Published on Web 07/11/2006

Synthesis, Characterization, and Self-Assembly of

Pencil-Shaped CoO Nanorods
Kwangjin An,† Nohyun Lee,† Jongnam Park,† Sung Chul Kim,† Yosun Hwang,‡
Je-Geun Park,‡ Jae-Young Kim,§ Jae-Hoon Park,§ Myung Joon Han,|
Jaejun Yu,| and Taeghwan Hyeon*,†
Contribution from the National CreatiVe Research InitiatiVe Center for Oxide Nanocrystalline
Materials and School of Chemical and Biological Engineering, Seoul National UniVersity,
Seoul 151-744, Korea, Department of Physics and Institute of Basic Science, Sungkyunkwan
UniVersity, Suwon 440-746, Korea, Department of Physics and Pohang Light Source,
Pohang UniVersity of Science and Technology, Pohang 790-784, Korea, and
School of Physics and CSCMR, Seoul National UniVersity, Seoul 151-747, Korea
Received February 6, 2006; E-mail: [email protected]

Abstract: We synthesized uniformly sized, pencil-shaped CoO nanorods by the thermal decomposition of
a cobalt-oleate complex, which was prepared from the reaction of cobalt chloride and sodium oleate. The
diameters and lengths of the CoO nanorods were easily controlled by varying the experimental conditions,
such as the heating rate and the amount of Co-oleate complex. The X-ray diffraction pattern revealed
that the CoO nanorods have an extraordinary wurtzite ZnO crystal structure. These uniformly sized nanorods
self-assembled to form both horizontal parallel arrangements and perpendicular hexagonal honeycomb
superlattice structures. Reduction of the nanorods by heating under a hydrogen atmosphere generated
either hcp Co or Co2C nanorods. Characterization of the CoO nanorods using X-ray absorption spectroscopy,
X-ray magnetic circular dichroism spectroscopy, and magnetic measurements showed that they contain a
small fraction of ferromagnetic Co impurities.

Introduction synthesized using several chemical synthetic procedures, includ-

ing the reduction of metal salts and the thermal decomposition
Magnetic nanocrystals have attracted a tremendous amount
of organometallic compounds.2 Murray, Sun, and their co-
of attention from researchers in various disciplines, not only
workers at IBM synthesized spherical cobalt nanocrystals with
for their fundamental size-dependent magnetism but also for
various crystal structures, including -phase, face-centered cubic
their many technological applications, including magnetic
(fcc), and hexagonal close-packed (hcp).2a Recently, uniformly
storage media, ferrofluids, contrast agents for magnetic reso-
sized one-dimensional (1-D) nanostructures such as nanorods
nance imaging, and magnetic carriers for drug targeting.1 For
have received much attention because of their unique properties,
many of these applications and fundamental studies, magnetic
which are derived from their dimensional anisotropy.3 The
nanocrystals with a uniform and controllable particle size and
Chaudret group reported the synthesis and self-assembly of
shape are desirable.1h Uniformly sized cobalt nanocrystals with
uniformly sized cobalt nanorods from the decomposition of a
various crystal structures, particle shapes, and sizes have been
(2) (a) Sun, S.; Murray, C. B. J. Appl. Phys. 1999, 85, 4325. (b) Dumestre, F.;
† National Creative Research Initiative Center for Oxide Nanocrystalline Chaudret, B.; Amiens, C.; Fromen, M.-C.; Casanove, M.-J.; Renaud, P.;
Materials and School of Chemical and Biological Engineering, Seoul Zurcher, P. Angew. Chem., Int. Ed. 2002, 41, 4286. (c) Dumestre, F.;
National University. Chaudret, B.; Amiens, C.; Respaud, M.; Fejes, P.; Renaud, P.; Zurcher, P.
‡ Department of Physics and Institute of Basic Science, Sungkyunkwan Angew. Chem., Int. Ed. 2003, 42, 5213. (d) Osuna, J.; Caro, D.; Amiens,
C.; Chaudret, B.; Snoeck, E.; Respaud, M.; Broto, J.-M.; Fert, A. J. Phys.
University. Chem. 1996, 100, 14571. (e) Puntes, V. F.; Krishnan, K. M.; Alivisatos A.
§ Department of Physics and Pohang Light Source, Pohang University
P. Science 2001, 291, 2115. (f) Puntes, V. F.; Gorostiza, P.; Aruguete, D.
of Science and Technology. M.; Bastus, N. G.; Alivisatos, A. P. Nat. Mater. 2004, 3, 263. (g) Puntes,
| School of Physics and CSCMR, Seoul National University.
V. F.; Krishnan, K. M.; Alivisatos, A. P. Appl. Phys. Lett. 2001, 78, 2187.
(1) (a) Schmid, G. Nanoparticles: From Theory to Application; Wiley-VCH: (h) Pileni, M. P. J. Phys. Chem. B 2001, 105, 3358. (i) Petit, C.; Taleb, A.;
Weinheim, 2004. (b) Klabunde, K. J. Nanoscale Materials in Chemistry; Pileni, M. P. J. Phys. Chem. B 1999, 103, 1805. (j) Petit, C.; Cren, T.;
Wiley-Interscience: New York, 2001. (c) Fendler, J. H. Nanoparticles and Roditchev, D.; Sacks, W.; Klein, J.; Pileni, M. P. AdV. Mater. 1999, 11,
Nanostructured Films; Wiley-VCH: Weinheim, 1998. (d) Fertman, V. E. 1198. (k) Legrand, J.; Petit, C.; Pileni, M. P. J. Phys. Chem. B 2001, 105,
Magnetic Fluids Guide Book: Properties and Applications; Hemisphere 5643. (l) Shafi, K. V. P. M.; Gedanken, A.; Prozorov, R. AdV. Mater. 1998,
Publishing Co.: New York, 1990. (e) Berkovsky, B. M.; Medvedev, V. 10, 590. (m) Russier, V.; Petit, C.; Pileni, M. P. Phys. ReV. B 2000, 62,
F.; Krakov, M. S. Magnetic Fluids: Engineering Applications; Oxford 3910. (n) Lin, X. M.; Sorensen, C. M.; Klabunde, K. J.; Hadjipanayis, G.
University Press: Oxford, 1993. (f) Ziolo, R. F.; Giannelis, E. P.; Weinstein, C. Langmuir 1998, 14, 7140. (o) Dinega, D. P.; Bawendi, M. G. Angew.
B. A.; O’Horo, M. P.; Ganguly, B. N.; Mehrotra, V.; Russel, M. W.; Chem., Int. Ed. 1999, 38, 1788. (p) Samia, A. C. S.; Hyzer, K.; Schlueter,
Huffman, D. R. Science 1992, 257, 219. (g) Alivisatos, A. P. Science 1996, J. A.; Qin, C.-J.; Jiang, S.; Bader, S. D.; Lin, X.-M. J. Am. Chem. Soc.
271, 933. (h) Hyeon, T. Chem. Commun. 2003, 927. (i) Zhang, J. Z.; Wang, 2005, 127, 4126. (q) Diehl, M. R.; Yu, J.-Y.; Heath, J. R.; Held, G. A.;
Z.-L.; Liu, J.; Chen, S.; Liu, G.-Y. Self-Assembled Nanostructures; Kluwer Doyle, H.; Sun, S.; Murray, C. B. J. Phys. Chem. B 2001, 105, 7913. (r)
Academic/Plenum Publishers: New York, 2003. (j) Pacholski, C.; Kor- Wu, N.; Fu, L.; Su, M.; Aslam, M.; Wong, K. C.; Dravid, V. P. Nano Lett.
nowski, A.; Weller, H. Angew. Chem., Int. Ed. 2002, 41, 1188. 2004, 4, 383.
10.1021/ja0608702 CCC: $33.50 © 2006 American Chemical Society J. AM. CHEM. SOC. 2006, 128, 9753-9760 9 9753
ARTICLES An et al.

cobalt organometallic compound under a hydrogen atmosphere workers also synthesized wurtzite CoO nanocrystals with rod
in the presence of a mixture of a long-chain amine and an and hexagonal pyramid shapes by the decomposition of Co-
acid.2b-d On the other hand, Alivisatos and co-workers synthe- (acac)3 in oleylamine.4e We further extended the synthesis, and
sized cobalt nanodisks from the thermal decomposition of herein we report on the synthesis of CoO nanorods with various
dicobalt octacarbonyl in hot coordinating surfactants.2e diameters and lengths and their self-assemblies. Moreover,
CoO nanocrystals have attracted much attention because they through their subsequent reduction by heat treatment under a
exhibit superparamagnetism or weak ferromagnetism, whereas hydrogen atmosphere, orthorhombic Co2C and hcp Co nanorods
bulk CoO is antiferromagnetic.4 Yin and Wang reported the were produced. We thoroughly characterized the crystal struc-
synthesis of tetrahedron-shaped CoO nanocrystals with a size tures and magnetic properties of the nanorods of CoO, Co2C,
of 4.4 nm by the decomposition of Co2(CO)8 in toluene under and Co using X-ray absorption (XAS) spectroscopy, X-ray
an oxygen atmosphere in the presence of sodium bis(2- magnetic circular dichroism (XMCD) spectroscopy, and SQUID
ethylhexyl)sulfosuccinate (Na(AOT)).4b Chaudret and co-work- measurements. We also performed theoretical studies using LDA
ers synthesized ∼2-nm nanoparticles of CoO and Co3O4 by the + U band calculations.
solid-state oxidation of 1.6-nm metallic cobalt nanoparticles.4c
Rao and co-workers synthesized CoO nanoparticles with sizes Experimental Section
ranging from 4 to 18 nm by the decomposition of Co(II)
Synthesis of Co-Oleate Complex. A 9.52 g portion of cobalt
cupferronate in decalin under solvothermal conditions.4d Our chloride hexahydrate (CoCl2‚6H2O, 40 mmol, Aldrich Chemical Co.,
group5 and two other groups6 reported the synthesis of uniformly 98%) and 24.36 g of sodium oleate (80 mmol, TCI Co., 95%) were
sized nanocrystals of transition metal oxides by the thermal added to a mixture composed of 30 mL of ethanol, 40 mL of distilled
decomposition of metal-surfactant complexes. In particular, we water, and 70 mL of n-hexane. The resulting mixture solution was
synthesized short, pencil-shaped CoO nanorods with an unusual heated to 70 °C and maintained at this temperature for 4 h. The solution
wurtzite ZnO structure.5a This was the first report on the was then transferred to a separatory funnel, and the upper organic layer
synthesis of wurtzite ZnO-structured CoO, not only in the form containing the Co-oleate complex was washed several times using
of nanocrystals but also in the bulk form. Later, Park and co- distilled water. Evaporation of the hexane solvent produced a purple
Co-oleate powder.
(3) (a) Xia, Y.; Yang, P.; Sun, Y.; Wu, Y.; Mayers, B.; Gates, B.; Yin, Y.; Synthesis of CoO Nanorods. A 3.12 g portion of the Co-oleate
Kim, F.; Yan, H. AdV. Mater. 2003, 15, 353. (b) Cui, Y.; Lieber, C. M. complex (5 mmol) was dissolved in 50 g of 1-octadecene (Aldrich
Science 2001, 291, 851. (c) Huynh, W. U.; Dittmer, J. J.; Alivisatos, A. P.
Science 2002, 295, 2425. (d) Huang, M.; Mao, S.; Feick, H.; Yan, H.; Wu, Chemical Co., 90%). The mixture solution was degassed at 120 °C for
Y.; Kind, H.; Weber, E.; Russo, R.; Yang, P. Science 2001, 292, 1897. (e) 2 h under a vacuum to remove the water and oxygen. The solution
Cui, Y.; Wei, Q.; Park, H.; Lieber, C. M. Science 2001, 293, 1289. (f) was then heated to 320 °C with vigorous stirring. The heating rate was
Gudiksen, M. S.; Lieber, C. M. J. Am. Chem. Soc. 2000, 122, 8801. (g)
Gudiksen, M. S.; Wang, J.; Lieber, C. M. J. Phys. Chem. B 2001, 105, controlled to produce CoO nanorods with various aspect ratios. When
4062. (h) Barrelet, C. J.; Wu, Y.; Bell, D. C.; Lieber, C. M. J. Am. Chem. the reaction temperature reached 320 °C, the initially purple solution
Soc. 2003, 125, 11498. (i) Hanrath, T. T.; Korgel, B. A. J. Am. Chem. Soc.
2002, 124, 1424. (j) Holmes, J. D.; Johnston, K. P.; Doty, R. C.; Korgel, became dark green. This color change indicated that the Co-oleate
B. A. Science 2000, 287, 1471. (k) Sigman, M. B., Jr.; Ghezelbash, A.; complex was thermally decomposed to generate CoO nanocrystals,
Hanrath, T.; Saunders, A. E.; Lee, F.; Korgel, B. A. J. Am. Chem. Soc.
2003, 125, 16050. (l) Larsen, T. H.; Sigman, M.; Ghezelbash, A.; Doty, R. whereupon nucleation occurred. The reaction mixture was maintained
C.; Korgel, B. A. J. Am. Chem. Soc. 2003, 125, 5638. (m) Tang, Z.; Kotov, at this temperature for 30 min to induce sufficient growth. The solution
N. A.; Giersig, M. Science 2002, 297, 237. (n) Nath, M.; Choudhury, A.; was then cooled to room temperature, and a mixture of acetone and a
Kundu, A.; Rao, C. N. R. AdV. Mater. 2003, 15, 2098. (o) Manna, L.;
Milliron, D. J.; Meisel, A.; Scher, E. C.; Alivisatos, A. P. Nat. Mater. 2003, small fraction of n-hexane was added to the solution to yield a waxy
2, 382. (p) Lee, S.-M.; Cho, S.-N.; Cheon, J. AdV. Mater. 2003, 15, 441. precipitate, which was separated by centrifugation. The resulting waxy
(q) Hu, J.; Bando, Y.; Liu, Z.; Ahan, J.; Golberg, D.; Sekiguchi, T. Angew.
Chem., Int. Ed. 2004, 43, 63. (r) Park, J.; Koo, B.; Hwang, Y.; Bae, C.; precipitate was found to be re-dispersible in many organic solvents,
An, K.; Park, J.-G.; Park, H. M.; Hyeon, T. Angew. Chem., Int. Ed. 2004, such as n-hexane and chloroform.
43, 2282. (s) Park, J.; Koo, B.; Yoon, K. Y.; Hwang, Y.; Kang, M.; Park,
J.-G.; Hyeon, T. J. Am. Chem. Soc. 2005, 127, 8433. (t) Song, J. H.; Wu, Heat Treatment of CoO Nanorods. For the heat treatment of the
Y.; Messer, B.; Kind, H.; Yang, P. J. Am. Chem. Soc. 2001, 123, 10397. CoO nanorods, a Si wafer passivated with a thermally grown SiO2 layer
(u) Zhang, D.; Liu, Z.; Han, S.; Li, C.; Lei, B.; Stewart, M. P.; Tour, J.
M.; Zhou, C. Nano Lett. 2004, 4, 2151. (v) Woo, K.; Lee, H. J.; Ahn, was used as the substrate to generate a mono- or multilayer thin film.
J.-P.; Park, Y. S. AdV. Mater. 2003, 15, 1761. (w) Wang, J.; Chen, Q.; A few drops of a hexane solution containing the CoO nanorods were
Zeng, C.; Hou, B. AdV. Mater. 2004, 16, 137. (x) Urban, J. J.; Yun, W. S.; dropped on the Si wafer. Hexane was then evaporated to generate the
Gu, Q.; Park, H. J. Am. Chem. Soc. 2002, 124, 1186. (y) Gu, G.; Zheng,
B.; Han, W. Q.; Roth, S.; Liu, J. Nano Lett. 2002, 2, 849. self-assembled CoO nanorods. The resulting CoO nanorods, assembled
(4) (a) Kodama, R. H. J. Magn. Magn. Mater. 1999, 200, 359. (b) Yin, J. S.; on the Si wafer, were heat-treated at 300 °C for 2 h under a H2 flow,
Wang, Z. L. J. Phys. Chem. B 1997, 101, 8979. (c) Verelst, M.; Ely, T.
O.; Amiens, C.; Snoeck, E.; Lecante, P.; Mosset, A.; Respaud, M.; Broto where the heating rate was 1.56 °C min-1 and the H2 flow rate was 60
J. M.; Chaudret, B. Chem. Mater. 1999, 11, 2702. (d) Ghosh, M.; mL min-1.
Sampathkumaran, E. V.; Rao, C. N. R. Chem. Mater. 2005, 17, 2348. (e)
Seo, W. S.; Shim, J. H.; Oh, S. J.; Lee, E. K.; Hur, N. H.; Park J. T. J. Am. For the large-scale reduction of CoO nanorods, ∼2 g of CoO
Chem. Soc. 2005, 127, 6188. (f) Xu, C.; Liu, Y.; Xu, G.; Wang, G. Chem. nanorods was loaded in an alumina boat and heat-treated using the
Phys. Lett. 2002, 366, 567. (g) Zhang, L.; Xue, D.; Gao, C. J. Magn. Magn.
Mater. 2003, 267, 111. (h) Wang, L.; Vu, K.; Navrotsky, A.; Stevens, R.; same procedure described above.
Woodfield, B. F.; Boerio-Goates, J. Chem. Mater. 2004, 16, 5394. (i) Flipse, Characterization of Materials. The nanorods were characterized
C. F. J.; Rouwelaar, C. B.; de Groot, F. M. F. Eur. Phys. J. D 1999, 9,
479. (j) Yin, J. S.; Wang, Z. L. Phys. ReV. Lett. 1997, 79, 2570. (k) Soriano, by low- and high-resolution transmission electron microscopy (TEM),
L.; Abbate, M.; Fernandez, A.; Gonzalez-Elipe, A. R.; Sirotti, F.; Sanz, J. electron diffraction (ED), X-ray diffraction (XRD), X-ray absorption
M. J. Phys. Chem. B 1999, 103,6676. (l) Skumryev, V.; Stoyanov, S.;
Zhang, Y.; Hadjipanayis, G.; Givord, D.; Nogues, J. Nature 2003, 423, spectroscopy (XAS), and X-ray magnetic circular dichroism (MCD)
850. spectroscopy. The TEM images and electron diffraction patterns were
(5) (a) Park, J.; An, K.; Hwang, Y.; Park, J.-G.; Noh, H.-J.; Kim, J.-Y.; Park, collected on a JEOL JEM-2010 electron microscope. The XRD patterns
J.-H.; Hwang, N.-M.; Hyeon, T. Nat. Mater. 2004, 3, 891. (b) Choi, S.-H.;
Kim, E.-K.; Park, J.; An, K.; Lee, N.; Kim, S.; Hyeon, T. J. Phys. Chem. were obtained using a Rigaku D/Max-3C diffractometer equipped with
B 2005, 109, 14792. a rotation anode and a Cu KR radiation source (λ ) 0.15418 nm). XAS
(6) (a) Yu, W. W.; Falkner, J. C.; Yavuz, C. T.; Colvin, V. L. Chem. Commun.
2004, 2306. (b) Jana, N. R.; Chen, Y.; Peng, X. Chem. Mater. 2004, 16, and MCD measurements at the Co L2,3-edges were carried out at the
3931. EPU6 beamline at the Pohang Light Source. The magnetic properties
9754 J. AM. CHEM. SOC. 9 VOL. 128, NO. 30, 2006
Pencil-Shaped CoO Nanorods ARTICLES

Figure 1. TEM images of pencil-shaped CoO nanorods obtained using various synthetic conditions. CoO nanorods with dimensions of 23 nm (base edge)
× 28 nm (height) (a), 12 nm × 19 nm (b), and 8 nm × 26 nm (c), synthesized at heating rates of 3.1, 1.9, and 1.0 °C min-1, respectively, with the same
Co-oleate concentration of 5 mmol. CoO nanorods with dimensions of 9 nm × 28 nm (d) and 20 nm × 38 nm (e) were synthesized using 10 and 15 mmol
of Co-oleate with the same heating rate of 1.9 °C min-1. (f) 9 nm × 46 nm CoO nanorods were synthesized using the Co-oleate concentration of 5 mmol
and a heating rate of 1.9 °C min-1, but an increased aging time of 1 h.

were studied using a magnetic property measurement system (MPMS), of wurtzite-structured nanocrystals, i.e., a thermodynamically
5XL Quantum design SQUID magnetometer, in the temperature range controlled regime, the growth rate along the c-axis is generally
of 5-300 K. much higher than that along the other directions, thereby leading
Results and Discussion to the production of anisotropic rod-shaped nanocrystals.8 In
the current synthesis, when the reaction temperature was slowly
Synthesis of CoO Nanorods. CoO nanorods with various increased, long CoO nanorods with a high aspect ratio were
aspect ratios were synthesized by the thermal decomposition produced (Figure 1c). In contrast, short, pencil-shaped CoO
of a Co-oleate complex in a long-chain hydrocarbon solvent, nanorods were produced when a high heating rate of 3.1 °C
followed by aging at the reflux temperature. The resulting CoO min-1 was used (Figure 1a, kinetically controlled regime).
nanorods were pencil-shaped, with a hexagonal basal plane. The The heating rate also affected the overall size of the
diameters and lengths of the CoO nanorods could be controlled nanocrystals. In the current synthesis of nanocrystals, the thermal
by varying the synthetic parameters, such as the monomer decomposition of the Co-oleate complex at a certain critical
concentration, heating rate, and aging time. The dimensions of temperature would be expected to generate nuclei.9 Under fast
the synthesized nanorods are quite uniform, and the size heating conditions, a relatively small number of nuclei seemed
distribution histograms of the nanorods are supplied in the to be generated because of the short nucleation period,
Supporting Information. Figure 1 shows the TEM images of consequently producing a small population of large nanocrys-
the short, pencil-shaped CoO nanorods with aspect ratios (length/ tals.10 On the other hand, a large number of small nanocrystals
diameter) of 1.22 (Figure 1a), 1.58 (Figure 1b), and 3.25 (Figure were produced at a low heating rate. As shown in Figure 1, the
1c), obtained by using different heating rates. When a reaction overall size of the CoO nanorods decreased as the heating rate
mixture composed of 5 mmol of Co-oleate complex and 50 g decreased. The overall size of the nanorods was also increased
of 1-octadecene was heated to 320 °C at a rate of 3.1 °C min-1, by increasing the amount of Co-oleate complex while keeping
and was subsequently refluxed at this temperature for 30 min, the other experimental conditions unchanged. For example,
23 nm (base edge) × 28 nm (height) CoO nanorods were when the amount of the Co-oleate complex was increased to
produced (Figure 1a). When the heating rate was decreased to 10 and 15 mmol at a heating rate of 1.9 °C min-1, 9 nm × 28
1.9 and 1.0 °C min-1, 12 nm × 19 nm (Figure 1b) and 8 nm × nm (Figure 1d) and 20 nm × 38 nm (Figure 1e) CoO nanorods
26 nm (Figure 1c) CoO nanorods were synthesized, respectively.
As mentioned above, as the heating rate decreased, the aspect (8) (a) Peng, X.; Manna, L.; Yang, W.; Wickham, J.; Scher, E.; Kadavanich,
ratio of the CoO nanorods increased, whereas the volume of A.; Alivisatos, A. P. Nature 2000, 404, 59. (b) Chen, Y.; Kim, M.; Lian,
G.; Johnson, M. B.; Peng, X. J. Am. Chem. Soc. 2005, 127, 13331.
the individual CoO nanorods decreased. The growth rates of (9) (a) Peng, Z. A.; Peng, X. J. Am. Chem. Soc. 2002, 124, 3343. (b) Yu, W.
the different crystal planes are known to be affected by the W.; Peng, X. Angew. Chem., Int. Ed. 2002, 41, 2368. (c) Park, J.; Privman,
V.; Matijevic, E. J. Phys. Chem. B 2001, 105, 11630. (d) Peng, Z. A.;
heating rates employed during the synthesis of nanocrystals.7 Peng, X. J. Am. Chem. Soc. 2001, 123, 1389. (e) Murray, C. B.; Kagan, C.
When sufficient thermal energy is supplied during the synthesis R.; Bawendi, M. G. Annu. ReV. Mater. Sci. 2000, 30, 545. (f) Jun, Y.-W.;
Jung, Y.-Y.; Cheon, J. J. Am. Chem. Soc. 2002, 124, 615.
(10) Shevchenko, E. V.; Talapin, D. V.; Schnablegger, H.; Kornowski, A.; Festin,
(7) Song, Q.; Zhang, Z. J. J. Am. Chem. Soc. 2004, 126, 6164. O.; Svedlidh, P.; Haase, M.; Weller, H. J. Am. Chem. Soc. 2003, 125, 9090.

J. AM. CHEM. SOC. 9 VOL. 128, NO. 30, 2006 9755

ARTICLES An et al.

Figure 2. (a) TEM image of the self-assembled CoO nanorods with dimensions of 9 nm × 46 nm. (b,c) TEM images and (d,e) the corresponding high-
resolution TEM (HRTEM) images of the top and side views of the parallel-aligned CoO nanorods. (f) Electron diffraction pattern of CoO nanorods.

were produced, respectively. The increased amount of Co- superlattice formation.13 Self-assembly of the uniform 9 nm ×
oleate complex seemed to contribute predominantly to the 46 nm CoO nanorods was performed by slowly evaporating a
growth source rather than to the nuclei, resulting in the synthesis few drops of the hexane solution containing the nanorods on a
of increased sized nanorods, which was consistent with the carbon-coated copper TEM grid. The large area TEM image,
previous synthesis of TiO2 and CdS nanorods.11 The size of shown in Figure 2a, demonstrates that the nanorods self-
the CoO nanorods was further controlled by varying the aging assembled to form both horizontal parallel arrangements and
time.12 When the aging time was increased from 30 min to 1 h, perpendicular hexagonal honeycomb superlattice structures. The
the length of the nanorods was increased from 19 nm (Figure inter-rod distance was 3-4 nm, which corresponds roughly to
1b) to 46 nm (Figure 1f), while their diameter was decreased two layers of the oleic acid surfactant. Figure 2b and c shows
slightly. the TEM images of the perpendicularly assembled and hori-
Self-Assembly. Self-assembly of magnetic nanocrystals, to zontally assembled arrays, respectively. The high-resolution
generate two- and three-dimensional (2-D and 3-D) superlattice TEM (HRTEM) image of the perpendicularly aligned nanorods
structures, is very important both from the viewpoint of the
fundamental interest in the collective interaction of nanocrystals (13) (a) Murray, C. B.; Kagan, C. R.; Bawendi, M. G. Science 1995, 270, 1335.
(b) Blaarderen A, V.; Ruel, R.; Wiltzius, P. Nature 1997, 385, 321. (c)
and for their potential applications in multi-terabit per square Park, J.; Kang, E.; Son, S. U.; Park, H. M.; Lee, M. K.; Kim, J.; Kim, K.
W.; Noh, H.-J.; Park, J.-H.; Bae, C. J.; Park, J.-G.; Hyeon, T. AdV. Mater.
inch magnetic storage media. In particular, the long-range self- 2005, 17, 429. (d) Politi, P.; Pini, M. G. Phys. ReV. B 2002, 66, 214414.
assembly of rod-shaped magnetic nanocrystals is of great interest (e) Redl, F. X.; Black, C. T.; Papaefthymiou, G. C.; Sandstrom, R. L.;
Yin, M.; Zeng, H.; Murray, C. B.; O’Brien, S. P. J. Am. Chem. Soc. 2004,
because perpendicular magnetic storage media with increased 126, 14583. (f) Stoeva, S.; Klabunde, K. J.; Sorensen, C. M.; Dragieva, I.
areal density could potentially be achieved using aligned J. Am. Chem. Soc. 2002, 124, 2305. (g) Stoeva, S.; Prasad, B. L. V.; Uma,
S.; Stoimenov, P. K.; Zaikovski, V.; Sorensen, C. M. J. Phys. Chem. B
magnetic nanorod arrays. It is well-known that the size 2003, 107, 7441. (h) Chen, M.; Nikles, D. E. Nano Lett. 2002, 2, 211. (i)
uniformity of nanocrystals is critical to achieve large-area Wang, Z. L. AdV. Mater. 1998, 10, 18. (j) Rogach, A. L.; Talapin, D. V.;
Shevchenko, E. V.; Kornowski, A.; Haase, M.; Weller, H. AdV. Funct.
Mater. 2002, 12, 653. (k) Shevchenko, E.; Talapin, D.; Kornowski, A.;
(11) (a) Cozzoil, P. D.; Kornowski, A.; Weller, H. J. Am. Chem. Soc. 2003, Wiekhorst, F.; Kötzler, J.; Haase, M.; Rogach, A. L.; Weller, H. AdV. Mater.
125, 14539. (b) Jun, Y.-W.; Lee, S.-M.; Kang, N. J.; Cheon, J. J. Am. 2002, 14, 287. (l) Weller, H. Philos. Trans. R. Soc. London A 2003, 361,
Chem. Soc. 2001, 123, 5150. 229. (m) Shevchenko, E. V.; Talapin, D. V.; Rogach, A. L.; Kornowski,
(12) Yin, M.; O’Brien, S. J. Am. Chem. Soc. 2003, 125, 10180. A.; Haase, M.; Weller, H. J. Am. Chem. Soc. 2002, 124, 11480.

9756 J. AM. CHEM. SOC. 9 VOL. 128, NO. 30, 2006

Pencil-Shaped CoO Nanorods ARTICLES

Figure 3. TEM images of CoO nanorods by tilting along the y-axis of TEM to confirm the self-assembled nanorod structures. Tilted TEM images obtained
at (a) -19°, (b) 0°, and (C) 19° along the y-axis, while fixed along the x-axis.

The strikingly intense (002) peak demonstrated the preferential

growth of the CoO nanorods along the c-axis, which was
consistent with the HRTEM data. Although there are many
reports on pencil-shaped ZnO crystals with a wurtzite crystal
structure, pencil-shaped CoO nanocrystals were only recently
reported, first by our research group5a and later by Park and
co-workers.4e Recently, Seshadri and co-workers prepared
wurtzite-structured CoO powder.15 The wurtzite crystal structure
is characterized by the hexagonal close-packing of oxygen and
metal atoms in space group P63mc, with metal atoms in the
tetrahedral sites.16 The typical rod-shaped ZnO nanocrystals have
a polar basal oxygen plane (001h) on the bottom of the rods, a
top tetrahedron corner-exposed polar metal (001) face, and a
low-index face composed of a nonpolar (1h00) face correspond-
ing to the lateral plane of the rod. The (001h) plane, which is a
low-symmetry nonpolar face with three-fold coordinated atoms,
Figure 4. X-ray diffraction (XRD) patterns of (a) CoO nanorods, (b) Co is the most stable, while the polar (001) plane is relatively
nanorods, and (c) Co2C nanorods. unstable due to the metal edge. In addition, there is no center
of inversion in the wurtzite structure. Consequently, the aniso-
showed that the basal plane of the nanorods was the (100) plane, tropic crystal growth along the c-axis, leading to the production
with a calculated d-spacing of 2.82 Å. On the other hand, the of pencil-shaped nanorods of ZnO and CoO, seems to be derived
HRTEM image of the horizontally aligned nanorods showed from the intrinsic wurtzite crystal structure.16
that the CoO nanorods grew along the [002] direction, with a Reduction of CoO Nanorods. We performed the reduction
calculated (002) d-spacing of 2.60 Å. These d-spacing values of the self-assembled CoO nanorod arrays to form ferromagnetic
matched very well with the standard data. To confirm that the nanorod arrays, to investigate their potential application to
2-D hexagonal arrays are perpendicularly assembled nanorod perpendicular magnetic storage media. When the CoO nanorod
arrays rather than assemblies of spherical nanocrystals, a series arrays, assembled on a silicon substrate, were reduced by heating
of tilting experiments were performed. The TEM images, after them at 300 °C for 2 h under flowing H2, hcp Co nanorods
tilting along the y-axis with tilting angles of -19° (Figure 3a), were generated. The XRD pattern (Figure 4b) of the heat-treated
0° (Figure 3b), and 19° (Figure 3c), clearly demonstrated that sample matched very well with the hexagonal Co structure
the CoO nanorods self-assembled to generate 2-D hexagonal (P63mmc, JCPDS No. 05-0727). However, when an alumina
arrays. boat was used as a container for the large-scale reduction of
Characterization Using XRD. The X-ray diffraction (XRD) CoO nanorods, Co2C nanorods were generated.17 The XRD
pattern of the CoO nanorods, shown in Figure 4a, revealed that pattern in Figure 4c reveals that the final product exhibits an
the peak positions were identical to the standard wurtzite ZnO orthorhombic Co2C structure (Pmnn, JCPDS No. 72-1369).4b
pattern (P63mc, a ) 3.249 Å, c ) 5.206 Å, JCPDS No. 36- The carbon in the Co2C nanorods seemed to have been produced
1451), and the overall pattern was nearly identical to that of from the thermal decomposition of the organic surfactants, which
the ZnO nanorods reported by our group and other groups.14 also caused the partially collapsed superlattice structure (Sup-

(14) (a) Joo, J.; Kwon, S. G.; Yu, J. H.; Hyeon, T. AdV. Mater. 2005, 17, 1873. (15) Risbud, A, S.; Snedeker, L. P.; Elcombe, M. M.; Cheetham, A. K.; Seshadri,
(b) Miguel, M.; Kahn, M. L.; Maisonnat, A.; Chaudret, B. Angew. Chem., R. Chem. Mater. 2005, 17, 834.
Int. Ed. 2003, 42, 5321. (c) Yin, M.; Gu, Y.; Kuskovsky, I. L.; Andelman, (16) (a) Li, W. J.; Shi, E. W.; Zhong, W. Z.; Yin, Z. W. J. Cryst. Growth 1999,
T.; Zhu, Y.; Neumark, G. F.; O’Brien, S. J. Am. Chem. Soc. 2004, 126, 203, 186. (b)Vayssieres, L.; Keis, K.; Hagfeldt, A.; Lindquist, S.-E. Chem.
6206. (d) Cozzoli, P. D.; Curri, M. L.; Agostiano, A.; Leo, G.; Lomascolo, Mater. 2001, 13, 4395. (c) Hu, J. Q.; Li, Q.; Wong, N. B.; Lee, C. S.; Lee,
M. J. Phys. Chem. B 2003, 107, 4756. (e) Shim, M.; Guyot-Sionnest, P. J. S. T. Chem. Mater. 2002, 14, 1216. (d) Parker, T. M.; Condon, N. G.;
Am. Chem. Soc. 2001, 123, 11651. (f) Johnson, J. C.; Knutsen, K. P.; Yan, Lindsay, R.; Leibsle, F. M.; Thornton, G. Surf. Sci. 1998, 415, 1046.
H.; Law, M.; Zhang, Y.; Yang, P.; Saykally, R. J. Nano Lett. 2004, 4, 197. (17) (a)Barriga-Arceo, L. D.; Orozco, E.; Garibay-Febles, V.; Bucio-Galindo,
(g) Greene, L. E.; Law, M.; Tan, D. H.; Montano, M.; Goldberger, J.; L.; Leon, H. M.; Castillo-Ocampo, P.; Montoya, A. J. Phys.: Condens.
Somorjai, G.; Yang, P. Nano Lett. 2005, 5, 1231. (h) Nyffenegger, R, M.; Matter 2004, 16, S2273. (b) Wang, H.; Wong, S. P.; Cheung, W. Y.; Ke,
Craft, B.; Shaaban, M.; Gorer, S.; Erley, G.; Penner, R. M. Chem. Mater. N.; Lau, W. F.; Chiah, M. F.; Zhang, X. X. Mater. Sci. Eng. C 2001, 16,
1998, 10, 1120. 147. (c) Liu, B. X.; Wang, J.; Fang Z. Z. J. Appl. Phys. 1991, 69, 7342.

J. AM. CHEM. SOC. 9 VOL. 128, NO. 30, 2006 9757

ARTICLES An et al.

porting Information). The intense (002) peak of the Co nanorods

(Figure 4b) and the (111) peak of the Co2C nanorods (Figure
4c) demonstrated that the preferential growth characteristics of
the CoO nanorods along the c-axis of wurtzite structure were
retained even after the reduction process.
The facile reduction and the subsequent effective removal
of the surfactant from the CoO nanorods assembled on a silicon
substrate with a nearly monolayer thickness seemed to be
responsible for the production of hcp Co nanorods. On the other
hand, the formation of Co2C nanorods from the large-scale
reduction of CoO nanorods can be explained by a retarded
removal of a carbon source generated from the decomposition
of surfactant. The formation of Co2C nanoparticles has been
well characterized by Wang and co-workers.4b
Characterization Using XAS and XMCD. In 1961, Neel
suggested that antiferromagnetic materials may become super-
paramagnetic or weakly ferromagnetic when the particles’ size
is reduced to the nanometer range, because of the uncompen-
sated number of spins on the two different sublattices.4a,18 Fcc-
structured CoO is one of the representative antiferromagnetic
materials.4 In spite of these interesting magnetic properties,
however, it is difficult to obtain pure CoO, because it often
contains a small fraction of impurities such as Co3O4 or Co
metal.4d To identify these impurities in the current CoO
nanorods, XAS and XMCD measurements at the Co L2,3-edges
were carried out at the EPU6 beamline at the Pohang Light
Source for the 9 nm × 46 nm CoO nanorods (Figure 5). As
shown in Figure 5a, the XAS spectrum of the CoO nanorods Figure 5. (a) Co L2,3-edge XAS spectra of 9 nm × 46 nm CoO nanorods
was very similar to that of bulk CoO. On the other hand, we in comparison with bulk CoO. (b) Co L2,3-edge XMCD spectrum (upper)
were able to characterize some of the ferromagnetic impurities and MCD signal (bottom: ∆F ) F+ - F-) of 9 nm × 46 nm CoO nanorods.
by Co L2,3-edge XMCD. The XMCD spectra (F+ and F-) for Because XMCD spectra for the two polarization directions are more or
less the same in this scale, they appear to overlap in the figure.
the different spin directions, which are parallel and antiparallel
to the photon helicity vector, are normalized by the photon flux, favors an A-type antiferromagnetic ground state with layer-by-
and the degree of circular polarization is taken into account in layer ordered magnetic moments along the c-axis direction,
the dichroism signal (∆F ) F+ - F-).19 In Figure 5b, the MCD similar to the case of bulk fcc CoO. The total energy difference
line shape was nearly identical to that of Co metal, indicating between the ferromagnetic and antiferromagnetic configurations
that the CoO nanorods contain ferromagnetic Co metal impuri- is about 50 meV, regardless of the effective on-site Coulomb
ties. Although the Co L2,3-edge XAS spectrum of the nanorods parameters that are used. We note that this energy difference
is dominated by that of CoO, the 50-times-enlarged dichroism of 50 meV between the ferromagnetic and antiferromagnetic
signal clearly demonstrates the presence of ferromagnetic Co configurations of wurtzite CoO is of the same order of
metal impurities.20 XMCD measurements at the Co L2,3-edges magnitude as the value of 117 meV found for bulk fcc CoO,
were also conducted for the hcp Co and Co2C nanorods, which which provides further evidence that wurtzite CoO has an
were obtained from the reduction of the CoO nanorods antiferromagnetic ground state. Consequently, the XMCD
(Supporting Information). The MCD spectra of both the hcp results, combined with the band structure calculations, suggested
Co and Co2C nanorods showed a line shape very similar to that that the small ferromagnetic magnetic signal observed in the
of typical ferromagnetic metallic Co, although the MCD XMCD spectra represents not the intrinsic characteristics of
intensity of the hcp Co nanorods was higher than that of the wurtzite CoO but rather the existence of a small fraction of Co
Co2C nanorods. metal impurities in the CoO nanorods.
To characterize the magnetic properties of the wurtzite- Magnetic Characterization. We measured the temperature
structured CoO, we carried out first-principles electronic and field dependences of the magnetization curves using a
structure calculations21 based on density functional theory22 by commercial superconducting quantum interference device
using the LDA + U method, which is known to be effective in (SQUID) magnetometer. Zero-field-cooling (ZFC) and field-
describing transition metal oxides and related systems.23 The
results of the total energy calculations showed that wurtzite CoO (21) We have performed the calculation for the periodic unit cell of wurtzite
CoO by using our open MX LDA + U code (http://staff.aist.go.jp/t-ozaki/
openmx), developed for the nanomaterials study. We employed a Troullier-
(18) Neel, L. C. R. Hebd. Seances Acad. Sci. 1961, 252, 4075. Martins-type pseudopotential with partial-core corrections and adopted 216
(19) (a) Chen, C. T.; Idzerda, Y. U.; Lin, H.-J.; Smith, N. V.; Meigs, G.; k-points for the Brillouin zone integration. All the calculational parameters
Chanban, E.; Ho, C. H.; Pellergin, E.; Sette, F. Phys. ReV. Lett. 1995, 75, used in this study have been extensively tested and checked for the bulk
152. (b) Groot, F. M. F.; Fuggle, J. C.; Thole, B. T.; Sawatzky, G. A. fcc CoO as a reference.
Phys. ReV. B 1990, 42, 5459. (22) (a) Hohenberg, P.; Kohn, W. Phys. ReV. 1964, 136, 864. (b) Kohn, W.;
(20) Kim, J.-Y.; Park, J.-H.; Park, B.-G.; Noh, H.-J.; Oh, S.-J.; Yang, J. S.; Sham, L. J. Phys. ReV. 1965, 140, 1133.
Kim, D.-H.; Bu, S. D.; Noh, T.-W.; Lin, H.-J.; Hsieh, H.-H.; Chen, C. T. (23) Anisimov, V. I. Strong Coulomb correlations in electronic structure
Phys. ReV. Lett. 2003, 90, 017401-1. calculation; Gordon and Breach Science Publishers: Amsterdam, 2000.

9758 J. AM. CHEM. SOC. 9 VOL. 128, NO. 30, 2006

Pencil-Shaped CoO Nanorods ARTICLES

phase. Interestingly enough, it was recently reported that 20-

nm Co3O4 nanoparticles exhibit a sharp peak structure in the
ZFC data near 25 K.24 Thus, it may not be too unrealistic to
suppose that smaller Co3O4 nanoparticles have the same peak
structure at lower temperatures as that observed in our sample.
It is also worthwhile to note that similar peak structures were
observed in the magnetization data of MnO nanoparticles, which
was found to be due to Mn3O4 impurity phases.25 We found
that, in the field dependence of the magnetization, shown in
the inset of Figure 6a, there is a clear, albeit small, hysteresis
in the data taken at 2 K, which weakens upon warming. There
are two more things we need to discuss about the data presented
in Figure 6a. The first comment concerns the irreversible point
in the FC and ZFC data. If we take it as a blocking temperature
of the wurtzite CoO, it basically implies that CoO nanorods
should have abnormal surface states since simple antiferromag-
netic nanoparticles cannot give rise to such a blocking behavior.
Although our LDA + U band calculations predict that wurtzite
CoO has an antiferromagnetic ground state with an energy
difference of 50 meV between antiferromagnetic (AF) and
ferromagnetic states, it is not very unusual that nanoparticles
with supposedly AF states show blocking behavior due to
uncompensated surface magnetic states. That the saturated
magnetic moment in the inset is 7 emu/g, somewhat smaller
than that of fcc CoO, may be due to either weaker magnetic
properties of wurtzite CoO compared with fcc CoO or, more
probably, an error in our estimate of sample mass without
including surfactant mass correctly. The second comment is
about the temperature dependence, in particular that below 100
K. Although the observed behavior is not entirely explainable
by wurtzite CoO with uncompensated surface spin states, it is
Figure 6. (a) Temperature dependence of magnetization for 9 nm × 46 also true that the temperature dependence of our magnetization
nm CoO nanorods measured with applied field of 100 Oe after zero-field- data may be contaminated by some small magnetic impurity.
cooling (filled circles) and field-cooling (open circles). The inset shows Therefore, we caution ourselves against interpreting the data
the field dependence of the magnetization taken at 2 and 300 K. (b)
Temperature dependence of magnetization for 9 nm × 46 nm Co nanorods solely on the basis of intrinsic properties of wurtize CoO,
after heat treatment, measured with an applied field of 100 Oe after zero- although we believe that the major part of the data should come
field-cooling (filled circles) and field-cooling (open circles). The inset from wurtize CoO simply because it is far larger in volume
exhibits the field dependence of the magnetization of CoO nanorods at 2
and 300 K. Since we prepared samples on top of Si substrate for heat
compared with other impurities. Closely related to this, Seshadri
treatment, we show here only the raw data without converting them into et al. synthesized wurtzite CoO crystals by a nonaqueous
the magnetization per unit mass. solution route.15 They showed that their wurtzite CoO contained
Co metal impurity and its magnetic properties were affected
cooling (FC) measurements are known to be a useful way of by the ferromagnetic Co impurity.
determining the so-called blocking temperature of magnetic We also measured the magnetization curves after the reduc-
nanomaterials. In principle, nanomaterials of pure antiferro- tion process. As shown in Figure 6b, there is a deviation between
magnetic compounds cannot show a blocking behavior unless the FC and ZFC data at a slightly higher temperature compared
there are abnormal surface states. In a few antiferromagnetic with the data taken before the heat treatment. Another noticeable
nanomaterials, such surface states are indeed known to exhibit effect is that the low-temperature peak structure is absent in
a blocking phenomenon in ZFC/FC measurements similar to the heat-treated sample. Similarly, the magnetic hysteresis is
those of superparamagnetic nanoparticles. Figure 6a shows the observed to be much stronger, as shown in the inset of Figure
typical data for the 9 nm × 46 nm CoO nanorods before the 6b, compared with the data obtained before the heat treatment.
heat treatment, measured with an applied field of 100 Oe after This rather drastic effect of the heat treatment can be understood
ZFC (filled circles) and FC (open circles). As shown in Figure in terms of Co clustering. As described above, the ferromagnetic
6a, the FC data deviate from the ZFC data well above 300 K, signal observed in our XMCD results is most likely due to the
although the ZFC data decrease rather smoothly before the Co metal clusters present in the CoO nanorods, in which case
temperature reaches 200 K. Upon further cooling, the ZFC data the most obvious heat treatment effect would be the clustering
show a peak centered at 5 K, and the FC data start to increase of Co. In fact, a similar Co clustering effect has been found in
in approximately the same temperature range. We observed Co-implanted anatase TiO2 thin films with increasing annealing
similar features, including the low-temperature peak in the ZFC temperature.26 Therefore, we believe that the rather high
data, in other samples measured under the same conditions
before the heat treatment. We speculate that the origin of the (24) Makhlouf, S. A. J. Magn. Magn. Mater. 2002, 246, 184.
(25) Park, J.; Kang, E.; Bae, C. J.; Park, J.-G.; Noh, H.-J.; Kim, J.-Y.; Park,
low-temperature peak has nothing to do with the wurtzite CoO J.-H.; Park, H. M.; Hyeon, T. J. Phys. Chem. B 2004, 108, 13594.

J. AM. CHEM. SOC. 9 VOL. 128, NO. 30, 2006 9759

ARTICLES An et al.

blocking temperature observed both before and after the heat media. The current synthetic procedure is very simple and highly
treatment, as well as the marked changes found in the magnetic reproducible and, consequently, is readily applicable to large-
properties after heat treatment, arises from Co clusters and may scale synthesis for potential industrial applications. For example,
not be entirely due to the wurtzite CoO phase, which is in when 12.5 g of the Co-oleate complex (20 mmol) was used in
agreement with the XMCD results and the band structure the synthesis, 4.6 g of uniformly sized CoO nanorods was
calculations. produced (Supporting Information).
Conclusions Acknowledgment. T.H. thanks the Korean Ministry of
In summary, we synthesized uniformly sized, pencil-shaped Science and Technology for financial support through the
CoO nanorods with a wurtzite crystal structure by the thermal National Creative Research Initiative Program of the Korea
decomposition of a cobalt-oleate complex. The dimensions of Science and Engineering Foundation (KOSEF). J.G.P. and J.Y.
the CoO nanorods were easily controlled by changing the thank the KOSEF for financial support through the Center for
synthetic parameters, such as the heating rate, the amount of Strongly Correlated Materials Research at the Seoul National
Co-oleate complex, and the aging time. Due to their size University. J.H.P. thanks KISTEP for financial support through
uniformity, the nanorods self-assembled to form both horizontal the X-ray/particle-beam Nanocharacterization Program.
parallel arrangements and perpendicular hexagonal honeycomb
Supporting Information Available: Photograph showing a
superlattice structures. Reduction of the CoO nanorods produced
balance weighing CoO nanorods and particle size distribution
either hcp Co nanorods or Co2C nanorods. The well-aligned
histograms; TEM and HRTEM images of Co2C nanorods;
arrays of the resulting Co2C and Co nanorods could potentially
XMCD and MCD spectra of Co and Co2C nanorods. This
be used as high-areal-density perpendicular magnetic storage
material is available free of charge via the Internet at
(26) Kim, D. H.; Yang, J. S.; Kim, K. S.; Kim, D.-W.; Noh, T. W.; Bu, S. D.; http://pubs.acs.org.
Kim, Y.-W.; Park, Y. D.; Pearton, S. J.; Jo, J.; Park, J.-G. Appl. Phys.
Lett. 2003, 83, 4574. JA0608702

9760 J. AM. CHEM. SOC. 9 VOL. 128, NO. 30, 2006