Journal of Nanoparticles

Journal of Nanoparticles / 2013 / Article

Research Article | Open Access

Volume 2013 |Article ID 405043 |

Kuan-Jen Chen, Fei-Yi Hung, Truan-Sheng Lui, Cheng-Hung Chen, Sheng-Po Chang, "The Influences of CuO/ZnO Ratios on the Crystallization Characteristics Electrical and Magnetic Properties of Powders", Journal of Nanoparticles, vol. 2013, Article ID 405043, 6 pages, 2013.

The Influences of CuO/ZnO Ratios on the Crystallization Characteristics Electrical and Magnetic Properties of Powders

Academic Editor: Yang Xu
Received18 Oct 2012
Accepted18 Jan 2013
Published24 Feb 2013


This study synthesizes powders using an aqueous solution method. The powders with different content ratios of CuO and ZnO (CuO : ZnO = 1 : 2, 1 : 1, and 2 : 1) were formed. The crystalline characteristics and electrical and magnetic properties depended primarily on the mixing effect and oxygenation. The electrical resistance of C0.5Z0.5O ( ) powder was lower than that of CuO ( ) powder after ZnO mixing in CuO. This reduction was attributed to the substitution of Cu+ ions at Zn2+ sites or the formation of electron trapping defect centers. The concentration ratio of Cu2O phase in powder mainly dominated the electrical resistance. The has a diluted ferromagnetism (DFM) and paramagnetism (PM). The electrical resistance of decreased; the magnetic behavior increased instead. This study also analyzes the chemical binding of Cu0.5Zn0.5O powders to confirm the contribution of Cu+ ions to the electrical and magnetic properties.

1. Introduction

Metal oxide nanostructures, such as ZnO [1], CuO [2, 3], SnO2 [4], In2O3 [5], and TiO2 [6], have attracted extensive attention for their optical, electrical and magnetic properties. They are widely applied in various optoelectronic devices, such as photocatalyzers [7], solar cells [8], photodiodes [9], and humidity sensors [10].

Recent reports on CuO-ZnO compound and CuO/ZnO heterojunction structures show the need for efficient characteristics [11, 12]. A few Cu dopants (<10 at.%) doped ZnO samples have been investigated [13, 14]. However, the effects of the higher Cu doping contents (>10 at.%) on electrical properties and magnetic behavior of ZnO were rarely reported. Thus, the electrical properties that dominate devices performance and the influences of higher dopant level on the electrical resistance of are topics worthy of further research. In addition, ZnO-diluted magnetic semiconductor (DMS) can enhance its magnetic behavior by Cu doping [15]. The influences of high CuO concentration on magnetic properties of ZnO are not clear.

The study uses an aqueous solution method to synthesize CuO and powders. Specifically, this study examines the effects of high ZnO content mixed with CuO on the structural, electrical, and magnetic properties of powders. The relation of electrical resistance and magnetic properties for powders was carried out to understand the influences of CuO mixing effects and clarify the contribution of CuO and Cu2O phase.

2. Experimental Procedures

The experiments in this study synthesized the CuO powder using an aqueous solution. To acquire the CuO powder, 0.25 M copper acetate [Cu(CH3COO)2] was synthesized in deionized water. The precursor solution was uniformly stirred at 80°C for 1 h and then dried at 120°C in an oven to evaporate the solvent. The resulting powder was then analyzed by a differential scanning calorimeter (DSC) and a thermogravimetric analyzer (TGA) to determine the thermal properties of fabricated CuO nanoparticles. The DSC and TGA results indicate that CuO powder could be obtained after thermal annealing in a furnace for 1 h. For powders, the copper acetate and the zinc acetate were mixed with different ratios (CuO : ZnO = 1 : 2, 1 : 1 and 2 : 1) and the molar ratio of zinc acetate to citric acid (C6H8O7) was 2. The powders were then designed according to the concentration ratio of CuO and ZnO as Cu0.3Zn0.67O, Cu0.5Zn0.5O, and Cu0.67Zn0.3O.

This study investigates the structural characteristics of powders using X-ray diffraction (XRD, Siemens/D5000) and scanning electron microscopy (SEM, Hitachi/S-4100). To understand the contribution of CuO on the electrical and magnetic characteristics of powders, a semiconductor parameter analyzer (Agilent/4155-B) and superconducting quantum interference device vibrating sample magnetometer (SQUID VSM) were used, respectively. The composition and chemical bonding of the crystallization were analyzed using an electron spectroscopy for chemical analysis (ESCA, PHI 5000 VersaProbe).

3. Results and Discussions

This study uses DSC and TGA analysis to determine the crystallization conditions of CuO precursors (Figure 1). The specimens were heated from room temperature to 1000°C at a rate of 10°C/min in air. The TGA data reveals a sharp weight loss in the powder at 270°C because of the evaporation of water and organics [16]. This result is consistent with the DSC curve, which shows an exothermic peak at 280°C. An endothermic peak appears at 480°C and the powder weight (TGA curve) gradually increases and then stabilizes as the temperature exceeds 500°C. The main reason is that the CuO crystallization gradually forms with increasing temperature [17]. Based on these reasons, the CuO powder was annealed at 500°C to estimate the CuO crystallization.

Figure 2(a) shows the XRD patterns of as-grown CuO precursors and CuO powder annealed at 500°C for 1 h. Both samples were polycrystalline and had a monoclinic structure. An additional diffraction peak of (CH3COO)2· Cu appeared in as-grown CuO precursors, indicating that a drying temperature of 120°C was insufficient for its evaporation. After thermal annealing at 500°C, the Cu(CH3COO)2 phase disappeared and the (111) diffraction peak dominated the CuO crystallization. The intensity of the major diffraction peaks increased, indicating that the sufficient thermal energy improved CuO crystallization. Based on the Scherrer formula [16], the grain size of CuO nanoparticles can be estimated from the full width at half-maximum (FWHM) of the (111) diffraction peak. The average grain size of CuO powder increased from 8 nm to 21 nm after thermal annealing at 500°C. This result is associated with the grains growing more easily under the higher temperature [16]. The ZnO powder was also synthesized and compared to powder. XRD analysis of ( , 0.33, 0.5, 0.67, and 1) powders were conducted to analyze the effects of ZnO on crystallization (Figure 2(b)). A small amount of ZnO mixing with CuO ( , ), the monoclinic structure of CuO dominated the Cu0.67Zn0.33O crystallization, and ZnO phases existed in the Cu0.67Zn0.33O matrix. With increasing the ZnO concentration in ( value increase from 0.67 to 0.33), the (101) diffraction peak of ZnO was the preferred orientation which indicated that the ZnO phases dominated the crystallization. A comparison of the CuO revealed that the diffraction peak of (111) for Cu0.33Zn0.67O shifted to higher degree. In contrast, the diffraction peak of (101) for Cu0.33Zn0.67O shifted to lower degree comparing with ZnO. These results are associated with compressive strain in the crystallization [4]. In addition, the related (220) diffraction peak of the Cu2O phase was attributed to insufficient oxidation [2]. Notably, the (200) diffraction peak of Cu2O phase did not appear in Cu0.5Zn0.5O crystallization, indicating that the compositional ratio of Cu2O phase was less than other (x = 0.33 and 0.67) powders. This result should affect the electrical properties of powders.

Figure 3 shows SEM images of (x = 0.33, 0.5, and 0.67) powders at an annealing temperature of 500°C. All powders displayed a particle-like structure, and the agglomeration of particles was randomly distributed. The morphology of Cu0.5Zn0.5O powder shows an irregular and its size for the agglomeration of particles is larger than that of Cu0.67Zn0.33O and Cu0.33Zn0.67O powders. The electrical properties of powder might be influenced by the particle size [18], therefore, the electrical resistance were examined.

Electrical measurements were conducted to determine the resistance value of CuO powder. The CuO powder was pressed to form ingots (Φ 10 mm/~2 mm thick) at a pressure of 30 kg/cm2 for 30 s before measuring their resistivity (Table 1). After annealing at 500°C, the resistivity of the CuO sample decreased from  Ω/□ to  Ω/□. After CuO mixing with ZnO, the electrical resistance of the Cu0.67Zn0.33O and Cu0.33Zn0.67O samples was higher than that of CuO. This increment of the electrical resistance may be attributed to the substitution of Cu+ ions at Zn2+ sites or the formation of electron trapping defect centers [19]. It is noted that the electrical resistance of Cu0.5Zn0.5O sample (1.5 × 105 Ω/□) decreased instead comparing with CuO sample. This result indicates that the ratio of the CuO phase to Cu2O phase in system decreased [20] and possessed a stable crystallization comparing with Cu0.67Zn0.33O and Cu0.33Zn0.67O samples.

SampleResistivity (Ω/□)Magnetism

Before annealing 8.6 × 1011
2.3 × 106AFM
Annealed at 500°C 1.0 × 107DFM + PM
1.5 × 105DFM + PM
8.2 × 108DFM + PM
9.0 × 108DM

To understand the contribution of CuO on the magnetic properties, the powders with different ratios of CuO and ZnO were measured. Figure 4 shows the magnetization (M) as a function of magnetic field (H) at the temperature of 10 K for the powders. All samples have a linear-like M-H variation at a magnetic field of 5000 Oe without measureable hysteresis, which indicates a paramagnetic behavior [21]. The magnetization of Cu0.33Zn0.67O sample was higher than that of Cu0.5Zn0.5O and Cu0.67Zn0.33O samples, which indicated that the Cu0.33Zn0.67O powder contains a better paramagnetism (PM). The increment of antiferromagnetic interaction possibly reduced the PM that resulted from the formation of CuO crystallization [21]. From XRD data (Figure 2(b)), the CuO phase dominated the Cu0.5Zn0.5O, Cu0.67Zn0.33O crystallization and affected their magnetic properties that were consistent with the result of M-H curves. In addition, the lower magnetization of Cu0.5Zn0.5O, Cu0.67Zn0.33O was also attributed to the secondary phase of Cu2O [22]. The low-field region of the hysteresis loops of powders was clearly observed (inset of Figure 4) which indicated that all powders also contained a diluted ferromagnetism (DFM). The FM could be developed by the distortion of ZnO structure by the substitution of remnant Cu2+ ions into ZnO lattice [22, 23]. It is found that the coercivity field of the Cu0.33Zn0.67O, Cu0.5Zn0.5O, and Cu0.67Zn0.33O powders is 75 Oe, 150 Oe, and 78 Oe, respectively. That is to say, the Cu0.5Zn0.5O powder has a good stability for thermal interference [24].

The chemical bonding of the Cu0.5Zn0.5O powder was examined by XPS with full region scanning from 0 eV to 1200 eV (Figure 5). In Figure 5(a), all peaks from oxygen, copper, zinc, and a trace of carbon are apparent, meaning that the Cu0.5Zn0.5O powder is substantially covered by Cu2+, Zn2+, and O−2. The high-resolution scanning information provided in Figures 5(b)5(d) is for the separate analysis of elements: O, Cu, and Zn, respectively. The high-resolution XPS spectrum of the O1s signal (Figure 5(b)) indicates that the binding energy of 530.3 eV can be attributed to oxidized ions in the CuO particles [25]. Multipeak Gaussian fitting shows another O1s peak located at 532.4 eV, indicating that this binding energy was dominated by Zn2+ ion doping [23]. The high-resolution XPS spectrum of the Cu2p3/2 mode (Figure 5(c)) appears at 932.3 eV, indicating the presence of Cu2+ ion [2]. The binding energy of 952.3 eV (Cu2p1/2 mode) can be attributed to Cu+ ions in Cu0.5Zn0.5O that resulted from Cu2O [26, 27]. This result is consistent with the observation of XRD data (Figure 3(b)). Figure 5(d) shows two strong peaks at 1021.5 eV and 1044.7 eV which correspond to Zn2p3/2 and Zn2p1/2, respectively. This is consistent with the Zn2+ ion binding in previous reports [28]. Based on these results, the Zn2+ ions were substituted by Cu+ to form the Cu2O phase that affects the electrical and magnetic properties.

The correlation of the magnetic properties and resistivity of powders were summarized in Table 1. The magnetic property of pure CuO powder varied from antiferromagnetism (AFM) to paramagnetism (PM) when ZnO to CuO. The resistivity of powders decreased; the values of the paramagnetic behavior decreased. These results indicate that the paramagnetic behavior in Cu0.33Zn0.67O powder is the highest. The lower carrier concentration may promote paramagnetic ordering in Cu0.33Zn0.67O [29].

4. Conclusions

The stability of oxide (CuO or Cu2O) depends primarily on the intensity of oxidation (annealing temperature). When ZnO participated in the CuO system, the crystalline quality of CuO powder deteriorated. The ZnO mixing effect increased the crystallization size and induced a compressive stress in the particle. Although the presence of ZnO phases deteriorated Cu0.5Zn0.5O crystallization, the electrical conductance was improved. A lower Cu2O phase concentration and stable crystallization reduced the electrical resistance of Cu0.5Zn0.5O powder. The electrical resistance of Cu0.5Zn0.5O powder was the lowest and the magnetic behavior was the smallest because CuO and Cu2O contents were higher. XPS analysis reveals that the Zn2+ ions were substituted by Cu2+ and Cu+ ions, forming CuO and Cu2O phases that confirmed the contribution of Cu2O on the electrical and magnetic properties.


The authors are grateful to the Instrument Center of National Cheng Kung University, the Center for Micro/Nano Science and Technology (D100-2700), and the National Science Council, Taiwan, for financially supporting this study under Grant nos. 101-2221-E-006-114 and NSC100-2622-E-006-030-CC3.


  1. B. Karthikeyan, T. Pandiyarajan, and K. Mangaiyarkarasi, “Optical properties of sol-gel synthesized calcium doped ZnO nanostructures,” Spectrochimica Acta A, vol. 82, pp. 97–101, 2011. View at: Google Scholar
  2. H. Qin, Z. Zhang, X. Liu, Y. Zhang, and J. Hu, “Room-temperature ferromagnetism in CuO sol-gel powders and films,” Journal of Magnetism and Magnetic Materials, vol. 322, no. 14, pp. 1994–1998, 2010. View at: Publisher Site | Google Scholar
  3. C. W. Zou, J. Wang, F. Liang, W. Xie, L. X. Shao, and D. J. Fu, “Large-area aligned CuO nanowires arrays: synthesis, anomalous ferromagnetic and CO gas sensing properties,” Current Applied Physics, vol. 12, pp. 1349–1354, 2012. View at: Google Scholar
  4. J. Wang, N. Du, H. Zhang, J. Yu, and D. Yang, “Large-scale synthesis of SnO2 nanotube arrays as high-performance anode materials of Li-ion batteries,” Journal of Physical Chemistry C, vol. 115, no. 22, pp. 11302–11305, 2011. View at: Publisher Site | Google Scholar
  5. H. G. Na, D. S. Kwak, H. W. Kim, and H. W., “Structural, Raman, and photoluminescence properties of double-shelled coaxial nanocables of In2O3 core with ZnO and AZO shells,” Crystal Research and Technology, vol. 47, pp. 79–86, 2012. View at: Google Scholar
  6. L. C. Chen, C. M. Huang, C. S. Gao, G. W. Wang, and M. C. Hsiao, “A comparative study of the effects of In(2)O(3) and SnO(2) modification on the photocatalytic activity and characteristics of TiO(2),” Chemical Engineering Journal, vol. 175, pp. 49–55, 2011. View at: Google Scholar
  7. J. P. Li, F. Q. Sun, K. Y. Gu et al., “Preparation of spindly CuO micro-particles for photodegradation of dye pollutants under a halogen tungsten lamp,” Applied Catalysis A, vol. 406, pp. 51–58, 2011. View at: Google Scholar
  8. R. Motoyoshi, T. Oku, H. Kidowaki et al., “Structure and photovoltaic activity of cupric oxide-based thin film solar cells,” Journal of the Ceramic Society of Japan, vol. 118, no. 1383, pp. 1021–1023, 2010. View at: Google Scholar
  9. H. T. Hsueh, S. J. Chang, W. Y. Weng et al., “Fabrication and characterization of coaxial p-copper oxide/n-ZnO nanowire photodiodes,” IEEE Transactions on Nanotechnology., vol. 11, pp. 127–133, 2012. View at: Google Scholar
  10. H. T. Hsueh, T. J. Hsueh, S. J. Chang et al., “CuO nanowire-based humidity sensors prepared on glass substrate,” Sensors and Actuators B, vol. 156, no. 2, pp. 906–911, 2011. View at: Publisher Site | Google Scholar
  11. J. X. Wang, X. W. Sun, Y. Yang et al., “Free-standing ZnO–CuO composite nanowire array films and their gas sensing properties,” Nanotechnology, vol. 22, no. 32, Article ID 325704, 2011. View at: Publisher Site | Google Scholar
  12. C. S. Dandeneau, Y. H. Jeon, C. T. Shelton, T. K. Plant, D. P. Cann, and B. J. Gibbons, “Thin film chemical sensors based on p-CuO/n-ZnO heterocontacts,” Thin Solid Films, vol. 517, no. 15, pp. 4448–4454, 2009. View at: Publisher Site | Google Scholar
  13. T. Ghosh, M. Dutta, S. Mridha, and D. Basak, “Effect of Cu doping in the structural, electrical, optical, and optoelectronic properties of sol-gel ZnO thin films,” Journal of the Electrochemical Society, vol. 156, no. 4, pp. H285–H289, 2009. View at: Publisher Site | Google Scholar
  14. H. Liu, J. Yang, Z. Hua et al., “The structure and magnetic properties of Cu-doped ZnO prepared by sol-gel method,” Applied Surface Science, vol. 256, no. 13, pp. 4162–4165, 2010. View at: Publisher Site | Google Scholar
  15. S. Y. Zhuo, X. C. Liu, Z. Xiong, J. H. Yang, and E. W. Shi, “Defects enhanced ferromagnetism in Cu-doped ZnO thin films,” Solid State Communications, vol. 152, pp. 257–260, 2012. View at: Google Scholar
  16. K. J. Chen, T. H. Fang, F. Y. Hung et al., “The crystallization and physical properties of Al-doped ZnO nanoparticles,” Applied Surface Science, vol. 254, no. 18, pp. 5791–5795, 2008. View at: Publisher Site | Google Scholar
  17. J. V. Bellini, M. R. Morelli, and R. H. G. A. Kiminami, “Ceramic system based on ZnO · CuO obtained by freeze-drying,” Materials Letters, vol. 57, no. 24-25, pp. 3775–3778, 2003. View at: Publisher Site | Google Scholar
  18. C. Karunakaran, V. Rajeswari, and P. Gomathisankar, “Optical, electrical, photocatalytic, and bactericidal properties of microwave synthesized nanocrystalline Ag–ZnO and ZnO,” Solid State Sciences, vol. 13, no. 5, pp. 923–928, 2011. View at: Publisher Site | Google Scholar
  19. D. Behera, J. Panigrahi, and B. S. Acharya, “Probing the effect of nitrogen gas on electrical conduction phenomena of ZnO and Cu-doped ZnO thin films prepared by spray pyrolysis,” Ionics, vol. 17, pp. 741–749, 2011. View at: Google Scholar
  20. X. B. Wang, D. M. Li, F. Zeng, and F. Pan, “Microstructure and properties of Cu-doped ZnO films prepared by dc reactive magnetron sputtering,” Journal of Physics D, vol. 38, no. 22, pp. 4104–4108, 2005. View at: Publisher Site | Google Scholar
  21. M. S. Seehra, P. Dutta, V. Singh, Y. Zhang, and I. Wender, “Evidence for room temperature ferromagnetism in CuxZn1xO from magnetic studies in CuxZn1xOCuO composite,” Journal of Applied Physics, vol. 101, no. 9, Article ID 09H107, 2007. View at: Publisher Site | Google Scholar
  22. J. Qi, D. Gao, L. Zhang, and Y. Yang, “Room-temperature ferromagnetism of the amorphous Cu-doped ZnO thin films,” Applied Surface Science, vol. 256, no. 8, pp. 2507–2508, 2010. View at: Publisher Site | Google Scholar
  23. O. Perales-Perez, A. Parra-Palomino, R. Singhal et al., “Evidence of ferromagnetism in Zn1−xMxO (M = Ni,Cu) nanocrystals for spintronics,” Nanotechnology, vol. 18, no. 31, Article ID 315606, 2007. View at: Publisher Site | Google Scholar
  24. X. Chen, Z. Zhou, K. Wang et al., “Ferromagnetism in Fe-doped tetra-needle like ZnO whiskers,” Materials Research Bulletin, vol. 44, no. 4, pp. 799–802, 2009. View at: Publisher Site | Google Scholar
  25. R. Al-Gaashani, S. Radiman, N. Tabet, A. R. Daud, and Synthesis a, “nd optical properties of CuO nanostructures obtained via a novel thermal decomposition method,” Journal of Alloys and Compounds, vol. 509, pp. 8761–8769, 2011. View at: Google Scholar
  26. L. Li, J. G. Lei, and T. H. Ji, “Facile fabrication of p-n heterojunctions for Cu(2)O submicroparticles deposited on anatase TiO(2) nanobelts,” Materials Research Bulletin, vol. 46, pp. 2084–2089, 2011. View at: Google Scholar
  27. H. Kim, B. K. Lee, K. S. An, and S. Ju, “Direct growth of oxide nanowires on CuO(x) thin film,” Nanotechnology, vol. 23, no. 4, Article ID 830474, 2012. View at: Publisher Site | Google Scholar
  28. K. J. Chen, F. Y. Hung, Y. T. Chen, S. J. Chang, and Z. S. Hu, “Surface characteristics, optical and electrical properties on sol-gel synthesized sn-doped ZnO thin film,” Materials Transactions, vol. 51, no. 7, pp. 1340–1345, 2010. View at: Publisher Site | Google Scholar
  29. C. O. Kim, S. Kim, H. T. Oh et al., “Effect of electrical conduction properties on magnetic behaviors of Cu-doped ZnO thin films,” Physica B, vol. 405, no. 22, pp. 4678–4681, 2010. View at: Publisher Site | Google Scholar

Copyright © 2013 Kuan-Jen Chen et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

More related articles

 PDF Download Citation Citation
 Download other formatsMore
 Order printed copiesOrder

Related articles

Article of the Year Award: Outstanding research contributions of 2020, as selected by our Chief Editors. Read the winning articles.