Journal of Non-Crystalline Solids 356 (2010) 17911794

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Journal of Non-Crystalline Solids

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / j n o n c r y s o l

Chamberless plasma polymerization of uorocarbon thin lms

Chun Huang a,, Chi-Hung Liu b, Wen-Tung Hsu b, Ta-Hsin Chou b
a b

Department of Chemical Engineering & Materials Science, Yuan Ze Fuel Cell Center, Yuan Ze University, 135 Yuan-Tung Road, Chung-Li, 32003, Taiwan, ROC Mechanical and Systems Research Laboratories, Industrial Technology Research Institute, Hsinchu, 310, Taiwan, ROC

a r t i c l e

i n f o

a b s t r a c t
Fluorocarbon thin lms were prepared and investigated using atmospheric pressure plasma jet. This atmospheric pressure plasma jet deposited uorocarbon lms without unfavorable contamination in plasma source. The atmospheric pressure plasma, generated with RF frequency power at 13.56 MHz, was fed with hexauorobenzene (C6F6) as the deposition precursor and helium as the carrier gas. After deposition, the uorocarbon lms were analyzed for chemical characteristic, elemental composition, and surface morphology. The chemical structures and surface properties of the lms were evaluated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) analyses. By reason of the XPS and FTIR data, atmospheric pressure plasma deposited uorocarbon lms are similar to original aromatic ring in chemical structure. This investigation demonstrates that atmospheric pressure plasma jet affords good control over uorocarbon lm properties. 2010 Elsevier B.V. All rights reserved.

Article history: Received 12 January 2010 Received in revised form 7 July 2010 Available online 12 August 2010 Keywords: Deposition; Fluorocarbon lms; Atmospheric pressure plasma; Plasma polymerization; Hexauorobenzene; Plasma jet

1. Introduction Low-temperature plasma polymerization of uorocarbon thin lms has been of great interest because it can achieve low dielectric constant, excellent chemical stability, and hydrophobic properties [1]. Conventionally, uorocarbon lms are deposited by low-pressure plasma polymerization and these lms are widely used in ULSI processing [24]. In spite of the well-developed processes involved, the currently available low-pressure plasma polymerization techniques have several major limitations, such as the restricted volume of the plasma reactor and one or more vacuum and chemical cycles required. Atmospheric-pressure plasma technique is a promising alternative to conventional low-pressure plasma techniques [5,6]. The processing can be conducted in the absence of a chamber so that there is no limitation on the reactor volume or vacuum equipment. However, the use of atmospheric-pressure plasma for uorocarbon plasma polymerization has not been the mainstream of research, and very few studies have been published. Low pressure plasma polymerized aromatic lms attracted much attention due to their interesting chemical, physical, electrical, and mechanical properties [7]. The simplest aromatic monomer, benzene, has been studied in RF plasma polymerization of continuous wave mode, since the 1960s [8]. Low-pressure plasma polymerization of uorobenzenes has also been extensively investigated and well documented [9,10]. The low pressure pulsed plasma polymerization with the control of the variable duty cycle (DC) especially has a great

effect on the aromatic structure of plasma polymers [11,12]. The goal of this work is to investigate the use of atmospheric-pressure plasma jet system to retain aromatic ring functionality in the plasmadeposited lm. This is signicant for low dielectric constant and intermetal dielectric materials where thermal stability and low moisture absorption are desired [1]. In this paper, we report that uorocarbon lms with aromatic ring structure can be achieved by chamberless plasma polymerization, and its surface characteristics are discussed on the basis of FTIR, XPS, and SEM analyses. 2. Experimental procedure 2.1. Atmospheric-pressure plasma deposition system Fluorocarbon thin lms were deposited by an atmosphericpressure plasma jet system as shown in Fig. 1. This system contains a plasma jet and a movable table. In general atmospheric pressure plasma system, the contaminations are always deposited in a plasma jet. To deal with this problem, a double-pipe type quartz tube is used as the plasma jet system, through which various gases ow at controllable ow rates. A quartz capillary (0.5 mm diameter) is inserted into the quartz tube with a bigger inner diameter (15.5 mm diameter) to form double-pipe quartz tube. For this design, precursor and carrier gas do not interfere each other during atmospheric pressure plasma processing since the quartz capillary acts as a barrier. The high-speed gas ow rate helium (10,000 sccm) is introduced from the upside of the plasma system and passes through the quartz capillary as the ionization gas. Precursor is guided in the plasma system through the annular space between the quartz tube and the capillary and serves as a precursor. The precursor ow rate is kept by

Corresponding author. E-mail address: chunhuang@saturn.yzu.edu.tw (C. Huang). 0022-3093/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.jnoncrysol.2010.07.021

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Fig. 1. Schematic diagram of atmospheric-pressure plasma jet system.

Fig. 2. FTIR spectrum of atmospheric-pressure plasma deposited uorocarbon thin lm. Plasma condition: RF power input of 100 W, helium gas ow rate of 10,000 sccm, and treatment time of 300 s.

the carrier gas (He) at 300 sccm by a mass ow controller. Two copper annular electrodes are placed face to face inside the quartz tube. An electrical eld is applied to the two electrodes located inside the quartz tube to ignite the plasma glow discharge by a 13.56 MHz RF power supply. A capacitive coupled RF plasma source power is in continuous mode (DRESSLER CESAR 1310, Advanced Energy). Hexauorobenzene (C6F6) precursor was introduced into a mixing system (evaporator) and the temperature was maintained at 150 C. Static deposition was carried out with the atmospheric pressure plasma jet pointing perpendicular to the substrate at a deposition rate of 75 nm/min. The surface remains at room temperature. The typical deposition times of 20 min were required to ensure a lm thickness sufcient for the uniform lm analysis. For this reason, the atmospheric pressure plasma jet was scanned along the x direction while the substrate was moved along the y direction to make a large and uniform lm (40 40 mm) at a scan speed of 2.5 mm/s. 2.2. Film characterization and analysis The thickness of the atmospheric-pressure plasma-deposited uorocarbon thin lms was measured using the optical thin-lm thickness detector at a wavelength of 632.8 nm. The chemical structure of the atmospheric-pressure plasma deposited uorocarbon thin lms was characterized using the Fourier transform infrared (FTIR) spectrometer (Perkin-Elmer LX 20000G). Each spectrum was obtained from an average of 64 scans in the range of 4004000 cm 1 at a resolution of 4 cm 1. The chemical composition of atmospheric-pressure plasma-deposited uorocarbon thin lms was investigated using an X-ray photoelectron spectroscopy (XPS) with the Mg K source (1253.6 eV). The surface morphology of the atmospheric-pressure plasma-deposited uorinated carbon thin lms was observed by scanning electron microscopy (SEM) with a JEOL model JSM-5600 apparatus. A tungsten lament was used as the electron source. A 15-KV accelerator voltage was used for scanning the atmospheric-pressure plasma-deposited uorocarbon thin lm surfaces. 3. Results Fig. 2 shows the FTIR spectrum of an atmospheric-pressure plasma deposited uorocarbon thin lm. It is different from the conventional FTIR spectra corresponding to the plasma-deposited amorphous a-C: F structure [13]. The difference of FTIR spectra between PECVD a-C:F and atmospheric pressure plasma-deposited uorocarbon lms is the thin lm with the original molecular shape from the precursor/ monomer. Under continuous mode PECVD, PECVD a-C:F lm cannot

obtain the original molecular shape of the precursor/monomer. This resulted in the precursor/monomer structure fully broken by continuous electrical energy from low pressure PECVD. From our experimental results, we succeed to form the uorocarbon thin lms with the original molecular shape of the precursor/monomer from capacitive coupled RF atmospheric pressure plasma jet in continuous mode. The characteristic absorption peaks can be clearly seen in Fig. 2, with the strong peak at 1220 cm 1 corresponding to the CF, CF2 and CFx groups, and the wide peak at approximately 1700 cm 1 corresponding to the unsaturated double bonds associated with C O, C C, C CF2 and CF CF2. The aromatic C C stretching mode is normally observed at 1600 cm 1 in organic compounds [4]. Moreover, the CF stretching absorption of F2C CF or F2C C bonds appeared around 1220 cm 1 [14]. The chemical composition of atmospheric-pressure plasma-deposited uorocarbon thin lms at core level and circular edge was investigated by X-ray photoelectron spectroscopy (XPS). The core level and circular edge would be dened as the positions of atmospheric-pressure plasma polymerization area of thin lms. Table 1 represents the atomic percentages of the uorine; carbon, oxygen, and nitrogen present in the atmospheric-pressure plasmadeposited uorocarbon thin lms at the core level and circular edge. As can be seen, the lms comprise 4.25 to 25.6 at.% uorine, 70.46 to 57.45 at.% carbon, 24.59 to 15.92 at.% oxygen and 0.7 to 1.03 at.% nitrogen, at core level and circular edge. Fig. 3 and Table 1 show the XPS survey spectrum and the elemental composition of the deposited lm, respectively. It was also found that small amounts of N and O were detected in lms deposited by atmospheric pressure plasma polymerization process, implying that the nitrogen and oxygen from

Table 1 Chemical composition of atmospheric-pressure plasma deposited uorocarbon thin lm. O% Core level Circular edge 24.6 15.9 N% 0.7 1.0 F% 4.2 25.6 C% 70.5 57.5 F/C ratio 0.06 0.45

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aromatic ring structure of the C6F6 precursor and the lm in circular edge has the highest retaining degree. Scanning electron microscopy (SEM) offers a directly forward method for identifying the surface morphology of atmosphericpressure plasma-deposited uorocarbon thin lms. Fig. 5 shows the scanning electron microscopy (SEM) images of atmospheric-pressure plasma-deposited uorocarbon thin lms. Fluorocarbon thin lms deposited by atmospheric-pressure plasma jet (see Fig. 5a), top-view

Fig. 3. XPS survey spectrum of atmospheric-pressure plasma deposited uorocarbon thin lm. Plasma condition: RF power input of 100 W, helium gas ow rate of 10,000 sccm, and treatment time of 300 s.

ambient air was reacted and dissociated with atmospheric pressure plasma and/or C, H, and F species in the plasma region. That is consistent with the fact that we observed CO and OH peaks of FTIR spectra (see Fig. 2). C1s XPS-spectra in the energy range of 280300 eV of atmospheric-pressure plasma-deposited uorocarbon thin lms were measured and evaluated as shown in Fig. 4. These spectra revealed the contribution of CCH (284.6 eV), CCFx (287.3 eV), CF (289.5 eV), CF2 (291.9 eV), and CF3 (294 eV) groups to the lms [2,4]. All atmospheric-pressure plasma-deposited uorocarbon thin lms at core level and circular edge show similar XPS spectra. In particular, the spectra showed that the content of CF groups is higher at circular edge. This implies that, the chemically reactive species in the atmospheric-pressure plasma polymerization jet are mainly created by the dissociation of gas molecules, which obtained less electrical energy [6] to cause minor decomposition of gas molecules at circular edge. The observation of XPS analysis is well consistent with the indication of aromatic ring structures, which are composed of CF and CCFx. Inclusion of CF and CCFx may be due to the fragmentation of hexauorobenzene (C6F6) precursor into small radicals, and their contribution to lm deposition. This result shows that only the lms deposited in this plasma polymerization process can preserve the

Fig. 5. SEM images of atmospheric-pressure plasma deposited uorocarbon thin lm at the center point. (a) Top-view; (b) cross-section. Plasma condition: RF power input of 100 W, helium gas ow rate of 10,000 sccm, and treatment time of 300 s.

Fig. 4. C1s region of XPS spectra of atmospheric pressure plasma deposited uorocarbon thin lms at center point and edge point. Plasma condition: RF power input of 100 W, helium gas ow rate of 10,000 sccm, and treatment time of 300 s.

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of thin lm) show continuous and smooth surface morphology. Moreover, the uorocarbon lms are dense (see Fig. 5b, cross-section of thin lm). These results indicated that the atmospheric-pressure plasma jet system did not much ion bombardment damage with plasma polymerization process. It also supports the implication that the dissociation precedes the ionization in this atmospheric-pressure plasma polymerization. 4. Discussion As seen in FTIR spectrum, the clear carbon ring peaks reveal that aromatic ring structures are incorporated in the atmospheric-pressure plasma-deposited uorocarbon thin lms with the original molecular shape of the C6F6 precursor. This observation indicates that the ionization in the atmospheric-pressure plasma jet does not achieve full fragmentation of the monomers. This further implies that, the chemically reactive species in this atmospheric-pressure plasma jet are not mainly created by the ionization, which should result in strong ion bombardments that can fully break monomers, but also the dissociation of gas molecules with low energy electrons. The dissociation plays an important role in atmospheric-pressure plasma polymerization, especially in the decomposition of monomer/precursor. Recent investigations on plasma polymerization of DC trimethylsilane glow discharge indicate that the glow characteristic of DC trimethylsilane plasma is entirely different from that of DC argon plasma [1517]. The existence of cathode glow in plasma polymerization system indicates that the major chemical reactions occur at the cathode surface, but not in the negative glow. It implies that, in plasma polymerization, the chemically reactive species are created by the low energy dissociation near cathode surface rather than by the ionization of gas molecules, which should occur at the fringe of the negative glow [6,15]. This nding of dissociation glow also infers that the dissociation could proceed prior to the ionization in plasma polymerization system. According to XPS analysis, it also indicates that the dissociation seems to play a key role in the deposition of the atmospheric-pressure plasma polymerization jet system. The increasing atomic presence of uorine in the lm expresses as incomplete decomposition of the hexauorobenzene (C6F6) precursor because of low-energy dissociation. Table 1 shows the photo-image of uorocarbon thin lms deposited by the atmospheric-pressure plasma polymerization jet. As can be seen, the presence of small vortices inside results in symmetric deposition proles. For double-pipe atmospheric-pressure plasma jet design, precursor and carrier gas do not interfere with the atmospheric-pressure plasma polymerization since the quartz capillary acts as a barrier. With proper operational parameters, the deposited uorocarbon thin lms are symmetrical and the deposition process is stable. From XPS analysis in Table 1, the increasing atomic presence of uorine at circular edge of atmospheric-pressure plasma

polymerization area indicates that the composition of the circular edge of atmospheric-pressure plasma deposited uorocarbon thin lm was the same as that of the precursor because the precursor deposited on the surface with little dissociation or the C6F6 molecule was dissociated to a small molecule and polymerized. 5. Conclusion In conclusion, an atmospheric-pressure plasma jet formed using a power supply of 13.56 MHz was employed to deposit uorocarbon thin lms. The FTIR, XPS, and SEM results shown here reveal that signicant lm characteristics occur during atmospheric-pressure plasma polymerization. FTIR spectra of the lms have indicated that the atmospheric-pressure plasma deposited uorocarbon lms contain aromatic ring structures. The low-energy dissociation in the plasma state is the major cause for deposition of uorinated carbon thin lms with the original molecular shape of the C6F6 monomer. The use of atmospheric-pressure plasma jet for the uorocarbon lm deposition has shown to be capable of controlling lm composition. This atmospheric-pressure plasma polymerization method opened a new way for fast and efcient deposition of aromatic uorinated carbon thin lms. Acknowledgments The authors are thankful for the support of the National Science Council under grant NSC 99-2221-E-155-077 and NSC 99-2632-E155-001-MY3 and the technical support of Mechanical and Systems Research Laboratories, Industrial Technology Research Institute, Taiwan. References
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