JP2004335791A - Processing method of fluorine added carbon film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reduce the leak current of a fluorine added carbon film. <P>SOLUTION: The method for processing a fluorine added carbon film formed on a substrate to be processed comprises a step for dissociating hydrogen gas to form hydrogen radicals, and a step for exposing the fluorine added carbon film to hydrogen radicals. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for treating an insulating film, and more particularly, to a method for treating a fluorine-added carbon film.
[0002]
[Prior art]
2. Description of the Related Art In recent years, with an increase in the performance of a semiconductor device, an attempt has been made to increase the operation speed of the semiconductor device by reducing the stray capacitance between wirings of the semiconductor device. In order to reduce the stray capacitance between wirings, for example, a method of using a material having a low dielectric constant for an interlayer insulating film formed between wirings of a semiconductor device has been adopted.
[0003]
Although a silicon oxide film (SiO ₂ film) having a relative dielectric constant of about 4 has been used as the interlayer insulating film, in recent years, a fluorine-added silicon oxide film having a relative dielectric constant of about 3 to 3.5 ( The use of a (SiOF film) has increased the speed of a semiconductor device.
[0004]
However, the above-mentioned SiOF film has a limitation in lowering the relative dielectric constant, and it has been difficult to achieve a relative dielectric constant of 3 or less.
[0005]
Although there are various candidate materials for a so-called low dielectric constant interlayer insulating film having a low relative dielectric constant, it is a necessary condition that the relative dielectric constant is low and the mechanical strength is high enough to be used in a semiconductor device. Therefore, attention has been paid to a fluorine-added carbon film (CF film) having a sufficient mechanical strength and a relative dielectric constant of about 2.5 or less. Attempts have been made to use it as a film in semiconductor devices.
[0006]
[Patent Document 1]
JP-A-11-162962
[Problems to be solved by the invention]
However, when the above-mentioned fluorine-containing carbon film is used as an interlayer insulating film of a semiconductor device, there is a problem that a leak current is large. When the leakage current of the interlayer insulating film is large, it causes a malfunction of a circuit when a semiconductor device is formed.
[0008]
Therefore, a method of reducing the leak current by performing a heat treatment on the formed fluorine-added carbon film has been attempted. For example, a method of reducing the leak current of the fluorinated carbon film by performing a heat treatment in a processing gas has been used in some cases.
[0009]
However, in the case of performing the above-described heat treatment, the effect of reducing the leak current is more remarkable as the temperature is higher, and in order to obtain a sufficient effect, it is necessary to set the fluorine-added carbon film to a high temperature of, for example, about 350 to 400 ° C. was there.
[0010]
However, when the above-described heat treatment is performed, there is a problem that the fluorine-added carbon film is decomposed by heat and the properties of the film are changed. For example, when a fluorine-added carbon film is heated to about 350 ° C. or more, F in the film is desorbed, the relative dielectric constant is increased, and the merit of using a material having a low dielectric constant is reduced. Was.
[0011]
Therefore, an object of the present invention is to provide a method for treating a fluorine-added carbon film that has solved the above-mentioned problems.
[0012]
A specific object of the present invention is to provide a substrate processing method for reducing a leakage current of a fluorinated carbon film without damaging the fluorinated carbon film by heating.
[0013]
[Means for Solving the Problems]
In the present invention, in order to solve the above problems,
As described in claim 1,
A method for treating a fluorine-containing carbon film formed on a substrate to be processed,
Dissociating hydrogen gas to form hydrogen radicals;
Exposing the fluoridated carbon film to the hydrogen radicals.
As described in claim 2,
The method according to claim 1, wherein the hydrogen radical is formed by plasma-exciting a plasma gas containing the hydrogen gas.
As described in claim 3,
The method according to claim 2, wherein the plasma gas includes a He gas.
As described in claim 4,
The plasma excitation is a microwave plasma excitation performed by a substrate processing apparatus, the substrate processing apparatus has a microwave antenna for introducing a microwave, the microwave antenna is fed by a coaxial waveguide, and an opening is provided. An antenna main body, a microwave radiating surface having a plurality of slots provided on the antenna main body so as to cover the opening, and a dielectric material provided between the antenna main body and the microwave radiating surface. The method for treating a fluoridated carbon film according to claim 2 or 3, further comprising:
As described in claim 5,
The substrate processing apparatus includes:
A processing container defined by an outer wall and including a holding table that holds the substrate to be processed;
An exhaust port for exhausting the processing container,
On the processing container, a microwave transmission window provided as a part of the outer wall so as to face the substrate to be processed,
The microwave antenna provided on the microwave transmission window, a microwave power supply is electrically connected,
A plasma gas supply unit that supplies the plasma gas into the processing container,
The fluorine-containing carbon according to claim 4, comprising a charged particle removing structure provided between the substrate to be processed and the microwave transmitting window on the holding table so as to face the substrate to be processed. Depending on the processing method of the membrane,
As described in claim 6,
The method according to claim 5, wherein the charged particle removing structure is made of a conductive material and is grounded.
As described in claim 7,
The method for treating a fluoridated carbon film according to claim 5 or 6, wherein the charged particle removing structure has a plurality of openings through which the hydrogen radicals pass and a collision portion that collides the charged particles. ,
As described in claim 8,
The fluorine-added device according to any one of claims 5 to 7, wherein the plasma gas supply unit is inserted between the processing container and the microwave transmission window to form a part of the outer wall. Depending on the processing method of the carbon film,
As described in claim 9,
The method according to claim 8, wherein the plasma gas supply unit is configured to supply the plasma gas between the microwave transmission window and the charged particle removal structure. Also,
As described in claim 10,
The microwave plasma excitation is substantially generated in a space formed between the microwave transmission window and the charged particle removing structure in the processing container. The problem is solved by the method for forming a fluorine-added carbon film according to item 1.
[Action]
According to the present invention, by exposing the fluorinated carbon film to hydrogen radicals, it is possible to reduce the leak current of the fluorinated carbon film without performing heat treatment. Therefore, it is possible to form a fluorinated carbon film excellent in film quality with low leakage current without causing deterioration of the fluorinated carbon film due to heat.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
[principle]
First, the principle of reducing the leakage current of a fluorinated carbon film by the method for treating a fluorinated carbon film according to the present invention will be described with reference to FIGS. 1 (A) and 1 (B).
[0015]
The fluorine-added carbon film is formed, for example, by dissociating a fluorocarbon-based gas containing carbon and fluorine and hydrogen or a hydrocarbon-based gas containing hydrogen with plasma.
[0016]
As shown in FIG. 1A, the formed fluorine-added carbon film typically has a CF bond, a CC bond, a CH bond, and the like, and has an unreacted bond. D1 exists. It is considered that the leak current of the fluorine-added carbon film mainly flows through the unreacted bond D1. That is, it is considered that the presence of the unreacted bond D1 in the film increases the leak current of the fluorinated carbon film.
[0017]
Therefore, in the present invention, as shown in FIG. 1 (B), the unreacted bond D1 is terminated with hydrogen to form a bond D2 which is a CH bond, and a path through which a current in the fluoridated carbon film easily flows. Is performed to reduce the leak current by reducing the unreacted bonds.
[0018]
Further, when a reaction terminating with hydrogen is caused to form the bond D2, the reactivity with the unreacted bond D1 is increased by using a hydrogen radical. For example, when an unreacted bond is also to be terminated with hydrogen using hydrogen gas, it is necessary to heat the fluorine-added carbon film to about 350 to 400 ° C.
[0019]
In that case, since the fluorine-added carbon film is weak to heat, it is known that the film starts to decompose at 350 ° C. to 400, for example, F is desorbed. Therefore, there is a problem that the relative dielectric constant of the fluorine-added carbon film increases.
[0020]
In the present invention, since a highly reactive hydrogen radical is used, it is not necessary to heat the fluorinated carbon film, and therefore, without affecting the fluorinated carbon film by heating, while maintaining the relative dielectric constant. By terminating unreacted bonds with hydrogen, it becomes possible to form a fluorine-added carbon film having a small leak current.
[0021]
Next, a substrate processing apparatus that performs the above-described processing will be described below.
[First embodiment]
FIGS. 2A and 2B show a configuration of a plasma processing apparatus 10 according to a first embodiment for performing a substrate processing method according to the present invention.
[0022]
Referring to FIG. 2 (A), the plasma processing apparatus 10 is provided with a processing container 11 and is preferably provided in the processing container 11 and holding a substrate 12 to be processed by an electrostatic chuck, preferably a hot isostatic pressing method. (HIP) and a holding table 13 made of AlN or Al ₂ O ₃ .
[0023]
The inside of the processing vessel 11 is roughly divided into a space 11B on the side close to the holding table 13 and a space 11A opposed to the space 11B with the charged particle removal structure 24 therebetween by a charged particle removal structure 24 described later. .
[0024]
The spaces 11 </ b> A and 11 </ b> B forming the inside of the processing container 11 are arranged at equal intervals so as to surround the holding table 13, that is, at least two places in a substantially axially symmetric relationship with the substrate 12 to be processed on the holding table 13. Preferably, the air is evacuated and decompressed by exhaust means such as a vacuum pump through exhaust ports 11D formed at three or more locations.
[0025]
The processing vessel 11 is preferably made of an Al alloy, and a microwave transmission window 17 for transmitting microwaves is installed in a portion of an outer wall of the processing vessel 11 corresponding to the substrate 12 to be processed. A plasma gas introduction ring 14 for introducing a plasma gas is inserted between the window 17 and the processing container 11 to define an outer wall of the processing container 11, respectively.
[0026]
The microwave transmitting window 17 has a stepped shape at the peripheral edge thereof, and the stepped portion engages with the stepped shape provided on the plasma gas introduction ring 14, and further, the inside of the processing space 11 is sealed by a seal ring 16 </ b> A. The airtight structure is maintained.
[0027]
A plasma gas is introduced into the plasma gas introduction ring from the plasma gas introduction port 14A, and diffuses in the substantially annular gas groove 14B. The plasma gas in the gas groove 14B is supplied to the space 11A from a plurality of plasma gas holes 14C communicating with the gas groove 14B.
[0028]
On the microwave transmitting window 17, a disk-shaped slot plate 18 closely contacting the microwave transmitting window 17 and having a number of slots 18a and 18b shown in FIG. A disk-shaped antenna body 22 and a retardation plate 19 made of a low-loss dielectric material of Al ₂ O ₃ , SiO ₂ or Si ₃ N ₄ sandwiched between the slot plate 18 and the antenna body 22. Is provided.
[0029]
The radial slot line antenna 30 is mounted on the processing chamber 11 via the plasma gas introducing ring 14, and the radial line slot antenna 30 is connected to an external microwave source (not shown) via a coaxial waveguide 21. ), A microwave having a frequency of 2.45 GHz is supplied.
[0030]
The supplied microwave is radiated from the slots 18a and 18b on the slot plate 18 into the processing vessel 11 through the microwave transmission window 17, and is supplied to the plasma gas in a space 11A immediately below the microwave transmission window 17. The plasma is excited in the plasma gas supplied from the supply hole 15A.
[0031]
Of the coaxial waveguide 21A, the outer waveguide 21A is connected to the disk-shaped antenna main body 22, and the center conductor 21B is connected to the slot plate 18 through an opening formed in the slow wave plate 19. It is connected to the. Then, the microwave supplied to the coaxial waveguide 21A is radiated from the slots 18a and 18b while traveling in the radial direction between the antenna main body 22 and the slot plate 18.
[0032]
FIG. 2B shows slots 18a and 18b formed on the slot plate 18. As shown in FIG.
[0033]
In the plasma processing apparatus 10 of FIG. 2A, for example, a substantially disk-shaped conductor is provided between the microwave transmission window 17 and the substrate 12 to be processed on the holding table 13 in the processing chamber 11. A charged particle removing structure 24 is provided.
[0034]
The charged particle removing structure 24 is fixed to a side wall of the processing container 11 by welding or screwing, is electrically connected to the processing container 11, and is grounded via the grounded processing container 11. The structure is
[0035]
The charged particle removing structure 24 has a plurality of gas passage holes 24A communicating from the space 11A to the space 11B. Radicals generated by plasma excitation in the space 11A pass through the gas passage holes 24 and are supplied to the space 11B to perform substrate processing. Next, details of the charged particle removing structure 24 will be described.
[0036]
FIG. 3 is a plan view showing the configuration of the charged particle removing structure 24 of FIG.
[0037]
Referring to FIG. 3, the charged particle removing structure 24 is formed of a substantially disk-shaped conductor such as an Al alloy, and has a plurality of substantially cylindrical gas passage holes 24A penetrating from the front surface to the back surface. ing.
[0038]
When the processing gas supply structure 24 is formed of a Mg-containing Al alloy, it is preferable to form a fluoride film or aluminum oxide on the surface. When the processing gas supply structure 24 is made of Al-added stainless steel, it is desirable to form a passivation film of aluminum oxide on the surface.
[0039]
Due to the presence of the charged particle structure 24, the processing target substrate 12 held in the space 11B is not directly exposed to the microwave plasma excited in the space 11A. In addition, ions and electrons in the plasma generated by exciting the microwave plasma in the space 11A are incident on the wall surface of the gas passage hole 24A or the structure main body 24B and are recombined. It cannot pass through the hole 24A. On the other hand, similarly, radicals generated by the plasma in the space 11A are more likely to pass through the gas passage holes 24A than ions.
[0040]
That is, by providing the charged particle removing structure, the active species that reach the space 11B out of the ions and radicals formed in the space 11A are dominated by radicals.
[0041]
In the method for treating a fluorinated carbon film according to the present invention, as described above with reference to FIG. 1, a treatment for terminating unreacted bonds in the fluorinated carbon film with hydrogen mainly using hydrogen radicals is performed. At that time, if ions having a large energy that collide with the fluorinated carbon film are present, the fluorinated carbon film may be damaged.
[0042]
Therefore, by providing the charged particle removing structure 24 as described above, ions in the plasma gas excited by plasma are removed, and hydrogen radicals necessary for substrate processing are selectively supplied to the surface of the substrate to be processed. Is possible.
[0043]
In the substrate processing method of the present invention, the substrate processing is performed by using a gas obtained by adding a hydrogen gas to a He gas as a plasma gas and exciting the plasma gas with a microwave plasma.
[0044]
For example, a plasma gas is formed by adding about 0.1 to 20% (preferably 1 to 5%) of hydrogen gas to He gas, and the plasma gas is supplied from the plasma gas supply ring 14 to the processing space 11A. Supply. Therefore, a microwave is introduced into the processing vessel 11 from the radial line slot antenna 30 through the microwave transmission window 17 to excite microwave plasma in the space 11A.
[0045]
The microwave plasma excited at that time generates a metastable He atom having a long life, and the collision with the hydrogen molecule dissociates the hydrogen molecule to generate a hydrogen radical. In addition, He ⁺ ions, H ₂ ⁺ ions, and the like are also generated by ionization.
[0046]
However, as described above, since the charged particles are strongly removed by the charged particle removing structure 24 and the ions having strong linearity are selectively removed, the substrate 12 on which the fluorine-doped carbon film is mainly formed is formed. And the substrate treatment that eliminates the damage of the fluorine-added carbon film due to the ions can be performed.
[0047]
Next, a specific substrate processing method will be described.
[Second embodiment]
FIG. 4 is a flowchart illustrating an example of the substrate processing method according to the present invention using the plasma processing apparatus 10.
[0048]
Referring to FIG. 4, first, in step 1 (denoted as S1 in the figure, the same applies hereinafter), the substrate 12 on which the fluorine-added carbon film is formed is placed on the holding table 13 and substrate processing is started. Then, in step 2, a plasma gas is introduced from the plasma gas supply ring 14 into the space 11A.
[0049]
At this time, as described above, a plasma gas obtained by adding 5% of hydrogen gas to He gas is used.
[0050]
Next, in Step 3, the microwave supplied from the coaxial space 21 is introduced into the space 11A from the radial line slot antenna 30 through the microwave transmission window 17, and microwave plasma is excited.
[0051]
Next, in step 4, as described above, the treatment of the fluorinated carbon film mainly with hydrogen radicals is performed. At that time, as described above, unreacted bonds existing in the fluorine-added carbon film are terminated by hydrogen. As a result, the number of unreacted bonds, that is, the paths through which the current easily flows can be reduced, and the leak current of the fluorinated carbon film after the substrate processing can be suppressed low.
[0052]
In addition, since hydrogen radicals having higher reactivity than hydrogen gas are used as described above, substrate processing can be performed at a low temperature, for example, 200 ° C. or less, and the fluorine-added carbon film is damaged by heating. The substrate processing can be performed without the need.
[0053]
Next, the introduction of the microwave is stopped in step 5, the supply of the plasma gas is stopped in step 6, and the substrate processing is completed in step 7.
[0054]
In the substrate processing method shown in the present embodiment, typically, under the conditions of a He flow rate of 300 sccm, a hydrogen flow rate of 15 sccm, a microwave frequency of 2.45 GHz, a microwave power of 900 W, a substrate temperature of 30 ° C., and a processing container pressure of 30 Pa, By performing the process of step 4 for 3 minutes, it is possible to obtain the effect of reducing the leak current of the fluorinated carbon film as described above.
[0055]
Further, in this embodiment, a plasma gas obtained by adding 5% of hydrogen gas to He gas is used, but this makes it easier to excite plasma as compared with a case where only hydrogen gas is used as plasma gas. In addition, there are the following reasons.
[Third embodiment]
In the plasma excitation, He plasma is excited to form He in a metastable state, and further, He atoms and hydrogen molecules collide in the gas phase to dissociate the hydrogen molecules by the energy of He atoms to form hydrogen radicals. are doing. At this time, the energy level of He atoms in the metastable state described above shows a high value of 20 eV, which is suitable for dissociating hydrogen molecules.
[0056]
FIG. 5 compares the energy levels of He and rare gases other than He, Ne, Ar, Kr, and Xe, in a metastable state. Referring to FIG. 5, it can be seen that He having a small atomic weight has an energy level of 20 eV, which is higher than that of a rare gas having a large atomic weight as compared with He.
[0057]
As described above, by mixing He having a high energy level in a metastable state with hydrogen and using it as a plasma gas, hydrogen molecules can be efficiently dissociated to form hydrogen radicals.
[0058]
Also, when He having a small atomic weight is used, the electron temperature becomes high and the ion energy becomes large, and there is a concern that the ion-implantation may damage the fluorine-added carbon film. However, as described above, the charged particle removing structure 24 is used. The removal of the ions prevents damage to the fluorine-added carbon film by the ions.
[Fourth embodiment]
Next, changes in the leak current of the fluorinated carbon film before and after the substrate processing when the substrate processing method is performed under the conditions described in the second embodiment will be described. FIG. 6 shows the leakage current with respect to the electric field strength of the fluorine-added carbon film formed on the silicon substrate. The figure shows both the results before the substrate processing according to the present invention and the results after the substrate processing according to the present invention.
[0059]
Referring to FIG. 6, first, the leakage current of the fluorinated carbon film before the substrate treatment according to the present invention shown in Experiment B in the figure is, for example, 2.4 × 10 ⁻ when an electric field of 1 MV / cm is applied. ^In Experiment A, which is a leakage current of the fluoridated carbon film subjected to the substrate treatment described above in the second embodiment according to the present invention, whereas the current is ⁸ A / cm ² , for example, the electric field is 1 MV / cm. shows 9 a / cm ² and low ^- 8 × ^10.
[0060]
This is because the substrate processing according to the present invention is performed, and as described above, the unbonded reactants in the film are terminated by hydrogen, and the number of paths through which current easily flows is reduced, so that the leak current value is suppressed to be low. It is thought that it is.
[0061]
Further, the relative dielectric constant of the fluorine-added carbon film does not change before and after the substrate processing, and the relative dielectric constant is maintained. This is because, as described above, since the substrate is processed at a low temperature of 200 ° C. or less at the time of substrate processing, it is possible to perform a process of reducing the leak current of the fluorinated carbon film without damaging the fluorinated carbon film by heat. It shows that it becomes.
[Fifth embodiment]
As described above, in the plasma processing apparatus 10 according to the present invention, by using the charged particle removing structure 24, ions are removed and the fluorine-added carbon film is prevented from being damaged by the ions. The charged particle removing structure is composed of a grounded conductor and has a structure having a gas passage hole and a structural body, but the shape can be changed as described below.
[0062]
FIG. 7 shows a charged particle removing structure 24 ′ which is a modified example of the charged particle removing structure 24. However, in the figure, the parts described above are denoted by the same reference numerals, and description thereof will be omitted.
[0063]
In the case of the charged particle removing structure 24 'shown in this figure, the gas passage hole 24A' has a rectangular parallelepiped shape, and the structure main body 24B 'has a lattice shape. In the present embodiment, the same effect as in the case of the charged particle removing structure 24 shown in the first embodiment is obtained, and among the radicals and ions formed in the space 11A, ions that are charged particles are removed. Thus, radicals can be supplied mainly to the surface of the substrate through the gas passage holes 24A '. Further, the shape of the gas passage hole can be changed to another shape regardless of the cylindrical shape or the rectangular parallelepiped.
[0064]
As described above, the present invention has been described with reference to the preferred embodiments. However, the present invention is not limited to the above-described specific embodiments, and various modifications and changes can be made within the scope of the claims.
[0065]
【The invention's effect】
According to the present invention, by exposing the fluorinated carbon film to hydrogen radicals, the leak current of the fluorinated carbon film can be reduced without performing heat treatment. For this reason, it has become possible to form a fluorinated carbon film excellent in film quality with low leakage current without causing deterioration of the fluorinated carbon film due to heat.
[Brief description of the drawings]
FIG. 1 is a view showing a principle of reducing a leak current of a fluorinated carbon film by a processing method according to the present invention.
FIG. 2 is a view schematically showing a plasma processing apparatus for processing a fluorine-added carbon film according to the present invention.
FIG. 3 is a diagram (part 1) illustrating a charged particle removing structure used in the plasma processing apparatus of FIG. 2;
FIG. 4 shows a flowchart of a processing method according to the present invention.
FIG. 5 is a diagram showing an energy level of a rare gas in a metastable state.
FIG. 6 is a diagram comparing the leakage current of a fluorinated carbon film before and after performing the treatment according to the present invention.
FIG. 7 is a diagram (part 2) illustrating a charged particle removing structure used in the plasma processing apparatus of FIG. 2;
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 Plasma processing apparatus 11 Processing container 11D Exhaust port 11A, 11B Space 12 Substrate to be processed 13 Holder 14 Plasma gas introduction ring 14A Plasma gas introduction port 14B Gas groove 14C Plasma gas holes 16A, 16B Seal ring 17 Microwave transmission window 18 Slot Plates 18a, 18b Slot 19, Slow plate 21 Coaxial waveguide 21A Outer waveguide 21B Inner feed line 22 Antenna body 23 Supporting part 24 Charged particle removing structure 24A Gas passage hole 24B Structural body 30 Radial line slot antenna

Claims (10)

A method for treating a fluoridated carbon film formed on a substrate to be processed,
Dissociating hydrogen gas to form hydrogen radicals;
Exposing the fluoridated carbon film to the hydrogen radicals. The method according to claim 1, wherein the hydrogen radicals are formed by plasma-exciting a plasma gas containing the hydrogen gas. 3. The method according to claim 2, wherein the plasma gas includes a He gas. The plasma excitation is a microwave plasma excitation performed by a substrate processing apparatus, the substrate processing apparatus has a microwave antenna for introducing microwaves, the microwave antenna is fed by a coaxial waveguide, and an opening is provided. An antenna main body, a microwave radiating surface having a plurality of slots provided on the antenna main body so as to cover the opening, and a dielectric provided between the antenna main body and the microwave radiating surface. The method for treating a fluoridated carbon film according to claim 2, wherein the method comprises: The substrate processing apparatus includes:
A processing container defined by an outer wall and including a holding table that holds the substrate to be processed;
An exhaust port for exhausting the processing container,
On the processing container, a microwave transmission window provided as a part of the outer wall so as to face the substrate to be processed,
The microwave antenna provided on the microwave transmission window, a microwave power supply is electrically connected,
A plasma gas supply unit that supplies the plasma gas into the processing container,
The fluorine-added carbon according to claim 4, further comprising a charged particle removing structure provided between the substrate to be processed and the microwave transmitting window on the holding table so as to face the substrate to be processed. How to treat the membrane. 6. The method according to claim 5, wherein the charged particle removing structure is made of a conductive material and is grounded. The method for treating a fluoridated carbon film according to claim 5, wherein the charged particle removing structure has a plurality of openings through which the hydrogen radicals pass, and a collision portion that collides the charged particles. 8. The fluorine-added device according to claim 5, wherein the plasma gas supply unit is inserted between the processing container and the microwave transmitting window to form a part of the outer wall. 9. Processing method of carbon film. 9. The method according to claim 8, wherein the plasma gas supply unit has a structure for supplying the plasma gas between the microwave transmission window and the charged particle removing structure. The microwave plasma excitation substantially occurs in a space formed between the microwave transmission window and the charged particle removing structure in the processing container, according to any one of claims 5 to 9, 2. The method for forming a fluorine-added carbon film according to claim 1.

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