Crystal structure of C

60
following compression under 31.1 GPa
in diamond anvil cell at room temperature
J.H. Rhee, D. Singh, Y. Li, S.C. Sharma
*
Department of Physics, The University of Texas at Arlington, Box 19059, Arlington, TX 76019, USA
Received 4 April 2003; accepted 8 May 2003 by A.H. MacDonald
Abstract
We have conducted X-ray diffraction experiments in order to examine modications in the crystal structure of C
60
following
compression under 31.1 GPa in a diamond anvil cell at room temperature. The material under ambient and 31.1 GPa is further
characterized by laser Raman spectroscopy. The high pressure phase is identied as a mixture of body-centered orthorhombic
Immm; rhombohedral R

3m; and an unidentied phase.

q 2003 Elsevier Ltd. All rights reserved.
PACS: 61.48.+c; 61.10.-i; 61.50.Ks
Keywords: A. Fullerene; C. X.-ray diffraction; E. Raman Spectroscopy
1. Introduction
The electronic and structural properties of fullerenes and
carbon Nanotubes continue to be of signicant interest. The
electronic and vibrational properties of these materials
under high pressure have been studied in some detail [13].
However, there are issues, related to the crystal structure of
the high-pressure phases that need further investigation. The
pressuretemperature (PT) phase diagram of C
60
has been
studied using quenched samples that are prepared by high-
pressure high-temperature (HPHT) treatments and sub-
sequently compressed under high pressures [3]. Since, the
eventual structure of the material may depend on the
synthesis route employed; it is of interest to investigate
effects of pressure on samples synthesized by techniques
that do not rely solely on the HPHT treatment.
In the present work, we have compressed C
60
under
31.1 GPa in a diamond anvil cell at room temperature and
studied its crystal structure and vibrational properties by
using X-ray diffraction (XRD) and laser Raman spec-
troscopy. Using high resolution Raman spectroscopy, we
observe that the vibrational properties of the material under
31.1 GPa in a diamond anvil cell at room temperature are
almost identical to the vibrational properties of the material
recovered upon release of the pressure. This facilitates
characterization of the crystal structure of the high pressure
phase of the material without facing practical difculties in
conducting XRD measurements on a sample compressed in
a diamond anvil cell. We identify the high-pressure
(31.1 GPa) structure of C
60
by conducting X-ray diffraction
measurements with a 300 mm diameter collimated X-ray
beam incident on the recovered sample.
2. Experimental details
C
60
powder of 99.9% purity and containing 110 mm
particles was used in this work. The X-ray diffraction data
were obtained by using a two-dimensional X-ray Diffract-
ometer system with a 300 mm diameter collimated X-ray
beam of wavelength 0.22897 nm from a Cr target and a
cylindrical imaging plate. In transmission mode, complete
Debye Sherrer rings were recorded, which were integrated
to produce the conventional intensity vs 2u plots and
structural details of the material by using standard data
analysis software [4]. High resolution Raman spectra were
measured by using 1.25 m, f/11 monochromator, 1200 and
0038-1098/03/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0038-1098(03)00430-7
Solid State Communications 127 (2003) 295297
www.elsevier.com/locate/ssc
*
Corresponding author. Tel.: 81-727-224-70; fax: 81-727-
236-37.
E-mail address: sharma@uta.edu (S.C. Sharma).
2400 g/mm ion-etched blazed holographic diffraction
gratings, liquid nitrogen cooled CCD camera, Super-
Notch-Plus lter, argon-ion laser operating at 514.5 nm,
and SpectraMax for Windows software. The C
60
powder
was loaded in a diamond anvil cell (DAC) containing pre-
indented stainless steel gasket with a 200 mm hole and a
mixture of methanol, ethanol, and water (16:3:1) as the
pressure transmitting medium. Applied pressures were
calculated by measuring pressure-induced shifts in the
Ruby uorescence peaks [5,6].
3. Results and discussion
3.1. Raman spectroscopy
Raman spectra for the well-known A
g
(2), and H
g
(8)
modes of C
60
measured under ambient pressure, 31.1 GPa,
and recovered sample (pressure released down to ambient
from 31.1 GPa) are shown in Fig. 1.
The reference spectrum, measured at ambient pressure,
provides values of 1465 and 1574 cm
21
for the Raman
frequencies of the A
g
(2) and H
g
(8) bands of C
60
. These
values are in excellent agreement with the theoretical and
experimental results for pristine C
60
[7,8]. The marked
changes in the spectrum at 31.1 GPa, compared to the
spectrum of Pristime C60 show that the sample has
undergone a structural phase transition. This is in good
agreement with the theoretical prediction of a structural
phase transformation from a 2D polymerized tetragonal
phase to 3D polymerized structure under uniaxial pressure
Fig. 1. Raman spectra of C
60
under ambient, 31.1 GPa and
recovered sample after 31.1 GPa.
Fig. 2. XRD spectrum for the recovered sample.
Fig. 3. XRD of C
60
at ambient pressure.
J.H. Rhee et al. / Solid State Communications 127 (2003) 295297 296
of about 20 GPa [9]. As seen in Fig. 1, the spectrum for the
recovered sample is almost identical to the spectrum
recorded for the sample under 31.1 GPa.
3.2. X-ray diffraction
Figs. 2 and 3 show XRD spectra measured for C
60
recovered after 31.1 GPa compression and pristine C
60
. In
good agreement with earlier work, we observe an fcc
crystalline phase in pristine C
60
[10]. In the case of the
recovered sample (31.1 GPa phase), we observe a total of 13
peaks, and they indicate that the recovered sample consists
of a mixture of structures.
In order to better understand the complex structure of the
material, we have carried out simulations for the intensity vs
2u patterns using crystallographic parameters for the expected
phases of the material. The simulations of the X-ray patterns
were made by starting with published values of the atomic
coordinates for the body-centered orthorhombic (BCO,
Immm), rhombohedral (R

3m), hard and super-hard body-

centered cubic, and tetragonal structures [11,12]. We made
renements in these simulations by varying, within reasonable
limits, the crystallographic parameters (lattice constants were
varied up to ^2%fromtheir values given in these references)
in order to improve agreement between the measured spectra
and the simulations. In these exercises, if the centroids of the
simulated and measured peaks (2u values) were within ^0.18,
the simulation was considered to be in agreement with the
measurement. As the results listed in Table 1 show,
the recovered material consists of a mixture of the body-
centered orthorhombic Immm; rhombohedral R

3m and an
unidentied structure. The crystallographic parameters for the
BCO Immm and rhombohedral R

3m phases, that provide

the best t for the measured XRDspectrum, are a 0.911 nm,
b 0.978 nm, c 1.450 nm, and r
av
0.355 nm for the
BCO Immm; and a 0.916 nm, c 2.450 nm, and
r
av
0.36 nm for the rhombohedral R

3m phases, respect-
ively. These parameters are in excellent agreement with those
published previously [11]. We have ruled out the presence of
the so-called hard and super-hard phases in the recovered
material; we do not obtain good ts between the measured and
simulated spectra when simulations are made by using
crystallographic parameters for the hard and super hard
structures [12].
4. Conclusions
The main results of our Raman and XRD experiments
are that; (1) the Raman spectrum of C
60
under 31.1 GPa is
dramatically different from the spectrum recorded at
ambient pressure, indicating a structural phase transform-
ation, (2) the Raman spectrum of the recovered sample is
almost identical to the spectrum of C
60
under 31.1 GPa, and
(3) the high pressure phase is a mixture of body-centered
orthorhombic Immm; rhombohedral R

3m; and an yet

unidentied structure.
Acknowledgements
Research supported, in part, by grants from the US
Department of Energy, grant No. DE-FG0300ER45840 and
Welch Foundation, grant No. Y-1484.
References
[1] L. Forro, L. Mihaly, Rep. Prog. Phys. 64 (2001) 649.
[2] U.D. Venkateswaran, E.A. Brandsen, U. Schlecht, A.M. Rao,
E. Richter, I. Loa, K. Syassen, P.C. Eklund, Phys. Status Solidi
(B) 223 (2001) 225.
[3] V.A. Davydov, L.S. Kashevarova, A.V. Rakhamanina, V.M.
Senyavin, O.P. Pronina, N.N. Oleynikoy, V. Agafonov, R.
Ceolin, H. Allouchi, H. Szwarc, Chem. Phys. Lett. 333 (2001)
224.
[4] Fast X-ray diffraction with area detector, The Rigaku Journal,
16, 1999, 1.
[5] S.C. Sharma, B. Ha, J.H. Rhee, Y. Li, et al., in: H.D.
Hochheimer (Eds.), Frontiers of High Pressure Research, vol.
II, 2001, pp. 493505.
[6] S.C. Sharma, B. Ha, J.H. Rhee, Y. Li, D. Singh, R.
Govinthasamy, Mater. Res. Soc. Symp. Proc. 695 (2002) 97.
[7] G.B. Adam, J.B. Page, Phys. Status Solidi (B) 226 (2001) 95.
[8] A.M. Rao, P.C. Eklund, J.-L. Hodeau, L. Marques, M. Nunez-
Regueiro, Phys. Rev. B 55 (1997) 4766.
[9] S. Okada, S. Saito, A. Oshiyama, Phys. Rev. Lett. 83 (1999)
1986.
[10] P.W. Stephens, L. Mihaly, P.L. Lee, R.L. Whetten, S.M.
Huang, R. Kaner, F. Diederich, K. Holczer, Nature 351 (1991)
632.
[11] M. Nunez-Regueiro, L. Marques, J.L. Hodeau, O. Bethoux, M.
Perroux, Phys. Rev. Lett. 74 (1995) 278.
[12] V.D. Blank, S.G. Buga, N.R. Serebryanaya, V.N. Denisov,
G.A. Dubitsky, A.N. Ivlev, B.N. Mavrin, M.Y. Popov, Phys.
Lett. A 205 (1995) 208.
Table 1
2u d
hkl
(A

) Identied structure
12.642 Unknown
14.146 Unknown
16.097 8.167 Rhombohedral
16.233 8.108 Body-centered orthorhombic
17.369 7.547 Rhombohedral
19.798 6.659 Rhombohedral
21.634 6.125 Rhombohedral
22.584 Unknown
26.986 4.907 Body-centered orthorhombic
27.096 4.890 Body-centered orthorhombic
28.287 Unknown
28.355 Unknown
38.410 Unknown
J.H. Rhee et al. / Solid State Communications 127 (2003) 295297 297