pubs.acs.

org/Langmuir 2009 American Chemical Society

Layer-by-Layer Self-Assembly of Graphene Nanoplatelets

Jianfeng Shen, Yizhe Hu, Chen Li, Chen Qin, Min Shi, and Mingxin Ye*
Department of Materials Science, Fudan University, The Key Laboratory of Molecular Engineering of Polymers, Ministry of Education, Shanghai, China Received January 12, 2009. Revised Manuscript Received February 17, 2009
In this report, graphene nanoplatelets were self-assembled through the layer-by-layer (LBL) method. The graphene surface was modified with poly(acrylic acid) and poly(acryl amide) by covalent bonding, which introduced negative and positive charge on the surface of graphene, respectively. Through electrostatic interaction, the positively and negatively charged graphene nanoplatelets assembled together to form a multilayer structure. Thermogravimetric analysis, Raman spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy were used to demonstrate the modification of graphene nanoplatelets. Fourier transform infrared spectroscopy and SEM proved this method is feasible for preparing graphene-containing films. Ultravioletvisible spectroscopy confirmed that the adsorption technique resulted in uniform film growth.

1.

Introduction

Recently, graphene has attracted a tremendous amount of attention. Its novel electronic, mechanical, and thermal properties have been well documented.1-7 However, just as with other newly discovered allotropes of carbon, such as carbon nanotubes (CNTs), material availability and processability have been the rate-limiting steps in the evaluation of graphene application.8,9 A number of works about growth and exfoliation of graphene have been reported.10-15 Among them, micromechanical cleavage is currently the most effective and reliable method to produce high-quality graphene sheets.10 However, the low productivity of this method makes it unsuitable for large-scale applications. High-yield production methods for graphene sheets are desirable for such applications as composite materials and conductive films. Nowadays, exfoliation of graphite oxide either by rapid thermal
*Corresponding author. Tel.: +86-021-55664095. Fax: +86-02155664094. E-mail address: mxye@fudan.edu.cn.

mez-Navarro, C.; Burghard, M.; Kern, K. Nano Lett. 2008, 8, (1) Go 20452049. (2) Liu, N.; Luo, F.; Wu, H. X.; Liu, Y. H.; Zhang, C.; Chen, J. Adv. Func. Mater. 2008, 18, 15181525. (3) Geim, A. K.; Nooselov, K. S. Nat. Mater. 2007, 6, 183191. (4) Meyer, J. C.; Geim, A. K.; Katsnelson, M. I.; Novoselov, K. S.; Booth, T. J.; Roth, S. Nature 2007, 446, 6063. (5) Ishigami, M.; Chen, J. H.; Cullen, W. G.; Fuhrer, M. S.; Williams, E. D. Nano Lett. 2007, 7, 16431648. mez-Navarro, C.; Weitz, R. T.; Bittner, A. M.; Scolari, M.; Mews, A.; (6) Go Burghard, M.; Kern, K. Nano Lett. 2007, 7, 34993503. (7) Ruoff, R. S. Nature 2008, 3, 1011. n, J. M. D. (8) Paredes, J. I.; Villar-Rodil, S.; Mart  nez-Alonso, A.; Tasco Langmuir 2008, 24, 1056010564. (9) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieval, I .V.; Firsov, A. A. Science 2004, 306, 666669. (10) Novoselov, K. S.; Jiang, D.; Schedin, F.; Booth, T. J.; Khotkevich, V. V.; Morozov, S.; Geim, A. K. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 1045110453. (11) Hernandez, Y.; Nicolosi, V.; Lotya, M.; Blighe, F. M.; Sun, Z. Y.; De, S.; McGovern, I. T.; Holland, B.; Byrne, M.; GunKo, Y. K.; Boland, J. J.; Niraj, P.; Duesberg, G.; Krishnamurthy, S.; Goodhue, R.; Hutchison, J.; Scardaci, V.; Ferrari, A. C.; Coleman, J. N. Nat. Nanotech. 2008, 3, 563568. (12) Stankovich, S.; Piner, R. D.; Nguyen, S. T.; Ruoff, R. S. Carbon 2006, 44, 33423347. (13) Subrahmanyam, K. S.; Vivekchand, S. R. C.; Govindaraj, A.; Rao, C. N. R. J. Mater. Chem. 2008, 18, 15171523. (14) Somani, P. R.; Somani, S. P.; Umeno, M. Chem. Phys. Lett. 2006, 430, 5659. (15) Worsley, K. A.; Ramesh, P.; Mandal, S. K.; Niyogi, S.; Itkis, M. E.; Haddon, R. C. Chem. Phys. Lett. 2007, 445, 5156.

expansion or ultrasonic dispersion has been one of the best approaches to obtain graphene oxide (GO) in bulk.16-18 Compared to other production techniques, this process is attractive because of its reliability, amenability to large-scale production, and exceptionally low material costs. Besides, GO consists of graphene-like sheets, chemically functionalized with compounds such as hydroxyls and epoxides, which stabilize the sheets in water. However, since GO is electrically insulating, which limits its usefulness for electronic devices, the chemical reduction of exfoliated GO is used to make it electrically conductive.19,20 Nowadays, one possible route to harnessing excellent properties of graphene sheets for applications is to incorporate them into composite materials.21-24 The manufacturing of such composites requires not only that graphene sheets be produced on a sufficient scale but also that they be incorporated, and homogeneously distributed, into various matrices. To achieve this goal, some researchers have focused attention on the processability of graphene sheets.25 Previous studies of our group26 have shown that polymer-grafted graphene
(16) McAllister, M. J.; Li, J. L.; Adamson, D. H.; Schniepp, H. C.; Abdala, A. A.; Liu, J.; Herrera-Alonso, M.; Milius, D. L.; Car, R.; Prudhomme, R. K.; Aksay, I. A. Chem. Mater. 2007, 19, 43964404. (17) Schniepp, H. C.; Li, J. L.; McAllister, M. J.; Sai, H.; Herrera-Alonso, M.; Adamson, D. H.; Prudhomme, R. K.; Car, R.; Saville, D. A.; Aksay, I. A. J. Phys. Chem. B 2006, 110, 85358539. (18) Si, Y. C.; Samulski, E. T. Nano. Lett. 2008, 8, 16791682. (19) Gilje, S.; Han, S.; Wang, M. S.; Wang, K. L.; Kaner, R. B. Nano. Lett. 2007, 7, 33943398. (20) Stankovich, S.; Dikin, D. A.; Piner, R. D.; Kohlhaas, K. A.; Kleinhammes, A.; Jia, Y. Y.; Wu, Y.; Nguyen, S. T.; Ruoff, R. S. Carbon 2007, 45, 15581565. (21) Stankovich, S.; Dikin, D. A.; Dommett, G. H. B.; Kohlhaas, K. M.; Zimney, E. J.; Stach, E. A.; Piner, R. D.; Nguyen, S. T.; Ruoff, R. S. Nature 2006, 442, 282286. (22) Wang, X.; Zhi, L. J.; Muellen, K. Nano Lett. 2008, 8, 323327. (23) Watcharotone, S.; Dikin, D. A.; Stankovich, S.; Piner, R.; Jung, I.; Dommett, G. H. B.; Evmenenko, G.; Wu, S. E.; Chen, S. F.; Liu, C. P.; Nguyen, S. T.; Ruoff, R. S. Nano Lett. 2007, 7, 18881892. (24) Ramanathan, T.; Abdala, A. A.; Stankovich, S.; Dikin, D. A.; Herrera-alonso, M.; Piner, R. D.; Adamson, D. H.; Schniepp, H. C.; Chen, X.; Ruoff, R. S.; Nguyen, S. T.; Aksay, I. A.; Prudhomme, R. K.; Brinson, L. C. Nat. Nanotech. 2008, 3, 327331. (25) Niyogi, S.; Bekyarova, E.; Itkis, M. E.; McWilliams, J. L.; Hamon, M. A.; Haddon, R. C. J. Am. Chem. Soc. 2006, 128, 77207721. (26) Shen, J. F.; Hu, Y. Z.; Li, C.; Qin, C.; Ye, M. X. Small 2009, 5, 8285.

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nanoplatelets with vey good solubility can be achieved through in situ radical polymerization. On the other hand, interest in layer-by-layer (LBL) selfassembly has increased dramatically in the past decade. It is widely used as a powerful and versatile method for the preparation of ultrathin multilayer films containing CNTs.27-31 Since polyelectrolytes (PEs) allow for interesting surface patterning structures, they are widely used in LBL preparation of CNT films.32-36 Despite some methods dealing with the assembly of graphene sheets being proposed, e.g., by filtration of colloid dispersions of functionalized graphene sheets,37-39 assembly of chemically converted graphene sheets,40,41 and assembly with molecular templates,42 whether graphene-based LBL films with PEs can be made remains unexplored since graphene sheets differ substantially from CNTs in their geometry, which should change the dynamics of adsorption. Here we outline a process for the assembly of graphenebased LBL films. Our basic strategy involved the complete exfoliation of graphite oxide into individual GO sheets followed by their in situ reduction to produce individual graphene sheets. After that, poly(acrylic acid) (PAA) and poly (acryl amide) (PAM) were covalently grafted on the graphene sheets by in situ living free radical polymerization. Then, we show formation of graphene-based multilayer LBL films through sequential adsorption of PE-functionalized graphene sheets (PEs-g-graphene) and other different charged PEs. There are three advantages of our method: (1) The prevention of aggregation in solution is of particular importance for graphene sheets because most of their unique properties are only associated with individual sheets. PEs-g-graphene used in this method can disperse pretty well in water, which can solve the aggregation problem. (2) Most of the continuous -electronic structure of graphene sheets can be sustained through this method. (3) The force between anionic and cationic PEsg-graphene layers of the composite will be relatively strong, which will be very useful for the investigation and application of these graphene-containing films.
(27) Lavalle, P.; Gergely, C.; Cuisinier, F. J. G.; Decher, G.; Schaaf, P.; Voegel, J. C.; Picart, C. Macromolecules 2002, 35, 44584465. (28) Shen, J. F.; Hu, Y. Z.; Qin, C.; Ye, M. X. Langmuir 2008, 24, 39933997. (29) Picart, C.; Mutterer, J.; Richert, L.; Luo, Y.; Prestwich, G. D.; Schaaf, P.; Voegel, J.; Lavalle, P. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 1253112535. :: (30) Caruso, F.; Lichtenfeld, H.; Donath, E.; Mohwald, H. Macromolecules 1999, 32, 23172328. (31) Katagiri, K.; Matsuda, A.; Caruso, F. Macromolecules 2006, 39, 80678074. (32) Mamedov, A. A.; Kotov, N. A.; Prato, M.; Guldi, D. M.; Wicksted, J. P.; Hirsch, A. Nat. Mater. 2002, 1, 190194. (33) Chattopadhyay, D.; Galeska, I.; Papadimitrakopoulos, F. J. Am. Chem. Soc. 2001, 123, 94519452. (34) Artyukhin, A. B.; Bakajin, O.; Stroeve, P.; Noy, A. Langmuir 2004, 20, 14421448. (35) Rouse, J. H.; Lillehei, P. T. Nano Lett. 2003, 3, 5962. (36) Huang, S. C.; Artyukhin, A. B.; Wang, Y. M.; Ju, J. W.; Stroeve, P.; Noy, A. J. Am. Chem. Soc. 2005, 127, 1417614177. (37) Zhu, Z. P.; Su, D. S.; Weinberg, G.; Schloegl, R. Nano Lett. 2004, 4, 22552259. (38) Dikin, D. A.; Stankovich, S.; Zimney, E. J.; Piner, R. D.; Dommett, G. H. B.; Evmenenko, G.; Nguyen, S. T.; Ruoff, R. S. Nature 2007, 448, 457460. (39) Xu, Y. X.; Bai, H.; Lu, G. W.; Li, C.; Shi, G. Q. J. Am. Chem. Soc. 2008, 130, 58565857. (40) Li, X. L.; Zhang, G. Y.; Bai, X. D.; Sun, X. M.; Wang, X. R.; Wang, E.; Dai, H. J. Nat. Nanotech. 2008, 3, 538542. (41) Li, D.; Mueller, M. B.; Gilje, S.; Kaner, R. B.; Wallace, G. G. Nat. Nanotech. 2008, 3, 101105. (42) Wei, Z. Q.; Barlow, D. E.; Sheehan, P. E. Nano Lett. 2008, 8, 31413145.

2.

Experimental Section

Materials. Expandable graphite (EG) 8099200 (180 m) was purchased from Qingdao BCSM. CO., LTD., which was supposed to expand to nearly 200 times its original size after being treated at about 1000 C. Dimethylformamide (DMF), 98% H2SO4, 30% H2O2, and potassium permanganate (KMnO4) were purchased from Shanghai Zhenxin Chemical Company. Poly(diallyldimethylammonium chloride) (PDDA; Mw: 20 000) and sodium polyacrylate (PAAS; Mw: 30 000) were purchased from Aldrich and used as received. All other reagents were at least of analytical reagent grade and used without further purification. Doubly distilled water was used in all the processes of aqueous solution preparations and washings. Preparation of PEs-g-graphene. EG was first treated at 1050 C in air for 15 s. The size was enlarged up to nearly 200 times its original amount. Expandable graphite oxide (EGO) was obtained based on Hummers method.43 Generally, 5 g of thermal treated EG powders was added to 115 mL of 98% H2SO4 in an ice bath. An amount of 15 g of KMnO4 was slowly added with stirring, and the rate of addition was controlled carefully to avoid a sudden increase in temperature. The mixture was then maintained at 35 C for 30 min. Deionized water (230 mL) was gradually added, causing an increase in temperature to 98 C. After 15 min, the mixture was further treated with 700 mL of deionized water and 50 mL of 30% H2O2 solution. EGO was washed with deionized water until the pH was 7 and then dried at 65 C in vacuum. EGO (30 mg) was loaded in a 250 mL dried four-necked flask, and 50 mL of solvent (9:1 DMF/water) was then added. After stirring and ultrasonication for 30 min, 0.0248 g (0.0064 mol) of NaBH4 was added to the mixture. The solution was heated in an oil bath at 80 C for 4 h, and reduced GO was observed (as confirmed in the Discussion section, they were shown to be graphene nanoplatelets). Acrylic acid (10 g or 5 g of acryl amide) and 40 mL of H2O were added to the flask. After stirring for 30 min, the solution was purged under dry nitrogen for 30 min to remove oxygen, followed by addition of 100 mg of (NH4)2S2O8 (dissolved in 80 mL of water) through a dropping funnel. The flask was placed in a thermostatted oil bath at 60 C under stirring and sonication. After 48 h the mixture was cooled to room temperature, diluted with 200 mL of H2O, bath sonicated for 1 h, and then centrifuged.28 Preparation of Multilayer Assemblies. The graphene nanoplatelet-based LBL films were obtained through a similar process based on ref 28. Adsorptions were carried out at room temperature in open beakers containing components. Substrates for film formation were either silicon or glass slides that were first made hydrophilic by treatment with 3:1 v/v % concentrated H2SO4 and HNO3, followed by extensive rinsing with doubly distilled water. Multilayer films were grown by cyclic immersion in positively charged water solution of PDDA (1 mg/mL containing 0.5 M NaCl), negatively charged solution of PAA-g-graphene (0.1 mg/mL), positively charged solution of PAM-g-graphene (0.1 mg/mL, pH = 3 by adding HCl to make it protonated), and negatively charged solution of PAAS (1 mg/ mL containing 0.5 M NaCl). Exposure times of 20 and 180 min were used for PEs and PEs-g-graphene, respectively. After every layer deposition, the sample was repeatedly immersed in pure distilled water 3 times to remove the excess of assembling materials and then dried with bubbling nitrogen. This sequence was repeated to obtain the desired number of layers, which was designated as {PDDA/PEs-g-graphene/PAAS}n. Instruments and Measurement. Water bath sonication was performed with a JYD 1200 L sonicator (250 W). The average molecular weight and molecular weight distribution were determined by a gel permeation chromatography (GPC) instrument (Waters Breeze, USA) with tetrahydrofuran (THF) as an eluant
(43) Hummers, W. S.; Offeman, R. E. J. Am. Chem. Soc. 1958, 80, 1339.

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Figure 1. Procedures used in this study.

and narrow polystyrene as the calibration standard. A Netzsch TG 209 apparatus was used for the thermogravimetric analysis (TGA). The analysis was fitted to a nitrogen purge gas at a 10 C/min heating rate. Before the tests, all the samples were carefully grinded to powders to ensure sufficient diffusion of heat. Raman spectra were recorded on a Dilor LABRAM-1B multichannel confocal microspectrometer with 514 nm laser excitation. Scanning electron microscopy (SEM) was performed with a Philips XL30 FEG FE-SEM instrument at an accelerating voltage of 25 kv. Samples were sputter-coated with 5 nm of gold to improve contrast. Atomic force micrographs (AFM) were obtained using a Multimode Nano4 in the tapping mode. The samples were prepared by depositing their dispersions on HOPG substrates and allowing them to air dry. Fourier transform infrared spectroscopy (FTIR) spectra were recorded on a NEXUS 670 spectrometer. Transmission ultraviolet-visible (UV-vis) spectra were recorded with an APADA UV-1800PC Spectrophotometer. Spectra were acquired from 800 to 200 nm at a scan speed of 200 nm/min and a spectra resolution of 1 nm.

3. Results and Discussion Just like CNTs and many other nanomaterials, a key challenge in the synthesis and processing of bulk-quantity graphene sheets is aggregation. Graphene sheets, due to their high specific surface area, tend to form irreversible agglomerates or even restack to form graphite through van der Waals interactions. The resulting graphene sheet agglomerates appear to be insoluble in water and organic solvents, making further processing difficult. In the present study, charge-rich PAA and PAM were wrapped along the graphene sheets through in situ radical polymerization. Like CNTs, graphene nanoplatelets can be activated by free radical initiators to open their -bonds and then participate in polymerization of monomers. Besides, graphene nanoplatelets will always have some defects on them, which make them able to be activated much more easily. Since PAA and PAM have good water solubility, they prevented graphene sheets from conglomeration and sedimentation. The Mn values of prepared PAA and PAM were 1.11 104 and 1.05 104, respectively (prepared and tested in
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a control experiment). The procedures used in this study were shown in Figure 1. TGA is a complementary technique that can reveal the composition and changes in thermal stability of the samples. Figure 2 shows TGA curves of EGO, reduced GO, PAM modified graphene sheets (PAM-g-graphene), and PAA modified graphene sheets (PAA-g-graphene). In agreement with previous reports in the reference,16 although EGO is thermally unstable and starts to lose mass upon heating even below 100 C, the major mass loss occurs at about 200 C, presumably due to pyrolysis of the labile oxygen-containing functional groups, yielding CO, CO2, and steam (Figure 2a-1). On the other hand, the removal of the thermally labile oxygen functional groups by chemical reduction increased thermal stability for reduced GO (Figure 2a-2), showing 2% weight loss in nitrogen atmosphere at 700 C. As for PE grafted graphene nanoplatelets, PAM-g-graphene and PAAg-graphene gave 65% and 82% weight loss at 700 C, respectively (Figure 2a-3 and Figure 2a-4). Therefore, the composite contains graphene nanoplatelets and PAM (PAA), with weight ratios of 1/2 (2/9), demonstrating high efficiency of the grafting polymerization. Furthermore, compared with the net polymers (Figure 2b), the decomposition of polymers during TGA experiments in the presence of graphene nanoplatelets follows a different pathway. Besides, the onset of decomposition temperature for PE-g-graphene seems to be lower than that for net polymers. This phenomenon is very interesting, and it indicates that the presence of graphene may affect the decomposition of the attached polymers. The mechanism and reason of this phenomenon are still under investigation. Raman scattering is strongly sensitive to the electronic structure of samples, and its result is often taken as evidence for the chemical functionalization of graphite materials.15 Figure 3 shows typical Raman spectra of raw graphite, reduced GO, PAA-g-graphene, and PAM-g-graphene. It is obvious in Figure 3 that after functionalization the characteristic peaks of graphite, namely, the D band at 1330 cm-1 (the disorder band) and the G band at 1580 cm-1 (the tangential
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Figure 2. (a) TGA of EGO (1), reduced GO (2), PAM-g-graphene (3), and PAA-g-graphene(4). (b) TGA of pure PAA and PAM. dispersion of the powder in a solvent. Representative atomic force microscopy (AFM) images of reduced GO, PAA-ggraphene, and PAM-g-graphene in tapping mode are shown in Figure 5. Well-dispersed graphene nanoplatelets were observed in Figure 5a. It was found that the average thickness of graphene nanoplatelets was 1.2 nm, leading to a conclusion that complete exfoliation of graphene nanoplatelets down to 13 layers was achieved under these conditions since the intersheet distance for graphene sheets was about 0.34 nm. As for the PAA-g-graphene (Figure 5b) and PAM-g-graphene (Figure 5c), because of the wrapping of PAA and PAM on graphene nanoplatelets, the average thicknesses of PAA-ggraphene and PAM-g-graphene become 2.0 and 1.8 nm, respectively. Since PAA-g-graphene and PAM-g-graphene are expected to be thicker due to the presence of the sp3hybridized carbon atoms slightly above and below the original graphene plane, we can expect that the heights of them are consistent with the data of reduced GO. In addition, it is found that the sizes of PEs-g-graphene are smaller than those of the reduced GO. Since PEs-g-graphene can disperse much better in solution, while reduced GO still tends to agglomerate though undersonication, the object size of reduced GO derived from AFM analysis will be enlarged. Besides, areas of low functionalization are also seen at lower heights with similar color to that of the background. We attribute the variability in the height to the local degree of functionalization, with high points indicating areas of the samples where the wrapping of PAA and PAM is especially dense, which is consistent with the result of TGA. To prepare LBL films, the uniform distribution of nanofillers within the matrix is the essential structural requirement. Besides, it is also widely known that graphene sheets tend to form irreversible agglomerates or even restack to form graphite through van der Waals interactions. In this work, we tried to use PEs-g-graphene to solve this problem. It is found that the PEs needed to be present in sufficient concentration to compete with the hydrophobic interaction between the graphene sheets. During the in situ radical polymerization process, PEs will covalently wrap themselves on the surface of graphene sheets, which disrupts the van der Waals interactions and leads to isolation of graphene sheets. Once enough PEs are attached to the surface of graphene sheets, further agglomeration of the sheets will be stopped. Figure 6 shows FTIR spectra of EGO (1), PAA-g-graphene (2), PAM-g-graphene (3), and PDDA/PEs-g-graphene/PAAS (4). In the spectrum of EGO, the peak at 1720 cm-1 is in
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Figure 3. Raman spectra of raw graphite, reduced GO, PAA-ggraphene, and PAM-g-graphene. vibration mode), have changed. After reduction, we discern a gradual decrease of the D band, indicating the successful removal of the oxygen-containing functional groups from GO. As to the bands of PAA-g-graphene and PAM-g-graphene, their G bands are broadened and slightly shifted to 1590 cm-1. Besides, comparing with raw graphite, the ratios of the intensities (ID/IG) for both PAA-g-graphene and PAMg-graphene were markedly increased, indicating the formation of the sp3 carbon after functionalization. Raman spectral results described above agree well with those reported by Stankovich and Xu,20,39 indicating that the covalent modification of graphene sheets by PEs was successful. In addition, this result is also consistent with TGA (Figure 2) and FTIR (Figure 6) data. Figure 4 shows SEM images of raw graphite, EGO, PAA-ggraphene, and PAM-g-graphene. Compared with graphite (Figure 4a), the general structure of EGO (Figure 4b) is not greatly changed, but the image of EGO is distinguishable from pristine graphite by the appearance of bright regions lacking ordered lattice features. They are most likely arising from the presence of oxygenated functional groups. As for PAA-ggraphene and PAM-g-graphene, the samples also consist of randomly aggregated, thin, crumpled sheets closely associated with each other and form disordered solids (Figure 4c and 4d). Besides, their structures seem to be flurry, which may be because of the attachment of the polymers. AFM has been one of the most direct methods of quantifying the degree of exfoliation to graphene sheets level after the
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Figure 4. SEM images of raw graphite (a), EGO (b), PAA-g-graphene (c), and PAM-g-graphene (d) before sonication, with a concentration of 0.1 mg/mL. correspondence to CdO stretching vibration. In the spectrum of PAA-g-graphene, the strong peak of the CdO stretching vibration can also be seen, while peaks at 3400 and 1420 cm-1 are related to the stretching vibration and deformation of O-H. In the spectrum of PAM-g-graphene, peaks at 3450 and 1650 cm-1 are due to the N-H stretching vibrations. As to the spectrum of PDDA/PEs-g-graphene/PAAS, we can see that peaks in the spectra of PAA-g-graphene and PAM-ggraphene still exist. Besides, we also observe the asymmetric C-H stretch of the alkyl group at 2960 cm-1 and the stretching peak of C-OH at 1220 cm-1, which also proves the existence of PDDA and PAAS. These results support that the preparation of PEs-g-graphene is successful, and the LBL process is practicable. SEM images of the films after one cycle (a) and three cycles (b) are shown in Figure 7. It is clearly seen that the first layer had a certain amount of graphene sheets (Figure 7a), revealing the successful deposition of graphene nanoplatelets on the substrate. Random networks of sheets oriented parallel to the surface were visible in the films, and the surface density of sheets increased with the number of cycles. After more deposition cycles (Figure 7b), PEs-g-graphene densely covered the substrate. Besides, it can also be seen that the size of the sheets in the films is much larger than that in the solution (as suggested by AFM data). Since the density of graphene nanoplatelets in solution is high, they will connect with each other and form these flakes during the absorption process, which enlarge the object size derived from SEM analysis. Given the overlapping morphology of the film, graphene
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adsorption occurs as a result of the adsorbing graphene nanoplatelets interacting with multiple layers already on the surface. As a consequence, a porous film, containing voids between the adsorbed layers of graphene nanoplatelets, was formed. While FTIR and SEM were proved to be useful for characterizing initial film growth, determining whether PEsg-graphene adsorption was occurring reproducibly was difficult from them. The prepared films were also characterized by UV-vis spectroscopy as shown in Figure 8. Figure 8a shows the increase in absorbance upon assembly of PEs-g-graphene in each layer on the glass slide, while Figure 8b shows the dependence of the absorption (at wavelength of 600 nm) on the number of LBL cycles for the films containing graphene nanoplatelets. The clear increase in the absorbance with the assembly step is indicative of the film deposition on the substrate. In addition, the linearity between the absorbance with the layer number (Figure 8b) further suggests that almost the same amount of PEs-g-graphene was loaded in each assembling step. Compared with the system of CNTs in our last study,28 though the same assembly systems are used, the adsorption of graphene nanoplatelets is quite different. As found in the last study, the dependence of CNTs with the number of deposited layers is nonlinear and exhibits a decaying mode. While in the system of graphene nanoplatelets, the dependence is linear. The mechanisms of the two systems may be as follows: both of the systems contain two kinds of PEs-g-graphene (PEs-gCNTs). One is strongly involved in interaction with PEs to
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Figure 5. AFM images of reduced GO (a), PAA-g-graphene (b), and PAM-g-graphene (c) solution after sonication, with a concentration of 0.01 mg/mL. Image dimensions are 1 m 1 m. thus acts as a perfect sink for the mobile PEs-g-graphene (PEsg-CNTs) in the film. The weakly bonded PEs-g-graphene (PEs-g-CNTs) constitutes the major out driving force. On the other hand, when exposed to different charged PEs, many PEs-g-graphenes (PEs-g-CNTs) will absorb on the film, and the strongly bonded part will be the major in driving force. Inside the film, there must always be equilibrium between free and bound PEs-g-graphene (PEs-g-CNTs). The exchange mechanism leads to continuous film restructuring.27 In the PEs-g-CNTs system, with the increase of the number of layers, though more and more MWCNT-PEs are deposited, the van der Waals force between them becomes stronger and stronger, leaving fewer and fewer strongly bonded PEs-g-CNTs on the surface. With higher density (2 mg/mL) in solution, increased electrostatic repulsion between like-charged components will be a compensation effect to reduce the number of adsorbed CNTs as the area of the film expands and the partial desorption of previously adsorbed CNTs will occur. As a result, the dependence of the thickness of the film is nonlinear and exhibits a decaying mode. While in the PEs-g-graphene system, the linear evolution of thickness increment can be due to less density (0.1 mg/mL) and longer deposition time
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Figure 6. FTIR spectra of EGO (1), PAA-g-graphene (2), PAM-ggraphene (3), and PDDA/PEs-g-graphene/PAAS (4). constitute the network of the multilayer, and the other kind is weakly bound to the PE surface (mobile PEs-g-graphene and PEs-g-CNTs) to form the film structure. The solution surface
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Figure 7. SEM images of the films after one cycle (a) and three cycles (b).

Figure 8. UV-vis spectra of {PDDA/PEs-g-graphene/PSS}n LBL assembled on a glass slide (a) and the absorbance at 385 nm versus the number
of adsorption cycles (b).

(denser structure will be formed with longer deposition time). The compensation effect of electrostatic repulsion and the increment effect of longer deposition will have a balance. Finally, each LBL adsorption step results in the formation of a continuous monolayer, and the repetition of n deposition cycles yields a composite homogeneous film whose thickness is proportional to n. Besides the different structure of graphene nanoplatelets and CNTs, the different densities of PAA and PAM on graphene nanoplatelets and CNTs may also be very important factors for the different behavior. Further experiments and more efforts are now needed to be able to prove the mechanisms of the two different systems.

4.

Conclusions

We present a detailed study on the preparation and characterization of graphene nanoplatelet-based LBL films. The general concept applied in this paper is to arrange a broad

range of macromolecules into highly ordered architectures by self-assembly through electrostatic interactions on flat templates. PAA-g-graphene and PAM-g-graphene, forming stable dispersion in water, were obtained by modifying graphene sheets with charge-rich PAA and PAM. Graphenebased multilayer LBL films were formed through sequential adsorption of PE-functionalized graphene sheets (PEs-g-graphene) and other different charged PEs. Taken together, FTIR, SEM, and UV-vis analysis suggest that the increase of PEs-g-SWCNTs in each assembly step is uniform. By using this process, important parameters such as size, geometry, and composition of the films can be readily controlled. All in all, this demonstration offers a new route to graphene-based multilayer films and composites. It would be reasonable to expect that this method can use the powerful electrostatic assembly technique to manipulate graphene nanoplatelets for creating new and potentially useful nanosystems.

6128

DOI: 10.1021/la900126g

Langmuir 2009, 25(11), 61226128