Jpn. J. Appl Phys. Vol. 42 2003) pp. 251-258 ars 1, No.1, Tanvary 2003 {©2008 The Japan Society of Applied Physics Raman Scattering Spectroscopy of Structure of Amorphous Carbon Nitride Films Yoshiaki ONKAWARA, Hiroki AKASAKA, Kei-ichi C, NAMIKI, Shigeo Orisitio, Haruhiko To and Hidetoshi SarTou Deparimen of Chniay, Nagaoka Univer of Technolgy, Kamitomiok, Negaks, Miata 9402188, Japan (Received May 8, 2002 accepted for publication September 4, 2002) Amorphous carbon nitride (a-CN,), films without hydrogen were deposited with dehydrated cyanogen bromide using ‘lectron-cyclotron-resonance plasmavenhanced chemical-vapor deposition, The structure of the a-CN, films was evaluated tusing a new Raman-active band at 1300 em", corresponding to sp'-hybrized carbon nitride, The Raman-actve scattering ‘band at ~1300em™ became clester with increasing hardness value of the films, suggesting thatthe hardness ofthe a films increases with extension of the thee-dimensional structure ofthe films composed of C-N bond. [DOF 10.1149/51AP.42.254) KEYWORDS: carbon nitide, ECR, chemical vapor depostion, nano-indentatio, IR spectroscopy, Raman scattering spectro scopy, hardness 1. Introduction, Amorphous carbon nitride (@-CN,) and amorphous hy- drogenated carbon nitride (a-CNy'H) films are materials of great interest for applications in the field of wear protection, field emission and hydrogen storage, Numerous studies have ‘been carried out to synthesize various carbon nitride films." For example, Tanaka et al. synthesized hard a- (CN, films that have fundamental structure similar to that of diamond-like carbon (DLC) with a hardness value of 21.6GPa using microwave (MW) plasma chemical-vapor deposition (CVD). Hammer et al, fabricated hard a-CNy films that have a hardness value of more than 20GPa using jon-beam-assisted sputtering,” In addition, Ohkawara eral reported the field emission property of a-CNeHI films deposited on ALZaO whiskers using MW plasma CVD. The a-CN,H films showed a threshold field of 1.5 Vm! ‘with an emission current density of 0.1 mA-cm™? at a field strength of 7.0V-um™?.® Sugimura ef al. also reported the field emission property of a-CN,H films deposited using are ion plating. The a-CN,-H films showed a threshold field of 13 V-umr! and an emission current density of 2uA-cm™? at a field strength of 20-V-um™!,” Furthermore, Ohkawara et al. evaluated the hydrogen adsorption capacity of a-CN,:H using volumetric analysis established for measuring the hhydrogen adsorption by metal alloys. They obtained a hydrogen capacity of 0.54w0% at room temperature under 12MPa.” We have proposed a model in which the a-CN,:H films are formed as nanosized clusters consisting of sp? or sp'- hybridized carbon and nitrogen."' A large number of hydrogen atoms also terminate the carbon nitride cluster, resulting in the formation of methyl, ethylene and secondary amino groups. Nitrogen atoms also terminate the carbon cluster forming the nitty! group. This model indicates that hhydrogen and nitrogen terminations limit the size of the carbon nitride clusters. In other words, hardening of the a- CNcH films is significantly prevented by formation of hydrogen and nitrogen terminations. During the deposition process, a-CN:H often absorbs @ large amount of hydrogen in its structure, The amount of hydrogen terminations in the structure strongly depends on ‘the deposition technique. In the CVD technique, a significant “Comesponding autor. E-mail address: e@naguokautac ip 256 amount of hydrogen atoms are incorporated into the films, because hydrogen and hydrocarbons are usually used as reactants and/or water is used in the deposition process. For example, the hydrogen contents in the aCNcH films obtained by RF-plasma decomposition of the methane- nitrogen mixture using the CVD technique were inthe range of 12-21 at.%."*" In addition, the hydrogen contents in the a@-CN,:H films obtained by dissociative excitation reaction of BrCN (containing H0) using the MW plasma CVD. technique were in the range of 20-30 t.%."® The hydrogen, content in the a-CNj:H films deposited by dehydration of eyanogen bromide using the MW plasma CVD technique was 10at.%.!° These resulls strongly suggest that hydrogen, should not be used as a reactant and water should be excluded from the deposition process for obtaining dehy- rogenated a-CN,. The electron-cyclotron-resonance (ECR) plasma-enhanced CVD technique is a powerful technique for fabrication of a-CN,:H films that prevents contamination. Because the ECR plasma CVD apparatus is operated under high-vacuum, contaminations depend on the control of the operation. We expect that the hydrogen content of the films obtained using ECR plasma CVD is lower than those of films obtained by MW plasma CVD and RF plasma CVD. The structural change of the a-CN,:H films is confirmed bby Raman spectroscopy and IR spectroscopy. These spectro- scopic analyses are the most popular techniques for the structural analysis of amorphous carbon and related films. In general, the positions and bandwidths of G (graphitic)- and D (disordered)-bands obtained by deconvolution using two- Gaussian fitting indicate the faction of the sp*-hybridized carbon and order of the sp? network, respectivily. Recently, wwe have reported that the Ar! laser Raman spectra are decomposed by the new band at a wave number of approximately 1300em™! in addition to the G- and D- bands." The new band corresponds to the amorphous phase consisting of sp’-hybridized carbon. This is strongly supported by the observation that the diamond peak obtained, in the Ar* laser Raman spectrum downshifts and becomes broad accompanied with reduction in the crystal quality." IF the carbon nitride cluster in the structure of the films deposited by ECR plasma CVD is grown, the intensity of the D-band is decreased and that of the new band at the wave number of around 1300cm™ is increased in the Raman spectra. In addition, a similar tendency should be observed in the IR spectra, In this study, the dehydrogenated a-CN,Spa. J Appl Phys. Vol. 42 (2008) PL 1, No.1 films are deposited from dehydrated BrCN using ECR plasma CVD. The structure of the a-CN, films will be determined using Raman spectroscopy and IR spectroscopy and discussed, 2. Experimental Procedure ‘The a-CN, films were deposited on nondoped Si (100) single-crystal wafers using the ECR plasma-enhanced CVD apparatus, as described in detail elsewhere." Prior to the deposition of the a-CN, films, a SiC thin layer was deposited as a buffer layer between silicon and the a-CN, films. The ECR plasma-enhanced CVD apparatus is composed of two parts: a plasma-generator room and a reactant feeding room. ‘The plasma-generator room produces argon plasma by applying a 2.45 GHz microwave. Argon plasma, composed of Ar('Po.2) radicals, Ar” and electrons, is carried toward the BrCN feeding room immediately. The BrCN reactant is ‘easily evaporated at room temperature, The BrCN vapor is introduced into the feeding room through a feeding nozzle with a diameter of I mm. In the reactor, the BrCN vapor is decomposed by the dissociative excitation reaction and then the solid-state a-CN, is deposited on the Si (100) substrate. The thickness of these samples was kepl constant at I um. During the deposition, the substrate was negatively biased at a voltage (V,) of 10-30V by applying an RF power of 13.S6MHz, All experiments were carried out under a total pressure of 3mTorr, The argon tank and BrCN initially possess only a small amount of water. Therefore, argon gas and the starting materials are dehydrated using the powder desiccant POs, ‘The structural analysis of the sample was performed using 1 Fourier transform infrared spectrophotometer (IMPACT- 410, Nicolet) and a Raman spectrometer (Model Labram Infinity, Jobin Yvon). IR spectra were measured in the attenuated total reflection mode with a resolution of 4.em~! in wave number. Raman spectra were obtained in the backscattering mode using an Art laser operating at @ wavelength of 514.5nm and a power of 100mW. The wavelength resolution was held at 1 em Indentation hardness was measured, as described in detail elsewhere,” using a Fischer H-100 ultralow-load micro- hhardness indenter (Fischer Co.). The function of this system is to determine the indentation depth at a resolution of 2nm using an indenter tip as a function of the applied force, at a resolution of 0.02mN. A Vickers indenter tip made of diamond was used in geometrical correction to accurately caleulate the indentation hardness, Measurements were performed by first increasing the loading steps to 10mN with an increasing rate of 0.33mN/s. Subsequently the loading force was decreased in similar steps. Then, force- displacement curves were obtained for each separated location on the specimen. Indentation hardness was caleu- lated from the average force-displacement relationship by performing measurements at ten locations. Indentation hhardness is equivalent to the average pressure under the indenter, calculated as the maximum loading force, 10mN, divided by the projected area of contact between the indenter and the sample, 3. Results and Discussion In a previous report? it is found that the aCN, film Y.omawsna ral 255 16 4 a2 S 10 38 = zo m4 2 0 0-10-20 -30 -40 Bias voltage (V) Fig 1 Hardee of CN ns depoted at vaso Has volags contains nitrogen at a fraction [NI/((C]+ {ND of 32 4Lat. The maximum indentation depth for a-CN, films de- creased from 0.226 to 0.163 um with increasing V,. Figure 1 shows the hardness values of a-CN, films deposited at various bias voltages. The hardness value increased from 7.0, to 14.0GPa with increasing V,. This maximum hardness value was almost equal to that obtained for the DLC film prepared using an ion-beam-assisted deposition technique.””” Figure 2 shows the IR spectra for CN, films with hardness values of (@) 14GPa, (b) 12GPa and (©) 8GPa. There is no absorption assigned to the hydrogen termination fon the spectra, The absorption band between 1500 and 1600 em" is assigned to the stretching vibrational modes of C=N and C=C bonds. The other absorption band at the wave number of 1050cm-" is attributable to the stretching vibrational mode of the Si-C bond originating from the SiC C=Nost.), C-Nost.) C=Cost,) Absorbance (arb. units) 4000 3000 2000 1000 Wave number (cm) Fig, 2. IR spectra obtained from o-CN, fms with harness of (3) 14GPa () 1202 and (6) 8GPa256 Ip. J. Appl. Phys. Vol. 42 2008) P. 1, No buffer layer. Furthermore, the absorption bands around 1300cm~' and 2200cm™' are assigned to the stretching vibrational modes of the C-N and C=N bonds, respective ly. The intensity of stretching vibrations for the C bond decreased with increasing hardness value of the films. It almost disappeared in the sample with a hardness value of 14GPa, On the other hand, the absorption assigned to the C N bond markedly inereased with increasing hardness value, suggesting that the nitrogen termination prevents hardening fof a-CN, films without hydrogen incorporation. That is, the size of the carbon nitride clusters is increased by the change between the C=N bond and C-N bond in the films. This structural change often induces the formation of a three- dimensional structure constructed by C-N bonds.” Figure 3 shows the deconvolution of typical Raman spectra for the a-CN, films: (a) two-Gaussian fitting and (b) three-Gaussian fitting. Two bands (G-band at approximately 1550cm™! and the D-band at approximately 1360em7) and three bands (G-, D-bands, and the new band) are used. The new Raman-active band at a wave number of 1300cm™! ray be correlated with the an IR-active absorption band of (C-N observed at a wave number of 1300 em~!, as shown in Fig. 2. The full-width at half-maximum (FWHM) values of the (a) G-band and (b) D-band obtained using two-Gaussian, fitting as a function of hardness value are shown in Fig. 4. No correlation between hardness and FWHM of the G-band was found, However, the FWHM of the D-band decreased with increasing hardness value. It is well known that the FWHM is proportional to the reciprocal of extension of the ‘carbon network." Therefore, the result in Fig. 4 suggests that the extension of disorder of the sp* carbon network ‘occurs with increasing hardness value. Figure 5 shows the positions of the (a) G-band and (b) D- band obtained using two-Gaussian fitting as a function of hhardness value. The positions of G- and D-bands were decreased with increasing the hardness value. It is reported that the G- and D-bands downshift as a result of increasing the sp? content and/or degree of bond-angle distortion.*~* Intensity (arb. units) 2000 1800 1600 1400 1200 1000 Wave number (cm!) Fig. 3. Deconvolution of typical Raman spect forthe CN, lis by (3) Two-Gausian Siting and (D) hee-Gaussian Sting YY. OmRAWARA eral (a) 220 200 180 160 140 120 100 5 7 9 Wo 13 15 Hardness (GPa) (b) FWHM of G-band 360 320 280 240 FWHM of D-band 200 5 7 9 WW 13° «15 Hardness (GPa) Fig, 4. FWHM values of (2) G-hand and (b) D-band obtained using e- Gaussian fing a funtion of hardness ‘Therefore, the result in Fig. 5 suggests sp? content increases with increasing hardness value. Three-Gaussian fiting was conducted for the analysis of Raman spectra, as shown in Fig. 6. The intensity ratio of Togn/(lp + Io) increased with increasing hardness value, suggesting thatthe sp* content also incveases. Typical values of Tyeu/(Ip + Ia) and the hardness values of the amorphous carbon and related films have been reported to be 0.06-0.46 and 10-45 GPa, respectively." In Fig. 6, the hardness value of 15GPa of the film is almost equal to that of amorphous carbon films obtained by MW plasma CVD, which is 0.23." A typical hardness value of 26GPa was obtained when we examined this CVD film: however, the hardness value of the films shown in Fig. 6 is lower than 26GPa despite their similar Iyrx/(Up + Ia) values. The reason for this difference may be the existence of a dangling bond in the structure We proposed a new model in which a-CN, films withoutSpa. J Appl Phys. Vol. 42 (2008) PL 1, No.1 (a) 2 = a a oS & 3 g 3s Posi 5 7 9 I 13 15 Hardness (GPa) (b) 1390, 2 1380 bat e Cd = 1370 1360 . = 1350 1340 1330 Position of D. 7 9 UW 13 15 Hardness (GPa) Fig. 5. Positions of (a) C-band and () D-band obtained using Wo ‘Gausian Siting asa funeton of hades. hydrogen are formed as nanosized clusters consisting of sp?- ‘or sp*-bybridized carbon and nitrogen, Not only nitrogen atoms but also dangling bonds terminate the carbon cluster. ‘This model indicates that nitrogen terminations and dangling bonds limit the size of the carbon nitride clusters, In other words, nitrogen terminations and dangling bonds prevent hardening of the a-CN,H films. 4. Conclusions In this study, a-CN, films were synthesized by dissocia- tive excitation reaction of BICN using the ECR plasma CVD, technique. A maximum hardness value of 14GPa was, obtained at a negative bias voltage of 30. The nitrogen contents (INJ/((N] + [C)) were in the range of 32-41 at.%. ‘The results of IR spectroscopy revealed that the termination structure (C=N) in the a-CN, films transformed tothe three- dimensional structure composed of C-N bonds with in- creasing hardness value of the films. 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