1

Supporting Information

Temperature dependent separation of metallic and semiconducting carbon

nanotubes using gel agarose chromatography

I. Yahya1‡

, F. Bonaccorso2,3

, S. Clowes1, A. C. Ferrari

2, S. R. P. Silva

1*.

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: s.silva@surrey.ac.uk

2

1. Raman spectra for DIPS-CNTs

100 150 200 250 300 350

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(a) Top band

DIPS-CNT 514 nm

1300 1400 1500 1600 1700

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(b) Top band

DIPS-CNT 514 nm

D

G-

G+

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(c) Bottom band

DIPS-CNT 514 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(d) Bottom band

DIPS-CNT 514 nm G+

G-

D

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.

3

100 150 200 250 300 350

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(a) Top band

DIPS-CNT 633 nm

1300 1400 1500 1600 1700

G+

G-

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(b)

D

Top band

DIPS-CNT 633 nm

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(c) Bottom band

DIPS-CNT 633 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1200 1400 1600

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(d) Bottom band

DIPS-CNT 633 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

G+

G-

D

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.

4

100 150 200 250 300 350

*

6oC 10

oC

18oC 24

oC

30oC 40

oC

50oC

In

ten

sity (

a.u

.)

Raman Shift (cm-1)

(a) 782 nmTop band

DIPS-CNT

1300 1400 1500 1600 1700

G+

G-

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(b) 782 nmTop band

DIPS-CNT

D

100 150 200 250 300 350

(12

,4)

(13

,13

)

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(c)

(17

,8)

(18

,3)

(19

,1)

(12

,1)

(8,7

)

*

Bottom band

DIPS-CNT 782 nm

1300 1400 1500 1600 1700

G+

G-

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(d)

D

Bottom band

DIPS-CNT 782 nm

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.

5

2. Raman spectra for AD-CNTs

100 150 200 250 300 350

In

ten

sity (

a.u

.)

Raman Shift (cm-1)

(a) 6oC

10oC

18oC

24oC

30oC

40oC

50oC

514 nmTop band

AD-CNT

1300 1400 1500 1600 1700

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(b) Top band

AD-CNT 514 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

DG

-

G+

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(c) Top band

AD-CNT 514 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(d) Top band

AD-CNT 514 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

G+

DG

-

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.

6

100 150 200 250 300 350

In

ten

sity (

a.u

.)

Raman Shift (cm-1)

(a) Top band

AD-CNT 633 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

G+

G-

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(b)

D

Top band

AD-CNT 633 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(c) Bottom band

AD-CNT 633 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

G+

G-

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(d)

D

Bottom band

AD-CNT 633 nm

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.

7

100 150 200 250 300 350

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(a) Top band

AD-CNT 782 nm

1300 1400 1500 1600 1700

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(b)

D G-

G+Top band

AD-CNT 782 nm

100 150 200 250 300 350

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(c) Bottom band

AD-CNT 782 nm

1300 1400 1500 1600 1700

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(d) Bottom band

AD-CNT 782 nmG

+

G-

D

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.

8

3. Raman spectra of HiPco-SWNTs

100 150 200 250 300 350

In

ten

sity (

a.u

.)

Raman Shift (cm-1)

(a) Top band

HiPco 514 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

G-

G-

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

D

(b) Top band

HiPco 514 nm

6oC

10oC

18oC

24oC

30oC

40oC

50oC

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(c) Bottom band

HiPco 514 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

G+

G-

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

D

Bottom band

HiPco(d)

514 nm

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.

9

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(a) Top band

HiPco 633 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

G+

G-

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(b)

D

Top band

HiPco 633 nm

6oC

10oC

18oC

24oC

30oC

40oC

50oC

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(c) Bottom band

HiPco 633 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

G+

G-

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(d)

D

Top band

HiPco 633 nm

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.

10

100 150 200 250 300 350

In

ten

sity (

a.u

.)

Raman Shift (cm-1)

(a) Top band

HiPco 782 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

G+

G-

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(b)

D

Top band

HiPco 782 nm

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(c) Bottom band

HiPco 782 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

G+

G-

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(d)

D

Bottom band

HiPco 782 nm

6oC

10oC

18oC

24oC

30oC

40oC

50oC

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.

11

4. Raman spectra of CoMoCAT-SWNTs

100 150 200 250 300 350

(a)

In

ten

sity (

a.u

.)

Raman Shift (cm-1)

Top band

CoMoCAT 514 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

(b)

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

Top band

CoMoCAT 514 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

G+

G-

D

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

Bottom band

CoMoCAT 514 nm(c) 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

G+

G-

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

D

Bottom band

CoMoCAT 514 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

(d)

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.

12

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(a) Top band

CoMoCAT 633 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(b) Top band

CoMoCAT 633 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oCD G

-

G+

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(c) Bottom band

CoMoCAT 633 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

G+

G-

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(d)

D

Bottom band

CoMoCAT 782 nm

6oC

10oC

18oC

24oC

30oC

40oC

50oC

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.

13

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(a) 6oC

10oC

18oC

24oC

30oC

40oC

50oC

Top band

CoMoCAT 782 nm

1300 1400 1500 1600 1700

G+

G-

6oC

10oC

18oC

24oC

30oC

40oC

50oC

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(b)

D

Top band

CoMoCAT 782 nm

100 150 200 250 300 350

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(c) Bottom band

CoMoCAT 782 nm 6

oC

10oC

18oC

24oC

30oC

40oC

50oC

1300 1400 1500 1600 1700

G+

G-

Inte

nsity (

a.u

.)

Raman Shift (cm-1)

(d) 6oC

10oC

18oC

24oC

30oC

40oC

50oC

D

Bottom band

CoMoCAT 782 nm

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.

14

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.