, structure, properties, and applications. Topics in Applied Physics, Vol. 80 Springer New York 29 -    DOI : 10.1007/3-540-39947-X_3