A new perspective on structural and morphological properties of carbon nanotubes synthesized by Plasma Enhanced Chemical Vapor Deposition technique 1 3 4 5 6 7 8 9 10 11 1 3 14 15 16 17 18 19 20 21 22[.]
RINP 563 No of Pages 5, Model 5G February 2017 Results in Physics xxx (2017) xxx–xxx Contents lists available at ScienceDirect Results in Physics journal homepage: www.journals.elsevier.com/results-in-physics A new perspective on structural and morphological properties of carbon nanotubes synthesized by Plasma Enhanced Chemical Vapor Deposition technique A Salar Elahi a,⇑, K Mikaili Agah b, M Ghoranneviss a 10 11 14 15 16 17 18 19 20 21 22 23 a b Plasma Physics Research Center, Science and Research Branch, Islamic Azad University, Tehran, Iran Department of Mathematics and Physics, East Tehran Branch, Islamic Azad University, Tehran, Iran a r t i c l e i n f o Article history: Received January 2017 Received in revised form 30 January 2017 Accepted 31 January 2017 Available online xxxx Keywords: Carbon nanotubes Cobalt nanocatalyst PECVD a b s t r a c t CNTs were produced on a silicon wafer by Plasma Enhanced Chemical Vapor Deposition (PECVD) using acetylene as a carbon source, cobalt as a catalyst and ammonia as a reactive gas The DC-sputtering system was used to prepare cobalt thin films on Si substrates A series of experiments was carried out to investigate the effects of reaction temperature and deposition time on the synthesis of the nanotubes The deposition time was selected as 15 and 25 for all growth temperatures Energy Dispersive Xray (EDX) measurements were used to investigate the elemental composition of the Co nanocatalyst deposited on Si substrates Atomic Force Microscopy (AFM) was used to characterize the surface topography of the Co nanocatalyst deposited on Si substrates The as-grown CNTs were characterized under Field Emission Scanning Electron Microscopy (FESEM) to study the morphological properties of CNTs Also, the grown CNTs have been investigated by High Resolution Transmission Electron Microscopy (HRTEM) and Raman spectroscopy The results demonstrated that increasing the temperature leads to increasing the diameter of CNTs Ó 2017 The Author Published by Elsevier B.V This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/) 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 Introduction 42 All different types of materials like plastic, glass, metal, textiles, etc can be coated with plasma based methods Also various methods using plasma are applied for a thin film formation with the desired characteristics for the different applications [1–3] One of these methods is plasma-enhanced Chemical Vapor Deposition (PECVD) PECVD is a process used to deposit thin films from a gas state to a solid state on a substrate Chemical reactions are involved in the process, which occur after creation of aplasma of the reacting gases The major advantage compare to simple Chemical Vapor Deposition is that PECVD can operate at much lower temperature [4,5] Carbon nanotubes (CNTs) are characterized as a graphene sheet rolled-up to form a tube, for example a singlewalled tube (SWNT) When two or more concentric tubes are placed one into another, multi-walled carbon nanotube (MWNT) is formed Initially, the arc discharge was employed to produce carbon nanotubes This method was known enough and utilized for the synthesis of carbon filaments and fibres Later on other techniques such as laser ablation or Chemical Vapor Deposition 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 ⇑ Corresponding author E-mail address: Salari_phy@yahoo.com (A.S Elahi) (CVD) were examined in the production of carbon nanotubes In fact, these are the three main production methods Some efforts were also made to look for other possibilities to grow nanotubes but they had less success The cause may be the expensive reaction apparatus, the state or the price of the catalyst material, the strange reaction conditions, e.g., high pressure, temperatures of liquid nitrogen So, ‘‘the old technologies” were improved, adapted to new conditions more than to discover new technologies Today, the arc discharge and Chemical Vapor Deposition methods are widely applied for the formation of carbon nanotubes Many studies were made to improve either the quality or the quantity of the produced material by optimizing the synthesis process As a result some types of CVD method were discovered such as plasmaenhanced, microwave-enhanced, radio-frequency-enhanced CVD Nanotechnology based on CNTs is developing very fast leading to decrease in the dimensions of electronic devices used in today’s technological applications, such as field effect transistors [1], field emitters [2], flat panel displays [3,4], sensors [5], etc Due to its very small diameter, which is on the order of few nanometers with the length up to centimeters [6], perfect electrical and thermal conductance properties [7], CNTs are expected to find applications in all industrial areas, also provide rich research subjects CNTs have been grown by various methods, such as laser ablation, ther- http://dx.doi.org/10.1016/j.rinp.2017.01.043 2211-3797/Ó 2017 The Author Published by Elsevier B.V This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/) Please cite this article in press as: Elahi AS et al A new perspective on structural and morphological properties of carbon nanotubes synthesized by Plasma Enhanced Chemical Vapor Deposition technique Results Phys (2017), http://dx.doi.org/10.1016/j.rinp.2017.01.043 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 RINP 563 No of Pages 5, Model 5G February 2017 A.S Elahi et al / Results in Physics xxx (2017) xxx–xxx Fig Schematic diagram of PECVD system of nanotube synthesis 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 mal decomposition of hydrocarbons, and Chemical Vapor Deposition (CVD) These three methods have been used the most for producing CNTs Among them, CVD has been shown to be the best method in producing vertically aligned CNTs uniformly in large quantities due to the ease in controlling the catalysts and temperature [8,9] Transition metals such as Fe, Ni, Co and their compounds or alloys have been widely used as the catalysts [10] CVD with these transition metals as a catalyst has several advantages over other deposition methods [11] CVD with a catalyst can be used to grow single-walled, double-walled, or multiwalled CNTs by controlling the particle size and chemical nature of the catalyst The adhesive force between the catalyst and the substrate has been often attributed as an important factor in determining the growth mechanisms of CNTs While weak contact between the catalyst and substrate favors a tip-growth mechanism, a strong interaction promotes base-growth [12,13] The growth of CNTs can be divided into four steps: (1) supply of carbon source on the catalyst surface by adsorption and the subsequent catalytic decomposition of the adsorbed carbon by carbon atoms; (2) desorption of the carbon atoms into a gas phase; (3) diffusion of the carbon atoms away from the catalyst surface through bulk or surface diffusion; and (4) precipitation and formation of a graphite structure [14–16] Formerly, some synthesis methods of carbon nanotubes, related materials and metal atoms agglomerate are analyzed [17–25] In this paper, we have systematically investigated the effects of growth temperatures and deposition time on carbon nanotubes grown by Plasma Enhanced Chemical Vapor Deposition using cobalt nanocatalyst 107 Experimental setup 111 P-type Si (400) wafers with the size of cm cm were used as substrates The wafers were cleaned by ultrasonic method in acetone and ethanol solutions to remove potential residual contaminants prior to deposition The samples were introduced into the planar DC-sputtering system and then pumped down to a base pressure of 101 Pa A cobalt plate was used as a cathode and was placed in parallel with the oven which was grounded The distance between the cathode and anode was about cm Argon was introduced into the chamber with a flow of 200 Standard Centimeter Cubic per Minutes (sccm) The cobalt nanocatalysts were sputtered on Si substrates when the substrate temperature gradually increased up to 100 °C Deposition time for cobalt sputtering was 30 The Plasma Enhanced Chemical Vapor Deposition (PECVD) system in the experiment (Fig 1) was an electric furnace composed of a horizontal quartz glass tube with an internal diameter of 7.5 cm and a length of 80 cm which was operated at atmospheric pressure Argon gas with a flow rate of 200 sccm was supplied into the CVD reactor to prevent the oxidation of catalytic metal while raising the temperature to 750 °C The samples were placed in the chamber and the temperature increased to 850 °C After that, Ar flow was switched off For CNT growth, we used C2H2/NH3 at 35/60 sccm for 15 The growth was terminated by turning off C2H2/NH3 flow and the samples were allowed to cool down to room temperature under Ar gas flow Same experiments were repeated at growth temperatures of 850 °C, 900 °C, 950 °C and 1000 °C during the deposition time of 15 and again at the deposition time of 25 while keeping other growth parameters constant 112 Results and discussions 140 All growth conditions are constant in order to study the temperature effects Prior to carbon nanotube growth, Energy Dispersive X-ray (EDX) measurements were done to investigate the elemental composition of the cobalt catalyst deposited on Si substrates (Fig 2) Atomic Force Microscopy (AFM) in contact mode was used for analyzing the surface morphology of Co film deposited on Si 141 Fig Energy Dispersive X-ray (EDX) measurements show the elemental composition of the cobaltnanocatalyst deposited on Si substrates Please cite this article in press as: Elahi AS et al A new perspective on structural and morphological properties of carbon nanotubes synthesized by Plasma Enhanced Chemical Vapor Deposition technique Results Phys (2017), http://dx.doi.org/10.1016/j.rinp.2017.01.043 108 109 110 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 142 143 144 145 146 RINP 563 No of Pages 5, Model 5G February 2017 A.S Elahi et al / Results in Physics xxx (2017) xxx–xxx Fig (a) 2D and (b) 3D AFM Images of Co film deposited on Si substrates Fig FESEM images of CNTs grown on the cobalt catalyst at growth temperatures of (a) 850 °C, (b) 900 °C, (c) 950 °C and (d) 1000 °C during the deposition time of 15 147 148 149 150 151 152 153 154 155 156 157 substrates (Fig 3(a,b)) AFM images have been obtained in a scanning area of mm mm As it is clear, the formation of catalyst particles with a relatively smooth surface can be observed For the analysis of the uniformity of catalyst distribution along the substrate surface, it is helpful to calculate the roughness value The average roughnesses is 1.91 nm Root-Mean-Square (RMS) roughnesses was measured over the whole area and it was 2.44 nm The RMS roughness of a surface is similar to the roughness average, with the only difference being the mean squared absolute values of surface roughness profile The effect of deposition temperature on CNTs as a function of growth time was investigated FESEM images of CNTs grown on the cobalt catalyst at growth temperatures of 850 °C, 900 °C, 950 °C and 1000 °C during the deposition time of 15 have been shown in Fig 4(a–d) For comparison purposes, the FESEM images of CNTs grown at growth temperatures of 850 °C, 900 °C, 950 °C and 1000 °C during the deposition time of 25 have been shown in Fig 5(a–d) As can be seen in Fig 4(a), the CNTs grown at 850 °C have smaller diameters and production yield is very high When the temperature enhanced and reached to 900 °C, the CNTs diameters have been increased and the efficiency was very low (Fig 4(b)) At 950 °C, the yield slightly increased (Fig 4(c)) and at Please cite this article in press as: Elahi AS et al A new perspective on structural and morphological properties of carbon nanotubes synthesized by Plasma Enhanced Chemical Vapor Deposition technique Results Phys (2017), http://dx.doi.org/10.1016/j.rinp.2017.01.043 158 159 160 161 162 163 164 165 166 167 168 RINP 563 No of Pages 5, Model 5G February 2017 A.S Elahi et al / Results in Physics xxx (2017) xxx–xxx Fig FESEM images of CNTs grown on the cobalt catalyst at growth temperatures of (a) 850 °C, (b) 900 °C, (c) 950 °C and (d) 1000 °C during the deposition time of 25 Fig the HRTEM image of the grown CNT at a growth temperature of 850 °C during the deposition time of 15 using Co as catalyst 169 170 171 172 173 174 175 176 177 178 179 180 181 1000 °C, the efficiency enhanced again but CNTs have large diameters From the Fig 5(a–d), it is found that the deposition time of 25 gave less CNTs population particularly for 900 °C, 950 °C and 1000 °C where large catalyst particles that remained un-reacted amidst the carbon nanotubes were seen At the temperatures of 900 °C and 1000 °C, nucleation was performed but the growth has not taken place On the other hand, the grown CNTs at the temperature of 850 °C among all of the samples during deposition time of 25 have a minimum diameter and maximum efficiency (Fig 5) It is supposed that at high temperature, the metal atoms agglomerate into bigger clusters leading to thick carbon nanotubes Simultaneously, high temperature promotes acetylene decomposition leading to more carbon generation and Fig The Raman spectrum of the produced CNTs at different growth temperatures during deposition time of 15 hence more wall formation Since agglomeration of catalyst particles produces greater particles with lower activities, the number of active sites decreases and the density of grown CNTs is reduced [25] Thus, The CVD temperature plays the central role in CNT growth Fig shows the HRTEM image of the grown CNT at a growth temperature of 850 °C during the deposition time of 15 using Co as catalyst, which confirms that the morphology seen in the FESEM image (Fig 4(a)) have tubular structure, i.e they are multi-walled carbon nanotubes (MWCNTs) The grown CNTs Please cite this article in press as: Elahi AS et al A new perspective on structural and morphological properties of carbon nanotubes synthesized by Plasma Enhanced Chemical Vapor Deposition technique Results Phys (2017), http://dx.doi.org/10.1016/j.rinp.2017.01.043 182 183 184 185 186 187 188 189 190 RINP 563 No of Pages 5, Model 5G February 2017 A.S Elahi et al / Results in Physics xxx (2017) xxx–xxx Fig The Raman spectrum of the produced CNTs at different growth temperatures during deposition time of 25 Table The ratios of the intensities of G and D peaks,IG/ID for produced CNTs at different growth temperatures during deposition time of 15 and 25 191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 Deposition Time Growth temperature G band (cm1) D band (cm1) IG/ID 15 15 15 15 25 25 25 25 850 °C 900 °C 950 °C 1000 °C 850 °C 900 °C 950 °C 1000 °C 1594.56 1595.69 1594.56 1586.82 1594.56 1594.56 1595.69 1586.82 1300.73 1294.29 1293.00 1293.00 1293.00 1300.73 1302.01 1293.00 0.8982 0.9563 0.9155 1.0444 1.0266 0.8102 1.1986 0.7904 were then characterized by Raman spectroscopy The Raman spectrum of the produced CNTs at different growth temperatures during deposition time of 15 is shown in Fig The well separated two Raman peaks at 1500–1605 cm1 for G peaks (graphite band) and at 1250–1450 cm1 for D peaks (disorder induced band) was observed for all samples Also, there is a signal peak in the region of the radial breathing mode (RBM), i.e bellow 300 cm1 of the spectrum The RBM Raman features correspond to the atomic vibration of the C atoms in the radial direction The G0 -band frequency is close to twice that of the D band and is found from 2500 to 2900 cm1 The G0 band is an intrinsic property of the nanotubes and graphite and present even in defect–free nanotubes for which the D-band is completely absent Also, the Raman spectrum of the produced CNTs at different growth temperatures during deposition time of 15 is shown in Fig The IG/ID ratios were calculated to estimate the variation of CNT crystallinity at different growth temperatures during the deposition time of 15 and 25 using Co catalyst (Table 1) This reveals that the trend of CNT crystallinity varies with synthesis temperature and deposition time Here, the ratio of IG /ID is greater than others for the grown CNTs at growth temperature of 950 °C and deposition time of 25 which indicates that these CNTs have good crystalline graphite structure, while from FESEM results found that the diameters of CNTs are raised and density is decreased From the FESEM results, we observed that our CNTs grew with the tip growth mechanism as the catalyst nanoparticles are seen from FESEM images that they are at the tip of the CNTs with brighter color than the nanotubes [15] 207 Conclusions 219 In this work, we demonstrated how growth temperature and deposition time affected the growth of carbon nanotubes using the Co nanocatalyst by the PECVD technique In both of deposition time (15 and 25 min), we changed the growth temperature while keeping other parameters strictly constant It was found that by raising the growth temperature, the degree of crystallinity of grown CNTs increases however agglomeration of nanocatalysts reduces their catalytic activities, which enhance graphite sheet defects 220 References 229 [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] Martel R et al Appl Phys Lett 1998;73:2447 Rinzler AG et al Science 1995;269:1550 Wang QH et al Appl Phys Lett 1998;72:22 Adhikari PD, Song W, Cha M-J, Park C-Y Thin Solid Films 2013;545:50–5 Collins PG et al Science 2000;287:1801 Li GD et al Carbon 2002;40:6 Dresselhaus MS et al Carbon nanotubes synthesis, structure, properties, and applications Berlin: Springer; 2001 Journet C, Master WK, Bernier P, Loiseau A, Lamy de la Chapelle M, Lefrant S, et al Nature 1997;388:756 Thess A, Lee R, Nikolaev P, Dai H, Petit P, Robert J, et al Science 1996;273:483 Dupuis AC Prog Mater Sci 2005;50:929 Gohier A, Ewels CP, Minea TM, Djouadi MA Carbon 2008;46:1331 Song IK, Cho YS, Choi GS, Park JB, Kim DJ Diam Relat Mater 2004;13:1210 Bower C, Zhou O, Zhu W, Werder DJ, Jin S Appl Phys Lett 2000;77:2767 Juang ZY, Chien IP, Lai JF, Lai TS, Tsai CH Diam Relat Mater 2004;13:1203 Aksak M, Kir S, Selamet Y J Optoelectron Adv Mater 2009;1:3 Croin L, Vittone E, Amato G Thin Solid Films 2014;573:122–7 Bartelt NC, McCarty KF MRS Bull 2012;37:1158 Lee Y-H, Lee J-H Appl Phys Lett 2010;96:083101 Su C-Y, Lu A-Y, Wu C-Y, Li Y-T, Liu K-K, Zhang W, et al Nano Lett 2011;11:3612 Ismach A, Druzgalski C, Penwell S, Schwartzberg A, Zheng M, Javey A, et al Nano Lett 2010;10:1542 Kaplas T, Sharma D, Svirko Y Carbon 2012;50:1503 Presland AEB, Price GL, Trimm DL Surf Sci 1972;29:424 Ye J, Thompson CV Appl Phys Lett 2010;97:071904 Szabó Andrea, Perri Caterina, Csató Anita, Giordano Girolamo, Vuono Danilo, Nagy János B Materials 2010;3:3092–140 Ramón ME, Gupta A, Corbet C, Ferrer DA, Movva HCP, Carpenter G, et al ACS Nano 2011;5(9):7198–204 Please cite this article in press as: Elahi AS et al A new perspective on structural and morphological properties of carbon nanotubes synthesized by Plasma Enhanced Chemical Vapor Deposition technique Results Phys (2017), http://dx.doi.org/10.1016/j.rinp.2017.01.043 208 209 210 211 212 213 214 215 216 217 218 221 222 223 224 225 226 227 228 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 251 252 253 254 255 256 257 258 259 260 261 ... Please cite this article in press as: Elahi AS et al A new perspective on structural and morphological properties of carbon nanotubes synthesized by Plasma Enhanced Chemical Vapor Deposition technique. .. cite this article in press as: Elahi AS et al A new perspective on structural and morphological properties of carbon nanotubes synthesized by Plasma Enhanced Chemical Vapor Deposition technique. .. supply of carbon source on the catalyst surface by adsorption and the subsequent catalytic decomposition of the adsorbed carbon by carbon atoms; (2) desorption of the carbon atoms into a gas phase;