Journal of Materials Chemistry C: Paper

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 lm 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 lm-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 lm 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 lm is at least 30 nm. Due to the ultra-low solubility of the carbon atoms in the nickel lm 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 lms with dierent thicknesses, whereas the G peak is enhanced with an increasing layer number of graphene which precipitates from thicker nickel lms. Saturation of the G peak for the 50 nm thick nickel lm is observed, due to the nite 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 cm1, 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
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.
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 metaloxidesemiconductor (CMOS) devices,8 and nonlinear saturable absorber locks for passively modelocked ber lasers911 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 dierent growth mechanisms in copper and nickel catalytic syntheses, the layer numbers of the synthesized graphene on the two hosts are quite dierent from each other. The growth of single-layer graphene
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Paper on the copper catalyst is usually executed with hydrogen-diluted methane at 1000 C. Without hydrogen and high temperature, single-layer graphene cannot be synthesized on the copper surface. In general, the copper substrate favors single-layer graphene deposition,20 whereas the nickel host is used initially for the dissolved deposition of decomposed carbon atoms and the subsequent reductive precipitation to yield few- or multilayer graphene.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),22,23 and such a synthesis can only be implemented using a hydrogen-diluted methane uence at a high radio-frequency plasma power (400 2000 W)24,25 and a relatively high temperature (650700 C).25,26 Even a conclusive statement has been made, that graphene can barely be synthesized without a hydrogen environment.17 Nonetheless, hydrogen-free PECVD has already been applied to synthesize other elementary semiconductors such as amorphous silicon, nanocrystalline silicon and silicon carbide.2731 In contrast to previous work, we demonstrate the hydrogenfree synthesis of graphene by PECVD with an argon-diluted methane uence. 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). In particular, the synthesis can be completed at a constant temperature as low as 475 C, without the need for a subsequent high-temperature procedure to sink the deposited carbon atoms into the nickel lm, and then the reductive precipitation of the dissolved carbon atoms into the graphene network on the surface by consecutively quenching the nickel lm. This unique reductive synthesis is based on selecting the critical phase transition temperature in the nickelcarbon phase diagram. The merit of such a lowtemperature process is that the number of nickel-absorbed carbon atoms could be limited to a small quantity, so that the nickel host would not precipitate a large number of carbon atoms aer cooling, owing to the extremely low solubility of carbon at low temperatures. The few-layer graphene can be synthesized successfully without hydrogen passivation. The structural quality of the reductively synthesized few-layer graphene is analyzed by Raman scattering spectroscopy and atomic force microscopy. The layer number-dependent transparency of graphene is measured by UV-Vis spectroscopy. Our experimental results observe the critical deposition temperature and time, and the optimized thickness of the nickel lm for reductively synthesizing the few-layer graphene by a hydrogen-free method.
Journal of Materials Chemistry C carbon atoms into the nickel lm, and subsequently precipitate them to form few-layer graphene on the nickel lm surface. Aer depositing 300 nm-thick SiO2 on the Si substrate, the nickel lms with dierent thicknesses were coated by E-beam evaporation. At the beginning, low-vacuum PECVD, with hydrogen-free methane, was employed to deposit the few-layer graphene on the 50 nm nickel at dierent temperatures of 350, 450 and 475 C. When the substrate temperature reached the target temperature and the chamber pressure was pumped down to 0.09 Torr, the mixed argon and methane gases with ow rates of 200 sccm and 3 sccm, respectively, were sent into the PECVD chamber with a total pressure of 0.31 Torr. The RF plasma power was kept as 100 W during deposition. Aer a deposition time of 100 s, the heater, gas ow and RF power were turned o and the substrate temperature was cooled down to 200 C within 30 minutes (with a cooling rate of 9.2 C min1) to allow graphene precipitation. Part two: tuning the nickel lm thickness Nickel lm substrates of dierent thickness were applied to grow graphene at 475 C, and the deposition time was kept constant as 100 s. The other factors such as the RF power, gas ow rate, deposition time and substrate cooling rate remained the same as those in part one. The nickel lm thicknesses were set as 1, 5, 10, 30, 50 and 100 nm. Part three: tuning the deposition time Dierent deposition times were adopted to grow graphene at 475 C on the 50 nm thick nickel lm substrate. The other factors such as the RF power, gas ow rate and substrate cooling rate were kept unchanged. The deposition times were set as 10, 100, 300 and 600 s.
Results and discussion

In contrast to copper, 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. The carbon atoms dissolve into the nickel host and form a NiC alloy temporarily at an appropriate substrate temperature. By then gradually cooling the substrate, the dissolved carbons are reductively adsorbed from the Ni host and precipitate on the nickel surface. To precisely control the growth mechanism of few-layer graphene on the nickel lm, the phase diagram of nickel and carbon32 should be considered, which is shown in Fig. 1. The right section of Fig. 1 shows enlarged versions of the phase diagram, with the atomic percentage of carbon ranging from 0% to 20% and from 0% to 0.45%. When the substrate temperature is increased beyond 475 C, the carbon atoms are absorbed by the nickel and form a solid solution. In Fig. 2, the dissolved carbon atoms are randomly arranged as an incomplete hexagonal ring structure in the interstices of nickel and the atoms.33 The lattice constant of graphene is 2.46 A lattice constant of hexagonally close-packed nickel in the (111) 34 Hence the lattice constant mismatch orientation is 2.49 A.
Experimental setup
The experiment can be separated into three parts to discuss the eect of the growth parameters (including the substrate temperature, nickel lm thickness and growth time) on the quality of the precipitated graphene. 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
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Fig. 1 Left: the phase diagram of carbon and nickel. Right: the enlarged phase diagrams with the atomic percentage of carbon ranging from 0% to 20% (top) and from 0% to 0.45% (bottom).
Fig. 3 Top: an illustration of the precipitation of absorbed carbon atoms on the nickel surface after gradually cooling the substrate to room temperature. Bottom: the images of the ultra-low temperature, PECVD-grown few-layer graphene samples synthesized with dierent deposition times and transferred onto a quartz substrate.
Fig. 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.
atom. All of these adjustments facilitate the decreased dissolution temperature of the carbon atoms. Images of the few-layer graphene samples on a quartz substrate, synthesized with dierent deposition times, are shown in the lower part of Fig. 3. UV-Visible optical spectroscopy was used to characterize the transmittance of the few-layer graphene samples, as shown in Fig. 4. For a deposition time of 10 s, the transmittance of graphene, measured at 550 nm, is nearly 100%, indicating that even single-layer graphene (with an absorbance of about 2.3%) cannot be synthesized in such a short time.37 The optical transmittance of the few-layer graphene decreases from 93% to 83% by increasing the deposition time from 100 to 600 s. When the few-layer graphene has fewer than 10 layers, the reectivity can be neglected, 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 1.2%, which does not induce the out-of-plane buckling phenomenon. Aer gradually cooling the substrate temperature to roomtemperature, the reductive precipitation of graphene onto the nickel surface occurs, with the layer number determined by the quantity of dissolved carbon atoms in the nickel host (see the upper part of Fig. 3). This observation is against the conventional approaches which require that the substrate temperature ranges from 550 C to 900 C.25,26,35 The carbon atoms may be quenched in the nickel substrate by enhancing the substrate cooling rate.36 In contrast, 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, during the medium-rate cooling process aer deposition in the PECVD chamber. In particular, the RF plasma utilized to enhance the decomposition of methane under hydrogen-free conditions is carefully tuned to control the quantity of carbon
Fig. 4 The transmittance of the ultra-low temperature, PECVD-grown few-layer graphene samples measured by UV-Visible optical spectroscopy.
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Paper 1 R2 ead yead ; 1 R2 e2ad 2Read cosq
(1)
where a denotes the absorption coecient, d is the thickness of few-layer graphene, R is the reectivity of few-layer graphene, q (4pn1d)/l, n1 is the index of refraction for few-layer graphene and l is the wavelength of incident light. The few-layer graphene has a lower layer number when the deposition time is reduced. The thinnest graphene can be synthesized within a deposition time of 100 s, with the layer number determined to be 3. For conrmation, the high-resolution transmission electron microscopy (TEM) image for fewlayer graphene grown for 100 s is shown in Fig. 5. The crosssectional bright-eld TEM image shows a very thin graphene layer sandwiched between the conductive glue and the nickel lm. Typically, the thickness of mono-layer graphene is about 0.34 nm,38 and 34 layers would exhibit a thickness between 1 and 1.3 nm. For our few-layer graphene sample, the layer thickness was approximately 1.2 nm. This observation correlates well with the optical transmittance analysis. The layer numbers for graphene grown for 300 s and 600 s were 5 and 8, respectively. The low solubility of carbon atoms into the nickel substrate at the threshold temperature is why the graphene layer number was not increased signicantly with the lengthening of the deposition time. In addition, atomic force microscopy (AFM) was employed to measure the surface uniformity of the graphene grown at 100 s, as shown in Fig. 6(a). During AFM analysis, a reference plane is set when scanning the surface roughness, and the deviation between the sample surface and the reference plane is recorded. Both the average and standard deviation of surface roughness by the root mean square value can be described as s n P Xi 2 p i 1 X1 2 X2 2 . Xn 2 p M p ; (2) n n
Fig. 6 (a) The AFM-characterized surface uniformity of the ultra-low temperature PECVD-grown few-layer graphene with a deposition time of 100 s, (b) the prole scans of our sample and (c) the distribution prole of the surface roughness.
Fig. 5 TEM image of the graphene deposited by PECVD, with hydrogen-free argon-diluted methane, at 475 C for 100 s.
where M is the root-mean-square deviation of the graphene sample, X denotes the deviation of the sample surface from a reference plane set in the AFM analysis, and n is the number of sampled points along the x and y directions. The experimental data give the surface height and roughness a root-mean-square value of 4 nm and 1.76 nm, taking into account the 70% uctuation of the roughness distribution prole (see Fig. 6(c)). In the manuscript, the root-mean-square value of the surface roughness is denoted as 1.76 nm. The surface proles are provided in Fig. 6(b). The sample was scanned in both the vertical (Y1, Y2) and horizontal (X1, X2) directions. In Fig. 6(b), the 70% uctuation of the scanned surface heights ranges between 1.76 and 1.76 nm. The roughness of the graphene surface is mainly caused by the PECVD-grown SiO2 layer between the Ni and Si substrates. Subsequently, Raman scattering spectral analysis was performed to optimize the carbon dissolution and graphene reduction temperature, as shown in Fig. 7. Similar discussions on the observed Raman scattering peak signals have been addressed in ref. 3946. The D-band Raman scattering peak, centered at 1350 cm1, indicates the presence of structural defects in the few-layer graphene, including point defects, dislocation-like defects, bilayer or multilayer bending, substitutional impurities, and carbon adatoms, etc.3943,46 The second peak at around 1580 cm1 is the G band which is contributed by the doubly degenerate phonon mode of carbon sp2 bonds, and this band certies the existence of graphene.47,48 The third peak at around 2700 cm1 is the so-called 2D band which is caused by the second order of zoneboundary phonon.44 No Raman scattering peaks appeared for the substrate temperatures below 450 C, a result of the failure of carbon
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Fig. 7 The Raman scattering spectra of few-layer graphene with dierent substrate temperatures.
dissolution and graphene reduction at these low temperatures. Although the RF plasma of PECVD could decompose methane and provide carbon atoms at any temperature, the carbon atoms are unable to dissolve into the nickel lm, thus failing to arrange in a hexagonal carbon ring structure at such a low temperature. A threshold temperature of 475 C is found in our experiment for carbon dissolution in nickel. Next, the eect of the nickel lm thickness on the quality of the few-layer graphene grown by hydrogen-free and low-temperature PECVD is characterized. The thickness of the nickel lm was increased to between 1 and 100 nm, and the deposition time was 100 s. Therefore, the number of carbon atoms provided by the PECVD plasma was almost the same for the nickel substrates of dierent thicknesses. However, the quantity of nickel-absorbed carbon atoms would change with the nickel thickness. The Raman scattering spectra shown in Fig. 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. Such thin lms are unable to dissolve sucient carbon atoms for the subsequent precipitation of few-layer graphene at the threshold temperature. A critical nickel lm thickness of 10 nm is observed, 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. The graphene characteristic peaks (D, G and 2D) eventually appear in the Raman spectrum when the nickel thickness is greater than 30 nm. 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 relationship between nickel lm thickness and the D, G and 2D peak intensities is shown in Fig. 8(b), in which the D peak intensities remain almost unchanged at thicknesses of 10, 30, 50 and 100 nm. This can be interpreted as the precipitated few-layer graphene showing the same structural quality and defect content on the dierent nickel lms.40 Moreover, the G and 2D peak intensities linearly increase with the nickel thickness and become saturated at nickel lm
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Fig. 8 (a) The Raman scattering spectra and (b) the D, G and 2D peak intensities of the ultra-low temperature PECVD-grown few-layer graphene with dierent nickel lm thicknesses.
thicknesses up to 30 nm, indicating that the quality of the fewlayer graphene becomes stabilized on nickel lms thicker than 50 nm. In more detail, 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. As shown in Fig. 9(a), small values of these parameters are the major factors which discriminate the quality of graphene.44 The ID/IG ratios and the G linewidths for the few-layer graphene precipitated on 10, 30, 50 and 100 nm thick nickel lms are 1.90, 1.02, 0.45 and 0.45, and 60, 44, 33 and 33, respectively. 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. Similar research40 reported that graphene fabricated at 700 C in hydrogen could only obtain an ID/IG ratio of 1.8. Our results conrm that the few-layer graphene with the lowest ID/IG of 0.45 can be obtained by a hydrogen-free uence method at a threshold dissolution and precipitation temperature as low as 475 C. The I2D/IG ratio of graphene versus nickel thickness is shown in Fig. 9(b), which shows that the I2D/IG ratio increases from 0.2 to 1.0 by increasing the nickel thickness from 10 to 30 nm. Conversely, this value decreases from 1.0 to 0.5 and
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Fig. 9 (a) The ID/IG intensity ratio (black line) and the G peak linewidth (blue line), and (b) the I2D/IG ratio of the ultra-low temperature PECVD-grown few-layer graphene with dierent nickel lm thicknesses.
Fig. 10 (a) The Raman scattering spectra, (b) the D, G and 2D peak intensities of the ultra-low temperature PECVD-grown few-layer graphene as a function of deposition time.
stabilizes when the nickel thickness further increases from 30 to 50 nm, indicating that both the number of precipitated carbon atoms and the layer number of graphene increase on increasing the nickel thickness. The saturation is mainly due to the controlled number of absorbed carbon atoms with a nite deposition duration. With the deposition time lengthening from 10 to 600 s (refer to part three for details), the corresponding Raman scattering spectra of the few-layer graphene is shown in Fig. 10(a). A deposition time as short as 10 s fails to dissolve a sucient number of carbon atoms in the 50 nm thick nickel lm. Increasing the deposition time suppresses the 2D and G peak intensities but strengthens the D peak, indicating that the precipitated carbon atoms not only form sp2 covalent bonds horizontally but also form sp3 covalent bonds vertically. The sp3 covalent bond induces V21(bb), V22(bb) and spiro-interstitial defects between the graphene stacked layers, which inevitably leads to a change in hybridization among the nearby carbon atoms.41,46 The relationship between the peak intensities (ID, IG and I2D) and the deposition duration is shown in Fig. 10(b). The D peak intensity exhibits the opposite trend to the 2D and G peak intensities, which is caused by an increase in the defects among the graphene layer.
The relationship between the deposition time and the ID/IG ratio, as well as the G band linewidth, is shown in Fig. 11(a). When shortening the deposition time from 600 to 100 s, the ID/ IG ratio is signicantly reduced from 1.8 to 0.45, and the G-peak linewidth shrinks from 67 cm1 to 33 cm1 concurrently. The lengthened deposition time from 100 s to 600 s enriches the dissolved carbon precipitated graphene, increasing the layer number from 3 to 8. As a result, the I2D/IG intensity ratio of the graphene samples decreases with the lengthened deposition duration, as shown in Fig. 11(b). Concurrently, the graphene defects caused by active ions and sp3 bonds in the graphene layers also increases with the lengthening of the deposition time. 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. Although our PECVD system is unable to deliver the hydrogen-diluted synthesis, 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. In previous work, Baraton et al. 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.35 In comparison, our recipe uses methane (3 sccm) and argon
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Paper Fig. 12(c)) synthesized defect-free graphene by mixing methane (2 sccm) with hydrogen (40 sccm) and argon (80 sccm),26 however, the synthesis requires a substrate temperature of up to 650 C. Without additional annealing, the few-layer graphene as-grown at the threshold temperature has a relatively comparable quality. The conditions required for growing graphene on the nickel and copper host substrates are not the same because of their dierent growing mechanisms. When growing on nickel, the carbon atoms decomposed from methane initially dissolve into the nickel lattice at a threshold temperature of 475 C, and subsequently precipitate on the nickel surface when the temperature decreases to 450 C and lower. In contrast, the temperature required for carbon to dissolve into the copper lattice is up to 2700 C, which is much higher than the temperature of 1000 C typically required for growing graphene on a copper substrate. That is, the formation of graphene on the copper substrate relies on the absorptiondecomposition of methane on the copper surface (with the assistance of hydrogen) rather than the dissolutionprecipitation of carbon from the copper host. The adsorption of methane ceases when the whole copper surface is occupied by carbon atoms, which eventually leads to the formation of mono-layer graphene. With a hydrogen-free environment and a limited heating temperature which is signicantly below 1000 C in our PECVD system, it is dicult to use copper as a host for graphene synthesis. In this case, the comparison of our sample with commercially available mono-layer graphene grown by thermal CVD is presented. The commercial mono-layer graphene is grown on a copper substrate using thermal CVD with mixed methane and hydrogen gas at 1050 C. The Raman scattering spectra for graphene synthesized on the Ni and Cu substrates are compared in Fig. 13(a). The slight shiing of the 2D peaks is caused by the dierent layer numbers of graphene. The zoomed-in view of the 2D peaks for both samples is shown in Fig. 13(b), in which the linewidths of the 2D peak for the graphene samples on Ni and Cu are 77 and 26 cm1, respectively. The quality of the commercial graphene sample is better than our sample as the structural defect-related D peak disappears. Although the graphene deposited on the copper substrate has the merit of superior lattice quality, it relies strictly on growth conditions assisted by hydrogen and high temperature. In contrast, the synthesis of graphene on the nickel substrate is a
Fig. 11 (a) The ID/IG intensity ratio (black line) and the linewidth of the G peak (blue line), and (b) the I2D/IG ratio of the ultra-low temperature PECVD-grown few-layer graphene as a function of deposition time.
(200 sccm) at 475 C with a plasma power of 100 W. The ID/IG ratio of our few-layer graphene shows a better value of 0.45 (see Fig. 12(a)) as compared with that of 1 reported with a similar recipe (see Fig. 12(b)). In contrast, Qi and co-workers (see
Fig. 12 Comparison of the Raman scattering spectra of the few-layer graphene samples synthesized by (a) this work, (b) Baraton et al., and (c) Qi et al.
Fig. 13 (a) Raman scattering spectra of the graphene samples grown on Cu and Ni substrates. (b) The zoomed-in 2D peaks of the graphene samples grown on Cu and Ni substrates.
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Table 1 The sheet resistance of graphene samples
Group Our work Our work Our work Reina et al. Su et al. Cote et al.
Method PECVD (CH4Ar) PECVD (CH4Ar) PECVD (CH4Ar) CVD (CH4H2) Exfoliation from graphite Reduction from GO lm
Layer number 3 5 8 89 (3 nm) 2 (T 96%) 2 (T 95%)
Sheet resistance (U sq1) 9142 6078 4226 770 43 200 1.9 107
Resistivity (U cm1) 9.6 104 1.1 103 1.2 103 2.3 104 1.5 102 6.7 101
Ref. 21 13 49
hydrogen-free process, and also exhibits greater tolerances on both the substrate temperature and the uence ratio. Finally, the sheet resistance and resistivity analyses are performed by a four-point probe instrument and are shown in Table 1. The other samples to be compared were synthesized by methods such as thermal CVD,21 electrochemical exfoliation from graphite13 and chemical reduction from graphene oxide.49 The smallest sheet resistance of 770 U sq1 , with a corresponding resistivity of 2.3 104 U cm1, can be obtained from CVD-grown graphene with a layer number of up to 8, owing to its perfect lattice. In comparison, the graphene chemically reduced from graphene oxide exhibits the highest sheet resistance of 1.9 107 U sq1, which corresponds to a resistivity as large as 0.67 U cm1. In comparison with previous work, the sheet resistance of the 8-layer thick graphene obtained by our method is about 4226 U sq1 (with a resistivity of 1.2 103 U cm1), which is about six times larger than that obtained by thermal CVD. Such a degradation of the resistivity, of nearly one order of magnitude, may result from the imperfect structure (defects) and the roughened surface of the graphene. This could be solved by replacing the PECVD-grown SiO2 buer with the one grown using thermal oxidation. Nevertheless, the hydrogenfree PECVD deposition of few-layer graphene has already shown comparable performance with those synthesized by other fabrication methods, which can be further improved for future electronic or photonic applications such as fast saturable absorbers46,47 in ultra-short pulsed ber lasers.
structural defects contributed by active ions and sp3 bonds is concurrently reduced in few-layer graphene. 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, which corresponds to a reduction of the layer number from 8 to 3. With the proper setting of the nite deposition time at 100 s and the threshold synthesis temperature at 475 C, the layer number and quality of the graphene can be precisely controlled with the ultra-low dissolution of carbon atoms in the nickel host.
Acknowledgements
This work was partially supported by the National Science Council, Taiwan, R.O.C. under the grants NSC 99-2662-E-002024-CC2, NSC 101-2622-E-002-009-CC2.
Notes and references

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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. The quenched precipitation of few-layer graphene is controlled with a temperature gradient of 0.15 C s1, a precise number of dissolved carbon atoms and a critical thickness of the nickel host lm. Raman scattering analysis reveals a critical nickel lm thickness of at least 5 nm for graphene synthesis with sucient carbon atoms. An enhanced I2D/IG ratio, by enlarging the nickel thickness to 30 nm, is attributed to the nite dissolution of carbon atoms in the nickel lm. More importantly, both the ID/IG ratio and the G band linewidth stabilize at 0.45 and 33 cm1, respectively, with the complete desorption of carbon from the nickel host. Shortening the deposition time from 600 to 100 s reduces the ID/IG ratio by one order of magnitude, as the
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