amorphous carbon nanocomposite thin film

Surface & Coatings Technology 229 (2013) 50–54

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Ion irradiation studies of silver/amorphous carbon nanocomposite thin film R. Singhal a,⁎, J.C. Pivin b, R. Chandra c, D.K. Avasthi a a b c

Inter University Accelerator Centre, Aruna Asaf Ali Marg, New Delhi 110067, India CSNSM, IN2P3-CNRS, Batiment 108, F-91405 Orsay Campus, France Institute Instrumentation Centre, Indian Institute of Technology Roorkee, Roorkee 247667, India

a r t i c l e

i n f o

Available online 9 June 2012 Keywords: Nanoparticles Surface plasmon resonance Raman spectroscopy Ion irradiation

a b s t r a c t We study the optical and microstructural properties of silver/amorphous carbon (Ag/a-C) nanocomposite thin film and its modification induced by swift heavy ion irradiation. Ag nanoparticles (NPs) embedded in a-C matrix were synthesized by co-sputtering of Ag and graphite by 1.5 keV neutral Ar atom beam. These Ag NPs were irradiated by 120 MeV Ag ions at different fluences ranging from 1 × 1012 to 3 × 1013 ions/cm2. Optical absorption studies revealed that surface plasmon resonance of Ag NPs in pristine film occurs at a wavelength of ~430 nm and it shows a blue shift (~26 nm) with increasing ion fluence up to 3 × 1013 ions/cm2. Transmission electron microscopy and Rutherford backscattering spectroscopy were used to quantify particle size and metal atomic fraction, respectively, in the nanocomposite films. The growth of Ag NPs with bi-model distribution at a fluence of 3 × 1013 ions/cm2 was observed with ion irradiation. Raman spectroscopy was used to investigate the effect of heavy ion irradiation on carbon matrix. The blue shift in plasmonic wavelength is explained in terms of increase in sp2 content in carbon matrix by heavy ion irradiation due to thermal energy deposition which leads to a decrease in dielectric properties of the matrix. © 2012 Elsevier B.V. All rights reserved.

1. Introduction Carbon is a unique element because, by simply changing its bonding, it can exist in different forms such as graphite, diamond, fullerene, carbon nanotube, graphene and amorphous carbon (a-C). These materials have been used in many applications due to their remarkable optical, electrical and mechanical properties. Many properties of these materials can be tuned by doping a small amount of metal into them in the form of nanocomposite material. Nanocomposite films that consist of small noble metal nanoparticles (NPs) embedded in insulating matrix such as amorphous carbon have attracted attention because such type of film is expected to have interesting optical property so called surface plasmon resonance (SPR). Noble metal NPs exhibit a pronounced resonance extinction of visible light due to the collective excitation of quasi free electrons of metallic system and this is known as surface plasmon resonance. The SPR characteristics such as spectral location, its magnitude and width depend on the intrinsic properties of the NPs size, shape and structure as well as on the local environment [1,2]. The SPR wavelength occurs in visible region for noble metal NPs and it leads to a variety of technological applications of noble metal NPs like sensors and in photonic devices [3-5]. The Ag NPs have been synthesized in various matrices such as SiO2 and Al2O3. The instability of silver NPs due to their oxidation, ⁎ Corresponding author. Current address: INSPIRE Faculty, National Physical Laboratory, New Delhi, India. E-mail address: [email protected] (R. Singhal). 0257-8972/$ – see front matter © 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2012.05.131

especially in the case of oxide matrices, has been a major concern [6,7]. Carbon based matrices are interesting to protect these particles against oxidation. A very little reactivity of carbon with silver makes it an interesting matrix for embedding Ag NPs. The properties of different forms of nanocomposite materials can be modified by irradiating them with heavy ions. An ion beam has been used as a post deposition technique to modify the properties in a controlled manner. Energetic ion loses its energy during the passage in the material via (i) collision with the electrons of target atoms (electronic energy loss: dominant at high energies greater than ~1 MeV/nucleon) and (ii) collisions with the nuclei of target atoms (nuclear energy loss: dominant at low energies of a few hundred keV). The strength of interaction between energetic ions and target atoms or molecules depends on the mass, charge and energy of the incident ions. For nanocomposite film, the energy deposition by the passage of energetic ions can change the size and shape of NPs [8-10] and also the dielectric properties of the matrix [2,11] and therefore the SPR wavelength of NPs. In most of the studies of the effect of ion irradiation on the SPR wavelength, NPs were embedded in a radiation-hard matrix such as silica and alumina, and changes in SPR wavelength were due to the changes in particle size and shape only. But if matrix is also sensitive to ion irradiation, the SPR wavelength after ion irradiation will be governed not only by the changes in the shape and size of NPs, but also by the changes in dielectric properties of medium by ion irradiation. In this paper we report a blue shift (~26 nm) in SPR wavelength of Ag/a-C nanocomposite thin film by energetic ion irradiation which is

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explained in terms of increase in C-sp2 content in the film due to ion bombardment. Here, we tried to understand the role of matrix, in which Ag NPs are embedded, with respect to ion beam irradiation for the overall variation in the optical properties of nanocomposite film. Ag NPs were therefore embedded in amorphous carbon matrix and the changes in the microstructure of amorphous carbon were investigated by Raman spectroscopy. The study of ion irradiation induced modifications of Ag/a-C nanocomposite thin films is also important because it throws light on the application of this nanocomposite thin film in radiation zones like in space or near reactors. 2. Experimental details Nanocomposite thin films of Ag/a-C were synthesized by atom beam sputtering setup indigenously designed and built at Inter University Accelerator Centre New Delhi [12]. In this setup fast Ar atoms (energy ~1.5 keV) are delivered by a wide beam atom source which is mounted at a distance of 10 cm from the target holder and at an angle of 45° inside a vacuum chamber. Substrate holder is placed 10 cm below the target holder. Substrate holder can be rotated with a DC motor in order to get uniform film throughout the substrate. The beam coming out from the atom source has a diameter of 5 cm. A thick (~2 mm) graphite disc of 6 cm diameter, with 0.2 mm thick Ag foils of 3 × 3 mm2 glued on this, was used for co-sputtering by Ar atoms. Ag foils were glued symmetrically throughout the graphite sheet to get uniform Ag distribution in the nanocomposite film. The graphite disc used for sputtering was a little bigger in diameter than that of target holder to avoid the sputtering from target holder material. The metal fraction in the film was decided by the relative areas and sputtering rates of Ag and graphite. The vacuum in the chamber before deposition was 3 × 10 − 6 mbar. During the flow of Ar gas (for processing of atom beam), vacuum was 1.5 × 10 − 3 mbar. The current was kept about 14.8 mA. The deposition was performed on few Si and glass pieces of 1 × 1 cm2. Carbon coated Cu grids were also mounted on substrate holder for transmission electron microscopy (TEM). Sputtering was done for a time period of about 4 h. These nanocomposite films on glass substrate and on TEM grids were irradiated with 120 MeV Ag ions delivered by 15 UD Pelletron accelerator at Inter University Accelerator Centre, New Delhi in material science beam line. The vacuum in the chamber during the irradiation was ~6 × 10− 7 mbar. Ion fluence was varied from 1 × 1012 to 3 × 10 13 ions/cm 2. In the case of 120 MeV Ag ions, the electronic (Se) and nuclear (Sn) energy losses in carbon are ~1.4 × 103 and 5.1 eV/Å, respectively, and the range of Ag ions in carbon is ~13.3 μm as calculated by SRIM programme [13]. The actual metal atomic fraction and thickness of the pristine film on Si substrate were measured by Rutherford backscattering spectroscopy (RBS). The detector was kept at an angle of 165° with respect to the direction of the 2.4 MeV He++ beam provided by ARAMIS accelerator at CSNSM Orsay France. UV-visible absorption spectra of pristine and irradiated nanocomposite films on glass substrates were recorded using a dual beam U-3300 Hitachi spectrophotometer. TEM observations of films deposited on carbon coated Cu grids were carried out using a FEI TECNAI 20 microscope equipped with a LaB6 filament and a CCD camera and was operated at a voltage of 200 kV. Raman measurements of pristine and irradiated nanocomposite films on glass substrate were performed using Renishaw in-Via Raman microscope with Ar ion laser excitation at 514 nm and at very low power (~1 mW, 20× objective) to avoid any heating effect.

Fig. 1. Rutherford backscattering spectrum of Ag/a-C thin film along with the RUMP fit.

spectrum was simulated by Rutherford universal manipulation program (RUMP) [14] and is shown in Fig. 1 by continuous line. The plateau region in spectrum represents the Si substrate. The Ag atomic fraction was estimated to be 17% in the pristine film. The film thickness, estimated by the RUMP simulation, was found to be ~ 11 nm. 3.2. UV-visible absorption spectroscopy The absorption spectra of pristine and 120 MeV Ag ion irradiated thin films of Ag/a-C nanocomposite are shown in Fig. 2. For an atomic fraction of 17% Ag, which is much above the solubility limit of Ag in carbon, a well defined SPR peak is observed in pristine film at a wavelength of ~ 430 nm. The SPR peak is broad due to the large size distribution of Ag NPs as shown later by TEM [1]. Some broadening is also possible due to the partial absorption by thin film of a-C as the SPR peak override on the absorption of a-C. The occurrence of a small shoulder at lower wavelength end is possible due to the variety of shapes of NPs present in the as deposited film. An excellent theoretical work has been carried out by Noguez et al. [15-18] for the influence of morphology (different geometries: spheres, ellipsoids, cubes, tetrahedra, cylinders, and pyramids) on the optical properties

3. Results 3.1. Rutherford backscattering spectroscopy Fig. 1 shows a RBS spectrum (open circles) of pristine Ag/a-C nanocomposite film on Si substrate. In order to measure the film thickness and quantify the metal atomic fraction in the film, the RBS

Fig. 2. UV-visible absorption spectra of pristine and irradiated films of Ag/a-C nanocomposite showing a blue shift of SPR wavelength. In figure, fluence is written in the unit of ions/cm2. Reprinted with permission from R. Singhal et al.; Chapter 16, ISBN 978-1-61668-209-5, © 2011 Nova Science Publishers, Inc.

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Ag/a-C 430

thickness of the pristine film in only ~11 nm and for such a small thickness, a sputtering of few nm of the film will decrease the absorption of the film significantly. Fig. 3 shows the variation of blue shift of SPR wavelength with increasing fluence of 120 MeV Ag ions.

SPR Position

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3.3. Transmission electron microscopy 420 415 410 405 400 0

5

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25

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Fluence x 1012(ions/cm2) Fig. 3. Variation of blue shift of the SPR wavelength of Ag/a-C nanocomposite with increasing fluence.

of metal NPs and proved that the optical spectrum was more complex for the particles with less symmetry. For all types of the NPs, a main resonance is with a dipolar character and other secondary resonances of less intensity exist due to deviation from the symmetry. With the increasing fluence of 120 MeV Ag ions, the SPR peak is blue shifted with significant decrease in FWHM. The decreasing FWHM indicates that the particle size increases [1] with ion irradiation. For the films irradiated at a fluence of 3 × 10 13 ions/cm 2, the SPR is centered at a wavelength of ~404 nm showing a total blue shift of ~ 26 nm with ion irradiation. It is also clear from Fig. 2 that the integrated intensity of the SPR peak decreases with increasing fluence. Due to the heavy ion bombardment on the film, sputtering of the film from the surface also occurs. In the present case, the

Fig. 4(a) shows the bright field image of pristine film of Ag/a-C nanocomposite. Majority of the particles are spherical but some deviates from spherical shape also. There is a variation in the sizes of spherical particles also and a broad size distribution was fitted with Gaussian function as shown in Fig. 4(b). The average particle size bD> is ~6.3 ± 0.8 nm. Fig. 4(c) shows the bright field image of the Ag/a-C nanocomposite, irradiated at a fluence of 3 × 10 13 ions/cm 2. A growth of Ag NPs is evidenced from this image with a bi-modal distribution as shown in Fig. 4(d) by measuring only spherical particles. The average particle sizes are found to be bD1> = 8.8 ± 0.8 nm and bD2> = 12.3 ± 0.6 nm. It is also clear from the Fig. 4(c) that few bigger particles are non-spherical in shape which is likely to be due to the agglomeration. The SAED pattern is shown at the right side of each bright field image. The rings are due to the Ag(111), Ag(200), Ag(220), Ag(311) and Ag(331) planes and are indexed in the pattern. Since carbon is in amorphous form, no ring was seen corresponding to carbon in the diffraction pattern. The diffraction rings are diffused in the SAED pattern of pristine film and become sharp at a fluence of 3 × 10 13 ions/cm 2, which is due to the growth of the Ag particles. 3.4. Raman spectroscopy Fig. 5 shows Raman spectra of pristine and 120 MeV Ag ion irradiated thin films of Ag/a-C nanocomposite. These spectra are fitted by two Gaussian curves and the background is subtracted. The spectra of pristine film of Ag/a-C shows widespread asymmetric band formed by the superposition of broad D and comparatively sharp G bands,

Fig. 4. Bright field images of pristine (a) and irradiated (c) film of Ag/a-C nanocomposite at a fluence of 3 × 1013 ions/cm2. Their size distributions are shown in (b) and (d). In figure, fluence is written in the unit of ions/cm2 Figures (a) and (c) are reprinted with permission from R. Singhal et al.; Chapter 16, ISBN 978-1-61668-209-5, © 2011 Nova Science Publishers, Inc.

R. Singhal et al. / Surface & Coatings Technology 229 (2013) 50–54 SiO2 Substrate

D peak

G peak

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Ag/a-C Pristine

Raman Scattering Intensity

1e12

3e12

6e12

1e13

3e13

800

1000

1200

1400

1600

1800

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Wavenumber (cm-1) Fig. 5. Raman spectra of pristine and 120 MeV Ag ion irradiated films of Ag/a-C nanocomposite at different fluences. The unit of fluence is ions/cm2. Reprinted with permission from R. Singhal et al.; Chapter 16, ISBN 978-1-61668-209-5, © 2011 Nova Science Publishers, Inc.

which are the characteristic of a-C structure with a significant degree of sp 2 hybridization [19]. The G mode involves the in-plane bond stretching motion (E2g symmetry) of pairs of C-sp 2 atoms. This mode does not require the presence of six fold rings and so it occurs at all sp 2 sites irrespective of their arrangements in rings or chains (Fig. 6). The D peak is a breathing mode of sp 2 atoms in rings (A1g symmetry). This mode is forbidden in prefect graphite and only becomes active in the presence of disorder. The peak positions of D and G bands in pristine film of Ag/a-C are ~1355 and ~ 1566 cm − 1, respectively. When these films are subjected to 120 MeV Ag ion irradiations, an increase in the intensity of D band is observed with increase in ion fluence, whereas G band is almost unaffected. The intensity of D peak arises only from clusters of sp 2 sites in six fold aromatic rings [20]. Its very broad nature in pristine film indicates that in-plane graphitic ordering is very poor in pristine film. The dominance of D peak (increase in intensity) with increasing fluence shows the increase in number of 6 fold aromatic rings in the a-C network, which in turn shows that with ion irradiation, carbon is driven to a thermodynamically preferred graphitic state. This type of transformation from amorphous to graphite like carbon by laser and ion irradiation has also been reported previously by many groups [21-26]. The intensity ratio of D and G bands, i.e. I(D)/I(G), determined using areas of D and G peaks, of pristine sample is ~ 1.6. Fig. 7 shows the pattern of change

Fig. 6. Schematic of vibrations of C atoms in a-C films, producing D and G bands in the Raman spectrum.

Fig. 7. Pattern of change in I(D)/I(G) ratio for irradiated samples of Ag/a-C nanocomposite at different fluences.

of I(D)/I(G) with increasing fluence. It is clear from the figure that I(D)/I(G) increases up to a fluence of 6 × 10 12 ions/cm 2, above which, it is linear with fluence. The intensity ratio of D to G bands, i.e. I(D)/I(G), is one of the key parameters to analyze the graphitic ordering in various forms of carbon. It is proportional to the number of ordered rings and diameter of cluster formed by the clustering of these rings. It is clear that cluster diameter (or net sp 2 content in the film) increases up to a fluence of 6 × 10 12 ions/cm2, after which it is constant. The effect of 120 MeV Ag ions on a-C is thus to make the microstructure of amorphous carbon more graphite like. Since the graphite like carbon is having conductivity higher than disordered a-C, a decrease in refractive index of the film with increasing fluence is expected.

4. Discussion UV-visible absorption spectra of irradiated films show that there is a blue shift in SPR position. The SPR depends on many factors such as shape and size of metal NPs, their distribution and also on the refractive index of the host medium. According to the Maxwell–Garnett theory, the blue shift in SPR position may occur if particles are getting dissolved in the matrix [1]. This is not the case here, because TEM studies confirm the growth of particles with irradiation. Other possible explanations for the blue shift in SPR wavelength with irradiation may be (i) mixing with glass substrate, (ii) oxygen contamination (iii) mixing at metal-carbon interface, (iv) slight change in shape of the particles, and (v) change in the microstructure of a-C by swift heavy ion irradiation. First four are ruled out as they can give a blue shift of only few nm. The large blue shift may occur by the change in shape of the particles it they become more symmetric [15-18], but in the present case with the ion bombardment, NPs are deviating from the symmetric shape. So, the most probable reason of the observed blue shift is the change in the optical properties of the host medium with ion irradiation. Since the optical properties of a-C carbon film depend on the sp 2 content in the film and it has been shown above by Raman data that there is an increase in the sp 2 content of the a-C film with ion irradiation, the blue shift in SPR wavelength can be explained by the decrease in the refractive index of the matrix. So the blue shift due to the change in the matrix dominates the small red shift due to the increase in the sizes of NPs. The rate of change in SPR position is initially fast which is due to the rapid graphitic like transformation of a-C up to a fluence of 6 × 10 12 ions/cm 2. Here it is also interesting to understand the change in the structural properties of the metal NPs with ion irradiation. A growth of Ag NPs

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can be understood on the basis of the following mechanism in the frame of the thermal spike model: When 120 MeV Ag ions pass through the Ag/a-C nanocomposite film containing metal NPs, they deposit the electronic energy of ~ 14 keV/nm in the material. In Ag/ a-C nanocomposite thin film, metal is essentially in the form of NPs with a certain size distribution and a little part of metal atoms is also expected to be in a solid solution. As a result of the transient temperature increase during the creation of latent track, both the a-C matrix and the Ag NPs are expected to be in transient molten state. It has been shown that due to the ion beam induced molten state diffusivity, the diffusion of clusters and atomic species occurs in transient molten state within the ion track [27-29]. Therefore the diffusion of metal atoms and smaller particles to bigger particles occurs which leads to the ripening of NPs in the latent track. In this way bigger particles grow at the expense of smaller particles. As the fluence increases, the overlapping of latent tracks leads to the further growth of metal NPs due to enhanced diffusivity of metal within the overlapped ion tracks. 5. Conclusion Thin films of a-C containing Ag NPs were deposited by atom beam sputtering. A blue shift of ~26 nm in the SPR wavelength of Ag NPs was obtained by 120 MeV Ag ion irradiation. The average size of Ag NPs increases upon swift heavy ion irradiation and a bi-model distribution was obtained at a fluence of 3 × 10 13 ions/cm 2. The blue shift is explained by the graphitic transformation of a-C matrix by 120 MeV Ag ion irradiation. The growth of Ag NPs can be explained in terms of dissolution and re-precipitation of Ag during the thermal spikes produced by ions Acknowledgement The crew of IUAC Pelletron group is highly acknowledged for providing stable 120 MeV Ag ion beam. R. Singhal is thankful to Dr. D. C. Agarwal and Dr. D. Kabiraj, IUAC New Delhi, for their help in synthesizing the Ag/a-C nanocomposite thin films.

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