Published on Web 04/09/2005

Phase- and Size-Controlled Synthesis of Hexagonal and Cubic CoO

Nanocrystals
Won Seok Seo,† Jae Ha Shim,† Sang Jun Oh,‡ Eun Kwang Lee,§ Nam Hwi Hur,*,§ and
Joon T. Park*,†
National Research Laboratory, Department of Chemistry and School of Molecular Science (BK 21), Korea
AdVanced Institute of Science and Technology, Daejeon, 305-701, Korea, Korea Basic Science Institute,
Daejeon, 305-333, Korea, and Center for CMR Materials, Korea Research Institute of Standards and Science,
Daejeon, 305-600, Korea
Received January 19, 2005; E-mail: joontpark@kaist.ac.kr; nhhur@kriss.re.kr

Transition metal oxide nanocrystals have a wide range of

applications in magnetic data storage, battery materials, catalysts,
sensors, and ferrofluids, mainly due to their chemical stability and
magnetic properties.1 Developing new methods for the preparation
of metal oxide nanocrystals with various sizes and shapes and
investigating their properties are thus of considerable interest.2 In
particular, cobalt monoxide (CoO) nanocrystals are significant
owing to their potential applications based on magnetic, catalytic,
and gas-sensing properties.3 Thus far, however, few methods have
been reported for the synthesis of CoO nanocrystals exclusively
with a cubic rock-salt structure.4
Herein we report results of a reliable synthesis of CoO nano-
crystals using a single precursor, Co(acac)3 (acac ) acetylacetonate). Figure 1. XRD patterns of (a) 11 × 40 nm rod-shaped and (b) 47 nm and
Remarkably, new wurtzite-type hexagonal CoO nanocrystals never (c) 83 nm hexagonal pyramid-shaped hexagonal CoO nanocrystals. XRD
patterns of (d) 13 nm, (e) 24 nm, and (f) 33 nm cubic CoO nanocrystals.
observed in bulk CoO have been isolated along with the well-known
cubic phase. ZnO is the only stable metal oxide previously
discovered to possess such a hexagonal structure.
Typical synthetic procedures are as follows.5 A green slurry of
cobalt precursor Co(acac)3 in oleylamine was heated at 135 °C under
an Ar atmosphere. Immediately after dissolution, the reaction was
initiated by flash-heating to 200 °C. After being annealed for 1 h,
the reaction mixture was cooled to room temperature, giving green
hexagonal CoO nanocrystals separated by centrifugation and puri-
fied by washing with ethanol. Cubic CoO nanocrystals were syn-
thesized under similar synthetic conditions using longer reaction
time at 135 °C. The green reaction mixture was heated at 135 °C
for 5 h under an Ar atmosphere, which slowly became red. This
solution was flash-heated to 200 °C and annealed for 3 h, giving
brown cubic CoO nanocrystals obtained by a similar workup
procedure.
EDX spectrometry and EELS5 for both nanocrystals yielded an
average atomic ratio of 49:51 (Co/O), which can be considered to
have almost stoichiometric compositions. The XRD patterns of the
Figure 2. TEM micrographs of hexagonal CoO nanocrystals: (a) TEM
CoO samples provided in Figure 1 clearly show pure nanocrystalline image, (b) SAED pattern, and (c) HRTEM image of rod-shaped nanocrystals
hexagonal and cubic phases. The diffraction peaks of the cubic with average width of 11 ( 1.7 nm and average length of 40 ( 7.3 nm.
phase (Figure 1d-f) are well matched with those of the corre- TEM images of hexagonal pyramid-shaped nanocrystals with average side
edge lengths of (d) 47 ( 4.6 nm and (e) 83 ( 9.2 nm.
sponding bulk CoO congener (Fm3m, a ) 4.26 Å), while peaks
are slightly broadened with decreasing nanocrystal size. As given shaped CoO nanocrystals were formed. Figure 2a shows rod-shaped
in Figure 1a-c, the diffraction patterns from hexagonal CoO nanocrystals with 11 ( 1.7 nm in width and 40 ( 7.3 nm in length.
nanocrystals are in good agreement with those from hexagonal ZnO The strong ring patterns from SAED given in Figure 2b can be
(P63mc, a ) 3.25 Å and c ) 5.21 Å). The calculated lattice well indexed to the wurtzite structure. This is consistent with the
parameters of a and c are 3.2518(2) and 5.1967(3) Å, respectively, XRD data given in spectra a-c of Figure 1. The HRTEM image
which is quite close to those of ZnO. in Figure 2c reveals that nanorods are grown along the unique c
The low- and high-resolution TEM images of various hexagonal axis of the hexagonal structure, which coincides with narrow (002)
CoO nanocrystals are illustrated in Figure 2. When a solution of peak in XRD of Figure 1a.6 The observed lattice spacing corre-
1:200 molar ratio of Co(acac)3 and oleylamine was employed, rod- sponding to the (002) lattice plane is estimated to be 2.60 Å.
Interestingly, size and shape of the CoO nanocrystals can be
† Korea Advanced Institute of Science and Technology.
‡ Korea Basic Science Institute.
controlled by changing the precursor concentration. For example,
§ Korea Research Institute of Standards and Science. hexagonal pyramid-shaped CoO nanocrystals of 47 ( 4.6 nm in
6188 9 J. AM. CHEM. SOC. 2005, 127, 6188-6189 10.1021/ja050359t CCC: $30.25 © 2005 American Chemical Society
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The temperature-dependent magnetic properties of the hexagonal

and cubic CoO nanocrystals, measured in both field-cooled and
zero-field-cooled conditions by using SQUID were very sensitive
to the structural phase but appeared to be irrelevant to the size.5
All the hexagonal samples showed paramagnetic behaviors, while
cubic CoO was antiferromagnetic. The most likely cause of their
different magnetic properties is that they have different structural
environments surrounding the magnetic Co ions. The cubic rock-
salt structure exhibits the 180° Co-O-Co superexchange interac-
tions, in which antiferromagnetic coupling is favored.11 However,
in the hexagonal phase, the exchange interaction between the Co
ions through oxygen is not effectively operative due to the tilted
Co-O-Co angle (ca. 110°), resulting in the absence of magnetic
ordering.
In conclusion, we have prepared previously unknown hexagonal
CoO nanocrystals by kinetically tuned thermal decomposition of a
single molecular precursor Co(acac)3 in oleylamine. The shape and
size of CoO nanocrystals are well controlled by changing the
precursor concentration and the reaction temperature. A remarkable
Figure 3. TEM micrographs of cubic CoO nanocrystals: (a) TEM image,
(b) SAED pattern, and (c) HRTEM image of 13 ( 1.6 nm nanocrystals. finding is that phase control between the hexagonal and cubic
TEM images of (d) 24 ( 3.3 nm and (e) 33 ( 4.5 nm nanocrystals. nanocrystals can be achieved by simple manipulation of the
precursor formation kinetics. The successful growth of hexagonal
side edge length and 24 ( 2.4 nm in basal edge length (Figure 2d) CoO nanocrystals may help to understand the Co-doped ZnO system
were obtained when a solution of 1:100 molar ratio of Co(acac)3 known as a diluted magnetic semiconductor. We are currently
and oleylamine was used. Similar shaped but larger nanocrystals investigating the full mechanistic studies on the preparation and
of 83 ( 9.2 nm in side edge length and 42 ( 4.5 nm in basal edge new physical properties for the hexagonal CoO nanocrystals.
length (Figure 1e) were grown from a 1:50 molar ratio solution. Acknowledgment. This research at KAIST was supported by
The hexagonal pyramidal shape was confirmed by tilting the the NRL Program of the MOST of Korea. N.H.H. thanks the
hexagon or triangle TEM images, in which the basal plane of the Creative Research Initiative Program for support of this work. We
hexagonal pyramid is (002) and the direction from the base to the thank the staffs of KBSI and KAIST for TEM analyses.
top of the hexagonal pyramid is [002].5 Apparently hexagonal
Supporting Information Available: Synthetic procedures and
pyramid-shaped nanocrystals are predominant over nanorods in EELS spectra of CoO nanocrystals, tilted TEM and HRTEM images
bigger nanocrystals, which are favored by abrupt decomposition of hexagonal pyramid-shaped CoO nanocrystals, and ZFC/FC magne-
in higher precursor concentration. tization curves of CoO nanocrystals. This material is available free of
Figure 3 shows TEM images of cubic nanocrystals with various charge via the Internet at http://pubs.acs.org
sizes. They have a quasi-cubic shape regardless of size. As can be
seen in the SAED pattern of Figure 3b, pure cubic symmetry was References
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J. AM. CHEM. SOC. 9 VOL. 127, NO. 17, 2005 6189