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Copper (II) oxide as a giant dielectric material

Sudipta Sarkar, Pradip Kumar Jana, B. K. Chaudhuri, and H. Sakata Citation: Appl. Phys. Lett. 89, 212905 (2006); doi: 10.1063/1.2393001 View online: View Table of Contents: Published by the American Institute of Physics.

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Copper II oxide as a giant dielectric material

Sudipta Sarkar, Pradip Kumar Jana, and B. K. Chaudhuria
Department of Solid State Physics, Indian Association for the Cultivation of Science, Kolkata, West Bengal 700032, India

H. Sakata
Department of Applied Chemistry, Tokai University, 1117 Kitakaname, Hiratsuka, Kanagawa 259-1292, Japan

Received 25 August 2006; accepted 13 October 2006; published online 22 November 2006 Bulk copper II oxide CuO , heat treated at 1223 K, shows extraordinarily high dielectric constant 4 r 10 , almost independent of temperature above 230 K and frequency in the kilohertz region. A sudden decrease of r is observed at lower temperature below 150 K . X-ray photoelectron spectroscopy and high resolution transmission electron microscopy studies conrm the presence of a microscopic amount of Cu3+ in annealed CuO. The dielectric behavior of CuO can be explained by Maxwell-Wagner-type polarization mechanism and thermally activated mechanism. 2006 American Institute of Physics. DOI: 10.1063/1.2393001 Copper II oxide, CuO with monoclinic structure, at room temperature is of special importance as it has close relationship to the problem of high-TC superconductivity. Several optical studies demonstrate CuO as a charge transfer insulator.1,2 But excess holes arising from the presence of microtraces of Cu3+ in CuO make it a semiconductor.3 Electron microscopic study also detects superlattice reections due to Cu3+ and charge stripes have been discovered in CuO.4 Previous measurement of dielectric constant of CuO 25 for polycrystalline showed surprisingly low r value sample and 3000 for single crystal .5 This large difference in the value of r for the CuO single crystal compared to that of the corresponding polycrystalline sample prompted us to perform dielectric measurement on pure polycrystalline CuO sample. Interestingly, we observe a very high dielectric constant value even in polycrystalline CuO comparable to those of recently discovered non-ferroelectric CaCu3Ti4O12 CCTO Refs. 6 and 7 and Li and Ti doped NiO LTNO Ref. 8 ceramics. The large r value with weak temperature and frequency dependency as observed in CCTO and LTNO is very much desirable for device implementation. Investigation of the dielectric properties of CuO would also be very interesting as it possesses excess charge in its microstructure. In this letter, we report high dielectric permittivity in the lead-free polycrystalline CuO suitable for its probable application in microelectronics as capacitors and memory devices. Attempt has also been made to explain the origin of such high r value in simple CuO from x-ray photoelectron spectroscopy XPS and electron microscopy studies. Powder sample of high purity CuO 99% was obtained from Merck. For our measurement purpose, CuO powder was rst heated at 873 K under atmospheric pressure for 8 h. The calcined powder was then ball milled for 5 h to obtain ultrane CuO powder. The powder was then pelletized. Finally the cold pressed pellets of synthesized powder were sintered at 1223 K for 10 h and allowed to cool at the rate of 1 K / min down to room temperature. Electrical contacts on the highly polished surface of the pellets were made by gold sputtering. Single phase character of CuO was conrmed

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from x-ray diffraction studies. Dielectric measurements were performed using an HP4192A impedance analyzer. The XPS Kratos Analytical Ltd., UK studies were carried out employing an Al K monochromatic x-ray source. High resolution transmission electron microscope JEOL JEM 2010 with an accelerating voltage of 200 keV was used for taking electron diffraction pattern EDP . Scanning electron microscopic image of the sample was obtained using eld emission scanning electron microscopy JEOL JSM 6700F . Temperature controlling for dielectric measurements was done with an accuracy of 0.5 K or better using a Eurotherm temperature controller. The temperature dependent dielectric constant of polycrystalline CuO shown in Fig. 1 a exhibits a striking feature of very high dielectric constant 2 104 comparable to those of the recently reported high dielectric materials CCTO and LTNO.7,8 Most importantly, such extraordinarily high dielectric constant is found to hardly depend on temperature above 230 K and frequency kilohertz region . The relative permittivity abruptly drops at low temperature 150 K resembling the behavior of CCTO or LTNO. The frequency dependent dielectric constant of CuO at various xed temperatures represented in Fig. 1 a inset also shows almost temperature independent behavior of r at lower frequencies and a steplike decrease of r at higher frequencies. Moreover, the characteristic frequency of the step shifts to the higher frequency side as temperature increases similar to CCTO and LTNO ceramics.7,8 The frequency dependent dielectric loss tan displayed in Fig. 1 b demonstrates that the dissipation peak shifts to the higher frequency side with increasing temperature. It indicates that thermally activated relaxation also occurs in CuO as observed earlier in the cases of CCTO and LTNO.7,8 Here it should be mentioned that around room temperature, in the low frequency region, the value of tan in CuO is higher than that of CCTO and increases with temperature which is possibly due to the contribution of the dc obconductivity. In Fig. 1 b inset the relaxation time tained from the tan curve has been plotted as a function of inverse temperature. The experimental data lled circles t well with the Arrhenius relation, = 0 exp Ea / kBT , within
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Sarkar et al.

Appl. Phys. Lett. 89, 212905 2006

FIG. 2. X-ray photoelectron spectrum of CuO showing a O 1s at 529.107 eV and b Cu 2p3/2 and Cu 2p1/2 at 933.307 and 953.246 eV, respectively. FIG. 1. a Temperature dependence of dielectric constant r of CuO at selected frequencies. The inset displays frequency dependent dielectric constant of CuO at various xed temperatures. b Dielectric loss tan of CuO at different xed temperatures. The inset shows typical Arrhenius plot of the relaxation time with inverse temperature of CuO sample.

the temperature range of 170 230 K. The activation energy Ea obtained from the tting curve solid line according to the above relation is found to be 0.248 eV. Collins et al.3 rst suggested the presence of a microquantity of Cu3+ as high as 0.7% in CuO. We believe this minute Cu3+ within CuO plays a signicant contribution to the observed high dielectric response of CuO. It is very hard to observe such a small quantity of Cu3+ from x-ray diffraction studies. As copper exists in the divalent state in CuO having mainly d9 character,1,2 XPS is a powerful technique to detect such a feeble amount of charge coexisting with Cu2+ in CuO. The high resolution spectra corresponding to O 1s and Cu 2p are displayed, respectively, in Figs. 2 a and 2 b which are plotted after correction of charging effects using a binding energy of 284.4 eV as C 1s peak. The O 1s spectra shown in Fig. 2 a indicate a peak at a binding energy of 529.107 eV and the corresponding peak t reveals a main peak at 529.105 eV along with a shoulder at 530.248 eV, also observed earlier by Robert et al.9 who attributed the appearance of the shoulder to chemisorption of oxygen. The O 1s spectra also indicate that Cu2O phase does not coexist with CuO as the main peak of Cu2O in O 1s spectra usually appears at 530.2 eV. The XPS detected Cu 2p3/2 and Cu 2p1/2 spectra respectively at 933.307 and 953.246 eV are shown in Fig. 2 b . The Cu 2p3/2 spectra also accompanied with a satellite on the higher binding energy side at about

9 eV agrees well with that reported earlier.1 In the case of CuO, the ground state contains d holes and in a photoelectron emission process, electron charges are transferred from the surrounding to the core holes. Such a situation causes the main peak to be associated with a satellite at higher binding energy having d9 shell conguration as shown here in CuO. In the case of Cu2O, the satellite peak is absent as Cu2O has a completely lled d shell d10 . The Cu 2p3/2 peak t reveals a large peak at 933.249 eV and a very small peak at 934.74 eV. The peak at 933.249 is characteristic of Cu2+ and the associated small peak at 934.74 eV corresponding to Cu3+ state arises due to slight excess oxygen in CuO. No evidence of Cu1+ has, however, been detected as normally Cu1+ peak is observed at lower binding energy in comparison with the corresponding Cu2+ peak. Electron diffraction pattern of polycrystalline CuO shown in Fig. 3 a exhibits superlattice reection in addition to the fundamental reection of CuO. The result is similar with that reported by Zheng et al.4 who performed a similar experiment with single crystal of CuO. The weak superlattice reection in Fig. 3 a is due to the presence of Cu3+, i.e.,

FIG. 3. a Selected area electron diffraction pattern of CuO. b Scanning electron micrograph of CuO sample.

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Sarkar et al.

Appl. Phys. Lett. 89, 212905 2006

excess holes in CuO which in turn form charge stripes in CuO. Scanning electron microscopic image of CuO represented in Fig. 3 b reveals distinct grain boundaries between CuO grains. The average grain size is around 1 m. As XPS and EDP conrm the presence of excess holes in CuO, the conduction mechanism in CuO is mainly governed by hole hopping between Cu2+ and Cu3+. Hopping of holes produces Cu3+ around Cu2+ causing CuO grains to be enriched with Cu3+ p-type conductance , which become semiconducting. But the grain boundary might consist of only Cu2+ and it behaves as an insulating wall. As a result, an array of boundary barriers and grains is formed and a giant dielectric value appears. Impedance spectroscopy analysis not discussed here also supports that point. The existence of Cu3+ leads to the formation of an internal boundary layer between grains and such a stable dielectric value over 230 K is mainly governed by an extrinsic mechanism such as Maxwell-Wagner-type polarization also known as interfacial polarization, similar to that observed earlier in other high dielectric materials such as CCTO,10 Bi2/3Cu3Ti4O12,11 and Li and Al doped NiO, Ref. 12 ceramics. As the permittivity of the CuO sample increases slightly with increase of temperature over the whole frequency range shown in Fig. 1 a thermally activated mechanism also plays its role partly in the high dielectric response of CuO. It is further noticed that changing the duration of heat treatment causes variations of r as well as dielectric loss. This implies that both grain size and concentration of Cu3+ in CuO depend on the duration of heat treatments. It is observed from Fig. 1 a that the r value decreases below 230 K at which temperature antiferromagnetic AF ordering was observed earlier.13 It appears that the AF ordering interaction acts as a pinning force5 for the charge superlattice causing decrease of r. The sudden large decrease of r below 150 K over the entire frequency range is due to freezing of excess holes stopping the movement of the trapped charges due to complete ordering of the spins to the AF ordering state in CuO. 25 of the CuO observed by The very small r value earlier authors5 in powder sample is, therefore, due to the absence of an appropriate amount of Cu3+ in their samples which is, however, present5 in the corresponding single crystal showing relatively large r value. No Cu3+ is, however,

present in the insulating single crystal of CuO which naturally showed very low dielectric constant 3 4 .5 Here it can be mentioned that the presence of Cu3+ is also important for the cuprate superconducting system. Even the importance of the presence of a minute amount of Cu3+ in CCTO cannot be ignored which is yet to be conrmed. In conclusion, high dielectric permittivity observed in CuO arises from the microquantity of Cu3+ conrmed by XPS and EDP studies. A simple oxide such as CuO appears to be an interesting low cost material showing giant dielectric constant which merely depends on temperature and frequency kilohertz region . Such a unique property of leadfree high dielectric material CuO seems to be of paramount importance in the microelectronic industry. Further studies on the conduction mechanism, impedance spectroscopy, and different heat treatments of CuO are going on and will be published elsewhere. One of the authors B.K.C. is grateful to the Council of Scientic and Industrial Research CSIR , Government of India for nancial assistance to complete the work.
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