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(12) United States Patent (10) Patent No.: US 9,017,474 B2 Geim Et Al US00901.7474B2 (12) United States Patent (10) Patent No.: US 9,017,474 B2 Geim et al. (45) Date of Patent: Apr. 28, 2015 (54) FUNCTIONALIZED GRAPHENE AND 2011/0186786 A1* 8, 2011 Scheffer et al. ............... 252/510 METHODS OF MANUFACTURING THE 2011/0186789 A1* 8, 2011 Samulski et al. .. ... 252/514 SAME 2012/0021293 A1 1/2012 Zhamu et al. .............. 429,2315 (75) Inventors: Andre Geim, Manchester (GB); Rahul OTHER PUBLICATIONS Raveendran-Nair, Manchester (GB); Kostya Novoselov, Manchester (GB) http://www.merriam-Webster.com/dictionary/composite; May 23, s 2014. (73) Assignee: The University of Manchester, Blake, P. et al., “Graphene-based liquid crystal device.” Nano Lett. Manchester (GB) 8(6): 1704-1708, (Apr. 30, 2008). Castro Neto, A., et al., “The electronic properties of graphene.” Rev. (*) Notice: Subject to any disclaimer, the term of this Mod. Phys., 81(1): 109-162, (2009). patent is extended or adjusted under 35 Charlier, J., et al., “First-principles study of graphite monofluoride U.S.C. 154(b) by 436 days. (CF).” Phys Rev. B. 47(24): 16162-16168, (1993). Cheng, S., “Reversible fluorination of graphene: towards a two (21) Appl. No.: 13/158,064 dimensional wide bandgap semiconductor. J. Am. Chem. Soc., 101:3832-3841, (1979). (22) Filed: Jun. 10, 2011 Conesa, J. and Font, R., “Poytetrafluoroethylene decomposition in air and nitrogen.” Polym. Eng. Scie., 41(12):2137-2147 (Dec. 2001). (65) Prior Publication Data Eda, C. and Chhowalla, M.. “Chemically derived graphene oxide: US 2011 FO3O3121 A1 Dec. 15, 2011 towards large-area thin-film electronics and optoelectronics.” Adv. • als Mater. 22(22):2392-2415, (Jun. 11, 2010). (30) Foreign Application Priority Data (Continued) Jun. 10, 2010 (GB) ................................... 1OO9718.6 51) Int. C Primary Examiner — Guinever Gregorio (51) Oil 31/04 (2006.01) (74) Attorney, Agent, or Firm — Greenberg Traurig, LLP: B82Y 30/00 (201 101) Chinh H. Pham; Natalie Salem B824.0/00 (2011.01) (52) U.S. Cl. (57) ABSTRACT CPC ............. COIB31/0484 (2013.01); B82Y 30/00 (2013.01); B82Y40/00 (2013.01); COIB The present invention relates to the novel material fluo 2204/30 (2013.01) rographene (FG), methods of making fluorographene, and its (58) Field of Classification Search applications in electronics and related fields. The fluo CPC combination set(s) only. rographene also finds use in improving the properties of com See application file for complete search history. posite materials by incorporating the fluorographene of the invention with one or more materials such as fluoropolymers (56) References Cited (FP) and the like. Conventionally, FP inter-chain interactions U.S. PATENT DOCUMENTS are very weak but spread over the area of FG, FG is able to act M as a very effective and compatible reinforcement. 2007/0231696 A1* 10, 2007 Yazami et al. ............. 429,231.7 2011 OO68290 A1* 3, 2011 Haddon et al. ......... 252/62.51 R. 2011/0156019 A1* 6, 2011 Tessler et al. ................... 257/40 13 Claims, 12 Drawing Sheets & US 9,017.474 B2 Page 2 (56) References Cited Ponomarenko, L., et al., “Chaotic dirac billiard in graphene quantum dots.” Science, 320(5874):356-358, (Apr. 18, 2008). OTHER PUBLICATIONS Robinson, J., et al., “Properties of fluorinated graphene films.” Nano Left, 10(8):3001-3005. (Aug. 11, 2010). Ruff, O. and Bretschneider, O., “Die reaktions.produkte der Elias, D., et al., “Control of graphene's properties by reversible verschiedenen Kohlenstoffformen mit Fluor II (Kohlenstoff hydrogenation: Evidence for graphene.” Science, 323(5914):610 monofluorid).” Z. Anorg. Allg. Chem. 217(1):1-18, (Feb. 23, 1934). 613, (Jan. 30, 2009). (English translation of abstract provided). Geim, A. and Novoselov, K. “The rise of graphene.” Nature Mater. Ruoff, R., "Calling all chemists.” Nature Nanotech. 3:10-11. (Jan. 6:83-191, (2007). 2008). Geim, A., “Status and prospects.” Science, 324(5934): 1530-1534, Schedin, F., et al., “Detection of individual gas molecules absorbed on graphene.” Nature Mater. 6:652-655, (2007). (Jun. 19, 2009). Sharma, R., "Anomalously large reactivity of single graphene layers Guinea, F., et al., “Energy gaps and a Zero-field quantum Hall effect and edges toward electron transfer chemistries.” Nano Lett. in graphene by strain engineering.” Nature Phys. 6:30-33, (2010). 10(2):398-405, (Jan. 7, 2010). Han, M., et al., “Energy band-gap engineering of graphene nanorib Sofo, J., et al., “Graphane: A two-dimensional hydrocarbon.” Phys. bons.” Phys. Rev. Lett., 98(20):206805, (2007). Rev. B., 75(15): 153401, (2007). Hernandez. Y., et al., “High-yield production of graphene by liquid Stauber, T., "Optical conductivity of graphene in the visible region of phase exfoliation of graphite.” Nat. Nanotechnol. 3:563-568, (Sep. the spectrum.” Phys. Rev. B, 78(8):085432, (2008). 2008). Takagi, Y. and Kusakabe, K., “Transition from direct band gap to Hills, M. and Arnold, G., “Chemical treatment of fused silica with indirect band gap in fluorinated carbon.” Phys Rev. B., xenon difluoride.” Applied Surface Science, 47(1):77-90, (Jan. 65(12): 121103, (2002). 1991). Takahagi, T., et al., "Chemicl structure and reactivity of a silicon Kita, Y., et al., "Chemical composition and crystal structure of graph single cyrstal surface fluorinated by xenon fluoride.” J. Appl. Phys. ite fluoride.” J. Am. Chem. Soc., 101 (14):3832-3841, (Jul. 4, 1979). 76(5):3140. (1994). Kravets, V., et al., “Spectroscopic ellipsometry of graphene and an Touhara, H., et al., “On the structure of graphite fluoride.” Z. Anorg. exciton-shifted van Hove peak in absorption.” Phys. Rev. B. Allg. Chem. 544(1):7-20, (Jan. 1987). 81(15): 155413, (2010). Watanabe, N. et al., “Graphite fluorides.” Elsevier Press, Amsterdam, Lee, C., et al., “Measurement of the elastic properties and intrinsic Ch. 2: 30-39 (1988). strength of monolayer graphene.” Science, 321 (5887):385-388, (Jul. Watanabe, N. et al., “Graphite fluorides.” Elsevier Press, Amsterdam, 18, 2008). Ch. 5: 149-203 (1988). Li, X., et al., "Chemically derived, ultrasmooth graphene nanoribbon Watanabe, N. et al., “Graphite fluorides.” Elsevier Press, Amsterdam, semiconductors.” Science, 319(5867): 1229-1232, (Feb. 29, 2008). Ch. 7228-239(1988). Liu, H., “Photochemical reactivity of graphene.” J. Am. Chem. Soc., Baraket et al., “The functionalization of graphene using electron 131(47): 17099-17101, (2009). beam generated plasmas”. Applied Physics Letters, vol. 96, No. 23, McFeely, F., et al., “Synchrotron photoemission investigation of the pp. 231501-1-231501-3, Jun. 8, 2010. initial stages of fluorine attack on Si Surfaces: Relative abundance of Bon et al., “Plasma Fluorination of Chemically Derived Graphene fluorosilyl species.” PRB, 30(2):764-770, (1984). Sheets and Subsequent Modification With Butylamine”, Chemistry Meyer, J., et al., “Hydrocarbon lithography on graphene mem of Materials, vol. 21, No. 14, pp. 3433-3438, Jul. 28, 2009. branes.” Appl. Phys. Lett. 92: 123110, (2008). Cheng et al., “Reversible fluorination of graphene: Evidence of a Morar, J., et al., “Synchrotron photoemission investigation: Fluorine two-dimensional wide bandgap semiconductor'. Physical Review B on silicon surfaces.” APL, 45(2):174. (1984). (Condensed matter and Materials Physics) American Physical Soci Nair, R., et al., “Fine structure constant defines visual transparency of ety, vol. 81, No. 20, pp. 205435-1-205435-5, May 3, 2010. graphene.” Science, 320(5881): 1308, (Jun. 6, 2008). Unger et al., “Fluorination of carbon nanotubes with xenon Nair, R., et al., “Fluorographene: a two-dimensional counterpart of difluoride'. Chemical Physics Letters, vol.399, No. 1-3, pp. 280-283, Teflon.”Small, 6(24):2877-2884, (Dec. 20, 2010). Nov. 21, 2004. Novoselov, K., et al., “Two-dimensional atomic crystals.” Proc. Natl. International Search Report for PCT/GB2011/051087 mailed Oct. Acad. Sci. USA, 102(30): 10451-10453, (Jul 26, 2005). 25, 2011. Park, S. and Ruoff, R., "Chemical methods for the production of graphenes.” Nature Nanotechnol. 4:217-224, (2009). * cited by examiner U.S. Patent Apr. 28, 2015 Sheet 1 of 12 US 9,017,474 B2 8 & p88& t agistegEru 3 ...8towai -- - - - & , , 8 , 8 8 8 expossie l to attatrix: * ficrg:xxxixx: ---------------------------------- FIGURE 1 U.S. Patent Apr. 28, 2015 Sheet 2 of 12 US 9,017,474 B2 3. & : FGURE 2 U.S. Patent Apr. 28, 2015 Sheet 3 of 12 US 9,017,474 B2 : s: : is Tass FGURE 3 U.S. Patent Apr. 28, 2015 Sheet 4 of 12 US 9,017,474 B2 FGURE 4 U.S. Patent Apr. 28, 2015 Sheet 5 of 12 US 9,017,474 B2 FGURE 5 U.S. Patent Apr. 28, 2015 Sheet 6 of 12 US 9,017,474 B2 88 & 50 ^ & & 's- f Fluoro graphene ------------------------------------------------6" SEG 38 Soo indefiation Osgii: {fi: &reaking for:8 (N. FIGURE 6 U.S. Patent Apr. 28, 2015 Sheet 7 of 12 US 9,017,474 B2 FGURE 7 U.S. Patent Apr. 28, 2015 Sheet 8 of 12 US 9,017,474 B2 i --- : 'S as: 2 at 38 R8; St (cm) FGURE 8 U.S. Patent Apr. 28, 2015 Sheet 9 of 12 US 9,017,474 B2 as as a sess asses as a sess as as as a.s.. ...- weakly suorinateafluorinated graphenearaphene o Partially fluorinated graphena ~~highly fiaotinated graphene: S-After 450°C annealing . --- After 250c anreating - After 258'c anaeating 1500 200 27go 3003 4200rviv. "503" iv. iv. ''''''''''' . .y-rvive:250 ww.wrwr:rrrrrrrrrrrrrrr' 3600 230"-- YYY - Y - Y - Y - Y - 150YYYYY - Y - Y - Y - 2400Y - -- Y - Y - Y - Y - 370YYYYYY - Y - Y - - - Y 3000- Y - Y - Raman Shift (cm) Raman Shift (cm) Ramar Shiittorn' FGURE 9 U.S. Patent Apr. 28, 2015 Sheet 10 of 12 US 9,017,474 B2 FIGURE O U.S. Patent Apr. 28, 2015 Sheet 11 of 12 US 9,017,474 B2 400. 200 as to incientation: Osgti in FGURE 11 U.S.
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