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VOLUME 92, N UMBER 1 9 JANUARY 2004

Ultrafast Spectroscopy of Excitons in Single-Walled Carbon Nanotubes

O. J. Korovyanko,1 C.-X. Sheng,1 Z.V. Vardeny,1 A. B. Dalton,2 and R. H. Baughman 2
1
Department of Physics, University of Utah, Salt Lake City, Utah 84112, USA
2
Nano Tech Institute, University of Texas at Dallas, Richardson, Texas 75083, USA
(Received 29 July 2003; published 9 January 2004)
We studied the femtosecond dynamics of photoexcitations in films containing semiconducting and
metallic single-walled carbon nanotubes (SWNTs), using various pump-probe wavelengths and
intensities. We found that confined excitons and charge carriers with subpicosecond dynamics dominate
the ultrafast response in semiconducting and metallic SWNTs, respectively. Surprisingly, we also found
from the exciton excited state absorption bands and multiphoton absorption resonances in the semi-
conducting nanotubes that transitions between subbands are allowed; this unravels the important role of
electron-electron interaction in SWNT optics.

DOI: 10.1103/PhysRevLett.92.017403 PACS numbers: 78.47.+p, [Link], [Link], [Link]

Because of the nanometer scale diameter and ex- amplifier having 100 fs pulses at photon energies of
tended dimension along the tube, single-walled carbon 1.55 eV and from 0.7 to 1.1 eV, as well as frequency-
nanotubes (SWNTs) are considered to be quasi-one- doubled pulses from 1.8 to 2 eV. Four percent of the out-
dimensional (1D) solids [1]. Depending on their chi- put was split to generate white light supercontinuum for
rality, SWNTs can be either semiconducting or metallic the probe beam in the spectral range from 1.2 to 2.7 eV.
[2]. In recent years, much effort has been devoted to For the low-intensity measurements, we used a titanium-
studying Coulomb interaction in quasi-1D electronic sapphire pumped optical parametric oscillator with
systems [3]. Peierls instability in electron-phonon 1D 100 fs pulses, which extended the transient photo-
metal [4] and large binding energy excitons in 1D semi- modulation (PM) spectral range into the mid-IR from
conductors [5] are two well-known examples of elec- 0.56 to 0.73 eV and 0.84 to 1.02 eV. The transient PM
tronic confinement in 1D systems. Nevertheless, the role signal,
Tt=T is the fractional change in transmis-
of electron-electron (e-e) interaction in SWNTs has not sion, which is negative for photoinduced absorption
yet been studied in detail. Recent improvements in (PA) and positive for photobleaching (PB). To obtain
sample preparation led to the discovery of fluorescence the transient polarization memory, Pt, we measured
in isolated SWNTs [6], and the realization that e-e inter- T=T for pump-probe polarizations either parallel
action in SWNTs is important [7–9]. In particular, it is Tp  or perpendicular Tpe  to each other, and calcu-
clear that excitons are responsible for the measured fluo- late Pt  Tp  Tpe =Tp  Tpe .
rescence [6], and that the use of tight binding approxima- The SWNTs were grown using a modified gas phase
tion to calculate the electronic band structure cannot process (HiPco), and were supplied by Carbon Nano-
account for various features seen in the optical absorption technologies Inc. The raw material was initially dispersed
spectrum of SWNTs [7–9]. in deionized water using an anionic surfactant lithium
In this Letter, we provide further experimental evi- dodecyl sulfate. SWNT thin films were subsequently
dence for the importance of e-e interaction in SWNTs. prepared on silica substrates by successive dip coating
We measured the ultrafast dynamics of photoexcitations followed by a ten-hour bake at 70  C. The films were
in films of SWNTs that contain both semiconducting (S) annealed for 5 h in Ar atmosphere at 600  C. The NTs
and metallic (M) nanotubes (NTs). From the transient contain approximately 12%–15% by weight Fe catalyst
photoinduced absorption bands, multiphoton absorption but are otherwise relatively free of carbonaceous impuri-
resonances, and polarization memory dynamics, we con- ties commonly associated with other production methods.
clude that the primary photoexcitations in S NTs are Atomic force microscopy and resonant Raman spectros-
confined excitons with allowed optical transitions be- copy suggested an average NT length of 400 nm, and a
tween subbands; these transitions are strictly forbidden diameter distribution ranging from 0.8 to 1.2 nm.
in the tight binding approximation. In contrast, the ultra- A typical absorption spectrum of the SWNT films is
fast photoresponse in M NTs is determined by hot carrier shown in the Fig. 1 inset. Three prominent absorption
dynamics. bands and a shoulder are seen at 0.8 eV (A), 1.35 eV (B),
We used the femtosecond two-color pump-probe corre- 1.9 eV (C), and 2.5 eV (D), respectively, which are super-
lation technique with linearly polarized light beams in a imposed onto broad background absorption [10,11]. Bands
broad spectral range from 0.6 to 2.6 eV, and pump inten- A, B, and D were previously assigned [1,11] to the in-
sities (I) ranging from 0.1 to 3000 J=cm2 . For the high- homogeneously broadened interband optical transitions
intensity measurements, we used a titanium-sapphire in S NTs from various valence subbands to their respec-
laser amplifier system followed by an optical parametric tive conduction subbands with the same index, m; namely

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15 2 t  500 fs, respectively, are shown in Fig. 1; the spectra

PB(A) D
contain contributions from both the high- and low-

Optical Density
1.5 A
C
B intensity laser systems, which were normalized to each
1
10 other in the mid-IR spectral range. The PM spectra reveal
0.5 two PB bands that peak at 0.79 [PB(A)] and 1.35 eV
[PB(B)], respectively; two PA bands with peaks around
∆T/T)

PB(B) 0 0.5 1 1.5 2 2.5 3 3.5 0.6 (PA1 ) and 1.6 eV (PA2 ),and the threshold of a third PA
5 Photon Energy (eV)
band (PA3 ) at 1.03 eV. Since the PB bands correspond to
10 (∆
3

pump absorption bands A and B of S NT (Fig. 1 inset), we assign

them as photobleaching of these two bands. The PB is due
0 to either k-space state filling [12] or Q-space filling [13],
PA depending on whether carriers [Fig. 2(a)] or excitons
3
(Fig. 2(b)] are photogenerated at t  0. From the transient
PA dynamics seen in Fig. 3, it is clear that PB(B) decays
-5 2
PA
1 much faster than PB(A), in agreement with previous
0.5 1 1.5 2 2.5
literature [10]. We thus explain PB(B) fast decay as due
to photoexcitation thermalization from m  2 to m  1
Photon Energy (eV)
subbands. The transient PA, on the other hand, was inter-
FIG. 1. The transient PM spectra of a SWNT film at preted [10] as due to transient dynamics of the absorption
t  0 (full line) and t  500 fs (dotted line) excited at
1.55 eV; the dashed line is a guide to the eye. Various PB 1.2
and PA bands are assigned. The inset shows the absorption PB(A)
spectrum of the film, where bands A to D are assigned. 1 (a) 1.5 0.45

∆T| (arb. units)

10 (∆Τ/Τ)
∆Τ/Τ)
1

P (t)
0.8

3
m  1, 2, and 3, respectively [Fig. 2(a)]. On the contrary, 0.5
band C at 1.9 eV was assigned [1,11] to the m  1 inter- 0.6 0 0
band transition in M NTs. PA -2 0 2 4 6 8
2
The transient PM spectra of a SWNT film at 300 K 0.4 t (ps)
excited at 1.55 eV and measured at delay times t  0 and
|∆

0.2
PA
1
0
E 3 E
eV Ex3
2.5
-0.2
2 -0.5 0 0.5 1 1.5 2 2.5 3
t (ps)
1
D PA2 PA3
1
(b)
Ex2
A B D PA
1.4 0.75
∆T| (arb. units)

3
Ex1 PA1
PB(B)
-1 0.8 0.5
B
-2
A 0.25
GS
|∆

-3
0
k Q 0

FIG. 2. Schematic representation of the excited states and

optical transitions of S NT in the tight binding (a) and exciton -0.5 0 0.5 1 1.5 2 2.5 3
picture (b), respectively. (a) The electron dispersion relation t (ps)
[Ek] and the allowed interband optical transitions involving
subbands with indices m of 1 to 3; optical transitions among FIG. 3. Transient dynamics of various PA and PB bands in
subbands in the conduction or valence bands are strictly for- the PM spectrum of Fig. 1. (a) PB(A) and its associated PA1
bidden. (b) Various excitons (Ex1 and Ex2 ) in the NT configu- and PA2 bands. (b) PB(B) and its associated PA3 . The inset in
ration coordinate, Q, and their associated optical transitions (a) shows Tt at 0.9 eV in parallel and perpendicular pump-
from the ground state (GS) (A to D, full lines), and Ex1 (PA1 to probe polarizations, and the consequent polarization memory
PA3 , double lines). Pt decay.
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background (Fig. 1). However, when examining the full B creates Ex2 that instantaneously forms PB(B) due to
PM spectrum obtained here (Fig. 1), we see that the PA phase space filling and a correlated PA band (PA3 ).
spectrum does not agree with this interpretation [10], Consequently, Ex2 excitons decay within 150 fs
since it contains two well-resolved peaks (PA1 and PA2 , [Fig. 3(b)] to the lower Ex1 excitons that form PB(A)
respectively) and a threshold of another (PA3 ). Moreover, and two associated PA bands, PA1 and PA2 , respectively,
the transient PA and PB are correlated, indicating that all having slower dynamics [Fig. 3(a)].
they share a common origin. Further support for the exciton picture is provided by
The transient dynamics of the various PA and PB bands the polarization memory dynamics, Pt given in the
in the PM spectrum are shown in Fig. 3. It is seen that, Fig. 3(a) inset. We discovered that all transient PB and
whereas PB(A) dynamics are similar to that of PA1 and PA bands in the PM spectrum possess polarization mem-
PA2 [Fig. 3(a)] showing a lifetime of about 700 fs, PB(B) ory, namely, Tp t
Tpe t [Fig. 3(a) inset]. Pt de-
dynamics are correlated with that of PA3 showing a life- cays within a few ps, and its dynamics are the same for
time of about 150 fs. In addition, the polarization memory each PB and its correlated PA bands. Photogenerated free
dynamics Pt of PB(A) [Fig. 3(a) inset] also correlates carriers in SWNTs cannot have polarization memory that
with Pt of PA1 and PA2 bands (not shown). Moreover, decays within several ps since they should be delocalized
from the initial P0 value of 0.45, we conclude that the along the tube (that is not straight) very quickly following
PA and PB bands are polarized parallel to the NT axis. their generation at t  0. The primary photoexcitations in
The correlation between the various PA and PB bands the alternative model are excitons, confined in space
indicates that the PA bands should be associated with the within a few lattice constants. Because of this localiza-
primary photoexcitations in S NT, rather than with the tion in space, such excitons would show polarization
global  plasmon [10]. It is noteworthy that photogen- memory at t  0, which may decay at t > 0 due to
erated carriers in more common semiconductors do not excitons diffusion along the NT. Similar photoinduced
show structured PA bands; instead their PA is in the form polarization memory and decay was seen before in quasi-
of a structureless Drude free carrier absorption that peaks 1D conducting polymers, and, in particular, for photo-
at low energies [14]. In SWNTs, however, there is the induced soliton pairs in fibrils of trans-CHx [16];
possibility that the PA bands associated with the photo- similarly, Pt was analyzed using soliton diffusion along
generated carriers would show peaks that correspond to the fibrils. Pt within this model is given by Pt 
transitions between subbands, namely, electron (hole) P0 exp4Dt=R2 , where D is the photoexcitation dif-
transitions from m to m  1 within the conduction (va- fusion constant, and R is the average ‘‘radius of curva-
lence) subbands [Fig. 2(a)]. These optical transitions that ture’’ of the fibrils in the film. Using this ‘‘exciton
are polarized along the NT are strictly forbidden in the diffusion along the NT’’ model to interpret the polariza-
tight binding model [1,15], since the angular momentum tion memory decay in SWNTs, we calculate from R 
is not conserved. We therefore conclude that ‘‘free’’ charge 300 nm a diffusion constant D
120 cm2 =s for the
carriers are not the primary photoexcitations in S NT. photogenerated excitons in S NTs.
Our results can be well explained, however, when e-h Additional support for allowed intersubband transi-
interaction [7–9] is taken into account. In this case, ex- tions in S NTs is provided by the resonant multiphoton
citons are the primary excitations in S NT, where the e-h excitations seen in Fig. 4(a). The transient PM spectrum
correlation leads to allowed optical transitions between at t  0 excited at 1 eV is shown at two different excita-
subbands. The optical transitions of photoexcited exciton tion intensities, I  300 J=cm2 and I  1:5 mJ=cm2 . In
can be viewed in this picture as an electron promotion addition to the trivial PB(A) [17] (not shown here) and its
from m  1 to higher m in the conduction subbands, and relatively longer decay, we also see PB(B) at low I. Since
simultaneously a symmetric hole promotion from m  1 band B lies higher than the excitation photon energy, then
to a lower valence subband with higher m. Such optical its photobleaching can be explained only by a two-
transitions are allowed since both linear and angular photon-absorption (TPA) process into states at 1.6 eV
momenta are conserved; namely, k  ke  kh  0, [13]. However, to account for such a strong T=T signal
and m  me  mh  0. Simultaneously, energy is also (
5%), the TPA process should be resonantly enhanced
conserved if the e-h binding energy is taken into account. via an intermediate allowed state. A reasonable assump-
A schematic representation of excitons and their optical tion for the TPA intermediate state is band A, whereas the
transitions is given in Fig. 2(b). In this picture, bands A, final state is band B. This again suggests that A ! B
B, and D are due to excitons, Ex1 , Ex2 , and Ex3 , respec- intersubband transition is allowed; consistent with the
tively. Excitons in 1D have relatively large binding energy exciton model presented in Fig. 2(b).
and ‘‘steal’’ most of the oscillator strength from the The PM spectrum at high I [Fig. 4(a)] shows that
interband transition [5,7] explaining the large absorption PB(B) is gradually overwhelmed by another PA band,
strength of bands A, B, and D in S NT [7]. Moreover, PA PAx , whereas the photobleaching of band C (M NT)
bands such as PA1 and PA2 from Ex1 and PA3 from Ex2 and band D (S NT) dramatically increase. We interpret
[see Fig. 2(b)] may be also formed. Our data can be well PB(D) and its large value (
10%) as resonant three-
explained using the exciton picture: Excitation into band photon absorption. Even though three-photon absorption
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0.1 carriers with extremely fast Pt decay (not shown

(a) PB(D) here). At t  0, these are ‘‘hot carriers,’’ for which the
PB(B) electronic temperature Te is not yet established; this
0.05 PB(C) explains the immediate appearance of PB(C) in the PM
spectrum. Because of e-e collisions, the electron system
reaches the quasiequilibrium state described by a tem-
∆ T/T

0 perature Te , whereas most of the PM spectrum of M NTs

occurs close to the Fermi energy [19]. This explains the
ultrafast decay (
200 fs) of PB(C) [Fig. 4(b) inset].
-0.05
PA PB(B) occurs in the PM spectrum [Fig. 4(b)] due to
x
PA ultrafast intertube interaction in which photoexcitations
2 can tunnel from M NTs into S NTs within the NT
bundles, as well as due to direct photoexcitation of states
-0.1
1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 with Q
0 in S NTs [Fig. 2(b)] with subsequent relaxa-
Photon Energy (eV) tion to states with Q  0.
0.06
We thank Dr. Efros and Dr. Garstein for important
(b) discussions. This work was supported in part by the
PB(B) NSF (DMR 02-02790) and the University of Utah; at
PB(C)
0.04 University of Texas at Dallas, the work was supported
by DARPA Grant No. MDA 972-02-C-005 and the Robert
A. Welch foundation.
∆ T/T

0.02
∆ T (arb. units)

0.9

0.6

0 0.3 [1] M. S. Dresselhaus, G. Dresselhaus, and Ph. Avouris,

PA 0
Carbon Nanotubes: Synthesis, Structures and Applica-
2 tions (Springer-Verlag, Berlin, 2001).
0 0.3 0.6 0.9
t (ps) [2] M. Bockrath et al., Nature (London) 397, 598 (1999).
-0.02
1.2 1.4 1.6 1.8 2 2.2 2.4 [3] M. Pope and C. E. Swenberg, Electronic Processes in
Organic Crystals and Polymers (Oxford University
Photon Energy (eV) Press, New York, 1999), 2nd ed.
[4] S. Mazumdar and S. N. Dixit, Phys. Rev. Lett. 51, 292
FIG. 4. Transient PM spectra at t  0 excited at (a) 1 eV at (1983).
two different pump excitation intensities, I  300 J=cm2 [5] R. J. Eliott and R. Loudon, J. Phys. Chem. Solids 15, 196
(squares) and I  1:5 mJ=cm2 (solid line), and (b) at 2.0 eV. (1960).
Various PB and PA bands are assigned. The inset in (b) shows [6] M. J. O’Connell et al., Science 297, 593 (2002);
the transient decay of PB(C) excited at 2.0 eV. S. Bachilo et al., Science 298, 2361 (2002).
[7] T. Ando, J. Phys. Soc. Jpn. 66, 1066 (1997).
[8] M. Ichida et al., Phys. Rev. B 65, 241407 (2002).
is in general a very weak process, resonant three-photon [9] C. L. Kane and E. J. Mele, Phys. Rev. Lett. 90, 207401
absorption is apparently strong [18]. This process can (2003).
be also viewed as sequential excitation via allowed in- [10] J.-S. Lauret et al., Phys. Rev. Lett. 90, 57404 (2003).
termediate states, namely A ! B ! D showing that [11] T. Pichler et al., Phys. Rev. Lett. 80, 4729 (1998), and
not only A ! B transition, but also B ! D transition references therein.
is allowed. [12] H. Haug and S.W. Koch, Quantum Theory and Electronic
The PM spectrum excited at 2 eV into band C (M NT) Properties of Semiconductors (World Scientific,
is shown in Fig. 4(b). Two PB bands are apparent; Singapore, 1990).
[13] S. Frolov et al., Phys. Rev. Lett. 85, 2196 (2000).
PB(B) of S NTs and PB(C) of M NTs. We note that
[14] J. I. Pankove, Optical Processes in Semiconductors
PB(C) occurs either upon interband transition at 2 eV (Dover, New York, 1971).
[Fig. 4(b)] or upon high-intensity excitation at 1 eV [15] A. Jorio et al., Phys. Rev. Lett. 90, 107403 (2003).
[Fig. 4(a)]. Since in M NTs there are no allowed optical [16] Z.V. Vardeny et al., Phys. Rev. Lett. 49, 1657 (1982).
transitions between 0.7 and 1 eV [1], we conjecture that [17] M. Ichida et al., Physica (Amsterdam) 323B, 237 (2002).
PB(C) simply occurs by carrier heating [19]. This shows [18] M. E. Brennan et al., Opt. Lett. 28, 266 (2003).
that the primary photoexcitations in M NTs are free [19] T. Hertel and G. Moos, Phys. Rev. Lett. 84, 5002 (2000).

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