Supporting Information
Temperature dependent separation of metallic and semiconducting carbon
nanotubes using gel agarose chromatography
I. Yahya1‡, F. Bonaccorso2,3, S. Clowes1, A. C. Ferrari2, S. R. P. Silva1*.
1
Advanced Technology Institute, University of Surrey, Guildford GU2 7XH, UK
2
Cambridge Graphene Centre, Cambridge University, Cambridge CB3 0FA, UK
3
Istituto Italiano di Tecnologia, Graphene Labs, 16163 Genova, Italy
‡
Currently at the Department of Electrical, Electronic and Systems Engineering, Faculty of
Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600, Malaysia
* Corresponding author email: [email protected]
1
1. Raman spectra for DIPS-CNTs
(b)
o
Top band
DIPS-CNT
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
514 nm
Top band
DIPS-CNT
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
514 nm G+
-
G
D
Intensity (a.u.)
Intensity (a.u.)
(a)
100
150
200
250
300
1300 1400 1500 1600 1700
350
-1
-1
Raman Shift (cm )
Raman Shift (cm )
o
100
(d)
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
514 nm
Bottom band
DIPS-CNT
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
514 nm G+
-
G
D
Intensity (a.u.)
Bottom band
DIPS-CNT
Intensity (a.u.)
(c)
150
200
250
300
-1
Raman Shift (cm )
350
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
Fi
g. S1.1: Raman spectra of DIPS-CNTs separated at different temperatures; excitation
wavelength 514 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and (d) D-G
regions for bottom band.
2
Top band
DIPS-CNT
(b)
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
Top band
DIPS-CNT
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
633 nm G+
-
G
D
Intensity (a.u.)
633 nm
Intensity (a.u.)
(a)
100
150
200
250
300
350
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
-1
Raman Shift (cm )
o
(d)
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
633 nm
Bottom band
DIPS-CNT
o
633 nm G
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
+
-
G
D
Intensity (a.u.)
Bottom band
DIPS-CNT
Intensity (a.u.)
(c)
100
150
200
250
300
-1
Raman Shift (cm )
350
1200
1400
1600
-1
Raman Shift (cm )
Fig. S1.2: Raman spectra of DIPS-CNTs separated at different temperatures; excitation
wavelength 633 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and (d) D-G
regions for bottom band.
3
(a)
Top band
DIPS-CNT
782 nm
o
(b)
o
6C
o
18 C
o
30 C
o
50 C
10 C
o
24 C
o
40 C
Top band
DIPS-CNT
o
782 nm
G
G
-
Intensity (a.u.)
Intensity (a.u.)
*
D
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
+
100
150
200
250
300
350
1300 1400 1500 1600 1700
-1
-1
Raman Shift (cm )
o
782 nm
(8,7)
(12,1)
Bottom band
DIPS-CNT
(12,4)
(c)
(13,13)
(17,8)
(18,3)
(19,1)
Raman Shift (cm )
100
(d)
Bottom band
DIPS-CNT
+
782 nm
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
G
-
G
D
Intensity (a.u.)
Intensity (a.u.)
*
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
150
200
250
300
-1
Raman Shift (cm )
350
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
Fig. S1.3: Raman spectra of DIPS-CNTs separated at different temperatures; excitation
wavelength 782 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and (d) D-G
regions for bottom band.
4
2. Raman spectra for AD-CNTs
o
Top band
AD-CNT
(b)
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
o
Top band
AD-CNT
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
+
514 nm G
-
G
D
Intensity (a.u.)
514 nm
Intensity (a.u.)
(a)
100
150
200
250
300
350
1300 1400 1500 1600 1700
-1
-1
Raman Shift (cm )
(c)
Raman Shift (cm )
o
Top band
AD-CNT
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
514 nm
(d)
Top band
AD-CNT
G
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
-
Intensity (a.u.)
Intensity (a.u.)
D
+
G
514 nm
100
150
200
250
300
-1
Raman Shift (cm )
350
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
Figure S2.1: Raman spectra of AD-CNTs separated at different temperatures; excitation
wavelength 514 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and (d) D-G
regions for bottom band.
5
o
Top band
AD-CNT
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
(b)
Top band
AD-CNT
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
633 nm
-
G
+
G
D
Intensity (a.u.)
633 nm
Intensity (a.u.)
(a)
100
150
200
250
300
350
1300 1400 1500 1600 1700
-1
-1
Raman Shift (cm )
o
100
(d)
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
633 nm
Bottom band
AD-CNT
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
633 nm
+
-
G
G
D
Intensity (a.u.)
Bottom band
AD-CNT
Intensity (a.u.)
(c)
Raman Shift (cm )
150
200
250
300
-1
Raman Shift (cm )
350
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
Fig. S2.2: Raman spectra of AD-CNTs separated at different temperatures; excitation
wavelength 633 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and (d) D-G
regions for bottom band.
6
o
Top band
AD-CNT
(b)
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
Top band
AD-CNT
+
782 nm
o
G
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
-
G
D
Intensity (a.u.)
782 nm
Intensity (a.u.)
(a)
100
150
200
250
300
350
1300 1400 1500 1600 1700
-1
-1
Raman Shift (cm )
100
band
(d) Bottom
AD-CNT
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
782 nm
+
782 nm
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
G
-
G
D
Intensity (a.u.)
Bottom band
AD-CNT
Intensity (a.u.)
(c)
Raman Shift (cm )
150
200
250
300
-1
Raman Shift (cm )
350
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
Fig. S2.3: Raman spectra of AD-CNTs separated at different temperatures; excitation
wavelength 782 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and (d) D-G
regions for bottom band.
7
3. Raman spectra of HiPco-SWNTs
o
Top band
HiPco
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
(b)
Top band
HiPco
-
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
G
514 nm
-
G
D
Intensity (a.u.)
514 nm
Intensity (a.u.)
(a)
100
150
200
250
300
350
1300 1400 1500 1600 1700
-1
-1
Raman Shift (cm )
Bottom band
HiPco
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
514 nm
100
(d)
Bottom band
HiPco
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
+
514 nm
G
-
G
D
Intensity (a.u.)
Intensity (a.u.)
(c)
Raman Shift (cm )
150
200
250
300
-1
Raman Shift (cm )
350
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
Fig. S3.1: Raman spectra of sample HiPco separated at different temperatures;
excitation wavelength 514 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and
(d) D-G regions for bottom band.
8
o
Top band
HiPco
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
(b)
Top band
HiPco
o
633 nm
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
+
G
-
G
D
Intensity (a.u.)
633 nm
Intensity (a.u.)
(a)
100
150
200
250
300
350
1300 1400 1500 1600 1700
-1
-1
Raman Shift (cm )
o
(d)
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
633 nm
Top band
HiPco
D
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
+
G
633 nm
-
G
Intensity (a.u.)
Bottom band
HiPco
Intensity (a.u.)
(c)
Raman Shift (cm )
100
150
200
250
300
-1
Raman Shift (cm )
350
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
Fig. S3.2: Raman spectra of HiPco-SWNTs separated at different temperatures;
excitation wavelength 633 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and
(d) D-G regions for bottom band.
9
o
Top band
HiPco
(b)
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
Top band
HiPco
D
o
G
782 nm
G
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
+
-
Intensity (a.u.)
782 nm
Intensity (a.u.)
(a)
100
150
200
250
300
350
1300 1400 1500 1600 1700
-1
-1
Raman Shift (cm )
o
100
(d)
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
782 nm
Bottom band
HiPco
o
+
G
782 nm
-
D
G
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
Intensity (a.u.)
Bottom band
HiPco
Intensity (a.u.)
(c)
Raman Shift (cm )
150
200
250
300
-1
Raman Shift (cm )
350
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
Fig. S3.3: Raman spectra of HiPco-SWNTs separated at different temperatures;
excitation wavelength 782 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and
(d) D-G regions for bottom band.
10
4. Raman spectra of CoMoCAT-SWNTs
o
Top band
CoMoCAT
(b)
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
Top band
CoMoCAT
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
+
514 nm G
-
G
D
Intensity (a.u.)
514 nm
Intensity (a.u.)
(a)
100
150
200
250
300
350
1300 1400 1500 1600 1700
-1
-1
Raman Shift (cm )
Bottom band
CoMoCAT
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
514 nm
100
(d)
150
200
250
300
-1
Raman Shift (cm )
350
Bottom band
CoMoCAT
G
+
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
514 nm
G
Intensity (a.u.)
Intensity (a.u.)
(c)
Raman Shift (cm )
-
D
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
Fig. S4.1: Raman spectra of CoMoCAT-SWNTs separated at different temperatures;
excitation wavelength 514 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and
(d) D-G regions for bottom band.
11
o
Top band
CoMoCAT
(b)
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
o
Top band
CoMoCAT
633 nm G+
-
G
D
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
Intensity (a.u.)
633 nm
Intensity (a.u.)
(a)
100
150
200
250
300
350
1300 1400 1500 1600 1700
-1
-1
Raman Shift (cm )
(c)
Bottom band
CoMoCAT
Raman Shift (cm )
o
633 nm
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
(d)
Bottom band
CoMoCAT
G
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
Intensity (a.u.)
Intensity (a.u.)
782 nm
-
D
100
+
G
150 200 250 300
-1
Raman Shift (cm )
350
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
Fig. S4.2: Raman spectra of CoMoCAT-SWNTs separated at different temperatures;
excitation wavelength 633 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and
(d) D-G regions for bottom band.
12
o
Top band
CoMoCAT
(b)
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
Top band
CoMoCAT
o
G
D
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
782 nm
G
+
-
Intensity (a.u.)
782 nm
Intensity (a.u.)
(a)
100
150
200
250
300
350
1300 1400 1500 1600 1700
-1
-1
Raman Shift (cm )
100
(d)
o
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
782 nm
Bottom band
CoMoCAT
o
782 nm
6C
o
10 C
o
18 C
o
24 C
o
30 C
o
40 C
o
50 C
+
G
D
-
G
Intensity (a.u.)
Bottom band
CoMoCAT
Intensity (a.u.)
(c)
Raman Shift (cm )
150
200
250
300
-1
Raman Shift (cm )
350
1300 1400 1500 1600 1700
-1
Raman Shift (cm )
Fig. S4.3: Raman spectra of CoMoCAT-SWNTs separated at different temperatures;
excitation wavelength 782 nm. (a) RBM and (b) D-G regions for top band; (c) RBM and
(d) D-G regions for bottom band.
13
5. Relative SWNT concentrations in the top and bottom bands after separation
Fig. S5: Ratio of optical absorption of the bottom band to the top band as a function of
process temperature. The optical absorption is directly proportional to the SWNT
concentration in the respective bands.
Fig. S5 reports the variation of the optical absorption with respect to temperature for each
sample at wavelengths corresponding to the optical transition boundaries, i.e. between the
excitonic transitions. The absorbance at these wavelengths is the background contribution due
to the carbon -plasmon, which is directly proportional to the SWNT concentration.
14