111111 1111111111111111111111111111111111111111111111111111111111111 US006756025B2 (12) United States Patent (10) Patent No.: US 6,756,025 B2 Colbert et al. (45) Date of Patent: Jun.29,2004 (54) METHOD FOR GROWING SINGLE-WALL 5,381,101 A * 1!1995 Bloom eta!. ............... 250/306 CARBON NANOTUBES UTILIZING SEED 5,503,010 A * 4/1996 Yamanaka ................... 73/105 MOLECULES 5,824,470 A * 10/1998 Baldschwieler eta!. ....... 435/6 6,183,714 B1 * 2/2001 Smalley eta!. ......... 423/445 B (75) Inventors: Daniel T. Colbert, Houston, TX (US); 6,333,016 B1 * 12/2001 Resasco et a!. .. ... ... 423/445 B Hongjie Dai, Sunnyvale, CA (US); FOREIGN PATENT DOCUMENTS Jason H. Hafner, Houston, TX (US); Andrew G. Rinzler, Houston, TX EP 1 176 234 A2 12/1993 (US); Richard E. Smalley, Houston, wo wo 9618059 * 6/1996 TX (US) OTHER PUBLICATIONS (73) Assignee: William Marsh Rice University, Chico et al., "Pure Carbon Nanoscale Devices: Nanotube Houston, TX (US) Heterojunctions", Physical Review Letters, vol. 76, No. 6, ( *) Notice: Subject to any disclaimer, the term of this Feb. 5, 1996, pp. 971-974.* patent is extended or adjusted under 35 Thess et al., "Crystalline Ropes of Metallic Carbon Nano­ U.S.C. 154(b) by 271 days. tubes", Science, vol. 273, Jul. 26, 1996, pp. 483-487.* Dresselhaus et al., "Science of Fullerenes and Carbon N ana­ (21) Appl. No.: 10/027,568 tubes", 1996, pp. 742-747, 818, 858-860.* Li, et al., "Large-Scale Synthesis of Aligned Carbon Nano­ (22) Filed: Dec. 21, 2001 tubes," Science, vol. 274, Dec. 6, 1996, pp. 1701-1703. ( 65) Prior Publication Data Liu, et al., "Fullerene Pipes," Science, vol. 280, May 22, US 2002/0092983 A1 Jul. 18, 2002 1998, pp. 1253-1256. Related U.S. Application Data (List continued on next page.) (62) Division of application No. 10/000,746, filed on Nov. 30, Primary Examiner-Jack Berman 2001, which is a continuation of application No. 09/242,040, (74) Attorney, Agent, or Firm-Winstead, Sechrest & filed as application No. PCT/US97/13896 on Aug. 8, 1997, Minick; Hugh R. Kress now abandoned. (60) Provisional application No. 60/023,732, filed on Aug. 8, (57) ABSTRACT 1996. This invention relates generally to a method for growing (51) Int. Cl? ................................................. DOlF 9/127 single-wall carbon nanotube (SWNT) from seed molecules. The supported or unsupported SWNT seed materials can be (52) U.S. Cl. ................................. 423/447.3; 423/445 B combined with a suitable growth catalyst by opening SWNT molecule ends and depositing a metal atom cluster. In one (58) Field of Search ........................... 423/447.3, 445 B embodiment, a suspension of seed particles containing attached catalysts is injected into an evaporation zone to (56) References Cited provide an entrained reactive nanoparticle. A carbonaceous U.S. PATENT DOCUMENTS feedstock gas is then introduced into the nanoparticle stream under conditions to grow single-wall carbon nanotubes. 4,785,189 A * 11/1988 Wells ...................... 250/492.2 Recovery of the product produced can be done by filtration, 5,126,574 A * 6/1992 Gallagher ................ 250/492.2 centrifugation and the like. 5,171,992 A * 12/1992 Clabes et a!. ............... 250/306 5,268,573 A * 12/1993 Weiss et a!. ................ 250/306 5,363,697 A * 11/1994 Nakagawa .................. 250/306 26 Claims, 14 Drawing Sheets 1012 1008 US 6,756,025 B2 Page 2 01HER PUBLICATIONS Dravid, et al., "Buckytubes and Derivatives: Their Growth and Implication for Buckyball Formation," Science, vol. Thess, et al., "Crystalline Ropes of Metallic Carbon Nano­ 259, Mar. 12, 1993, pp. 1601-1604. tubes," Science, vol. 273, Jul. 26, 1996, pp. 483-487. Tohji, et al., "Purifiying single-walled nanotubes," Nature, Smalley, "From dopyballs to nanowires," Materials Science vol. 383, Oct. 24, 1996, pp. 679. and Engineering, vol. B19, 1993, pp. 1-7. Tohji, et al., "Purification Procedure for Single-Walled Chen, "Growth and Properties of Carbon Nanotubes," The­ Nanotubes," J. Phys. Chern. B., vol. 101, No. 11, 1997, pp. sis for the degree Master of Science, Rice University Hous­ 1974-1978. ton, Texas, May 1995. Ajayan, et al., "Nanometre-size tubes of carbon," Rep. Prog. Phys., vol. 60, 1997, pp. 1025-1062. Rinzler, et al., "Field Emission and Growth of Fullerene Fishbine, "Carbon Nanotube Alignment and Manipulation Nanotubes," Presented at the Fall. 1994 MRS Meeting, Using Electrostatic Fields," Fullerene Science & Technol­ Nov. 28, 1994, Boston, submitted for MRS proceedings, vol. ogy, vol. 4(1), 1996, pp. 87-100. 359. Ajayan, et al., "Aligned Carbon NanotubeArrays Formed by Gamaly, et al., "Mechanism of carbon nanotube formation in Cutting a Polymer Resin-Nanotube Composite," Science, the arc discharge," Physical Review B, vol. 52, No.3, Jul. 15, vol. 265, Aug. 26, 1994, pp. 1212-1214. 1995-I, pp. 2083-2089. Wang, et al., "Properties of Buckytubes and Derivatives," Carbon, vol. 33, No. 7, 1995, pp. 949-958. Ge, et al. "Scanning tunneling microscopy of single-shell Sen, et al., "Structure and Images of Novel Derivatives of nanotubes of carbon," Appl. Phys. Lett., vol. 65(18), Oct. 31. Carbon Nanotubes, Fullerenes and Related New Carbon 1994, pp. 2284-2286. Forms," Fullerene Science and Technology, vol. 5(3), 1997, pp. 489-502. * cited by examiner U.S. Patent Jun. 29, 2004 Sheet 1 of 14 US 6,756,025 B2 100__.# --102 FIG. lA -122 FIG. 18 140 .. ~ -142 -144 FIG. IC U.S. Patent Jun. 29,2004 Sheet 2 of 14 US 6,756,025 B2 160~ FIG. I D .,-._ 184 FIG. IE U.S. Patent Jun. 29, 2004 Sheet 3 of 14 US 6,756,025 B2 Jlm 15 FIG. 2A 10 0 Jlm FIG. 28 Jlm 0.2 6 4 FIG. 2C 0.1 2 ' 0 0---- 0 U.S. Patent Jun.29,2004 Sheet 4 of 14 US 6,756,025 B2 50 A .. ...... 40 E c I ~ w 30 ) -c :::> c; ~ "' ......... ::3 20 8 ""' Cl.. "-'- :E / c( / -- 10 - - -- ..-" 0 252 253 254 255 256 FREQUENCY CkHz) FIG. 3A 50~--------------------------------------~ . 40 ...... A_.:~--. __ E c ~ 30 .... I --._\ 0 :::> __ ... /c ·---~ ~ 20 Cl..::e .· ·/ 8 ."-._ c( .. ·/ · ................ .....;,.;..- 10 .. .;..;.;.-- 0~==~==~========~~--~~~~--~~ 252 253 254 255 256 FREQUENCY (kHz) FIG. 38 U.S. Patent Jun.29,2004 Sheet 5 of 14 US 6,756,025 B2 35 30 'E 2s c: t A -~ 20 ;::) ~ ..J 15 ~ :E <C( -40 -30 -20 -10 0 10 20 30 z(nm) FIG. 3C U.S. Patent Jun.29,2004 Sheet 6 of 14 US 6,756,025 B2 1.0 11m 0.5 1.0 1.5 flm FIG. 4A FIG. 4C o so 100 150 200 zsonm 50 2.0 !lffi 100 150 FIG. 48 F!G.40 200 250 nm U.S. Patent Jun.29,2004 Sheet 7 of 14 US 6,756,025 B2 sor-------------------------------------- 40 '"""E . ......c:: NANOTUBE:. w 30 JNAJR . a . ·. :;:) f- :::J Cl 20 ~ <( ... 10 0 233 234 235 236 237 FREQUENCY (kHz) FIG. 5A ...... 70 E 60 .s 50 ~40 @ 234.74 kHz :;:) 30 1- ....................... ~ 20 ~ 10 <( 0 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -o.2 -0.1 0.0 0.1 z(IJm) FIG. 58 50 ...... E 40 ......c:: w 30 a @ 235.65 kHz ~ 20 ..J Cl 10 ~ <( 0 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 z(IJm) FIG. 5C U.S. Patent Jun.29,2004 Sheet 8 of 14 US 6,756,025 B2 12.5 10.0 7.5 nm 5.0 2.5 0 0 2.5 5.0 7.5 10.0 12.5 nm FIG. 6 U.S. Patent Jun.29,2004 Sheet 9 of 14 US 6,756,025 B2 FIG .. 7A U.S. Patent Jun.29,2004 Sheet 10 of 14 US 6,756,025 B2 FIG. 78 U.S. Patent Jun.29,2004 Sheet 11 of 14 US 6,756,025 B2 8 -Ill (.) §__, 1'- e (,) . a: (!) LL- ~,..... 8 Ill S/S:JO U.S. Patent Jun. 29,2004 Sheet 12 of 14 US 6,756,025 B2 FIG. 8 902 FIG. 9 U.S. Patent Jun. 29, 2004 Sheet 13 of 14 US 6,756,025 B2 1012 1008 1016 1016 1004 1002 1014 1014 I 1006 1000 1010 FIG. 10 1100 1100 1100 1100 l ) \ ) I:'1102 L=1102 r=ll02 r:ll02 l r I I I 1 ~1106 1104 1104 1104 1104 FIG. I I U.S. Patent Jun.29,2004 Sheet 14 of 14 US 6,756,025 B2 FIG. 12 FIG. 13 US 6,756,025 B2 1 2 METHOD FOR GROWING SINGLE-WALL Conventional probe microscope tips also are very rigid in CARBON NANOTUBES UTILIZING SEED comparison to many of the objects to be examined, and with MOLECULES "soft" samples (e.g., biomolecules like DNA) conventional AFM tips misrepresent the thickness of the object imaged, RELATED APPLICATIONS 5 because that object is literally compressed by the action of the tip. This application is a division of co-pending prior appli­ Thus, there is a need for macroscopically manipulable cation Ser. No. 10/000,746, filed on Nov. 30, 2001, which is nanoscale devices for observing, fabricating or otherwise a continuation of prior application Ser. No. 09/242,040 filed manipulating individual objects in a nanoscale environment on Sep. 13, 1999, now abandoned, which is the 35 U.S.C. § 10 that address the foregoing and other disadvantages of the 371 national application of International Application Num­ prior art. ber PCT/US97/13896 filed on Aug. 8, 1997, which desig­ nated the United States, claiming priority to provisional U.S. SUMMARY OF THE INVENTION patent application Serial No.