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Stable glow plasma at atmospheric pressure

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 1988 J. Phys. D: Appl. Phys. 21 838 (http://iopscience.iop.org/0022-3727/21/5/028) View the table of contents for this issue, or go to the journal homepage for more

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J. Phys. D: Appl. Phys. 21 (1988) 836-840. Printed in the UK

S Kanazawa, M Kogoma, T Moriwaki and S Okazaki

Faculty of Science and Technology, Sophia University, Kioi-cho 7-1, Chiyoda-ku, Tokyo 102, Japan Received 23 February 1988

Abstract. A stable glow plasma at atmospheric pressure has been achieved for plasma treatment under selected conditions, for example the structure of electrodes, the kind of dilute gas, and the frequency of power. The surface fluorination of PET film and carbon thin-film deposition by such a plasma is described here. The surface energy can be controlled by plasma treatment of various concentrations (O,/CF,/He) in the same way as the lower pressure method that has been reported by Kogoma and co-workers. Active species in plasma are identified by emission spectroscopy.

Thin-film deposition (of, e.g., amorphous carbonfilms) and surface modification (e.g. wettability controls) by plasma processes are employed for manypractical purposes. Most of these processes occur at low pressures (a few torr) except for the process employing corona discharge (Rouzbehi et a f 1985). If the same process can be carried out at atmospheric pressure, that method would be much more advantageous from the viewpoint of the cost of apparatus and the construction of large-scale a system. However, discharge a at atmospheric pressure tends to translate to thermal plasma (cf anarcdischarge). So it is importantto achieve a stable and continual glow discharge for plasma processes at atmospheric pressure (Kanazawa et af 1987). InthisLetter we shall reportthe necessaryconditionsandthestructure of the apparatus needed to establishaplasmaprocess with a glow dischargeat atmospheric pressure. The results of the surface fluorination of PET (polyethylene terephthalate) film and the deposition of carbon thin film by that process are reportedandcompared with the results obtained by the lower pressure plasmas. The two kinds of plasma, at atmospheric pressure and at lower pressure, are analysed and compared by emission spectroscopy. A glow discharge was created in a Pyrex glass reactor (see figure 1) at atmospheric pressure. The lower electrode was heated and its temperature was measured by a thermocouple. The requirements for a stable glow discharge are as follows. (i) Helium is used as dilute gas. (ii) It is most important that an insulating plate be set on the lower electrode plate (figure 1). The kind of insulator
0022-37271881050838

materialmustbeselected by consideringheat resistance : kapton for 3000 Hz and mica or quartz glass for RF (13.56 MHz). (iii) The brush-style electrode is better for the upper electrode. It consists of 25 fine wires of stainless or tungsten metal. (iv) The continuous stable discharge is created by using 3000 Hzor RF. When using 50 Hz, the discharge was not stable. The surface
HV

Gas

Heater

Figure 1. The experimental apparatus.

+ 03 $02.50 @ 1988 IOP Publishing Ltd

Letter to the Editor

100

3
T r e a t m etnl m ti m e lnl

Figure 2. The relationship of plasma treatment time with contact angle. Curves: A, the atmospheric pressure method, He 1950 ml min-l, CF, 56.4 ml min-l, 3000 Hz, 16 W; B, the lower pressure method, CF, 5Torr, RF 50 W; C, as curve A but also washed by Daiflon solvent.

O,/(O,

CF'I

fluorination of PET was carried out by only 3000 Hz glow because RF glow plasma created a high temperature, which the PET could not resist, on the electrode surface. A carbon thin film was obtained from plasma deposition by RF power, which could provide sufficient energy. A glow discharge sustained in CF4 O 2 He can keep its stability for long a time. When using C H 4 H2 He,a black product (graphite) was deposited at the endof the wire of the upper electrode, so when a discharge was continued for a long time, it gradually lost stability. Figure 2 shows the contact angle as a function of treatment time for the surface fluorination of PET films by He + CF4. The frequency of power was 3000 Hz and the source gas was CF4(2.65%).CurveA was obtained by surfacefluorination by theatmospheric pressure method and curve B was obtained when PET was treated by thelowerpressuremethod.CurveC indicates the valueof the contact angle after the surface

Figure 3. The surface treatment by various concentrations of CF, O2 He. Curves: A, the atmospheric pressure method, He 4900 ml min", CF, 68 ml min", O2 0-68 ml min", 3000 Hz, 23 W, 5 min; B, the lower pressure method, total gas pressure 3 Torr, RF 50 W, 5 min.

was washed by Daiflonsolvent(C2C13F3) to remove any oligomers. By the atmospheric pressure method, a higherequilibriumvalue was achievedforashorter time of treatment than by the lower pressure method. Afterwashing,thecontact anglebecamesomewhat smaller, but the surface fluorination was confirmed by comparisonwiththecontact angle of theuntreated surface. The surface modification of PET film by He CF, + O 2 was carried out as follows. The PET surface was treated in plasma with various concentrations of O 2 with CF4. The contactanglecould be varied by the 0 2 / ( 0 2 CF4) ratio (Kogoma et a1 1987), as is demonstrated in figure 3. Amonotonic decrease of the contact angle occurs on increasing the 02/(0 +2 CF4) ratio by either method. However, the

Table l . Carbon film deposition in He-CH,-H2. Total gas flow rate: 4600-4900 ml mit"', power: 200 W, treatment time: 30 min.
CH,IHe 0.037 H2ICHI 1.26 0.79 0.41 1.65 1.04 """_ 0.54 0.19 1.45 0.75 0.27 0.41 0.25 Thickness (,urn) cannot measure 0.17 0.17 0.07 0.19 0.67 _ ~ ~ "_ " " ~ _ ~ ~ _ 0.35 cannot measure cannot measure cannot measure Properties of film State of discharge

"

0.021 0.014

cannot measure

non-uniform transform to arc black, uniform dark blue, unstable black, soft dark blue, stable non-uniform transform to arc ~""~""""""~"~"------"black, uniform dark blue, stable , black, uniform dark blue, stable - - - - - " " " " _ ~ ~ ~ " ~ ~ ~ " ~ dark blue, stable black,soft non-uniform transform to arc black transform to arc black dark blue, stable light blue no products black dark blue
~

~ " ~ ~ " ~

839

Letter to the Editor

He

Ha

h c

1 0

c
W c

LOO0

5000

6000

7000

Wavelength ( % l

Figure 4. The emission spectrum obtained by the atmospheric pressure method. He 4500 ml min, CH, 130 m1 min, H2 70 m 1 min, RF 200 W.
1 1

lower pressure method acquires a higher 02/02CF4 ratio for the same value of the contact angle than the atmospheric pressure method. The aging effect at a treated surface was observed. We will report on the details of this in a future paper. Carbon thin films were prepared on the Pyrex or quartz glass substrates by decomposition of CH4 H z He in the glow discharge by the atmospheric pressure method. Variousmixing ratios of CH,/He or H2/CF4 are shown in table 1. A carbon film with betterproperties was preparedat mixing ratios bound by the broken line in table 1. The carbon films with better properties were deposited at about400 C. The carbon films which were deposited at 300 C tended to be soft and non-uniform. At 500-600 C,depositedproductswere black and were composed of small particles. The emission spectra during carbon film deposition, in the wavelength region 4000-7000 A, are shown in figures 4 and 5. The analysis of the emissionspectra hasshown the presence of emissionlinesandbands originating from electronic excited states of H , C 2and CH.Thesame kinds of species were identified in

LOO0

5000

6000

7000

Wavelength 1 % )

Figure 5. The emission spectrum obtained by the lower pressure method. CH4 0.04 Torr, H2 0.06 Torr; RF 100 W.

plasma by both methods. By comparing the intensity of the C2 band head with that of the CHband head, we find that the C2 band head obtained by the atmospheric pressuremethod was strong,butthat by the lower pressure method was relatively weak. The authors wish to thank The Murata Science Foundation for partial financial support for this work.
References

Kanazawa S, Kogoma M, Moriwaki T and Okazaki S 1987 Proc. ISPC-8 3 1839 Kogoma M, Kasai H, Takahashi K, Moriwaki T and Okazaki S 1987 J . Phys. D:Appl. Phys. 20 147 Rouzbehi F, Arefi F, Catoire B. Goldman M and Amouroux J 1985 Proc. ISPC-7 2 485

840