JPS63247371A - Thin film treating equipment - Google Patents

Abstract

PURPOSE:To prevent the corrosion damage due to corrosive gas, by specifying a Cr, Co, Ni, Ti, Zr, Nb, etc., as a material for both electrodes of cathode and anode disposed in a vacuum tank. CONSTITUTION:This thin film treating equipment is provided with a vacuum tank and both electrodes of cathode and anode for exciting electric discharge in the above vacuum tank. Both electrodes mentioned above are composed of, by weight, 10-40% Cr and the balance Co, or composed of 10-40% Co, 1.5-20% Ni, 0.2-4% of one or more elements among Ti, Zr, and Nb, <=0.2% of one or more elements among Y, La, and Ce, and the balance Co.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a thin film processing apparatus for forming a thin film on a substrate or etching a thin film on a substrate.

(Prior art) As a method for forming a thin film having insulating, photoconductive, semiconducting properties, etc. on a substrate having a flat or cylindrical shape, for example, there is a method using plasma discharge. It is used in the formation of insulating films for circuits, the production of solar cells, and the production of electrophotographic photoreceptors.

As a film forming method using plasma discharge, plasma C
The VD method is known. In this plasma CVD method, a reaction gas for film formation is introduced into a reduced pressure vacuum chamber, and the reaction gas is decomposed by plasma energy to excite highly active particles (radicals) to form the above-mentioned particles on the substrate. It forms a thin film, and while the conventional thermal CVD method forms a film at a temperature of 5 Co° C. or higher, the plasma CVD method is characterized in that it can form a healthy film at a low temperature of around 3 Co° C.

A typical example of an apparatus used in such a plasma CVD method will be explained with reference to FIGS. 1 and 2.

FIG. 1 shows a plasma CVD apparatus suitable for forming a film on a plate-like substrate, and numeral 1 in the figure is a vacuum chamber. This vacuum TL! A vacuum evacuation system 2 composed of a vacuum pump and the like is connected to Il. A pair of parallel plate electrodes 3.4 are arranged within the vacuum chamber l. One electrode 3 is connected to a high frequency power source 5 and functions as a cathode electrode. The other electrode 4 is normally grounded and functions as an anode electrode. A heater 6 is arranged near the bottom of the anode electrode 4. Further, the vacuum W
A gas introduction system 7 configured with a gas cylinder, a gas distribution valve, a gas flow rate adjustment valve, etc. for supplying a reaction gas is connected to It. In a plasma CVD apparatus having such a configuration, a flat substrate 8 is installed on the anode electrode 4, and a vacuum exhaust system 2 is installed.
While maintaining the vacuum chamber 1 at a predetermined degree of vacuum by operating the
The base body 8 is heated to about 3Co°C to 350 °C by the heater 6, and when the temperature of the base body 8 becomes constant, the gas introduction system 7 is heated.
When a high frequency voltage of 13.58 MHz is applied to the cathode electrode 3 from the high frequency power supply 5, the reactive gas is activated by the discharge excited between the electrodes 3.4. , a desired thin film is formed on the substrate 8 held on the anode electrode 4.

FIG. 2 shows a plasma CVD apparatus suitable for forming a film on a cylindrical substrate, and 11 in the figure is a vacuum chamber.

A vacuum evacuation system 12 composed of a vacuum pump and the like is connected to the vacuum chamber 11. A pair of coaxial counter electrodes 13, 14 are arranged within the vacuum chamber 11. One electrode 13 is connected to a high frequency power source 15 and functions as a cathode electrode. The other electrode 14 is normally grounded and functions as an anode electrode, as well as the rotation mechanism 1
It has a structure that rotates by B. A heater 17 is inserted inside the anode electrode 14 . Also,
A gas introduction system 1B is connected to the vacuum chamber 11, which is configured to supply a reaction gas with a gas cylinder, piping, a gas flow rate adjustment valve, or the like. In a plasma CVD apparatus having such a configuration, the cylindrical substrate 19 is held by the anode electrode 14, and the substrate 19 is held while the vacuum exhaust system 12 is operated to maintain the interior of the vacuum chamber 1 at a predetermined degree of vacuum. While rotating the anode electrode 14 using the rotating mechanism 1B, the base body 19 is uniformly heated to about 3Co to 350 °C by the heater 17, and when the temperature of the base body 19 becomes constant, the gas introduction system 1 is heated.
A reaction gas is supplied from B into the vacuum chamber 11, and a high frequency power source 15 of 13.56 MHz is supplied to the cathode electrode 13.
When a high frequency voltage of 13. is applied, the reaction gas flows to the electrode 13.
A desired thin film is formed on the cylindrical substrate 19 held by the anode electrode 14 by the discharge excited between the electrodes 14 and 14 .

The above-mentioned plasma CVD apparatus is used to form insulating films, silicon oxide for passivation films, silicon nitride, and amorphous silicon for photoelectric conversion elements mainly using monolan gas (SI H,) and ammonia gas (NH3).
, nitrous oxide gas (N20), nitrogen gas (N2), and the like are used. When a film formation process is performed several times using such a reaction gas, a thin film is also deposited on the electrode surface, and the discharge between the electrodes becomes unstable, making it difficult to obtain a thin film having desired characteristics. Therefore, every time a film with a thickness of several μm is deposited on the electrode, freon (CF4) and oxygen (02)
Plasma cleaning is performed to vaporize and remove the deposited film using a mixed gas of

However, since conventional cathode electrodes and anode electrodes are made of stainless steel such as 5US304 and 5US316L, when they come into contact with a highly corrosive gas such as the Freon and oxygen mixture, the electrodes corrode. Produces a corrosion film on the surface. When a corrosion film is formed on the electrode surface in this way, the corrosion film is peeled off during subsequent film formation and becomes floating dust within the apparatus, which is mixed into the film formation process.

As a result, in semiconductor devices, for example, problems such as poor electrical conduction of wiring occur, resulting in a reduction in manufacturing yield.

On the other hand, as a method for etching a thin film on a substrate, for example, there are methods using dry etching technology, such as etching silicon oxide for contact openings, etching polycrystalline silicon for forming gate electrodes, and even etching AI!
It is used to form wiring patterns.

Dry etching technology involves introducing a reactive gas into a vacuum chamber and etching a thin film on a substrate using radicals and ions generated by glow discharge between electrodes, and is classified into plasma etching and reactive ion etching. Plasma etching mainly utilizes radicals in plasma, whereas reactive ion etching utilizes the reactivity of radicals and ion etching.

A typical example of such a dry etching device is shown in the third section.
This will be explained with reference to FIG.

FIG. 3 shows a parallel plate type plasma etching apparatus, and numeral 21 in the figure is a vacuum chamber that is evacuated by an exhaust system (not shown). Inside this vacuum chamber 21, a pair of parallel plate electrodes 22 and 23 are arranged. A high frequency power source 24 is connected to one electrode 22 and functions as a cathode electrode. The other electrode 23 is grounded and functions as an anode electrode. In a plasma etching apparatus having such a configuration, the substrate 25 is placed on the anode electrode 23, and after the vacuum chamber 21 is brought to a predetermined degree of vacuum by an exhaust system (not shown), etching gas is introduced into the vacuum chamber from a gas introduction pipe (not shown). 21 and when a high frequency voltage is applied to the cathode electrode 22 from the high frequency power source 24, plasma is generated between the electrodes 22 and 23, and the radicals therein cause the substrate 25 to
The thin film deposited on the surface is etched.

FIG. 4 shows a parallel plate type reactive ion etching apparatus, and numeral 31 in the figure is a vacuum chamber that is evacuated by an evacuation system (not shown). A pair of parallel plate electrodes 32, 33 are arranged within this vacuum 1431. One electrode 32 is grounded and functions as a cathode electrode. The other electrode 33 is connected to a high frequency power source 34 and functions as an anode electrode.

In the plasma etching apparatus having such a configuration, the substrate 35 is installed on the anode electrode 33, and after the vacuum chamber 31 is brought to a predetermined degree of vacuum by an exhaust system (not shown), etching gas is introduced into the vacuum chamber from a gas introduction pipe (not shown). When a high frequency voltage is applied to the anode electrode 33 from the high frequency power source 34, plasma is generated between the electrodes 32 and 33, and the ions in the plasma are accelerated by the cathode sheath and have high energy. The ions are incident on the thin film deposited on the surface of the substrate 35, thereby etching the thin film.

When etching silicon oxide for insulation, polycrystalline silicon for gate electrodes, and aluminum for wiring using the dry etching equipment described above, fluorine gas such as Freon (CF4) or chlorine gas such as tetrachloromethane (CCI!4) is used. gas is used.

However, since the conventional cathode 7u electrode and anode electrode are made of stainless steel such as 5US304, 5US316L, etching using the highly corrosive gas causes corrosion damage to the electrodes, which can cause damage within the device. Generates dust. When the generated dust adheres to the thin film on the substrate, the dust acts as an etching mask and causes wiring short circuits, contact opening defects, etc., resulting in a reduction in the manufacturing yield of semiconductor devices and the like.

(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned conventional problems. The present invention aims to provide a thin film processing apparatus capable of high-yield film formation or highly reliable etching.

[Structure of the Invention] (Means for Solving the Problems) The invention of Section 1 of the present application provides a vacuum chamber to which a reactive gas is supplied, and a thin film provided with a cathode electrode and an anode electrode for exciting discharge in the chamber. In the processing apparatus, the cathode electrode and the anode electrode contain 10 to 40% Cr by weight, with the remainder being substantially C.

This is a thin film processing apparatus characterized by comprising:

Next, the role of the metal in the alloy constituting the electrode of the thin film processing apparatus of the invention of Section 1 of the present application and the reason for limiting the blending amount will be explained in detail. Note that % in the following description means mQ%.

Cr is a fundamental element in order to maintain halogen resistance and oxidation resistance at high temperatures. The blending amount of Cr is 10
If it is less than 40%, sufficient halogen resistance and oxidation resistance will not be obtained, whereas if it exceeds 40%, σ phase will be generated, reducing hot workability and oxidation resistance. let

In addition to the above-mentioned Cr, in order to further improve the high-temperature strength through solid solution and precipitation strengthening and the adhesion of the protective coating, Ni
1.5 to 20%, and 0.2 to 4% of at least one of TI, ZrsNb, and YlLa, Ca
At least one of these can be contained in an amount of 0.2% or less.

The above Ni is an element that is effective in improving halogen resistance,
Particularly in a high-temperature halogen atmosphere and in the coexistence of Cr, N
i Forms a dense fluoride film mainly composed of F2, significantly improving high-temperature halogen resistance. If the Ni content is less than 1.5%, the effect of Ni cannot be sufficiently achieved, and on the other hand, if the content exceeds 20%, no increase in the effect can be expected.

The above-mentioned "rt", Zr, and Nb react with C and N to form fine carbonitrides in the matrix, and are effective in improving thermal strength and suppressing hot working cracks.Such elements If the blending amount is less than 0.2%, the blending effect cannot be fully achieved, whereas if the blending amount exceeds 4.0%, the alloy will become brittle.Please note that any of these elements One type may be added alone, or two or more types may be added in combination, and the blending amount may be in the range of 0.2 to 4.0%.

The above Y, La, and Ce are elements that are effective in improving the adhesion of the protective coating. The amount of such elements is 0.2%
Exceeding this may cause the coating to lose its protective effect. Note that even if any one of these elements is added alone, 2
Seeds or more may be added in combination, with the upper limit of the total amount being 0.2%.
The following is sufficient.

A more preferable blending amount of these elements is 0.02 to 0.
It is in the range of 1%.

The invention of Section 2 of the present application provides a thin film processing apparatus provided with a vacuum chamber to which a reaction gas is supplied, and a cathode electrode and an anode electrode for exciting discharge in the chamber, in which the cathode electrode and the anode electrode are arranged in a weight ratio. TI s Zr,, Hr,
Nbs Tas 30 to 85% of at least one of the hard phases consisting of carbides of Cr and Si, and 2 to 2 Cr
0% Co, 5 to 15% Co, and the balance is Ni.

Next, the role of the metal in the alloy constituting the electrode of the thin film processing apparatus of the invention of Section 2 of the present application and the reason for limiting the amount to be mixed will be explained in detail. In addition, % in the following description means weight %.

The hard phase has the effect of improving halogen resistance and oxidation resistance at high temperatures. The amount of this hard phase is 30
If the amount is less than 85%, the blending effect will not be obtained, while if the amount exceeds 85%, the toughness will deteriorate.

Cr, which is a component of the binder phase, is an element that dissolves in Ni and improves the halogen resistance and oxidation resistance of the alloy. If the content of Cr is less than 2%, sufficient halogen resistance and oxidation resistance cannot be obtained, whereas if the content exceeds 20%, Cr 23 C7 phase will precipitate and the strength will decrease. .

Co, which is a component of the binder phase, is an element that is effective in improving the ductility of Ni, improving strength, and improving pitting corrosion resistance. If the blending amount of Co is less than 5%, the blending effect cannot be sufficiently achieved, but if the blending amount exceeds 15%, the Cr solid solution in Ni decreases and Cr23C7 phase precipitates. In addition, Ni (TI
A, l? ) is suppressed, resulting in a decrease in high temperature strength.

In order to further improve the high temperature strength and corrosion resistance through solid solution and precipitation strengthening, 5% of at least one of Mo, AI, and Ti is added to the alloy composition of the electrode of the thin film processing apparatus of the second invention of the present application described above. The following can be contained.

The above M'o is an element that dissolves in Ni and has the effect of improving high temperature strength. When the content of Mo exceeds 5%, the strength of the alloy decreases due to the precipitation of lower carbides containing Mo.

The above AI is an element that is effective in improving oxidation resistance, especially in the presence of Cr in a high temperature oxidizing atmosphere.
Forms a dense oxide film mainly composed of , significantly improving high-temperature oxidation resistance. In addition, Ni and intermetallic compounds (Ni
3 A, f? ) to improve high temperature strength. When the blending amount of AI exceeds 5%, precipitation of Ni 3 A phase increases too much, and the strength tends to decrease.

When T1 coexists with Cr, it prevents Cr from producing carbides and forming a Cr-depleted layer, thereby exhibiting the effect of preventing pitting corrosion. In addition, together with AI, γ′ phase [N
i3 (AiTl)] to improve high temperature strength. If the content of Ti exceeds 5%, the alloy tends to become extremely brittle due to the precipitation of lower carbides.

The particle size of the hard phase in the second invention of the present application is preferably 3 μm or less. The reason for this is that the particle size of the hard phase is 3 μm.
If it exceeds m, the strength at the interface between the hard phase and the binder phase decreases, the porosity increases, and the corrosion resistance deteriorates.

Note that if the particle size of the hard phase is made too small, agglomeration of the hard phase will occur during the mixing process, resulting in a decrease in strength. A more preferable particle size range of the hard phase is 0.1 to 2 μm.

In order to manufacture the alloy used in the second invention of the present application, the following method may be adopted, for example. First, the mixed powder is filled into a graphite mold and hot pressed, or the mixed powder is filled with a molding aid such as paraffin or resin and then pressure molded, or a rubber press, etc. Formed using a hydrostatic press. By sintering the powder compact formed in this way without pressure or under pressure in a non-oxidizing atmosphere, or by sintering it at 1250°C to 16Co°C in a reduced pressure gas atmosphere or vacuum. Manufacture alloys. In addition, by reprocessing the sintered material using hot isostatic pressing (HIP),
An alloy with even higher toughness can be obtained.

A third invention of the present application is a thin film processing apparatus provided with a vacuum tank to which a reaction gas is supplied, and a cathode electrode and an anode electrode for exciting discharge in the tank, wherein the surfaces of the cathode electrode and the anode electrode are TIC. ,TI N,TI
This thin film processing apparatus is characterized in that it is coated with a compound film having a thickness of 2 μm to 50 μm and made of at least one of CN, TI Co, and TI CNO.

As a means for forming the cathode electrode and the anode electrode from the compound film, for example, a CVD method or a PVD method can be employed. In addition, in order to improve the adhesion between the electrode and the coating,
It is desirable to previously coat the electrode surface with a metal such as Ni s Cr s Fc before coating.

The reason for limiting the thickness of the above compound coating is that the thickness is 2
This is because if the thickness is less than μm, the desired corrosion resistance cannot be obtained, whereas if the thickness exceeds 50 μm, cracks are likely to occur due to thermal shock or the like.

(Function) According to the first invention of the present application, by using the cathode electrode and the anode electrode made of the above-mentioned alloy composition,
Since the halogen resistance and oxidation resistance of the electrode can be significantly improved, highly reliable film formation can be achieved by preventing dust generated from corrosion of conventional stainless steel electrodes from being mixed into the formed film. Furthermore, it is possible to obtain a thin film processing apparatus that can achieve highly reliable thin film processing by preventing formation defects of a predetermined pattern.

Furthermore, according to the invention in Box 2, by using the cathode and anode electrodes made of the above-mentioned alloy composition, the halogen resistance and oxidation resistance of the electrodes can be significantly improved. It is possible to achieve highly reliable film formation by preventing dust generated due to gas corrosion from entering the formed film, and also to achieve highly reliable thin film processing by preventing formation defects in the specified pattern. A thin film processing apparatus can be obtained.

Furthermore, according to the invention in Box 3, the surfaces of the cathode electrode and the anode electrode are TI CS TI N, Ti CN5.
By coating the electrode with a compound film of at least one of TI Co and Ti CNO and having a predetermined thickness, the halogen resistance and oxidation resistance of the electrode can be significantly improved, making it superior to conventional stainless steel electrodes. It is possible to achieve highly reliable film formation by preventing dust generated due to corrosion by etching gas from entering the formed film, and also to prevent defective formation of a given pattern, resulting in highly reliable thin film processing. It is possible to obtain a thin film processing device that achieves this goal.

In addition, because the thermal expansion coefficient of the compound is similar to that of stainless steel, which is the electrode material, the coating does not peel off even when used at high temperatures, and the electrode has excellent halogen resistance for a long time. , can provide oxidation resistance.

(Embodiments of the Invention) Hereinafter, embodiments of the present invention will be described with reference to the above-mentioned drawings.

Example 1 The cathode electrode and the anode electrode were made of Co as shown in Table 1 below.
Parallel heating plasma CV made of alloy and shown in Fig. 1
It was installed in apparatus D, and plasma etching (electrode durability test) was performed five times in a row using a mixed gas of CF4 and 02 under the following conditions.

Gas flow rate...CF4:8Co SCCM, 0
2: 808CoM Vacuum chamber pressure: 1 torr RF power density: 0.2 W/c Vacuum chamber temperature: 350°C Etching time: 150 win However,
After etching, the amount of corrosion was measured by the change in the weight of the electrode. Also, insert a quartz tube with a diameter of 101111 into the device,
The dust was collected by suction into a membrane filter with a pore size of 0.2 μm, and the amount of dust generated was measured.

These results are also listed in Table 1. For comparison, the conventionally used 5US304 (sample consideration 11)
), 5US310S (sample consideration 12) and 5US31
The results for the electrode made of 6L (sample Ni113) are also listed in Table 1.

As is clear from Table 1 above, sample points 1 to 1 of this Example 1
The content of j in electrode No. 10 was reduced to 1/40 or less compared to the comparative examples 5US304 (sample Nα11), 5US310S (sample Nα12) and 5US316L (sample Nα13), and the electrode used in the thin film processing apparatus of the present invention It was found to have excellent halogen resistance and oxidation resistance.

In addition, the dust generation of the electrodes of samples Nα1-10 of Example 1 was reduced to 1/40 or less compared to the electrodes made of stainless steel of samples Nα11-13 of the comparative example, and can be used in the thin film processing apparatus of the present invention. It was found that the electrode is very effective in reducing corrosion dust generation.

Next, using 5IH4 gas as the reaction gas for film formation, the gas flow rate and the pressure in the vacuum chamber during film formation were adjusted to 2Co0 SC.
A 5102 insulating film was formed on a 5-inch Sl wafer by applying a high frequency wave of H, 56 M)lz to the cathode electrode while maintaining the substrate temperature at 350° C. and CM of 0.5 torr. The amount of impurities in the obtained 5io2 film was measured using a flameless atomic absorption spectrometer to evaluate the degree of contamination in the film. The results are shown in Table 2 below.

Table 2 (X 10" atotAs/cr13) As is clear from the above Table 2, in the thin film processing apparatus using the electrodes of samples Nα1 to Nα10 of Example 1, sample N (111-1
Compared to the thin film processing equipment using No. 3 electrodes, impurity elements such as Fe, Cr, and AJ! We were able to significantly reduce the amount of contaminants such as

In addition, in the above-mentioned Example 1, parallel plate type plasma C
Although an example in which the present invention is applied to a VD apparatus has been shown, it is of course possible to apply the present invention to an electron cyclotron resonance plasma CVD apparatus, a photoexcited plasma CVD apparatus, or the like instead.

Example 2 Co alloy of sample points 1 to 10 shown in Table 1, which already describes the cathode electrode and anode electrode, and sample NC shown in Table 1
It was made of LII-13 stainless steel and installed in the parallel plate type plasma etching apparatus shown in Fig. 3.
A and +7 films on a 5-inch Sl wafer were etched using a gas.

As a result of evaluating the electrical characteristics of the obtained devices, the short circuit occurrence rate of devices using comparative stainless steel (samples NCL11 to 13) was 10 to 30%;
In Example 2 (sample Ntll-10 in Table 1), no short circuit was observed.

Example 3 Si C, Cr 3 C2, T with an average particle size of 0.5 μm
a C5Nb C, HrC, Zr C, TI C, 1,
Mo, A, and TI powders of 5 μm Nt s Cr s Co s 1-2 um were mixed into the composition shown in Table 3 below, and this was placed in a stainless steel container together with a cemented carbide ball. Milled for 72 hours. Next, it is dried and molded while being heated uniformly to prevent the formation of aggregates, and vacuum sintered (10° 3 m
Cathode electrode and anode electrode were prepared by HIP treatment at a temperature of 1350'C in argon after s+Hg)L.

Each of the obtained electrodes was assembled into a parallel plate type plasma CVD apparatus shown in FIG. 1, and a mixed gas of CF4 and 02 was used.
Plasma etching (electrode durability test) was performed five times in a row under the following conditions.

Gas flow rate...CF4:8Co SCCM, 0
2: 80 SCCM vacuum chamber pressure...1 tor
r RF power density...0.2W/cJ Vacuum chamber temperature...350°C Etching time...150 winHowever,
Is the amount of corrosion determined by the change in electrode weight after etching? 111
Established. Further, a quartz tube with a diameter of 10 mm was inserted into the apparatus, and dust was collected by suction into a membrane filter with a pore diameter of 0.2 μm to measure the amount of dust generated.

These results are also listed in Table 3. For comparison, the conventionally used 5US304 (sample Ni1
ll), 5US310S (sample point 12) and 5US
The results for the electrode made of 316L (sample Ni113) are also listed in Table 3.

As is clear from Table 3 above, sample Nα1 of Example 3
The corrosion amount of the electrodes 10 to 10 is the comparative example 5US304 (sample Nαif), 5US310S (sample point 12) and 5
US316L (compared to sample N (113)) decreased to 1/1 Co or less, indicating that the electrode used in the thin film processing apparatus of the present invention has excellent halogen resistance and oxidation resistance.

In addition, the amount of dust generated by the electrodes of samples mt~10 of Example 3 is reduced to 1/1Co or less compared to the electrodes made of stainless steel of samples NQII~13 of comparative examples, and can be used in the thin film processing apparatus of the present invention. It was found that the electrode is very effective in reducing corrosion dust generation.

Next, using 5IH4 gas and N20 gas as reaction gases for film formation, the gas flow rate and pressure in the vacuum chamber during film formation were adjusted to 2.
Co0 SCCM, 1Co0 SCCM, 0.5t
orr, the substrate temperature was kept at 350°C, and H,5[i
A high frequency of MHz was applied to the cathode electrode, and a 5-inch Si
A 5102 insulating film was formed on the wafer. Obtained 510
2114! The amount of impurities in the film was measured using a flameless atomic absorption spectrometer to evaluate the degree of contamination in the film. The results are shown in Table 4 below.

Table 4 (x10” atoms/n3) As is clear from Table 4 above, sample Nα1 of Example 3
~In the thin film processing device using the IO electrode, sample N of the comparative example
Compared to thin film processing equipment using electrodes QII to 13, the impurity elements Fa, Cr, A, l? We were able to significantly reduce the amount of contaminants such as

In addition, in the above-mentioned Example 3, parallel plate type plasma C
Although an example in which the present invention is applied to a VD apparatus has been shown, it is of course possible to apply the present invention to an electron cyclotron resonance plasma CVD apparatus, a photoexcited plasma CVD apparatus, or the like instead.

Example 4 A cathode electrode and an anode electrode were fabricated using the blending composition of sample Ncil-10 shown in Table 3 and the stainless steel of samples Nα11 to 13 shown in Table 3, and the parallel plate type shown in FIG. Incorporated into plasma etching equipment, CC
I! 11 on a 5 inch S1 wafer using 4 gases. The film was etched.

As a result of evaluating the electrical characteristics of the obtained devices, the short-circuit occurrence rate of devices using comparative stainless steel (samples Nα11 to 13) was 10 to 30%, but this example 4 (Table 7) No short circuit was observed in samples Nα1 to Nα10).

Example 5 A cathode electrode and an anode electrode made of stainless steel whose surfaces were coated with the compounds shown in Table 5 below by the CVD method were prepared, and these electrodes were incorporated into a parallel plate type plasma CVD apparatus shown in FIG. Plasma etching (electrode durability test) was performed five times in a row under the following conditions using a mixed gas of CF and 02.

Gas flow rate...CF4:8Co SCCM,
02: 808CoM Vacuum chamber pressure: 1 torr RFg force density: 0.2 W/cd Vacuum chamber temperature: 350°C Etching time: 150 min However,
After etching, the amount of corrosion was measured based on the change in the weight of the electrode. Further, a quartz tube with a diameter of ioH was inserted into the apparatus, and dust was collected by suction into a membrane filter with a pore diameter of 0.2 μm to measure the amount of dust generated.

These results are also listed in Table 5. For comparison, the conventionally used 5US304 (sample NC)
LII), 5US310S (sample Na12) and 5
The results of the electrode made of US316L (sample Nα13) are also listed in Table 5.

As is clear from Table 5, sample Nc of Example 5
The amount of corrosion of the l-to electrode is 5US304 (comparative example).
Sample Milli), 5US310S (sample tooth 12)
and 5US316L (sample NCL 13) l/
It was found that the electrode used in the thin film processing apparatus of the present invention has excellent halogen resistance and oxidation resistance. In addition, the amount of dust generated by the electrode of sample Ni1l-10 of Example 5 is reduced to 1/1Co or less compared to the electrode made of stainless steel of samples NQII to 13 of the comparative example, and it can be used in the thin film processing apparatus of the present invention. It was found that the electrode is very effective in reducing corrosion dust generation.

Next, using SiH4 gas and N20 gas as reaction gases for film formation, the gas flow rate and pressure in the vacuum chamber during film formation were adjusted to 2.
Co SCCM, 1Co0 SCCM, 0.5 to
rr, keeping the substrate temperature at 350°C, 13.56 M
A high frequency of Hz was applied to the cathode electrode to form a 5to2 insulating film on a 5-inch Sl wafer. Obtained 3102
The amount of impurities in a was measured using a flameless atomic absorption spectrometer to evaluate the degree of contamination in the film. The results are shown in Table 6 below.

Table 6 As is clear from Table 6 above, sample points 1 to 1 of this Example 5
In the thin film processing apparatus using 10 electrodes, the sample Nα of the comparative example
Compared to the thin film processing apparatus using electrodes No. 11 to 13, the amount of impurity elements such as Fe, Cr, A, and i' could be significantly reduced.

In addition, in the above-mentioned Example 5, parallel plate type plasma C
Although an example has been shown in which the present invention is applied to a VD i device, it goes without saying that the present invention may be applied to an electron cyclotron resonance plasma CVD device, a photoexcited plasma CVD device, or the like instead.

Example 6 A cathode electrode and an anode electrode were made of stainless steel coated with the compound of sample points 1 to 10 shown in Table 5 and stainless steel of samples NQ, 11 to 13 shown in Table 5, and The device was installed in a parallel plate type plasma etching apparatus shown in FIG. 3, and the A and l' films on a 5-inch Si wafer were etched using CC-4 gas.

As a result of evaluating the electrical characteristics of the obtained device, the short circuit occurrence rate of the device using stainless steel (Samples Null to 13) as a comparative example was 10 to 30%, but it was No short circuit was observed in samples Nα1 to Nα10).

[Effects of the Invention] As detailed above, according to the present invention, it is possible to solve the problems of foreign matter contamination in the film produced by plasma etching and poor pattern formation in conventional thin film processing equipment, and achieve high reliability and high yield. It is possible to provide a thin film processing apparatus that can achieve highly reliable film etching.

[Brief explanation of the drawing]

1 and 2 are longitudinal sectional views showing a plasma CVD apparatus, respectively, and FIG. 3 and 4 are longitudinal sectional views showing a dry etching apparatus, respectively. 1, IL 21.31...vacuum chamber, 2.12...
・Vacuum exhaust system, 3.13.22.32...Cathode electrode, 4.14.23.33...Anode electrode, 5.1
5.24.34...High frequency power supply, 6.17...Heater, 7.18...Gas introduction system, 8.19.25.35
...substrate. Applicant's agent Patent attorney Takehiko Suzue Figure 2 Figure 1a3 Figure 4

Claims (5)

[Claims] (1) In a thin film processing apparatus provided with a vacuum chamber to which a reaction gas is supplied, and a cathode electrode and an anode electrode for exciting discharge in the chamber, the cathode electrode and the anode electrode have a weight ratio of Cr of 10 A thin film processing device characterized in that Co contains 40% and the remainder substantially consists of Co. (2), the cathode electrode and the anode electrode are Cr by weight ratio
10-40%, Ni 1.5-20%, and Ti, Zr,
0.2 to 4% of at least one kind of Nb, further Y,
2. The thin film processing apparatus according to claim 1, wherein the thin film processing apparatus contains at least one of La and Ce in an amount of 0.2% or less, and the remainder substantially consists of Co. (3) In a thin film processing apparatus provided with a vacuum chamber to which a reaction gas is supplied, and a cathode electrode and an anode electrode for exciting discharge in the chamber, the cathode electrode and the anode electrode are composed of Ti and Zr in weight ratio. , Hf, Nb, Ta, Cr
, 30 to 85% of at least one of the hard phases consisting of Si carbide, 2 to 20% of Cr, and 5 to 15% of Co.
and a binder phase, the remainder of which is Ni. (4), the cathode electrode and anode electrode are Ti, Zr,
30 to 85% of at least one of the hard phases consisting of carbides of Hf, Nb, Ta, Cr, and Si, and Cr2 to
20% Co, 5 to 15% Co, at least one of Mo, Al, Ti, and 5% or less, and the balance is Ni. thin film processing equipment. (5) In a thin film processing apparatus provided with a vacuum chamber to which a reaction gas is supplied, and a cathode electrode and an anode electrode for exciting discharge in the chamber, the surfaces of the cathode electrode and the anode electrode are TiC, TiN, TiCN. , TiCO, T
2μ thick made of at least one type of iCNO
1. A thin film processing device characterized by being coated with a compound film having a thickness of m to 50 μm.