Journal of Materials Chemistry C

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Cite this: J. Mater. Chem. C, 2013, 1, 3862

Hydrogen-free PECVD growth of few-layer graphene on an ultra-thin nickel film at the threshold dissolution temperature
Kaung-Jay Peng,a Chung-Lun Wu,a Yung-Hsiang Lin,a Yen-Ju Liu,b Din-Ping Tsai,b Yi-Hao Paic and Gong-Ru Lin*a
The synthesis of few-layer graphene sheets on an ultra-thin nickel film-coated SiO2/Si substrate using hydrogen-free plasma-enhanced chemical vapor deposition (PECVD) with in situ low-temperature carbon dissolution is preliminarily demonstrated. The deposited carbon atoms are initially dissolved into the nickel matrix and subsequently precipitate out onto the nickel film surface. The threshold carbon dissolution temperature for synthesizing few-layer graphene is observed to be as low as 475  C, and the critical thickness of the host nickel film is at least 30 nm. Due to the ultra-low solubility of the carbon atoms in the nickel film at a threshold temperature of 475  C, the layer number in few-layer graphene can be precisely controlled. Raman scattering analysis indicates almost identical D and 2D peak intensities for nickel films with different thicknesses, whereas the G peak is enhanced with an increasing layer number of graphene which precipitates from thicker nickel films. Saturation of the G peak for the 50 nm thick nickel film is observed, due to the finite carbon dissolution within a limited deposition time, and results in a stabilized, high quality precipitated few-layer graphene. The linear transmittance of few-

Received 20th February 2013 Accepted 9th April 2013 DOI: 10.1039/c3tc30332b www.rsc.org/MaterialsC

layer graphene at 550 nm increases from 83 to 93% when the deposition time is shortened from 600 to 100 s, which corresponds to a decrease of the graphene layer number from 8 to 3 layers. The Raman scattering peak ratio of ID/IG decreases from 1.8 to 0.2 and the G-band linewidth shrinks from 67 to 37.2 cmÀ1, providing strong evidence for the improved quality of few-layer graphene synthesized by hydrogen-free PECVD at the threshold temperature on an ultra-thin nickel host.

Introduction
Graphene mechanically exfoliated from graphite was rst demonstrated by K. S. Novoselov et al.,1 and consists of a single˚ layer hexagonal network of carbon atoms with 1.42 A-long carbon sp2 hybridized bonds. This unique structure gives graphene excellent physical and chemical properties, including a high Young's modulus,2 Dirac fermions with high carrier mobility,3 high thermal conductivity,4 and broadband nonlinearly saturable absorbance. These features have led to interest in graphene for electronic, optoelectronic and photonic applications recently. For example, graphene-based transparent electrodes5 for organic light emitting diodes6 and organic solar cells,7 high mobility carrier channels for nano-scale

a

Graduate Institute of Photonics and Optoelectronics, Department of Electrical Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 106, Taiwan R.O.C. E-mail: grlin@ntu.edu.tw; Fax: +886-2-33669598; Tel: +886-233663700 ext. 235 Department of Physics, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 106, Taiwan R.O.C.

b

c Department of Opto-Electronic Engineering, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd., Shoufeng, Hualien 97401, Taiwan R.O.C.

complementary metal–oxide–semiconductor (CMOS) devices,8 and nonlinear saturable absorber locks for passively modelocked ber lasers9–11 have been reported comprehensively. Versatile methods have emerged for the synthesis of graphene in addition to its mechanical cleavage from bulk graphite, such as chemical or electrochemical exfoliation,12,13 grinding or trituration with dispersant separation,14,15 and thermal or chemical vapor deposition.16,17 Among the well developed approaches, mechanical cleavage and chemical exfoliation are not suitable for even medium-scale production. The reductive synthesis of graphene from SiC or from carbon-dissolved metallic lm requires a very high temperature ranging from 1000  C to 1300  C.18,19 Alternatively, plasma enhanced chemical vapor deposition (PECVD) has been developed to synthesize graphene on a relatively large scale. This approach can be executed at a lower temperature than that required for conventional syntheses. Nickel and copper are two commonly used metal substrates for the PECVD synthesis of graphene. Owing to the different growth mechanisms in copper and nickel catalytic syntheses, the layer numbers of the synthesized graphene on the two hosts are quite different from each other. The growth of single-layer graphene

3862 | J. Mater. Chem. C, 2013, 1, 3862–3870

This journal is ª The Royal Society of Chemistry 2013

The reductive synthesis of few-layer graphene is preliminarily performed on the sputtered ultra-thin nickel lm (50 nm or less) at an extremely low RF plasma power (equivalent to or below 100 W). Downloaded by National Physical Laboratory (NPL) on 06/06/2013 08:00:50. gas ow and RF power were turned off and the substrate temperature was cooled down to 200  C within 30 minutes (with a cooling rate of À9.20 whereas the nickel host is used initially for the dissolved deposition of decomposed carbon atoms and the subsequent reductive precipitation to yield few. and subsequently precipitate them to form few-layer graphene on the nickel lm surface. 30. we demonstrate the hydrogenfree synthesis of graphene by PECVD with an argon-diluted methane uence. At the beginning. deposition time and substrate cooling rate remained the same as those in part one. 2013. Without hydrogen and high temperature.22. Mater. gas ow rate and substrate cooling rate were kept unchanged. In general. 450 and 475  C. without the need for a subsequent high-temperature procedure to sink the deposited carbon atoms into the nickel lm. Results and discussion In contrast to copper. which is shown in Fig. The nickel lm thicknesses were set as 1. the nickel lms with different thicknesses were coated by E-beam evaporation. The RF plasma power was kept as 100 W during deposition. Chem.View Article Online Paper on the copper catalyst is usually executed with hydrogen-diluted methane at 1000  C. owing to the extremely low solubility of carbon at low temperatures. the phase diagram of nickel and carbon32 should be considered. The structural quality of the reductively synthesized few-layer graphene is analyzed by Raman scattering spectroscopy and atomic force microscopy. To precisely control the growth mechanism of few-layer graphene on the nickel lm. that graphene can barely be synthesized without a “hydrogen” environment. the growth of graphene on the nickel substrate can be performed at lower temperature and in a hydrogen-free environment. Nickel does not really serve as a catalyst during the synthesis. and then the reductive precipitation of the dissolved carbon atoms into the graphene network on the surface by consecutively quenching the nickel lm.49 A. and the deposition time was kept constant as 100 s. The other factors such as the RF power. the mixed argon and methane gases with ow rates of 200 sccm and 3 sccm. 50 and 100 nm. The merit of such a lowtemperature process is that the number of nickel-absorbed carbon atoms could be limited to a small quantity. the synthesis can be completed at a constant temperature as low as 475  C. When the substrate temperature reached the target temperature and the chamber pressure was pumped down to 0. The other factors such as the RF power. The right section of Fig. Journal of Materials Chemistry C carbon atoms into the nickel lm.2  C minÀ1) to allow graphene precipitation.27–31 In contrast to previous work. low-vacuum PECVD. 10. so that the nickel host would not precipitate a large number of carbon atoms aer cooling. the copper substrate favors single-layer graphene deposition.26 Even a conclusive statement has been made. the dissolved carbons are reductively adsorbed from the Ni host and precipitate on the nickel surface. 5.17 Nonetheless. the dissolved carbon atoms are randomly arranged as an incomplete hexagonal ring structure in the interstices of nickel ˚ and the atoms. single-layer graphene cannot be synthesized on the copper surface. Part two: tuning the nickel lm thickness Nickel lm substrates of different thickness were applied to grow graphene at 475  C.21 Most research groups have reported that the synthesis of graphene strictly relies on the use of a thick nickel substrate (usually more than 200 nm). 2. This unique reductive synthesis is based on selecting the critical phase transition temperature in the nickel–carbon phase diagram. and the optimized thickness of the nickel lm for reductively synthesizing the few-layer graphene by a hydrogen-free method.23 and such a synthesis can only be implemented using a hydrogen-diluted methane uence at a high radio-frequency plasma power (400– 2000 W)24. 1.33 The lattice constant of graphene is 2. with the atomic percentage of carbon ranging from 0% to 20% and from 0% to 0. respectively. Part three: tuning the deposition time Different deposition times were adopted to grow graphene at 475  C on the 50 nm thick nickel lm substrate. C. Part one: observing the threshold substrate temperature The few-layer graphene was intended to be grown at a threshold substrate temperature that could dissolve the lowest number of This journal is ª The Royal Society of Chemistry 2013 J. nanocrystalline silicon and silicon carbide.09 Torr. with hydrogen-free methane. 300 and 600 s. The layer number-dependent transparency of graphene is measured by UV-Vis spectroscopy. By then gradually cooling the substrate.25 and a relatively high temperature (650–700  C). The carbon atoms dissolve into the nickel host and form a NiC alloy temporarily at an appropriate substrate temperature. When the substrate temperature is increased beyond 475  C. were sent into the PECVD chamber with a total pressure of 0. Experimental setup The experiment can be separated into three parts to discuss the effect of the growth parameters (including the substrate temperature. the carbon atoms are absorbed by the nickel and form a solid solution. gas ow rate. Published on 09 April 2013. The deposition times were set as 10. nickel lm thickness and growth time) on the quality of the precipitated graphene. 100. hydrogen-free PECVD has already been applied to synthesize other elementary semiconductors such as amorphous silicon.or multilayer graphene.45%.31 Torr. the heater. The few-layer graphene can be synthesized successfully without hydrogen passivation.46 A lattice constant of hexagonally close-packed nickel in the (111) ˚ 34 Hence the lattice constant mismatch orientation is 2. 3862–3870 | 3863 . In particular. Aer a deposition time of 100 s. was employed to deposit the few-layer graphene on the 50 nm nickel at different temperatures of 350. 1 shows enlarged versions of the phase diagram.25. Aer depositing 300 nm-thick SiO2 on the Si substrate. In Fig. Our experimental results observe the critical deposition temperature and time. 1.

4.45% (bottom). the RF plasma utilized to enhance the decomposition of methane under hydrogen-free conditions is carefully tuned to control the quantity of carbon Fig. UV-Visible optical spectroscopy was used to characterize the transmittance of the few-layer graphene samples. synthesized with different deposition times. 4 The transmittance of the ultra-low temperature. Images of the few-layer graphene samples on a quartz substrate.37 The optical transmittance of the few-layer graphene decreases from 93% to 83% by increasing the deposition time from 100 to 600 s.35 The carbon atoms may be quenched in the nickel substrate by enhancing the substrate cooling rate. with the layer number determined by the quantity of dissolved carbon atoms in the nickel host (see the upper part of Fig. PECVD-grown few-layer graphene samples measured by UV-Visible optical spectroscopy. Aer gradually cooling the substrate temperature to roomtemperature. the transmittance of graphene. 3 Top: an illustration of the precipitation of absorbed carbon atoms on the nickel surface after gradually cooling the substrate to room temperature. All of these adjustments facilitate the decreased dissolution temperature of the carbon atoms. the reectivity can be neglected. as shown in Fig. indicating that even single-layer graphene (with an absorbance of about 2. is nearly 100%. the low temperature methane decomposition and carbon dissolution strictly controls the quantity of dissolved carbon atoms to achieve a precise control on the layer number of the precipitated graphene. Right: the enlarged phase diagrams with the atomic percentage of carbon ranging from 0% to 20% (top) and from 0% to 0. Mater. 3. Fig. during the medium-rate cooling process aer deposition in the PECVD chamber. When the few-layer graphene has fewer than 10 layers. measured at 550 nm. PECVD-grown few-layer graphene samples synthesized with different deposition times and transferred onto a quartz substrate.25. are shown in the lower part of Fig.3%) cannot be synthesized in such a short time. 1 Left: the phase diagram of carbon and nickel.View Article Online Journal of Materials Chemistry C Paper Published on 09 April 2013. Chem. 2 The schematic diagram of carbon atoms dissolved into the nickel host using a hydrogen-free PECVD system at a threshold substrate temperature as low as 475  C. 3). Downloaded by National Physical Laboratory (NPL) on 06/06/2013 08:00:50. In particular. Bottom: the images of the ultra-low temperature. 2013. This observation is against the conventional approaches which require that the substrate temperature ranges from 550  C to 900  C. the reductive precipitation of graphene onto the nickel surface occurs. which does not induce the out-of-plane buckling phenomenon. 3862–3870 This journal is ª The Royal Society of Chemistry 2013 .26.2%. C. For a deposition time of 10 s. Fig. Fig. and the layer number of the few-layer graphene lm can be estimated by simulating the transmittance of few-layer graphene as between hexagonally close-packed nickel (111) and graphene is only 1. 3864 | J. 1.36 In contrast. atom.

dislocation-like defects. the layer thickness was approximately 1.76 nm. The low solubility of carbon atoms into the nickel substrate at the threshold temperature is why the graphene layer number was not increased signicantly with the lengthening of the deposition time. 39–46. 6(a).38 and 3–4 layers would exhibit a thickness between 1 and 1. 2013. The roughness of the graphene surface is mainly caused by the PECVD-grown SiO2 layer between the Ni and Si substrates.39–43. 3862–3870 | 3865 . The experimental data give the surface height and roughness a root-mean-square value of 4 nm and Æ1. The surface proles are provided in Fig. as shown in Fig. bilayer or multilayer bending. The layer numbers for graphene grown for 300 s and 600 s were 5 and 8. including point defects. Y2) and horizontal (X1. and n is the number of sampled points along the x and y directions. a result of the failure of carbon This journal is ª The Royal Society of Chemistry 2013 J.47. This observation correlates well with the optical transmittance analysis. Chem.View Article Online Paper ð1 À RÞ2 eÀad yeÀad .76 nm. Fig. 1 þ R2 eÀ2ad À 2ReÀad cosðqÞ Journal of Materials Chemistry C T¼ (1) Published on 09 April 2013. etc. 6(c)). Mater. C. In addition. with hydrogen-free argon-diluted methane. The sample was scanned in both the vertical (Y1. taking into account the 70% uctuation of the roughness distribution prole (see Fig. 5. q ¼ (4pn1d)/l. 6(b). (2) n n Fig. For conrmation.48 The third peak at around 2700 cmÀ1 is the so-called 2D band which is caused by the second order of zoneboundary phonon. n1 is the index of refraction for few-layer graphene and l is the wavelength of incident light. In the manuscript. Both the average and standard deviation of surface roughness by the root mean square value can be described as sffiffiffiffiffiffiffiffiffiffiffiffiffi n P Xi 2 pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi i ¼1 X1 2 þ X2 2 þ . R is the reectivity of few-layer graphene. indicates the presence of structural defects in the few-layer graphene. X denotes the deviation of the sample surface from a reference plane set in the AFM analysis. For our few-layer graphene sample. 1. and the deviation between the sample surface and the reference plane is recorded. The crosssectional bright-eld TEM image shows a very thin graphene layer sandwiched between the conductive glue and the nickel lm. 5 TEM image of the graphene deposited by PECVD.34 nm. d is the thickness of few-layer graphene. In Fig. with the layer number determined to be 3. and carbon adatoms. and this band certies the existence of graphene. X2) directions. the root-mean-square value of the surface roughness is denoted as 1.3 nm. The few-layer graphene has a lower layer number when the deposition time is reduced. atomic force microscopy (AFM) was employed to measure the surface uniformity of the graphene grown at 100 s. Raman scattering spectral analysis was performed to optimize the carbon dissolution and graphene reduction temperature.44 No Raman scattering peaks appeared for the substrate temperatures below 450  C. a reference plane is set when scanning the surface roughness. The thinnest graphene can be synthesized within a deposition time of 100 s. where M is the root-mean-square deviation of the graphene sample.76 and 1. centered at 1350 cmÀ1. as shown in Fig. the 70% uctuation of the scanned surface heights ranges between À1.46 The second peak at around 1580 cmÀ1 is the G band which is contributed by the doubly degenerate phonon mode of carbon sp2 bonds. the high-resolution transmission electron microscopy (TEM) image for fewlayer graphene grown for 100 s is shown in Fig. substitutional impurities. The D-band Raman scattering peak. the thickness of mono-layer graphene is about 0. Typically. respectively. During AFM analysis. (b) the profile scans of our sample and (c) the distribution profile of the surface roughness. 6(b).2 nm. Downloaded by National Physical Laboratory (NPL) on 06/06/2013 08:00:50. where a denotes the absorption coefficient. Similar discussions on the observed Raman scattering peak signals have been addressed in ref. 6 (a) The AFM-characterized surface uniformity of the ultra-low temperature PECVD-grown few-layer graphene with a deposition time of 100 s. Subsequently. þ Xn 2 pffiffiffi M ¼ pffiffiffi ¼ . 7. at 475  C for 100 s.76 nm.

Such thin lms are unable to dissolve sufficient carbon atoms for the subsequent precipitation of few-layer graphene at the threshold temperature. thus failing to arrange in a hexagonal carbon ring structure at such a low temperature. 33 and 33. thicknesses up to 30 nm.90. which supports the growth of an amorphous graphene structure with only two distinct peaks (D and G) and a very weak 2D peak observed in the Raman spectrum. 8 (a) The Raman scattering spectra and (b) the D. The relationship between nickel lm thickness and the D. 1. Mater. the Raman intensity ratio of the D and G peaks (ID/IG) and the linewidth of the G peak also vary with nickel lm thickness. which shows that the I2D/IG ratio increases from 0.5 and This journal is ª The Royal Society of Chemistry 2013 . As shown in Fig. The I2D/IG ratio of graphene versus nickel thickness is shown in Fig. 9(a). respectively. 8(a) indicate that there were no graphene-related peaks in the samples with a nickel lm thickness as low as 1 and 5 nm. 3862–3870 Fig. indicating that the quality of the fewlayer graphene becomes stabilized on nickel lms thicker than 50 nm.44 The ID/IG ratios and the G linewidths for the few-layer graphene precipitated on 10. Similar research40 reported that graphene fabricated at 700  C in hydrogen could only obtain an ID/IG ratio of 1.View Article Online Journal of Materials Chemistry C Paper Published on 09 April 2013. A threshold temperature of 475  C is found in our experiment for carbon dissolution in nickel. the effect of the nickel lm thickness on the quality of the few-layer graphene grown by hydrogen-free and low-temperature PECVD is characterized.8. G and 2D peak intensities of the ultra-low temperature PECVD-grown few-layer graphene with different nickel film thicknesses. Our results conrm that the few-layer graphene with the lowest ID/IG of 0. In more detail.0 to 0. 0. A critical nickel lm thickness of 10 nm is observed. Downloaded by National Physical Laboratory (NPL) on 06/06/2013 08:00:50.40 Moreover. G and 2D) eventually appear in the Raman spectrum when the nickel thickness is greater than 30 nm. Therefore. 9(b).45 and 0. 50 and 100 nm. C. small values of these parameters are the major factors which discriminate the quality of graphene. and 60. The thickness of the nickel lm was increased to between 1 and 100 nm.45 can be obtained by a hydrogen-free uence method at a threshold dissolution and precipitation temperature as low as 475  C. Both the ID/IG values and the G linewidths stabilize at a minimum for the graphene on the nickel lm with a thickness of 50 nm or thicker. Conversely. the number of carbon atoms provided by the PECVD plasma was almost the same for the nickel substrates of different thicknesses. Next. this value decreases from 1. 44. the quantity of nickel-absorbed carbon atoms would change with the nickel thickness. 30. the carbon atoms are unable to dissolve into the nickel lm. This demonstrates that a 30 nm or thicker layer of nickel can absorb enough carbon atoms to form graphene layers at the threshold temperature. the G and 2D peak intensities linearly increase with the nickel thickness and become saturated at nickel lm 3866 | J. Chem. in which the D peak intensities remain almost unchanged at thicknesses of 10. 7 The Raman scattering spectra of few-layer graphene with different substrate temperatures. and the deposition time was 100 s. This can be interpreted as the precipitated few-layer graphene showing the same structural quality and defect content on the different nickel lms. dissolution and graphene reduction at these low temperatures.45. G and 2D peak intensities is shown in Fig. 2013. However. 30.2 to 1. 8(b). The Raman scattering spectra shown in Fig. The graphene characteristic peaks (D. Fig.0 by increasing the nickel thickness from 10 to 30 nm. 50 and 100 nm thick nickel lms are 1. 1. Although the RF plasma of PECVD could decompose methane and provide carbon atoms at any temperature.02.

which inevitably leads to a change in hybridization among the nearby carbon atoms.8 to 0. 10 (a) The Raman scattering spectra.41. Baraton et al. 11(a). V22(bb) and spiro-interstitial defects between the graphene stacked layers. Concurrently. which is caused by an increase in the defects among the graphene layer. stabilizes when the nickel thickness further increases from 30 to 50 nm. is shown in Fig. 10(a). Although our PECVD system is unable to deliver the hydrogen-diluted synthesis.35 In comparison. G and 2D peak intensities of the ultra-low temperature PECVD-grown few-layer graphene as a function of deposition time. the ID/ IG ratio is signicantly reduced from 1. as shown in Fig. Fig. This leads to the observation of obtaining the highly crystallized defect-free few-layer graphene by using a hydrogenfree and threshold-temperature PECVD synthesis with a deposition time as short as 100 s. (b) the D. The relationship between the deposition time and the ID/IG ratio. In previous work. 11(b). the corresponding Raman scattering spectra of the few-layer graphene is shown in Fig.45. the I2D/IG intensity ratio of the graphene samples decreases with the lengthened deposition duration. 1. and (b) the I2D/IG ratio of the ultra-low temperature PECVD-grown few-layer graphene with different nickel film thicknesses. The saturation is mainly due to the controlled number of absorbed carbon atoms with a nite deposition duration.46 The relationship between the peak intensities (ID. With the deposition time lengthening from 10 to 600 s (refer to part three for details).View Article Online Paper Journal of Materials Chemistry C Published on 09 April 2013. 2013. the Raman scattering results of the few-layer graphene sample can be compared with those grown on the nickel substrate by the hydrogen dilution method as reported by other groups. increasing the layer number from 3 to 8. the graphene defects caused by active ions and sp3 bonds in the graphene layers also increases with the lengthening of the deposition time. Mater. C. and the G-peak linewidth shrinks from 67 cmÀ1 to 33 cmÀ1 concurrently. 10(b). A deposition time as short as 10 s fails to dissolve a sufficient number of carbon atoms in the 50 nm thick nickel lm. Downloaded by National Physical Laboratory (NPL) on 06/06/2013 08:00:50. Fig. As a result. Chem. The lengthened deposition time from 100 s to 600 s enriches the dissolved carbon precipitated graphene. When shortening the deposition time from 600 to 100 s. The sp3 covalent bond induces V21(bb). indicating that the precipitated carbon atoms not only form sp2 covalent bonds horizontally but also form sp3 covalent bonds vertically. our recipe uses methane (3 sccm) and argon This journal is ª The Royal Society of Chemistry 2013 J. Increasing the deposition time suppresses the 2D and G peak intensities but strengthens the D peak. 3862–3870 | 3867 . IG and I2D) and the deposition duration is shown in Fig. as well as the G band linewidth. indicating that both the number of precipitated carbon atoms and the layer number of graphene increase on increasing the nickel thickness. 9 (a) The ID/IG intensity ratio (black line) and the G peak linewidth (blue line). synthesized graphene by using methane (10 sccm) and hydrogen (50 sccm) at 450  C with a plasma power of 70 W and a growth time of 120 s. The D peak intensity exhibits the opposite trend to the 2D and G peak intensities.

13(b). C. in which the linewidths of the 2D peak for the graphene samples on Ni and Cu are 77 and 26 cmÀ1. The slight shiing of the 2D peaks is caused by the different layer numbers of graphene. That is. and subsequently precipitate on the nickel surface when the temperature decreases to 450  C and lower. the formation of graphene on the copper substrate relies on the absorption–decomposition of methane on the copper surface (with the assistance of hydrogen) rather than the dissolution–precipitation of carbon from the copper host. Although the graphene deposited on the copper substrate has the merit of superior lattice quality. 13 (a) Raman scattering spectra of the graphene samples grown on Cu and Ni substrates.View Article Online Journal of Materials Chemistry C Paper Fig. In contrast. The zoomed-in view of the 2D peaks for both samples is shown in Fig. In contrast. The adsorption of methane ceases when the whole copper surface is occupied by carbon atoms. it is difficult to use copper as a host for graphene synthesis.45 (see Fig. The quality of the commercial graphene sample is better than our sample as the structural defect-related D peak disappears. which eventually leads to the formation of mono-layer graphene.26 however. 3868 | J. Chem. Mater. the synthesis requires a substrate temperature of up to 650  C. 2013. When growing on nickel.. Qi and co-workers (see Fig. the few-layer graphene as-grown at the threshold temperature has a relatively comparable quality. respectively. The conditions required for growing graphene on the nickel and copper host substrates are not the same because of their different growing mechanisms. and (c) Qi et al. it relies strictly on growth conditions assisted by hydrogen and high temperature. 11 (a) The ID/IG intensity ratio (black line) and the linewidth of the G peak (blue line). Fig. With a hydrogen-free environment and a limited heating temperature which is signicantly below 1000  C in our PECVD system. In contrast. 13(a). (b) Baraton et al. (200 sccm) at 475  C with a plasma power of 100 W. Without additional annealing. The Raman scattering spectra for graphene synthesized on the Ni and Cu substrates are compared in Fig. 3862–3870 This journal is ª The Royal Society of Chemistry 2013 . which is much higher than the temperature of 1000  C typically required for growing graphene on a copper substrate. 1. 12 Comparison of the Raman scattering spectra of the few-layer graphene samples synthesized by (a) this work. The ID/IG ratio of our few-layer graphene shows a better value of 0. Fig. 12(c)) synthesized defect-free graphene by mixing methane (2 sccm) with hydrogen (40 sccm) and argon (80 sccm). Downloaded by National Physical Laboratory (NPL) on 06/06/2013 08:00:50. The commercial mono-layer graphene is grown on a copper substrate using thermal CVD with mixed methane and hydrogen gas at 1050  C. the comparison of our sample with commercially available mono-layer graphene grown by thermal CVD is presented. (b) The zoomed-in 2D peaks of the graphene samples grown on Cu and Ni substrates. In this case. and (b) the I2D/IG ratio of the ultra-low temperature PECVD-grown few-layer graphene as a function of deposition time. 12(a)) as compared with that of 1 reported with a similar recipe (see Fig. 12(b)). the temperature required for carbon to dissolve into the copper lattice is up to 2700  C. the carbon atoms decomposed from methane initially dissolve into the nickel lattice at a threshold temperature of 475  C. the synthesis of graphene on the nickel substrate is a Published on 09 April 2013.

E. MacDonald.49 The smallest sheet resistance of 770 U sqÀ1 . 2009. More importantly. A. Y. Privitera. Lee. Bao. V. Zhang.3 Â 10À4 1. G. 8. Shortening the deposition time from 600 to 100 s reduces the ID/IG ratio by one order of magnitude. Cote et al. Solid State Commun. both the ID/IG ratio and the G band linewidth stabilize at 0. 880–886. Ghosh. 803–810. Morozov.. 2032–2045. Calizo. Sun. Zhao. D. Basko and A. 98. 3 K. S. Reddy and A. M.C. Kim. Z. 12 Y. P. D. I. A. Proc. Fudenberg. Y. In comparison with previous work. B. with the complete desorption of carbon from the nickel host. T. Z. 2010. 321. the sheet resistance and resistivity analyses are performed by a four-point probe instrument and are shown in Table 1. W. R. Banerjee. 1. S. 306. Geim. 457. 43–48. Kim. H. H. Wang. Method PECVD (CH4–Ar) PECVD (CH4–Ar) PECVD (CH4–Ar) CVD (CH4–H2) Exfoliation from graphite Reduction from GO lm Layer number 3 5 8 8–9 (3 nm) 2 (T ¼ 96%) 2 (T ¼ 95%) Sheet resistance (U sqÀ1) 9142 6078 4226 770 43 200 1. The linear transmittance of the synthesized few-layer graphene at a wavelength of 550 nm is increased from 83% to 93% on shortening the deposition time from 600 to 100 s. The other samples to be compared were synthesized by methods such as thermal CVD. M. K.-C. Laser Physics Letters. Conclusions The few-layer graphene synthesized on an ultra-thin nickel lm by hydrogen-free PECVD at the threshold carbon dissolution temperature of 475  C is successfully demonstrated. Ferrari. owing to its perfect lattice. which is about six times larger than that obtained by thermal CVD. S. S. S. respectively. Klima. 146. 9.1 Â 10À3 1. Agrawal. Bao. J. Hasan. 351–355. W.5 Â 10À2 6. In comparison. M. N. 2010. Peumans. is attributed to the nite dissolution of carbon atoms in the nickel lm. 6 J. and also exhibits greater tolerances on both the substrate temperature and the uence ratio. ACS Nano. which corresponds to a resistivity as large as 0. the layer number and quality of the graphene can be precisely controlled with the ultra-low dissolution of carbon atoms in the nickel host. H. With the proper setting of the nite deposition time at 100 s and the threshold synthesis temperature at 475  C. V. Miao and C. F. 4. Dubonos. Jang. T. J. De. M. G. 7 X. structural defects contributed by active ions and sp3 bonds is concurrently reduced in few-layer graphene. Y.67 U cmÀ1. Y. D. 8. which can be further improved for future electronic or photonic applications such as fast saturable absorbers46. Kim.-R. Sikes. Y. Lee. Science. F. may result from the imperfect structure (defects) and the roughened surface of the graphene. Y. Jiang. Kim. 3862–3870 | 3869 . F. 4. 2004. 2012. Gunko.7 Â 10À1 Ref.2 Â 10À3 U cmÀ1). M. with a corresponding resistivity of 2. Mater. Grigorieva and A. This could be solved by replacing the PECVD-grown SiO2 buffer with the one grown using thermal oxidation. F. of nearly one order of magnitude. Lett. Lin. The quenched precipitation of few-layer graphene is controlled with a temperature gradient of À0. M.47 in ultra-short pulsed ber lasers. as the This journal is ª The Royal Society of Chemistry 2013 J. 706–710. hydrogen-free process. L. a precise number of dissolved carbon atoms and a critical thickness of the nickel host lm. by enlarging the nickel thickness to 30 nm. Taiwan. 8. D. 5 K. H. Wu. Nevertheless. Holland. Becerril. Basu.21 electrochemical exfoliation from graphite13 and chemical reduction from graphene oxide. 398– 404. K. Bonaccorso. C. Choi and B. An enhanced I2D/IG ratio. 9 Z. L. Mcgovern.9 Â 107 Resistivity (U cmÀ1) 9.. X. Su et al. — — — 21 13 49 Published on 09 April 2013. 2008. H. 666–669. 902–907. 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