Hyperbranched copper phthalocyanine (CuPc) with uniform spherical morphology has been firstly obtained by ethylene glycol solvothermal synthetic route. The highly dispersed spherical CuPc aggregates with a diameter of ~500 nm. X-ray diffraction indicated that the molecules were stacked into one-dimensional b-axis aggregate. In addition, the split Soret band together with the broadened and blue-shifted Q-bands in the optical spectra suggested the H (face-to-face) type of interactions in the arrangement of macrocycles in a dense-packed structure. Due to its good symmetrical structure and unique morphology, the hyperbranched spherical CuPc showed excellent broadband microwave absorption behaviors in a frequency of 2-18 GHz. Over an absorber of 5 mm thickness, an absorption bandwidth of 12 GHz corresponding to reflection loss below -10 dB can be obtained. The high value of microwave reflection about -50 dB at the frequency of 16.5 GHz also suggested that the hyperbranched spherical CuPc can be used as promising microwave absorbing materials.
This is a preview of subscription content, access via your institution.
We’re sorry, something doesn't seem to be working properly.
Please try refreshing the page. If that doesn't work, please contact support so we can address the problem.
F. Meng, R. Zhao, M. Xu, Y. Zhan, Y. Lei, J. Zhong, and X. Liu: Fe–phthalocyanine oligomer/Fe3O4 nano-hybrid particles and their effect on the properties of polyarylene ether nitriles magnetic nanocomposites. Colloids Surf., A 375, 245–251 (2011).
X.F. Zhang, X.L. Dong, H. Huang, Y.Y. Liu, W.N. Wang, X.G. Zhu, B. Lv, J.P. Lei, and C.G. Lee: Microwave absorption properties of the carbon-coated nickel nanocapsules. Appl. Phys. Lett. 89, 053115–053118 (2006).
C.C. Lee and D.H. Chen: Ag nanoshell-induced dual-frequency electromagnetic wave absorption of Ni nanoparticles. Appl. Phys. Lett. 90, 193102 (2007).
S. Ohkoshi, S. Kuroki, S. Sakurai, K. Matsumoto, K. Sato, and S. Sasaki: A millimeter-wave absorber based on gallium-substituted e-iron oxide nanomagnets. Angew. Chem. Int. Ed. 46, 8392–8395 (2007).
Y.J. Chen, P. Gao, R.X. Wang, C.L. Zhu, L.J. Wang, M.S. Cao, and H.B. Jin: Porous Fe3O4/SnO2 core/shell nanorods: Synthesis and electromagnetic properties. J. Phys. Chem. C 113, 10061–10064 (2009).
Y.J. Chen, P. Gao, C.L. Zhu, R.X. Wang, L.J. Wang, M.S. Cao, and X.Y. Fang: Synthesis, magnetic and electromagnetic wave absorption properties of porous Fe3O4/Fe/SiO2 core/shell nanorods. J. Appl. Phys. 106, 054303 (2009).
Q. Liu, D. Zhang, and T. Fan: Electromagnetic wave absorption properties of porous carbon/Co nanocomposites. Appl. Phys. Lett. 93, 013110–013112 (2008).
A. Namai, S. Sakurai, M. Nakajima, T. Suemoto, K. Matsumoto, M. Goto, S. Sasaki, and S. Ohkoshi: Synthesis of an electromagnetic wave absorber for high-speed wireless communication. J. Am. Chem. Soc. 131, 1170 (2009).
T. Higuchi, T. Murayama, E. Itoh, and K. Miyairi: Electrical properties of phthalocyanine based field effect transistors prepared on various gate oxides. Thin Solid Films 499, 374–379 (2006).
T. Yasuda and T. Tsutsui: Organic field-effect transistors based on high electron and ambipolar carrier transport properties of copper-phthalocyanine. Chem. Phys. Lett. 402, 395–398 (2005).
C. Schlebusch, J. Morenzin, B. Kessler, and W. Eberhardt, Organic photoconductors with C60 for xerography. Carbon 37, 717–723 (1999).
Q.X. Tang, L.Q. Li, Y.B. Song, Y.L. Liu, H.X. Li, W. Xu, Y.Q. Liu, W.P. Hu, and D.B. Zhu: Photo switches and phototransistors of organic single crystalline sub-micro/nanometer ribbons. Adv. Mater. 19, 2624 (2007).
W.F. Cao, H.Y. Tu, J. Wang, H. Tian, Y. Wang, D.H. Gu, and F.X. Gan: Synthesis and optical properties of axially bromo-substituted subphthalocyanines. Dyes Pigm. 54, 213–219 (2002).
J.H. Yum, S.R. Jang, R.H. Baker, M. Grätzel, J.J. Cid, T. Torres, and M.K. Nazeeruddin: Effect of coadsorbent on the photovoltaic performance of zinc pthalocyanine-sensitized solar cells. Langmuir 24, 5636–5640 (2008).
P.A. Troshin, R. Koeppe, A.S. Peregudov, S.M. Peregudova, M. Egginger, R.N. Lyubovskaya, and N.S. Sariciftci: Supramolecular association of pyrrolidinofullerenes bearing chelating pyridyl groups and zinc phthalocyanine for organic solar cells. Chem. Mater. 19, 5363–5372 (2007).
B.O. Agboola and K.I. Ozoemena: Efficient electrocatalytic detection of epinephrine at gold electrodes modified with self-assembled metallo-ctacarboxyphthalocyanine complexes. Electroanalysis 20, 1696–1707 (2008).
F. Bedioui, S. Griveau, T. Nyokong, A.J. Appleby, C.A. Caro, M. Gulppi, G. Ochoa, and J.H. Zagal: Tuning the redox properties of metalloporphyrin- and metallophthalocyanine-based molecular electrodes for the highest electrocatalytic activity in the oxidation of thiols. Phys. Chem. Chem. Phys. 9, 3383–3396 (2007).
X. Wang, J. Zhuang, Q. Peng, and Y. Li: A general strategy for nanocrystal synthesis. Nature 437, 121–124 (2005).
J. Gao, C. Cheng, X. Zhou, Y. Li, X. Xu, X. Du, and H. Zhang: Synthesis of size controllable cu-phthalocyanine nanofibers by simple solvent diffusion method and their electrochemical properties. J. Colloid Interface Sci. 342, 225–228 (2010).
K. Guo, S. Yoshimoto, and K. Itaya: Two-dimensional self-organization of phthalocyanine and porphyrin: Dependence on the crystallographic orientation of Au. J. Am. Chem. Soc. 125, 14976–14977 (2003).
L. Wu, Q. Wang, J. Lu, Y. Bian, J. Jiang, and X. Zhang: Helical nanostructures self-assembled from optically active phthalocyanine derivatives bearing four optically active binaphthyl moieties: Effect of metal-ligand coordination on the morphology, dimension, and helical pitch of self-assembled nanostructures. Langmuir 26, 7489–7497 (2010).
R. Zhao, K. Jia, J. Wei, J. Pu, and X. Liu: Hierarchically nanostructured Fe3O4 microspheres and their novel microwave electromagnetic properties. Mater. Lett. 64, 457 (2010).
F. Meng, R. Zhao, Y. Zhan, Y. Lei, J. Zhong, and X. Liu: One-step synthesis of Fe-phthalocyanine/Fe3O4 hybrid microspheres. Mater. Lett. 65, 264 (2011).
F. Meng, R. Zhao, Y. Zhan, Y. Lei, J. Zhong, and X. Liu: Preparation and microwave absorption properties of Fe-phthalocyanine oligomer/Fe3O4 hybrid microspheres. Appl. Surf. Sci. 257, 5000 (2011).
J. Wei, R. Zhao, Y. Zhan, F. Meng, X. Yang, M. Xu, and X. Liu: One-step solvothermal syntheses and microwave electromagnetic properties of organic magnetic resin/Fe3O4 hybrid nanospheres. Appl. Surf. Sci. 258, 6705–6711 (2012).
M. Guo, X. Yan, Y. Kwon, T. Hayakawa, M. Kakimoto, and Goodson T. III: High frequency dielectric response in a branched phthalocyanine. J. Am. Chem. Soc. 128, 14820–14821 (2006).
A.W. Snow and N.L. Jarvis: Molecular association and monolayer formation of soluble phthalocyanine compounds. J. Am. Chem. Soc. 106, 4706–4711 (1984).
Z. Chen, C. Zhong, Z. Zhang, Z. Li, L. Niu, Y. Bin, and F. Zhang: Photoresponsive j-aggregation behavior of a novel azobenzene-phthalocyanine dyad and its third-order optical nonlinearity. J. Phys. Chem. B 112, 7387–7389 (2008).
Y. Zhan, X. Yang, F. Meng, J. Wei, R. Zhao, and X. Liu: Controllable synthesis, magnetism and solubility enhancement of graphene nanosheets/magnetite hybrid material by covalent bonding. J. Colloid Interface Sci. 363, 98–104 (2011).
P.J. Camp, A.C. Jones, R.K. Neely, and N.M. Speirs: Aggregation of copper(II) tetrasulfonated phthalocyanine in aqueous salt solutions. J. Phys. Chem. A 106, 10725–10732 (2002).
Z. Xu, H. Li, K. Li, Y. Kuang, Y. Wang, Q. Fu, Z. Cao, and W. Li: Carbon nanotube-templated copper phthalocyanine derivative assemblies via solid-phase synthesis: Effects of hydrogen bond on the structure of the assemblies. Cryst. Growth Des. 9, 4136 (2009).
Y. Luo, J. Gao, C. Cheng, Y. Sun, X. Du, G. Xu, and Z. Wang: Fabrication micro-tube of substituted Zn–phthalocyanine in large scale by simple solvent evaporation method and its surface photovoltaic properties. Org. Electron. 9, 466 (2008).
J. Fox, T. Katz, S. Elshocht, T. Verbiest, M. Kauranen, A. Persoons, T. Thongpanchang, T. Krauss, and L. Brus: Synthesis, self-assembly, and nonlinear optical properties of conjugated helical metal phthalocyanine derivatives. J. Am. Chem. Soc. 121, 3453–3459 (1999).
M.K. Debe and K.K. Kan: Effect of gravity on copper phthalocyanine thin films II: Spectroscopic evidence for a new oriented thin film polymorph of copper phthalocyanine grown in a microgravity environment. Thin Solid Films 186, 289–325 (1990).
P.H. Lippel, R.J. Wilson, M.D. Miller, C. Wöll, and S. Chiang: High-resolution imaging of copper-phthalocyanine by scanning-tunneling microscopy. Phys. Rev. Lett. 62, 171–174 (1989).
A.N. Yusoff, M.H. Abdullah, S.H. Ahmad, S.F. Jusoh, A.A. Mansor, and S.A.A. Hamid: Electromagnetic and absorption properties of some microwave absorbers. J. Appl. Phys. 92, 876–883 (2002).
Z. Ma, C. Cao, Q. Liu, and J. Wang: A new method to calculate the degree of electromagnetic impedance matching in one-layer microwave absorbers. Chin. Phys. Lett. 29, 038401–038405 (2012).
This work was financially supported by the Fundamental Research Funds for the Central Universities (Grant No. 103.1.2.E022050205), Major Science and Technology Project in Sichuan Province (Grant No. 2010 FZ 0117), “863” National Major Program of High Technology of China (Grant No. 2012AA03A212), and National Natural Science Foundation (Grant No. 51173021).
About this article
Cite this article
Zhao, R., Tang, H., Guo, H. et al. A facile preparation of hyperbranched copper phthalocyanine microspheres and their wideband microwave absorption properties. Journal of Materials Research 28, 1609–1616 (2013). https://doi.org/10.1557/jmr.2013.152