Nanostructured mesoporous nickel oxide thin films
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It is a promising material for applications such as electro-chromic display devices. smart windows. Nickel oxide is an interesting candidate for this class with a wide band gap of 3.1088/0957-4484/18/11/115613
Nanostructured mesoporous nickel oxide thin ﬁlms
B Sasi and K G Gopchandran
Department of Optoelectronics. University of Kerala. Phase imaging was used to examine the surface contaminants. Thiruvananthapuram. electrical and optical properties are discussed. More research into these effects will underpin much of the future applications of materials science. and solar thermal absorbers. luminescent materials and solid electrolytes. Although stoichiometric NiO is an insulator. the crystal boundaries are associated with various degrees of structural and compositional disorder. sensors. morphological. adhesion and hardness and height imaging to evaluate the height proﬁle of the ﬁlms. and is a transparent conducting. X-ray diffraction and x-ray photoelectron spectroscopy investigations indicate the presence of Ni2 O3 in the as-deposited ﬁlms. ribbons. channels and other shapes display unique properties that make them suitable for many new applications such as transparent conductors. ﬁbres.
1. the vast majority of experimental studies are based on nanocrystalline bulk or thin-ﬁlm oxide materials characterized by the presence of a large number of grain boundaries between regions with dissimilar crystallographic orientations. Most of the well-known transparent conducting oxides. A very simple but successful way is a slightly controlled oxidation of the surface. Because of quantum and other size effects. Currently.0 eV . having a large span optical density.6–4.
0957-4484/07/115613+09$30. The grain size of materials affects their characteristics. Thin ﬁlms of p-type semiconductors are required in many optoelectronic device applications. and the possibility of manufacture by a variety of techniques are the most attractive features of nickel oxide . Depending on the properties and fabrication route. India E-mail: gopchandran@yahoo.IOP PUBLISHING Nanotechnology 18 (2007) 115613 (9pp)
NANOTECHNOLOGY doi:10. electro-chromic and antiferromagnetic material having a wide range of technological applications at the nanoscale . electron beam
© 2007 IOP Publishing Ltd Printed in the UK
. Having an excellent durability and electrochemical stability.org/Nano/18/115613 Abstract Nanostructured nickel oxide thin ﬁlms were prepared by the pulsed laser ablation technique. Introduction
Nanostructured oxides prepared in the form of rods. catalyst for CO oxidation. Kariavattom-695 581. being a promising ion storage material in terms of cyclic stability. A transformation to cubic NiO with growth along (111) and (200) planes with increase of annealing temperature is also observed. Morphological investigations using atomic force microscopy and scanning electron microscopy indicate a strong inﬂuence of the annealing process on the surface roughness and particle size. vacuum evaporation. such as indium oxide. the properties of nanosized oxide materials differ from those of the bulk. The novel use of nanocrystals currently seen in photovoltaic cells demands more research into the type of material used. This is related to the large area of grain boundary per unit weight of material. and photo electrolysis [2–9]. A self-assembly of nanocrystals agglomerating together to form an island-like structure is observed in ﬁlms annealed at 773 K. and may have major implications for other applications. in ﬁnal form 19 December 2006 Published 7 February 2007 Online at stacks. are n-type semiconductors with free electrons resulting from extrinsic donors as well as intrinsic donors . fuel cell electrodes.00 1
Nickel oxide is a transition metal oxide semiconductor. and zinc oxide. its resistivity can be lowered by an increase of Ni3+ ions resulting from the addition of monovalent atoms or by the introduction of nickel vacancies and/or interstitial oxygen in NiO crystallites . with low material cost. active optical ﬁbres. lasers. gas sensors. indium tin oxide. which make use of hole injection . The effects of annealing on the structural.iop. which needs to have a surface for light absorption and charge separation. smart windows. Many techniques that involve sputtering.com
Received 5 October 2006.
the ﬁtting analysis was done by ﬁtting the experimental reﬂectivity pattern with a simulated one using the program Parratt32. Spectra-Physics) with 55 mJ of laser energy at 532 nm. 2
Figure 1. 3. then maintaining the temperature for 2 h and gradually lowering it to room temperature. Experimental details
Nickel oxide thin ﬁlms were prepared on amorphous fused quartz substrates by the pulsed laser deposition (PLD) technique. friction. which is given by
qz = 2k sin θ =
4π sin θ. The colour of the as-deposited ﬁlm is dark brown. qz
where α is the fringe spacing at high angles and qz is the x-ray momentum transfer along the surface normal direction.15 0. The x-ray source was Al Kα . using a double beam UV–vis spectrophotometer. chemical deposition. The presence of Ni2 O3 in the as-deposited ﬁlm is also conﬁrmed by XPS measurements. and is due to the presence of Ni3+ ions in the Ni2 O3 assignment. Results and discussion
3. By mapping the phase of the cantilever oscillation during the tapping mode scan. The XRD spectrum of as-deposited ﬁlm exhibits the nanocrystalline nature of the ﬁlm. using Nanoman II. (Quanta-ray INDI-Series.25 0. On annealing to a temperature of 573 K. XRD studies Figure 2 shows the GIXRD patterns of as-deposited and annealed nickel oxide thin ﬁlms. XRR studies X-rays are reﬂected from interfaces between materials of differing electron density. the thickness. pulse width 8 ns.6 eV and base vacuum 6 × 10−10 mbar. The composition of the ﬁlm was evaluated by energy-dispersive x-ray analysis (EDX).20 q (A–1) 0. 30 mA).01 1E–3 1E–4 1E–5 0. The peaks are indexed according to ASTM data cards of Ni2 O3 (14-481) and NiO (4-0835).Nanotechnology 18 (2007) 115613
B Sasi and K G Gopchandran
1 Intensity (a. surface morphology and electrical and optical properties of nanoscale NiO is important. Jasco-D 550. and the preferential growth is along the (200) plane. X-ray reﬂectivity of as-deposited NiO ﬁlm with curve ﬁtting. λ
However. in step scanning mode with steps of 0. operated with a monochromatic Cu Kα radiation source (λ = 0. The powder target was isostatically pressed and sintered at 1173 K for 5 h.30
evaporation.33◦ can be observed. structure.4 cm. For a single-layer ﬁlm.05◦ with a scan speed of 4 s/step. and repetition frequency 10 Hz. it shows only a weak diffraction peak which is from the (200) face of Ni2 O3 . Veeco instruments.
3. X-ray reﬂectivity represents the interference pattern of the reﬂected x-rays from the surface and interfaces of the ﬁlm and provides an accurate measurement of the thickness of the ﬁlm. for a period of 2 h. The NiO target was prepared from nickel oxide powder of 99. spray pyrolysis. t . this peak is found to vanish and the appearance of two peaks at 2θ = 37.2.99% purity (Sigma-Aldrich). using a Siemens D-5000 diffractometer. and numerous other properties. 40 kV. can be estimated roughly by
2π . The resistivity of the ﬁlms was measured by the four-probe method using a nanovoltmeter model 2182 A and current source meter model 6430 (Keithley).u) 0. to form pellets of diameter 1. for higher accuracy. The reﬂectivity of a system having n thin layers can be obtained by a recursive method attributed to Parratt . The ﬁlms were deposited at room temperature under a vacuum of 10−6 mbar and subsequently annealed at different temperatures up to 1173 K. phase imaging goes beyond simple topographical mapping to detect variations in composition.154 18 nm. from which the thickness is obtained as 32 nm. Phase imaging is a powerful extension of tapping mode AFM that provides nanometrescale information about surface structure and properties often not revealed by other scanning probe microscopy (SPM) techniques. acting as colour centres . using a Q-switched Nd:YAG laser. Three-dimensional.1. These peaks are attributed to the diffractions from (111) and (200) planes of the cubic NiO lattice. In this study we describe the preparation of nanocrystalline nickel oxide ﬁlms by the pulsed laser ablation technique and the effect of annealing. adhesion. Optical measurements were performed in the wavelength range from 300 to 900 nm. composition.
2. For technological applications. using a Quanta 200 system. The structure and crystallinity of the ﬁlms were investigated by grazing incidence x-ray diffraction (GIXRD). The target–substrate distance was 7 cm and the deposition time was 30 min.1 0. Figure 1 shows the XRR curve along with the simulated one of the as-deposited NiO ﬁlm. viscoelasticity. A chemical binding energy analysis was performed using x-ray photoelectron spectroscopy (XPS) using a VSW (UK) system. and sol–gel processes [15–19] have been used for the preparation of nickel oxide thin ﬁlms. The calculated
.6 eV binding energy to the C 1s peak. phase and height images of the samples were studied. ﬁtted with an energy-dispersive spectrometer.05 0. and scanning electron microscopy (SEM). The heat treatment consisted of raising the temperature at a range of 5 K min−1 . at 1486. Charge corrections were made by assigning 284. two-dimensional. The x-ray reﬂectivity (XRR) technique was used to determine the thickness of the ﬁlms.28◦ and 43. The surface morphology and roughness of the ﬁlms at the nanoscale were investigated by atomic force microscopy (AFM). The target was rotated with constant speed to avoid pitting of the target at any given spot and to obtain uniform ablation. a detailed understanding of the size.10 0.
The peaks obtained at binding energies of 856.417 57 nm. EDX analysis Energy-dispersive spectroscopy was carried out for elemental analysis of the ﬁlm surface. The ﬁlm exhibits oxygen-rich stoichiometry.u)
873. enabling it to be of a better crystalline nature.2 eV indicate the presence of NiO. the Ni 2p3/2 peak at 855.47 eV corresponds to the O 1s peak of NiO.
880. The transformation of Ni2 O3 to NiO in thin ﬁlms by an annealing process has already been reported [22. The intensity of the peaks in the diffraction patterns is found to increase with annealing temperature. No impurity in the ﬁlm was observed. The spectrum indicates the presence of NiO and Ni2 O3 . XPS spectra of the as-deposited and ﬁlm annealed at 773 K in the Ni 2p and O 1s range are shown in ﬁgures 4 and 5 respectively.4.
20 30 40 2θ (deg. the kinetics of these phase transformations is still poorly understood. XPS spectra of NiO ﬁlms in the Ni 2p range: (a) as-deposited ﬁlm and (b) annealed ﬁlm at 773 K.
done only on the surface layer and not on the entire proﬁle. deconvoluted by Gaussian curves corresponding to peaks of nickel oxides. Despite the various transformation models that have been proposed in the past.Nanotechnology 18 (2007) 115613
NiO (200) NiO (111)
B Sasi and K G Gopchandran
Intensity (arb. In general. Scanning was 3
Intensity (a. which is in good agreement with ASTM value. The atomic ratio O/Ni was approximately 93. The reason for this is that non-stoichiometric nickel oxide contains many Ni2+ vacancies.9
value of lattice parameter is found to be 0.58/6. Satellite peaks due to shake-up processes  appear at the 861–862 eV (Ni 2p3/2 ) and 879–881 eV (Ni 2p1/2 ) regions in both the ﬁlms. Figure 5(a) shows the O 1s spectrum of the as-deposited NiO ﬁlm and (b) that of the ﬁlm annealed at 773 K. They govern the kinetics of many phase transformations and recrystallizations that take place during processing. This may be due to the enhanced oxidation kinetics and improvement in crystallinity. and to keep the
. EDX spectrum of as-deposited NiO thin ﬁlm. Annealing provides a restructuring of the ﬁlm.1 873. 15]. the major oxygen-containing compounds in the ﬁlms.4 eV for the as-deposited ﬁlm suggest the presence of NiO [26. annealed at (b) 573 (c) 773 and (d) 1173 K.42.) 50 60
855. 27].2 861.7 eV (Ni 2p1/2 ) and the shoulder at 853. along with reported XPS peaks for nickel oxides found in the literature. (a) As deposited. In the EDX spectrum of the as-deposited NiO thin ﬁlm shown in ﬁgure 3. The binding energy values of peaks obtained from the spectrum are summarized in table 1.3. 3. and was found to be 16 nm for the ﬁlm annealed at 773 K and 23 nm for the ﬁlm annealed at 1173 K. The grain size of the crystallites was calculated for the (200) peak using Scherrer’s formula . XPS studies The binding energy measured using XPS allows detection of different chemical states of bonded elements.5 eV (Ni 2p3/2 ) and 873. consistent with the results of the XRD analysis. The peak having less intensity at a binding energy of 529. The intense peak having binding energy of 531. units)
Ni Ni2O3 (200) b Ni Ni
Full Scale 3737 cts Cursor: 0. The ﬁnal average grain size after the transformation is directly related to the strength of the material. 3. a smaller average grain size results in a stronger material.5 862
880 870 860 Binding energy (eV)
Figure 4.1 eV and Ni 2p1/2 peak at 873. This implies that the ﬁlm contains both Ni2+ and Ni3+ .7 856. which describes the behaviour of individual grains in the bulk of the material.000 keV
Figure 3.54 eV for the as-deposited ﬁlm indicates the presence of Ni2 O3 . For the ﬁlm annealed at 773 K. which is an indication of increase in grain size. no other lines besides those corresponding to nickel and oxygen were detected. GIXRD patterns of NiO thin ﬁlms. In this work the width of the diffraction peaks are found to decrease with increase of annealing temperature. Grain nucleation and growth are important phenomena in nanocrystalline materials. because of the possibility of changing the properties of the material during the ion bombardment etching procedure. Most of these models are based on the classical nucleation theory  and the law of parabolic grain growth as derived by Zener .
82 531.1 857.9 Ni 2p1/2 (eV) 869.03 nm and it changes to 7. a deforming grain is forced to rotate in response to the external stresses exerted upon it by its neighbours.82 Ni 2p3/2 (eV) 852. This suggests that Ni2 O3 turns into NiO when the ﬁlm is annealed. AFM and SEM studies AFM observations in tapping mode have been used to investigate the surface morphology and roughness of the ﬁlms. 33] [34. This also supports our observations. It can be observed that.8 531.5 531. Every δ Ni2+ ion lost from NiO will result in the production of 2δ Ni3+ ions.5 873. Figure 8 shows the SEM photographs of ﬁlms annealed at 773 and 1173 K.54 529.
Table 1.5 Multiplet satellites (eV) 861. The particulate formation is a disadvantage of the pulsed laser
. which usually occur only at elevated temperatures . The 4
surface topography reveals the nanocrystalline nature of the ﬁlms.56
Material Ni metal NiO Ni2 O3 As deposited ﬁlm Annealed ﬁlm
Reference  [30. XPS binding energies of nickel oxides. The presence of Ni3+ in the Ni2 O3 assignment conforms to the non-stoichiometric nickel oxide.5 863 862 861. It has been reported that the presence of Ni2 O3 in nickel oxide ﬁlms would give rise to the dark brown colour . In general. These photographs clearly show the increase of porosity between agglomerated nanograins with increase of annealing temperature. Grain rotation during deformation often accompanies the formation of texture and is accomplished by a microscopic dislocation glide on multiple active slip systems in the grains.5.56 eV and NiO at 529. and it becomes more and more transparent with increase in annealing temperature.2 Multiplet satellites (eV) 879. Annealing the samples gives rise to O 1s peaks corresponding to Ni2 O3 at 531.3 856.47
1000 1000 524 526 528 530 532 534 536 538 540 Binding energy (eV) 522 524 526 528 530 532 534 536 538 540 Binding energy (eV)
Figure 5. A similar mechanism of transformation has been reported by Chang et al for sputtered ﬁlms .47 531.1
charge near the Ni2+ vacancies neutral. 3. O 1s (eV) 530 529. This is due to the formation of a self-assembly of spherical nanocrystals as seen in its three-dimensional image.3 855 854 856.Nanotechnology 18 (2007) 115613
B Sasi and K G Gopchandran
531. in the annealed ﬁlm.56 529. The particle size of the ﬁlms is found to be signiﬁcantly inﬂuenced by annealing. compared to the O 1s peak of the as-deposited ﬁlm.24 nm for ﬁlms annealed at 573 and 773 K respectively.36 and 6.54
4000 3500 3500 Intensity (cps) Intensity (cps) 3000
529. 35] This work This work
855. Figure 6 shows two-dimensional and three-dimensional AFM images of the as-deposited and annealed NiO ﬁlms. some of the Ni2+ were oxidized to Ni3+ . The roughness of the as-deposited ﬁlm is 6.7 873. indicating the formation of a mesoporous ﬁlm. Figure 9 shows the phase and height images of the AFM images shown in ﬁgure 6. Thus mixed states of Ni appear . On annealing at 773 K the nanocrystals agglomerate together in groups to form an islandlike structure with voids in the nanoscale between them.8 880 880 880. The colour of the as-deposited ﬁlm in this work is dark brown.82 eV.5 531.8 856. 31]  [32.7 873 873. Grain rotation can also be caused by extensive grain boundary sliding and diffusion.1 861. The section analysis shown in ﬁgure 7 shows sharp changes in the height proﬁle for the ﬁlm annealed at 773 K. the concentration of the Ni2 O3 component has been decreased and that of NiO increased correspondingly. XPS spectra of NiO ﬁlm in the O 1s range: (a) as-deposited ﬁlm and (b) annealed ﬁlm at 773 K.2 857.
5. AFM images (2D and 3D) of NiO thin ﬁlms: (a) as deposited. 3.6.0 nm 500 nm
375 500 nm 250 375 125 250
500 nm 125 250
500. and 1173 K in the wavelength
. adhesion and hardness.3 nm 0.0 nm 500 nm 400 500 nm 300 400 200 300 100 200 100 500 nm
0. The formation of particulates in the asdeposited ﬁlm can easily be seen in the phase image of the asdeposited ﬁlm.
deposition technique. annealed at (b) 573 and (c) 773 K.0 nm 0. Phase imaging was used to examine the surface contaminants.0 nm 0.0 1: Height 509.8 nm
Figure 6. The phase and height images shown here are a very good tool for understanding the presence of particulates and the inhomogeneous height proﬁle. and height imaging to evaluate the height proﬁle of the ﬁlms.0 1: Height 505.3 nm
B Sasi and K G Gopchandran
5. 773. It can be seen that the particulates disappear on annealing at 573 K. Optical and electrical properties The spectral transmittance of the NiO ﬁlms in the as-deposited state and annealed at 573.0 nm
30. In thermal annealing.Nanotechnology 18 (2007) 115613
19. the mobility to annihilate defects is increased. leading to better order.0 nm 500 nm
375 500 nm 250 375 125 250
0. but the height images of the ﬁlms show that the constraints to maintain an equilibrium surface layer remain. The phase image of the ﬁlm annealed at 773 K exhibits 5
the high quality of the ﬁlm in respect of uniform adherence and hardness.
The calculated values of refractive index and porosity of the ﬁlms are given in table 2. with a sharp decrease near the band edge in the visible region.42 84.33) . E g of the ﬁlms was estimated from the optical measurements on the basis of the relation αhν = A(hν − E g )1/2 .72 to 3.72 3. The change in the optical band gap may be due to the change in homogeneity and crystallinity in the ﬁlm.82
21. Since a crystallographic structural change of NiO ﬁlms was not observed after the heat treatment above 573 K. It can be observed that the crystallinity of the ﬁlms after heat treatment improved with increasing annealing temperature. Band gap ( E g ).
of the ﬁlm is NiO. The absorption coefﬁcient has been calculated from Lambert’s formula.79
Figure 8. which is in good agreement with our report.65
75.36 47. The optical band gap. Similar observations of absorption in NiO ﬁlms prepared by other deposition techniques are found in the literature [14. using the pointwise unconstrained minimization approach . A strong temperature-dependent transmittance can be observed.4–3. An increase in the transmittance is observed with increasing annealing temperature.12 2. with consequent absorption in the visible region . Figure 10 shows the variation of optical density (αt ) with photon energy for the NiO ﬁlms. grain size (d ).65 eV as the annealing temperature increases from 573 to 1173 K. The ﬁlms that are heat treated to 573 K and above showed an average transmittance of above 80%. Reported band gap energies for NiO ﬁlms are in the range 3.
where T and t are the transmittance and thickness of the ﬁlms respectively. Section analysis of NiO thin ﬁlms: (a) as deposited. and Ni2 O3 is present as a minority phase. The refractive indices of the ﬁlms were determined from transmission spectra. (This ﬁgure is in colour only in the electronic version)
Table 2.68 3. refractive index (n ).83
— 16 23
2. (n 2 − 1) T
1 1 ln t T
. the improvement in crystallinity may be attributed to the decrease in native defects such as interstitial oxygen and nickel vacancies . The band gap is determined by extrapolating the linear portion of the plot to the energy axis. transmittance at 550 nm (T ). It is noticed that the value of the band gap shifts towards lower energy and the slope of the plot decreases with increasing annealing temperature. The nature of the plots indicates the existence of a direct optical transition. (5) where A is a constant and hν is the photon energy. But the NiO ﬁlms deposited in this study show some absorption in the visible region. annealed at (b) 573 and (c) 773 K. The as-deposited ﬁlm
.Nanotechnology 18 (2007) 115613
10 5 1 0 –5 nm 50 100 150 200 nm 0 –1 –2 nm 50 100 150 200 nm 3 2 15 10 5 0 –5 –10 nm 50 100 150
B Sasi and K G Gopchandran
200 250 nm
Figure 7. The value of E g decreases from 3. The presence of Ni3+ ions in the oxide lattice shows a charge transfer transition. (2) two adjacent divalent nickel atoms become Ni3+ due to the charge transfer process caused by the presence of a nickel vacancy. Temperatures (K) 573 773 1173
3. The porosity of the ﬁlms was calculated using the following equation :
p = 1−
(n 2 − 1) × 100(%). and porosity ( P ) of ﬁlms annealed at different temperatures. The absorption has its minimum at low energy and increases with optical energy in a manner similar to the absorption edge of semiconductors. SEM micrographs of NiO thin ﬁlms annealed at (a) 773 and (b) 1173 K. The possible reasons for this may be (1) the main stoichiometry 6
where n is the refractive index of the ﬁlm and n T is the refractive index of NiO (n T = 2. Figure 11 shows the plot of (αhν)2 versus photon energy. and (3) excess oxygen together with hydrogen may be present in the ﬁlm as OH groups.
range 300–900 nm are shown in the inset of ﬁgure 11.01 1.11 31. NiO is a wide band gap semiconductor with the absorption edge in the UV region and no absorption in the visible region. 37].32 92. The optical properties obtained are listed in table 2. It is found that the absorption coefﬁcient decreases with decrease of photon energy.8 eV .
is dark brown in colour and shows a metallic-like conductivity. it can be seen that the values obtained in the present study. Using the sputtering technique.Nanotechnology 18 (2007) 115613
150. show a comparable electrical resistivity.0
Figure 9. Conclusions
Nanostructured mesoporous nickel oxide thin ﬁlms have been prepared using the pulsed laser ablation technique. resistivities m with transmittance in the range from 1.6 eV.2
0. The resistance of the ﬁlms increases and the colour of the ﬁlms changes from opaque dark brown to transparent as the annealing temperature increases. annealed at (b) 573 and (c) 773 K. For transparent conducting from 1 × 10−1 to 104 NiO ﬁlms prepared by the sputtering technique.0
5.5 nm 173. The increase in resistivity with heat treatment may be due to the decrease in native defects acting as shallow acceptors . smaller grain size and better transmittance. Varkey and Fort  have deposited insulating NiO ﬁlms with a transmittance of 80% using a dip coating technique.0 μm
4. The ﬁlm annealed at 773 K is found to have a sheet resistance of 2.3 M and a resistivity of 1.0 °
0.4 × 10−3 m with a low transmittance of about 40% in the 7
visible region.88×10−1 m.0 μm
0.18 × 10−1 to 3 varying from 55 to 60% in the visible region have been reported [42–45]. The high degree of reproducibility resulting from the absence of a reactive atmosphere during the ﬁlm deposition and the use of a minimum number of growth parameters makes the present study attractive and suitable for device applications. AFM images (height and phase) of NiO thin ﬁlms: (a) as deposited.0
B Sasi and K G Gopchandran
69.0 nm 100. The electrical resistivity of NiO ﬁlms has been studied by many researchers and the reported resistivity is in the range m . Comparing with reported values.0
5. for ﬁlms annealed at 773 K. Sato et al  reported the preparation of NiO ﬁlms with a resistivity of 1.0 μm
0. Nanocrystalline NiO ﬁlms prepared by the solution growth route  give a resistance of several M cm−2 with a band gap 3.
annealed at (b) 573. Appl.
of as-deposited ﬁlms at 573 K resulted in the formation of cubic NiO ﬁlms with preferential growth along the (200) crystal plane. 33 6656  Yamada S.0
Figure 11. Velevska J and Ristov M 2002 Sol. (c) 773 and (d) 1173 K. Xu R. Dr Raghavendra Reddy and Dr Phase of the UGC-DAE Consortium. Phys. Neumann M and Wetzel S 1991 Z. electrical and optical properties of the ﬁlms. Manoj P K. Phys. Miyashita M.Nanotechnology 18 (2007) 115613
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B Sasi and K G Gopchandran
The work was supported by the Kerala State Council for Science Technology and Environment. Electroanal. 8
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