Supplementary Figures SUPPLEMENTARY INFORMATION Supplementary Figure S1. Schematic Representation of temperature-controlled sonication apparatus. 1
Solution Abs (a.u.) 0.18 HiPco SWNT Dispersion in rr-p3ddt/toluene rr-p3ddt solution 0.16 rr-p3ddt Film 0.14 0.12 0.10 0.08 0.06 0.04 0.02 S 33 or S 44 M 11 S 22 S 11 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 Film Abs (a.u.) 0.00 0.0 300 450 600 750 900 1050 1200 1350 1500 Wavelength (nm) Supplementary Figure S2. Absorption Spectra of SWNT and rr-p3ddt. Comparison of the absorption peaks for SWNT/rr-P3DDT dispersion (black line) and the solid film of rr- P3DDT (blue line). The starting amounts of SWNT and the polymer for the dispersion is 5 mg of each in 25 ml of toluene. The absorption spectrum of the polymer solution was obtained from a solution with a concentration of 0.2 mg/ml. The vibronic peaks of rr-p3ddt at 553nm and 602 nm can be seen in the solid rr-p3ddt film and in the SWNT/rr-P3DDT solution. The absorption peaks from 900 nm to 1500 nm represent the first optical transition (S 11 ) of dispersed SWNTs. 2
(a) (b) (c) (d) Supplementary Figure S3. Differential Scanning Calorimetry of various Polymers. (a) regioregular poly (3-hexylthiophene) (rr-p3ht), (b) regioregular poly (3-octylthiophene) (rr- P3OT), (c) regioregular poly (3-decylthiophene) (rr-p3dt), and (d) regioregular poly (3- dodecylthiophene) (rr-p3ddt), recorded at 10 o C/min. The scans are started from heating at - 50 o C. A clear side chain melting occurs for rr-p3ddt at around 50 o C. 3
(a) Separated SWNT Intensity (a.u.) 50000 24000 Separated SWNT 532 nm (2.33 ev) 22000 As-produced HiPCo SWNT 20000 40000 18000 16000 30000 14000 12000 20000 10000 8000 6000 10000 4000 2000 1300 1350 1400 1450 1500 1550 1600 1650 1700 wavenumber (cm -1 ) As-produced SWNT Intensity (a.u.) (b) Separated SWNT Intensity (a.u.) 5000 4000 3000 2000 1000 0 Separated SWNT As-produced HiPco SWNT 1300 1350 1400 1450 1500 1550 1600 1650 1700 wavenumber (cm -1 ) 785 nm (1.58 ev) 18000 16000 14000 12000 10000 8000 6000 4000 2000 0 As-Produced SWNT Intensity (a.u.) (c) Separated SWNT Intensity (a.u.) 40000 Separated SWNT As-Produced HiPco SWNT 633 nm (1.96 ev) 35000 30000 25000 20000 15000 10000 5000 1300 1350 1400 1450 1500 1550 1600 1650 1700 wavenumber (cm -1 ) 50000 40000 30000 20000 10000 0 As-produced SWNT Intensity (a.u.) Supplementary Figure S4. Resonant Raman Spectra of G-Mode. G-Mode for before (black upside down triangle) and after sorting (black sphere) with the three excitation lines of 532 nm (A), 633 nm (B) and 785 nm (C). The G-modes of 633 nm and 785 nm became narrower after sorting. The G-mode of 532 nm was very weak because most metallic SWNTs, resonant with 532 nm, were removed. From 532 nm and 633 nm, the peaks from ring stretching modes of the polymer are strongly seen at 1365 cm-1 and 1458 cm -1 4
(A) (B) Polymer peak 532 nm excitation (C) (D) 633 nm excitation 785 nm excitation Supplementary Figure S5. Resonant Raman Spectroscopy in the RBM Mode before and after Polymer Burn-off. The substrates were heated at 450 C for one hour under argon to remove the polymer. (A) shows raman spectrum at 633 nm excitation for P3DDT dispersed CNTs before and after polymer removal. The peaks from the polymers disappeared after burning off, indicating removal of the polymers. (B)-(D) are Raman spectra taken for different laser excitation wavelengths. The SWNTs dispersed by SDS do not have any enrichment in semiconducting or metallic tubes. The metallic peaks disappeared in P3DDT dispersed tubes as can be seen for 532 nm and 633 nm excitation. 5
(a) 50 40 No. of CNTs 30 20 10 (b) 0 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 Diameter (nm) No. of CNTs 30 25 20 15 10 5 0 0.0 0.5 1.0 1.5 2.0 CNT Length (μm) Supplementary Figure S6. Histogram of SWNT Dimensions. Histogram of (a) diameter and (b) length distribution of the sorted SWNTs. This measurement is performed with AFM and SEM images, respectively. The samples are prepared by spin-coating at 3000 rpm for 3 min, and annealed for 90 sec. at 90 o C. The average diameter and length of the sorted SWNTs were 1.58 ± 0.26 nm and 0.9997 ± 0.3999 μm, respectively. 6
M M 11 11 S S 22 22 S S 11 11 Supplementary Figure S7. Absorption Spectra of various CNT films. UV-Vis-NIR for SWNT films after heating at 450 C for one hour in argon to remove the polymers. Even though the peaks are not well resolved, it can be seen that metallic CNTs present in the SDS dispersed SWNTs (no sorting) and in the sediment. However, the M11 region for P3DDT dispersed SWNTs do not show clear peaks indicating little to no metallic tubes are present. Note: The two peaks in the overlap region marked for both M11 and S22 are corresponding to energy of 1.87eV (662nm) and 1.66eV (745nm). From the Kataura plot (http://www.photon.t.u-tokyo.ac.jp/~maruyama/kataura/kataura.html#kataura), the peak at 1.87eV (662nm) peak will correspond to: (7,6) at S22 region at diameter of 0.89nm, (10, 3) at S22 region at diameter of 0.94nm or (11,8) at M11 region at diameter of 1.31nm 1.66eV (745nm) peak will correspond to: (8,6) at S22 region at diameter of 0.97nm, (13,0) at S22 region at diameter of 1.03nm, (12,2) at S22 region at diameter of 1,04 nm or (12,9) at M11 region at diameter of 1.45nm, (19,1) at M11 region at diameter of 1.55nm From our Raman RBM peaks, the diameter of our CNTs are all below 1.2nm, so we can conclude that the two peaks in the overlap region are in the S22 region for semiconducting tubes rather than M11 region for the large diameter metallic tubes. 7
A C 400 300 PL Intensity (a.u.) 200 100 0 1000 1100 1200 Emission (nm) 1300 1400 550 600 650 800 750 700 Excitation (nm) B D (10,2) / /(10,2) Supplementary Figure S8. PLE 3D and 2D maps for SWNTs dispersed with rr-p3ddt and SDS. rr-p3ddt: (A, B) and SDS: (C, D). Yellow circle, air-suspended SWNT; purple triangle, SWNT dispersed with SDS in water; black box-thin, SWNT dispersed with rr- P3DDT in toluene; black box-thick, SWNTs dispersed in rr-p3ddt in relatively higher concentrations. 8
(0,0) (1,0) (2,0) (3,0) (4,0 ) (5,0 ) (6,0 ) (7,0) (8,0) (9,0) (10,0) (11,0) (12,0) (13,0) 0.079 nm 0.159 nm (12,2)/(13,0),1) (2,1) (3,1) (4,1) (5,1) (6,1) (7,1) (8,1) (9,1) (10,1) (11,1) (12,1) (10,6) (11,4) (10,3) 0.238 nm (2,2) (3,2) (4,2) (5,2) (6,2) (7,2) (8,2) (9,2) (10,2) (11,2) (1 2,2 ) (11,1) 0.317 (9,5) nm (8,7) (3,3) (4,3) (5,3) (6,3) (7,3) (8,3) (9,3) (10,3) (11,3) (9,7) 0.396 nm Chiral Vector (n,m) (10,5) (8,6) (11,3) (12,1) (8,4) (7,6) (9,4) (11,0)/(10,2) (7,5) 0.476 nm (4,4 ) (5,4 ) (6,4) (7,4) (8,4) (9,4) (10,4) (11,4) 0.555 nm 0.634 nm (5,5 ) (6,5 ) (7,5 ) (8,5 ) (9,5 ) (10,5 ) 0.713 nm (6,6 ) (7,6 ) (8,6) (9,6 ) (10,6) 0.793 nm (8,3) 0 0.2 0.4 0.6 0.8 1 1.2 Normalized PL Intensity (a.u.) 0.872 nm (7,7) (8,7) (9,7) 0.951 nm 1.03 nm Normalized PL Intensity Weak (< 0.4) In term ed iate (0.4-0.8) Strong (>0.8) Supplementary Figure S9. Normalized PL intensities for SWNT/SDS in aqueous solvent on the graphene sheet map. Each PL peak intensity was symbolized by the line thickness and darkness of color of hexagons. For example, the darker color and the thick perimeter of a hexagon represent higher PL intensity. The hexagons correspond to the coordinates of chiral vectors. Each peak was normalized by the maximum peak intensity. 9
50 On/Off R atio Statistics (L c = 1.5um ) Percentage of D evices 45 40 35 30 25 20 15 10 5 0 H istogram -122 D evices 10-100 100-1000 1000-10000 10000-100000 R>100000 O n /O ff R atio (R) Supplementary Figure S10. Histogram of on/off current ratios. Our CNTs have about 1μm of the average length. This histogram was obtained from 1.5 um channel length. This histogram shows 90% or more working devices with an on/off current of 10 3 or higher from 122 device measurements. Moreover, all device showed transistor characteristics. This result supports the observation of nearly 100% semiconducting SWNTs in our sorted tubes, analyzed by optical spectroscopic methods. 10
Supplementary Figure S11. AFM and Histogram of On/Off Ratios of individual SWNT Devices (A) AFM phase image of a short channel SWNT device, and (B) its corresponding topography image. The devices were fabricated using a method previously reported (W.M. Wang, M.C. LeMieux, S. Selvarasah, M.R. Dokmeci, Z. Bao, Dip-Pen Nanolithography of Electrical Contacts to Single-Walled Carbon Nanotubes, ACS Nano, 3, 3543-3551, 2009.). The channel length for this particular device was 348 nm, corresponding to the length of the SWNT connecting the electrodes. (C) Using such short channel devices, on/off ratios of 80 SWNTs have been characterized. As our data indicates, all of the 80 randomly selected SWNTs exhibited semi-conducting behavior. 11
rr-p3ddt rra-p3ddt 0.06 0.05 0.04 0.03 0.02 0.01 0.00 Abs (a.u.) rr-p3ddt rra-p3ddt 800 900 1000 1100 1200 1300 1400 1500 Wavelength (nm) Supplementary Figure S12. Optical absorption for regiorandom and regioregular P3DDT. The regiorandom P3DDT showed no dispersion of SWNTs. This result indicates that the regularity of side chain is an important parameter in dispersion. 12
Supplementary Tables Supplementary Table S1. Molecular weight and polydispersity values for various polymers. The polymers were dissolved in tetrahydrofuran (THF) at 1 mg/ml and polystyrenes was used as the references. Polymer Mw PDI Poly (3-hexyl-thiophene-2,5-diyl) 64,000 2 Poly (3-octyl-thiophene-2,5-diyl) 145,000 2.46 Poly (3-decyl-thiophene-2,5-diyl) 209,000 2.09 Poly (3-dodecyl-thiophene-2,5-diyl) 77,000 1.97 Poly (3,3 -didodecyl-quarter-thiophene) 15,000-30,000* 1.7-3.5* Poly (3-methyl-4-decyl-thiophene-2,5-diyl) 40,000-100,000* 1.7* *, data provided by vendor. 13
Supplementary Table S2. Chiral Assignment of optical transition energies E11 and E22 for SWNTs in air/vacuum, SDS/water and rr-p3ddt/toluene. Available HiPco/SDS in HiPco/rr-P3DDT Air-Suspended Diameter Excitation of water in toluene Chirality (nm) Resonant E11 E22 E11 E22 E11 E22 Raman (ev) (ev) (ev) (ev) (ev) (ev) (8,3) 0.782 NA NA 1.289 1.851 NA NA (7,5) 0.829 1.96 ev (633 nm) 1.261 1.950 1.193 1.908 1.159 1.837 (11,0)/(10, 0.873/0.8 1.58 ev (785 2) 84 nm) 1.244 1.722 1.165 1.676 1.151 1.570 (9,4) 0.916 1.188 1.782 1.112 1.699 1.084 1.319 (7,6) 0.895 1.147 1.941 1.095 1.908 1.067 1.851 (8,4) 0.84 NA NA 1.103 2.102 NA NA (12,1) 0.995 1.58 ev (785 nm) 1.109 1.602 1.040 1.550 1.018 1.476 (11,3) 1.014 1.58 ev (785 nm) 1.085 1.615 1.019 1.550 NA NA (8,6) 0.966 1.114 1.771 1.048 1.722 1.022 1.664 (10,5) 1.05 (9,7) 1.103 (8,7) 1.032 1.58 ev (785 nm) 1.041 1.629 0.978 1.570 0.960 1.494 1.58 ev (785 nm) 0.990 1.610 0.934 1.550 0.906 1.494 1.58 ev (785 nm) 1.032 1.749 0.971 1.676 0.945 1.621 (9,5) 0.976 NA NA 0.991 1.824 0.965 1.797 (10,3) 0.936 1.96 ev (633 nm) NA NA 0.984 1.938 0.942 1.922 (11,4) 1.068 0.957 1.766 0.899 1.722 NA NA (10,6) 1.111 1.58 ev (785 nm) 0.952 1.682 0.894 1.632 0.861 1.610 (12,2)/(13, 1.041/1.0 0) 32 NA NA 0.894 1.797 NA NA 14
Supplementary Table S3. Assigned chiralities from RBMs of 2.33 ev (532 nm) excitation. (n,m) wrbm (cm-1) Diameter (nm) As Produced HiPco SWNT (9,6) 227 1.038 met (10,4) 237 0.992 met (12,0) 247 0.953 met (9,3) 272 0.859 met (10,0) 294 0.794 sc After dispersing (10,0) 294 0.794 sc Electronic Type Supplementary Table S4. Assigned chiralities from RBMs of 1.96 ev (633 nm) excitation. (n,m) wrbm (cm-1) Diameter (nm) As Produced HiPco SWNT (9,9) 193 1.238 met (12,3) 218 1.091 met (10,3) 251 0.936 sc (11,1) 256 0.916 sc (7,5) 283 0.829 sc After dispersing (10,3) 253 0.936 sc (7,5) 284 0.829 sc Electronic Type Supplementary Table S5. Assigned chiralities from RBMs of 1.58 ev (785 nm) excitation. (n,m) wrbm (cm-1) Diameter (nm) As Produced HiPco SWNT (9,8)/(13,3) 203 1.17 sc (9,7) 213 1.111 sc (10,5) 223 1.068 sc (8,7) 231 1.032 sc (10,2)/(11,0) 265 0.884/0.873 sc Electronic Type 15
After dispersing (8,7) 231 0.936 sc (12,1) 237 0.995 sc (10,2)/(11,0) 269 0.884/0.873 sc Supplementary Table S6. Summary of the metallic (m) and semiconducting (sc) tubes selected experimentally using resonant Raman and photoluminescence measurements. Metallic CNTs eliminated according to Raman spectra (9,9), (12,3) @ 633nm (9.3), (9.6), (10,4), (12,0) @ 532nm 785nm excitation cannot be used to observe metallic tubes SC CNTs observed in Raman spectra (7,5) (8,7) (10,0) (10,2) (10,3) (11,0) (12,1) SC CNTs eliminated according to Raman spectra (9,7) (9,8)/(13,3) (10,5) (11,1) PL intensity strong (8,6) (9,4) (9,5) (11,3) (12,1) PL intensity weak (7,5) (7,6) (8,7) (9,7) (10,6) 16
Supplementary Table S7. Semiconducting SWNTs predicted to be selected by the model. We see that all the SC tubes that are observed experimentally have a mismatch smaller than 0.21. All the SC tubes that are eliminated by the process have a mismatch larger than 0.22 except for (11,1) which cannot be distinguished from (9,4). Eleven SC tubes observed in either Raman or PL experiments are predicted by the model. Four SC tubes that are eliminated in the experiment are rejected by the model. One SC tube (11,1) that is eliminated in the experiment has a small mismatch (0.17) and is accepted by the model. In both the SC and metallic cases, double helical wrapping gave the best match between predicted ones and those observed experimentally. (m,n) p q N s R CNT R thio Θ ΔR (7,5) 2 3 12 4.086790 7.604242 61.07 0.130719 (8,6) 1 6 12 4.762116 8.075050 24.34-0.073799 (8,7) 2 4 12 5.088766 8.267435 53.61-0.208063 (9,4) 1 6 12 4.514347 8.075050 24.34 0.173970 (9,5) 2 4 12 4.810138 8.267435 53.61 0.070564 (10,0) 2 2 12 3.914435 7.092667 69.77-0.208501 (10,2) 2 3 12 4.358931 7.604242 61.07-0.141422 (10,3) 1 6 12 4.615051 8.075050 24.34 0.073266 (11,0) 2 3 12 4.305879 7.604242 61.07-0.088370 (11,3) 2 4 12 4.997616 8.267435 53.61-0.116914 (12,1) 2 4 12 4.904773 8.267435 53.61-0.024071 17
Supplementary Table S8. Semiconducting SWNTs predicted to be eliminated by the model. Note that (9,8) (13,3) have a mismatch larger than 0.3 and are not listed here. In addition, (9,4) and (11,1) have the same diameter and cannot be distinguished by the model. (9,4) appears in the list of selected of strong PL intensity, but (11,1) is in the list of eliminated according to Raman data. Both have a mismatch of 0.17397 with a polymer tube of p=1,q=6. (m,n) p q N s R CNT R thio Θ ΔR (9,7) 2 5 12 5.438107 9.048972 47.35 0.224132 (10,5) 2 4 12 5.178311 8.267435 53.61-0.297609 (11,1) 1 6 12 4.514347 8.075050 24.34 0.173970 Supplementary Table S9. Metallic SWNTs predicted to be eliminated by the model. (m,n) p q N s R CNT R thio Θ ΔR (9,3) 2 3 12 4.234109 7.604242 61.07-0.016600 (9,6) 2 4 12 5.118788 8.267435 53.61-0.238086 (10,4) 1 6 12 4.889128 8.075050 24.34-0.200811 (10,4) 2 4 12 4.889128 8.267435 53.61-0.008426 (12,0) 1 6 12 4.697322 8.075050 24.34-0.009005 (12,0) 2 4 12 4.697322 8.267435 53.61 0.183380 (12,3) 2 5 12 5.381459 9.048972 47.35 0.280781 18