Surface and Coatings Technology 123 (2000) 256260 www.elsevier.

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A phenomenological approach for the I /I ratio and d g sp3 fraction of magnetron sputtered a-C lms
S. Zhang a, *, X.T. Zeng a, H. Xie a, P. Hing b
a Gintic Institute of Manufacturing Technology, 71 Nanyang Drive, Singapore 638705, Singapore b School of Applied Science, Nanyang Technological University, Nanyang Avenue, Singapore 639798, Singapore Received 21 June 1999; accepted in revised form 19 September 1999

Abstract Amorphous carbon coatings (a-C and a-C:H ) less than 100 nm thick were deposited on KBr and silicon wafer substrates via magnetron sputtering of a graphite target in argon, argon/hydrogen and argon/nitrogen atmospheres. Electron energy loss spectroscopy (EELS ) analysis was used to quantify the sp2/sp3 bonding in the lms. Free-standing lms of amorphous carbon were produced by sputtering onto compressed KBr pellets and then oating o in distilled water for EELS study. Raman spectroscopy was used to measure the peak intensity ratio of the D-band to that of the G-band (I /I ). This showed that the sp3 d g fraction is inversely proportional to the band ratio I /I . At the same time, the G-band peak position P decreases while the sp3 d g g fraction increases. 2000 Elsevier Science S.A. All rights reserved.
Keywords: a-C; Diamond-like carbon; Electron energy loss spectroscopy; Raman shift; sp3 bonding

1. Introduction Raman spectroscopy, EELS and nano indentation are some of the most commonly used techniques in characterizing thin solid lms of diamond, amorphous diamond-like carbon (DLC ) and amorphous carbon. In Raman spectra, amorphous DLC lms are characterized by a broad single peak centered around 1530 cm1 (G-band ) with a shoulder at around 1350 cm1 (D-band ). The shoulder is the signature of the DLC lm (otherwise a sharp peak at around 1580 cm1 would be that of a highly oriented pyrolytic graphite).The peak intensity ratio and peak position have been commonly used in the characterization of diamond-like carbon or amorphous carbon lms[13]. The peak positions and the ratio of the peak intensities (sometimes referred to as band intensities) vary from lm to lm. This variation comes from the structural change or disturbance of an otherwise full three-fold coordination of carbon network (sp2) as four-fold coordinated structures (sp3) are introduced through vapor deposition. EELS analysis can distinguish atomic elements and dierentiate graph* Corresponding author. Tel.: +65-793-8577; fax: +65-792-2779. E-mail address: szhang@gintic.gov.sg (S. Zhang)

ite, amorphous carbon, diamond and a variety of diamond-like carbon materials, and enables quantication of the sp2 and sp3 bonding in carbon lms [46 ]. The aim of this paper is to clarify, for a-C or DLC, the relationship between the Raman spectroscopic peak ratio (I /I ) and four-fold coordination fraction (sp3) d g through EELS studies.

2. Experimental procedure 2.1. Coating deposition process There are a number of ways to deposit amorphous carbon coatings[7]. Unbalanced magnetron sputtering [8,9] has been used to deposit ceramic hard coatings on cemented carbide and tool steels[10], a-C on cemented carbide [11] for tribological applications, and on magnetic recording disks in computer disk applications[12]. In this study, the system was used to deposit a-C coatings on silicon wafers and KBr pellets with varying bias and target power levels. The background pressure in the sputtering chamber was pumped below 5105 Torr before sputtering gases were introduced. The substrates were placed in a rotary sample holder

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facing a rectangular (330133 mm) graphite target (99.9%) situated 85 mm above the sample. A standard radio frequency (13.56 MHz) bias power was applied to the substrate to provide power during pre-coating cleaning and to eliminate charge accumulation during deposition. The coating thickness was controlled by deposition time. 2.2. Raman spectroscopy The coating thickness was characterized using a Laser Stylus Prolometer (Rank Taylor Hobson Form Talysurf Series). Raman peaks were obtained with a Raman imaging microscope (Rennishaw Model 127) using a HeNe laser beam of 632.8 nm as the excitation source. After data acquisition, the spectra were deconvoluted into two Gaussian peaks for band intensities in terms of counts, and peak positions in terms of wave number (cm1). 2.3. EELS characterization The samples for parallel electron energy loss spectrum (PEELS) analysis were prepared on potassium bromide ( KBr) pellets. The free standing TEM samples were prepared by oating o the carbon lm on the surface of distilled water. The specimens were examined in a Philips EM430 electron microscope tted with a Gatan 666 PEELS Spectrometer operating at 200 keV. The PEELS analysis [13,14]was performed in two stages rst the low-loss or plasmon region at 050 eV of the energy loss spectrum, and then the core loss region at 200300 eV where the carbon K-edge (281 eV ) is located. The majority of energy loss events occurs in the low-loss region, where the losses arise from interactions of the fast electrons with electrons in the outer atomic shells. One important interaction is the plasmon oscillation which can be described as the fast electrons interacting with quasi-free electrons of the solid to produce a plasma oscillation [15] of frequency: v =[ne2(e m)]1/2, where v is the plasmon frequency, p 0 p n the number of electrons per unit volume, and m the eective electron mass. In measurement, n was assumed to be equal to the atomic density multiplied by the number of outer-shell valence electrons. The plasmon region was studied in two ways rst, the microscope was used in a diraction mode with a focal length of 640 mm; and then used with a parallel probe at a magnication of 5070, with a 2 mm EELS entrance aperture with the microscope operating at 200 keV. For the core region, the diraction mode, with a camera length of 640 mm, was used in analyzing the carbon K-edge to determine the sp2 fraction. First, the glassy carbon K-edge was collected and assumed to be 100% graphitic (sp2=1), then these spectra were analyzed to determine the number of counts in the 1s-p1 pre-edge

feature. The number of counts in the 1s-p1 feature (I ) were then normalized for the calibration sample gp1 using the integral counts under the 1s-s1 peak [I (dE )]. g For samples of unknown sp2 fraction, the sp2 fraction ( f ) was calculated from the experimentally measured I and I (dE ) through the following relation [16 ]: up1 u I I (dE ) f= up1 g . (1) I I (dE ) gp1 u Assuming that the amorphous carbon or DLC lm comprises only sp2 and sp3 structures, then the fraction of sp3 structure is: sp3 fraction=1 f. (2)

3. Results and discussion 3.1. Ratio of I /I and peak position as revealed by d g Raman spectroscopy The Raman spectra of the a-C coatings exhibit a typical DLC spectrum: a broad single peak centered around 1530 cm1 with a shoulder at around 1350 cm1. The spectra shape and the peak positions in the Raman spectra of the DLC coating on KBr pellets and those on silicon substrates obtained under the same deposition condition were indistinguishable from each other. As shown in Fig. 1, the Raman spectrum can be deconvoluted into two Gaussian peaks (bands) plus a linear background. Schwan et al. [1] pointed out that carbon lms prepared by magnetron sputtering show two additional Raman features at 1180 and 1490 cm1 in addition to the G and D peaks. The one around 1000 cm1 is also obvious in Fig. 1. However, this paper will concentrate on the G and D peaks because they are

Fig. 1. Typical Raman spectra of the a-C coatings deposited on a silicon wafer. The spectrum is deconvoluteable into two Gaussian peaks centered around 1330 cm1 (D-band) and 1530 cm1 (G-band).

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S. Zhang et al. / Surface and Coatings Technology 123 (2000) 256260

Fig. 2. Ratio of peak intensity and G-band peak shift as a function of target power density at constant hydrogen ow rate and substrate bias power.

Fig. 3. Zero Loss prole of an a-C sample deposited by magnetron sputtering of graphite target.

the most prominent and less prone to measurement errors. The peak at around 1350 cm1 is the D-band and the other at round 1530 cm1 is the G-band. The ratio of the peak intensity of D-band over that of the G-band, I /I , usually has the same trend as the the ratio of the d g area under the D-peak over that under the G-peak, A /A . Either of the ratios is the signature of the atomic d g bonding structure of the DLC coating. Therefore, in later discussions, we will use only I /I . d g We plotted the peak intensity ratio (I /I ) and the d g G-band peak positions (cm1) for coatings obtained under dierent deposition conditions and obtained Fig. 2. It can be seen from the plot that initially, when the G-band peak position shifts down, the peak intensity ratio also shifts to lower values with increasing sputtering target power density. However, with further increase in power density, both I /I and G-band peak position d g increases, indicating more graphitic structure (sp2). In fact, this trend was observed also in thick (2~3 mm) titanium-doped hydrogenated carbon (Ti-C:H ) sputterdeposited on WC/Co and high speed steel tool materials. It was conrmed by direct EELS measurement as discussed in the next section. 3.2. Ratio of sp3/sp2 as revealed by EELS A typical EELS zero loss prole is shown in Fig. 3 as photodiode counts vs. energy loss (eV ). This can be used to determine plasmon energy. Fig. 4 depicts a core loss prole for the same sample. The core loss prole was used to determine the sp2 fraction, Eq. (1), and sp3, Eq. (2). The sp3 values thus determined were plotted as a function of deposition power density in Fig. 5. A few points are noteworthy: rstly, the highest sp3 fraction is around 60%, compared to 80~90% for tetrahedral a-C reported in the literature [1719]. The sp3 fraction increases with power density

Fig. 4. Typical EELS core loss prole of an a-C sample.

Fig. 5. EELS sp3 fraction as a function of deposition power density.

and then decreases. This correlates well with the Raman results discussed earlier in Fig. 2, except in a reverse manner: the band intensity ratio I /I decreases with d g power density and then increases. Decreasing I /I indicates a reduction in the total d g

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Fig. 6. EELS sp3 fraction as a function of deposition bias for nonhydrogenated (a-C ) amorphous carbon.

number and/or size of graphitic micro domains, and therefore an increase in the number of four-fold coordinated carbon atoms (sp3/sp2), as demonstrated by Lee et al. [20], Marchon et al. [21] and Ager [22] in hydrogenated amorphous carbon lms with increasing hydrogen content. The inuence of the target power density is believed to come from the increased degree of ionization and temperature as the target power density is increased. However, too high a temperature [23] or too high an energy [24] would promote graphitic deposition instead of sp3 coordination. This is also demonstrated in Fig. 5: while increasing the deposition power density increases sp3 formation, when power density becomes excessive, sp3 formation starts to decrease. According to theoretical work by Beeman et al. [25], a shift of the Raman G-peak to lower frequency indicates a greater sp3/sp2 bonding ratio. As a result of the decrease in average CMC bond angle, the peak position of G-band in a-C shifts towards a lower wave number relative to pure graphite. The D-band is caused by the lack of long range order in the DLC. Thus an alternation of deposition condition results in a variation of the coating structure, or the proportion of the sp3 to sp2 bonding, changes of the peak intensity ratio (I /I ) and d g bands peak position occur [2628]. Though caution should be exercised, since the residual stresses may also induce a down shift of the G-Band and a decrease in hardness, in general a high sp3/sp2 bonding ratio correlates well [29] with the G-band shift to a lower frequency and an increase in diamond-like structures may increase the wear resistance and hardness. Experiments were also conducted at dierent bias to assess the eect of bias on sp3 formation. Fig. 6 is the resulting plot. A few observations are important: rstly, the sp3 fraction increases with bias power until around 150 V, followed by a decrease at extreme bias power. The eect of bias in this case is similar to that of the target power density. Too high a bias power creates too

high a temperature, which in turn hinders the formation of sp3 coordination. Such is the case because the formation of sp3 is favored only in a specic carbon ion energy window. McKenzie et al. [30] noted that this window is 20~200 eV, and Robertson [31] pointed out that the sp3 bonding arises from C ions entering subsurface atomic sites and producing a quench-in density increase. For this process, the optimum ion energy is about 100 eV because the C ions must have sucient energy to penetrate the surface, but any excess energy could anneal out the density increment. Also note that in Fig. 5 the samples are hydrogenated while in Fig. 6 the samples are non-hydrogenated. The similar trends (increase rst, then decrease) of sp3 fraction variation with power density and bias voltage indicate that power density and bias power both result in the rise of the carbon ion energy. Moderate increase promotes the sp3 formation, but excess of it results in graphitization.

4. Conclusions Amorphous carbon lms less than 100 nm thick were deposited on KBr and silicon wafer substrates via magnetron sputtering of a graphite target. EELS was carried out to quantify the sp2/sp3 bonding in relation to the Raman I /I ratio. The following points are emphasized: d g 1. The I /I ratio decreased with target power density, d g followed by an increase when power density was further increased. A similar trend was observed for G-band peak position shift with regard to power density variation. 2. As determined by EELS studies, the sp3 fractions are inversely proportional to the Raman peak intensity ratios I /I . At the same time, the G-band peak d g position P decreases while the sp3 fraction increases. g 3. Increase of deposition power density and substrate bias power both bring about an increase in sp3 formation to a certain extent. Too high a power density or too high a bias power both reduce the carbon four-fold coordination, resulting in a decrease in sp3 fraction. This is true for both non-hydrogenated and hydrogenated a-C samples studied.

Acknowledgements This work was funded by Singapore National Science and Technology Board via Gintic upstream project U96-P-059 in collaboration with the School of Applied Science, Nanyang Technological University. The authors are indebted to the Australian Key Centre for Microscopy and Microanalysis for their assistance in PEELS analysis.

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