JP2001152342A - Semiconductor producing system and method for producing semiconductor system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce foreign matters and to improve the working ratio by suppressing the deposition of a film on the place other than a substrate to be deposited with a thin film in a CVD system. SOLUTION: The inner wall of a reaction vessel is coated with a film composed of any material selected from W, Cu, Ti, Ta, Pt, SiC, Si3N4, TiN and Al2O3, a film composed of a mixture containing any of them or a multilayered film obtained by laminating any films, by which the deposition of the film on the inner wall of the reaction vessel can remarkably be reduced. By this invention, the deposition of the film on the place other than a substrate to be deposited with the thin film in a CVD system can be suppressed, and the generation of foreign matters and the reduction of the concentration of a gaseous starting material can be suppressed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a CVD apparatus used in a process for manufacturing a semiconductor integrated circuit and a CVD apparatus using the same.
More particularly, the present invention relates to a CVD apparatus for uniformly depositing a noble metal electrode represented by Ru and a CVD method using the same.

[0002]

2. Description of the Related Art As a semiconductor memory, a DRAM (Dynamic) characterized by high-speed rewriting of data is used.
Random Access Memory). This DRAM has entered an era of increasing the capacity of 256 M and 1 G bits with the progress of high density and high integration technology. For this reason, miniaturization of circuit components is required, and in particular, miniaturization of capacitors for storing information is being performed. Among these, the miniaturization of the capacitor includes thinning of the dielectric material, selection of a material having a high dielectric constant, flattening of the structure composed of the upper and lower electrodes and the dielectric to three-dimensionalization, and the like. The use of a noble metal as an electrode material that satisfies this requirement is being studied. Particularly, the use of Ru has attracted attention because of its advantages of excellent fine workability and that oxides also have conductivity. For the three-dimensional structure, a CVD method (chemical vapor deposition method) having excellent step coverage on a substrate (coverage) is advantageous.

When the film forming reaction is repeated by the CVD method, by-products of the film forming reaction are deposited on the inner wall of the reaction vessel. When the film thickness of the deposited film exceeds the limit value, the film is peeled off due to internal stress, and a defect is generated in the deposited film by falling on the substrate. In addition, since the raw material gas is consumed by the amount deposited on the inner wall of the reaction vessel, the concentration of the raw material gas is changed, and there is a disadvantage that uniform film quality cannot be obtained.

In order to avoid the first problem, a method of disassembling the CVD apparatus and dissolving and removing the inner wall deposits with an acid or the like, or a method of removing the inner wall deposits by gas etching, for example, Si ₃ N ₄ Japanese Patent Application Laid-Open No. 4-155827 for system coating
Japanese Patent Application Laid-Open Publication No. Hei 11 (1995) discloses a method for supplying a cleaning gas containing ClF ₃ . However, when it becomes necessary to frequently remove the deposited film, this is one of the causes for lowering the operation rate of the apparatus. As a method of avoiding the second problem, a method of partially heating only the substrate using a high-frequency heating mechanism and a resistance heating mechanism as disclosed in Japanese Patent Application Laid-Open No. H11-236675, etc. Are disclosed. However, it is necessary to keep the temperature of the reaction vessel equal to or higher than the melting point of the source gas in order to prevent the source gas from aggregating on the reaction vessel, and there is a limit in suppressing the accumulation of by-products only by controlling the temperature. .

[0005]

As described above, the conventional C
In the VD apparatus, there is a disadvantage that a reactant is deposited on the inner wall of the reaction vessel, and the film is separated and scattered and adheres to the substrate, thereby causing a defect in the deposited film.
In addition, it is necessary to perform periodic cleaning for removing the deposited film, and there is a problem that the operation rate of the apparatus is reduced.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a CVD apparatus which suppresses the deposition of a reactant on the inner wall surface of a reaction vessel and has a small number of defects in a film to be deposited and has a high equipment operation rate.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide W, Cu, Ti, Ta, Pt, SiC, Si ₃
This can be achieved by coating with a film made of any material of N ₄ , TiN, and Al ₂ O ₃ , a film made of a mixture containing any of them, or a multilayer film in which any film is laminated.

[0008] The CVD method is a method in which a predetermined amount of a source gas is blown onto a substrate heated to a predetermined temperature, and a film is deposited by a film forming reaction on the substrate. As shown in FIG. 1, the CVD apparatus includes a reaction vessel 1 which is a space for forming a thin film on a predetermined substrate 2, a gas supply system 5 for supplying a raw material gas or the like into the reaction vessel, and a vacuum pump 9 comprises a gas exhaust system for exhausting gas and a substrate heating heater 3 for heating the substrate. When the film formation reaction needs to be performed under a constant pressure, the pressure adjusting valve 8 is used.

FIGS. 2 and 3 show two types of relationships (film formation characteristics) between the film formation time and the film thickness when a film is formed by the CVD method. The zero point of the film forming time is the time when the supply of the CVD raw material into the reaction vessel through the shower head is started. FIG. 2 shows a type in which film formation starts immediately after the start of CVD material supply, and FIG.
This type does not form a film for a while. The time during which no film is formed in FIG. 3 is referred to as an incubation time, and the incubation time when a thermally stable CVD material such as the ruthenium cyclopentadienyl complex used in the Ru CVD method of Example 1 is used. Appears remarkably.
This incubation time tends to strongly depend on the substrate on which the film is formed. In a film-forming experiment of a Ru thin film using a ruthenium cyclopentadienyl complex by a CVD method,
When Ru and Ir are used as bases, R of 30 to 50 nm is used.
Under the same conditions that the u thin film was formed, W, Cu, Ti,
When using Ta, Pt, SiC, Si ₃ N ₄ , TiN, and Al ₂ O ₃ , formation of a Ru thin film was not confirmed on any of the bases. This phenomenon is caused by the fact that R
The phenomenon is not limited to u, and similar phenomena can be seen in the same noble metals such as Pt and Ir.

[0010] Thus, for the CVD raw material used,
If a material for the base that gives the incubation time is selected and the inner wall of the reaction vessel is coated with a film made of the material, deposits on the inner wall of the reaction vessel due to the film formation reaction can be significantly reduced.

In the case where a base material showing the incubation time is used for the coating film on the inner wall of the reaction vessel, if the film formation time can be selected to be shorter than the incubation time, deposits due to the CVD film formation reaction are formed on the inner wall of the reaction vessel. It becomes possible to make it almost zero.

Further, as a CVD raw material, disethylcyclopentadienyl ruthenium (RuE) used in the examples was used.
tCp2) complex or dismethylcyclopentadienyl ruthenium (RuMtC
Use of a material having high thermal stability, such as a cyclopentadienyl complex such as p2) complex, is preferable because the incubation time becomes remarkable.

The coating described above is not only applied directly to the inner wall of the reaction vessel as shown in FIG. 1, but is also effective in the following cases.

FIG. 4 is a block diagram of a CVD apparatus in which a sheet with a coating film, which is easy to handle, is attached to the inner wall of the reaction vessel or fixed at several places. This method forms a coating film on the sheet,
This is a cheaper method than coating the inner wall of the reaction vessel. According to this method, in addition to the advantage of reducing the deposit on the inner wall of the reaction vessel, even when the deposit has increased on the sheet due to long use, it can be easily replaced. It is possible to minimize a decrease in the device operation rate.

FIG. 5 is a block diagram of a CVD apparatus in which a deposition wall coated with the above-described film is provided in the reaction vessel to suppress deposits due to a film formation reaction on the inner wall of the reaction vessel. It can be seen that this method can provide the same effect as the method of FIG. 4 by making the structure of the deposition barrier easy to remove from the reaction vessel.

The above-mentioned coating film needs to be thick, and is desirably at least 0.1 μm in order not to be peeled off by rubbing at the time of assembling the apparatus. Also,
The reaction vessel is in a state where a heat cycle is applied between room temperature and the holding temperature at the time of film formation. For this reason, when the coating film is too thick, the internal stress generated due to the difference in the thermal expansion coefficient from the material to be coated cannot be reduced, and the coating film is easily peeled. Therefore, the coating film thickness is 1
The thickness is preferably 0 μm or less.

[0017]

Embodiments of the present invention will be described below in detail.

Example 1 A Ru thin film was subjected to CVD using a reaction vessel in which Ta was coated on the inner wall of the reaction vessel by about 1000 nm by a vapor deposition method. The CVD method is described below. Using a disethylcyclopentadienyl ruthenium (RuEtCp2) complex, it was prepared in a THF (tetrahydrofuran) solvent at a concentration of 0.05 to 0.25 mol / l to obtain a CVD raw material. The CVD raw material was supplied at a rate of 0.1 to 3 sccm using a liquid mass flow controller. After setting the temperature of the vaporizer to 80 to 150 ° C. to convert the CVD raw material from a liquid to a gas at once, the Ar gas 198 to 5 was used.
It was transported at 00 sccm. Next, after mixing the CVD / Ar gas with the oxygen gas 2 to 800 sccm,
The pressure in the reaction vessel was set to 0.01 to 50 torr, and the film was formed at a temperature of 180 ° C. to 400 ° C. for 10 to 20 minutes. The reaction was carried out in a state where the temperature of the reaction vessel was kept at 80 ° C. or more and 200 ° C. or less. In addition, as a substrate, T
An EOS raw material on which 800 nm of SiO ₂ was formed was used.

In this way, 20 substrates are placed on 500 substrates.
A ~ 30 nm Ru thin film was formed. The specific resistance was measured for each substrate on which the Ru thin film was deposited.
It was found to be a low resistance film of cm. 1st sheet and 500
The specific resistance measurement result of the first substrate is 52 μΩcm for the first substrate,
The 500th sheet had a thickness of 59 μΩcm, indicating that the specific resistance of the film did not depend on the number of times of film formation.

Further, when the number of foreign matters of 0.2 μm or more adhering to the substrate was counted, it was found that the number of foreign matters was 20 or less per substrate, and it was found that the generation of foreign matters could be suppressed.

Further, after the 500th deposition, the C
As a result of examining the inside of the VD apparatus, there was no change in the appearance of the inner wall of the reaction vessel, and no deposition of the film and no condensation of the raw material were observed.

In the CVD apparatus described above, an example in which Ta was coated on the inner wall of the reaction vessel was shown, but W, Cu, Ti, Pt, SiC, Si ₃ N ₄ , T
Similar results were obtained when the inner wall of the reaction vessel was coated with a material such as iN, Al ₂ O ₃ . Also CVD
The thin film to be formed is not limited to Ru, but may be Ir or P
Similar results were obtained when a noble metal thin film such as t was formed.

According to the present embodiment, since deposits on the inner wall of the reaction vessel are reduced, the generation of foreign matter from the inner wall of the reaction vessel can be suppressed, and a good film can be obtained even after a large number of depositions. .

(Example 2) Ta was deposited to about 15
Using a reaction vessel in which a 00 nm-coated sheet was attached to the inner wall of the reaction vessel, CVD of a Ru thin film was performed. The CVD method is described below. Using disethylcyclopentadienyl ruthenium (RuEtCp2) complex,
0.05-0.25mo in THF (tetrahydrofuran) solvent
It was prepared at a concentration of l / l to obtain a CVD raw material. The CVD raw material was supplied at a rate of 0.1 to 3 sccm using a liquid mass flow controller in a gas supply system. Set the vaporizer temperature to 8
After setting the temperature to 0 to 150 ° C. to convert the CVD raw material from a liquid to a gas at once, the Ar gas was transported at 198 to 500 sccm.
Next, after mixing the CVD / Ar gas with an oxygen gas of 2 to 800 sccm, the mixture was supplied into the reaction vessel via a shower head.
The pressure in the reaction vessel was set to 0.01 to 50 torr, and the film was formed at a temperature of 180 ° C. to 250 ° C. for 10 to 20 minutes. The reaction was carried out in a state where the temperature of the reaction vessel was kept at 80 ° C. or more and 200 ° C. or less. In addition, as a substrate, T
An EOS raw material on which 800 nm of SiO ₂ was formed was used.

In this way, 20 substrates are placed on 500 substrates.
A ~ 30 nm Ru thin film was formed. The specific resistance was measured for each substrate on which the Ru thin film was deposited.
It was found to be a low resistance film of cm. 1st sheet and 500
The specific resistance measurement result of the first substrate was 55 μΩcm for the first substrate,
The 500th sheet had 63 μΩcm, indicating that the specific resistance value of the film hardly depends on the number of times of film formation.

Further, when the number of foreign substances having a size of 0.2 μm or more adhering to the substrate was counted, it was found that the number of foreign substances was 30 or less per substrate, and it was found that the generation of foreign substances could be suppressed.

Further, after the 500th deposition, the C
As a result of examining the inside of the VD apparatus, there was no change in the appearance on the sheet attached to the inner wall of the reaction vessel, and no deposition of the film and no condensation of the raw material were observed.

In the CVD apparatus described above, a sheet in which Ta is coated at about 1500 nm by a vapor deposition method is used, but W, Cu, Ti, P is used as a coating material.
Similar results were obtained when the inner wall of the reaction vessel was coated with materials such as t, SiC, Si ₃ N ₄ , TiN, and Al ₂ O ₃ . Further, the thin film to be formed by CVD is not limited to Ru, and similar results were obtained when a noble metal thin film such as Ir or Pt was formed.

According to this embodiment, the same effects as those of the first embodiment can be obtained, and in addition, there is an advantage that it is inexpensive because a sheet which can be easily coated is used. Furthermore, since the handling is easy, a further number of CVs is required.
Even when a deposit is formed on the sheet due to the D film formation, since the replacement is easy, a decrease in the operation rate of the apparatus can be minimized.

Example 3 Ta was evaporated to about 12 by a vapor deposition method.
The deposition prevention wall coated with 00 nm was set in the reaction vessel, and the CVD of the Ru thin film was performed. The CVD method is described below. Disethylcyclopentadienyl ruthenium (R
A u-EtCp2) complex was prepared in a THF (tetrahydrofuran) solvent at a concentration of 0.05 to 0.25 mol / l to obtain a CVD raw material. The CVD raw material was supplied at a rate of 0.1 to 3 sccm using a liquid mass flow controller. After setting the temperature of the vaporizer to 80 to 150 ° C. to convert the CVD raw material from a liquid to a gas at once, an Ar gas of 198 to 500 sc
transported in cm. Next, CVD / Ar gas and oxygen gas 2-8
After that, the pressure in the reaction vessel was adjusted to 0.01 to 50 torr and the film forming temperature was set to 18 through a shower head.
The film was formed at a temperature of 0 ° C. or more and 250 ° C. or less for 10 to 20 minutes.
In addition, the reaction was carried out in a state where the temperature of the reaction vessel was kept at 80 ° C. or more and 200 ° C. or less.
The structure was such that it could be maintained at a temperature of not more than ℃. The substrate is S
800 nm SiO ₂ using TEOS material on i-substrate
What formed the was used.

In this manner, 20 substrates are placed on 500 substrates.
A ~ 30 nm Ru thin film was formed. The specific resistance was measured for each substrate on which the Ru thin film was deposited.
It was found to be a low resistance film of cm. 1st sheet and 500
The measurement result of the specific resistance of the first substrate is 54 μΩcm for the first substrate,
The 500th sheet had a thickness of 61 μΩcm, indicating that the specific resistance of the film did not depend on the number of film formations.

Further, when the number of foreign substances having a size of 0.2 μm or more adhering to the substrate was counted, it was 35 or less per substrate, and it was found that the generation of foreign substances could be suppressed.

Further, after performing the 500th film formation,
As a result of examining the inside of the VD apparatus, there was no change in the appearance of the deposition prevention wall, and no deposition of the film, no condensation of the raw material, and the like were observed.

In the above-described CVD apparatus, an example is shown in which a deposition-preventing wall coated with Ta by a vapor deposition method is installed in a reaction vessel, but W, Cu, T is used as a coating material.
Even when the inner wall of the reaction vessel is coated with a material such as i, Pt, SiC, Si ₃ N ₄ , TiN, Al ₂ O ₃ ,
Similar results were obtained. Also, as a thin film to be formed by CVD,
The results are not limited to Ru, and similar results were obtained when a noble metal thin film such as Ir or Pt was formed.

According to the present embodiment, the same effects as in the first embodiment can be obtained. In addition, by making the deposition barrier a removable structure, even if deposits are formed on the sheet due to the additional number of times of CVD film formation, it is easy to replace the sheet. Can be minimized.

(Embodiment 4) In the sectional view of the dielectric element shown in FIG. 6, reference numeral 20 denotes a Si substrate on which a MOS portion (not shown) is formed. First, the Si substrate 11 is
A control diameter is formed on the SiO ₂ layer 14 formed by thermal oxidation at 0 ° C., and then a Si plug 16 is formed. Next, a 10 nm-thick barrier layer 13 of a TiN layer was formed on the Si plug by a sputtering method. Further, an 800 nm thick SiO ₂ insulating layer 15 is formed by a plasma CVD method using a TEOS material, and then a diameter of 240 nm is centered on the control diameter.
By processing the holes, an undersubstrate having a concave opening was prepared.
The aspect ratio (hole depth / hole width) of this three-dimensional structure is about 3.3.

Subsequently, the lower electrode 17 was manufactured using the CVD apparatus of the present invention. In order to manufacture the lower electrode 17,
Dis (ethylcyclopentadienyl) ruthenium (Ru
The (EtCp) 2) complex was prepared in a tetrahydrofuran (THF) solvent at a concentration of 0.05 to 0.25 mol / l to prepare a CVD raw material. The CVD raw material was supplied at a rate of 0.1 to 3 sccm using a liquid mass flow controller. The temperature of the vaporizer was set to 80 to 150 ° C., and the CVD raw material was changed from a liquid to a gas at a stretch, and then conveyed by Ar gas at 198 to 500 sccm. Next, CVD / Ar gas and oxygen gas 2 to 800 sccm
And then introduced into the reaction vessel. The pressure in the reaction vessel is set to 0.1 to 50 torr, and the film formation temperature is set to 180 ° C. or higher and 250
1 to 20 min.
m of Ru film was obtained. Next, SOG was applied by a spin coating method, and flattened by filling in irregularities. After the SOG was cured by applying a heat treatment at 300 ° C., the SOG was polished by a chemical mechanical polishing method using a phosphoric acid solution until the surface of the SiO ₂ insulating film 15 appeared. After that, the SOG remaining in the concave portion of the Ru film was removed to form the lower electrode 17. N ₂ atmosphere 350
The Ru lower electrode 17 was heat-treated for densification by performing a heat treatment at 600 ° C. Next, on the lower electrode 17, (Ba, Sr) TiO ₃ (BST) as the dielectric 18 was formed by a CVD method. Barium bis dibivaloyl methanate (Ba (dp
m) 2), strontium bisdibivaloyl methanate (Sr (dpm) 2), and diisopropoxytitanium dibivaloyl methanate (Ti (O-iPr) 2 (dpm) 2) as starting materials. In THF solvent from 0.05 to 0.25.
It was prepared at a concentration of mol / l to obtain a CVD raw material. Each CV
With respect to the D raw material, 0.
The mixture was supplied at a rate of 1 to 3 sccm to a vaporizer set at 250 ° C. A CVD source gas was introduced into the reaction vessel with an Ar carrier gas of 200 sccm, and an oxygen gas of 5 to 100 sccm was also introduced into the reaction vessel. The pressure in the reaction vessel is 0.1 to 50 torr
And a film formation temperature of 420 ° C. to form a film for 3 minutes.
A T thin film 18 was formed to a thickness of 30 nm. Next, in an oxygen atmosphere 6
Heat treatment was performed at 50 ° C. for 30 to 60 seconds to improve crystallinity. An upper electrode 19 was formed on the dielectric film 18 again using the CVD apparatus of the present invention. The lower electrode 17
The Ru film 19 is formed by the same method and under the same conditions as the formation of the Ru film.
Was formed to complete the dielectric element. The εr at 1 V of the obtained dielectric element was 300, showing extremely excellent electric characteristics.

According to the present embodiment, it can be seen that a thin film suitable for the lower and upper electrodes of a dielectric element can be obtained by using the CVD apparatus of the present invention.

[0039]

As described above, according to the present invention, CVD
Film formation on a device other than the thin film forming substrate of the apparatus can be suppressed, and generation of foreign matter and reduction in the concentration of the source gas can be suppressed. Further, since the cleaning of the reaction vessel becomes almost unnecessary, the operation rate can be greatly improved.

Furthermore, the noble metal thin film produced by using the CVD apparatus of the present invention exhibits very good characteristics, and can provide a thin film suitable for use as a capacitor electrode in a DRAM of 1 Gbit or more.

[Brief description of the drawings]

FIG. 1 is a block diagram of a CVD apparatus provided with a coating film of the present invention.

FIG. 2 is a diagram illustrating one type of a relationship between a film formation time and a film thickness in a CVD method.

FIG. 3 is a diagram showing a relationship between a film forming time and a film thickness on a material used for a coating layer of the present invention.

FIG. 4 is a block diagram showing a CVD apparatus in which a sheet provided with a coating film of the present invention is attached to an inner wall of a reaction vessel.

FIG. 5 is a block diagram showing a CVD apparatus in which a deposition barrier provided with a coating film of the present invention is disposed in a reaction vessel.

FIG. 6 is a sectional view of a dielectric element manufactured by using the CVD apparatus of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Reaction container, 2 ... Substrate, 3 ... Heater for substrate heating, 4 ...
Source gas, 5: gas supply system, 6: shower head, 7: heater for heating the reaction vessel, 8: pressure regulating valve, 9: vacuum pump, 10: coating film, 11: sheet for preventing deposition of reactants, 12: reaction 13: TiN
Barrier layer, 14: SiO ₂ layer, 15: SiO ₂ insulating layer,
16: Si plug, 17: lower electrode (Ru thin film) manufactured using the CVD apparatus of the present invention, 18: dielectric BST thin film, 19: upper electrode (Ru thin film) manufactured by using the CVD apparatus of the present invention, 20 ... Si substrate.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuhiko Murata 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Inside Hitachi Research Laboratory, Hitachi, Ltd. (72) Inventor Takaaki Suzuki 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture No. 1 Hitachi, Ltd. Hitachi Research Laboratory (72) Inventor Tetsuo Fujiwara 1-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Inside Hitachi Research Laboratory Hitachi, Ltd. (72) Inventor Seiji Watahiki Hitachi, Ibaraki Prefecture 7-1-1, Omikacho Hitachi Research Laboratory, Hitachi, Ltd. (72) Inventor Mitsuo Hayashihara 7-1-1, Omikamachi, Hitachi, Ibaraki Prefecture F-term in Hitachi Research Laboratory, Hitachi Ltd. 4K030 AA11 BA01 BA42 BB12 CA04 DA02 DA09 FA10 KA08 KA12 KA23 KA47 LA15 4M104 BB04 DD44 DD45 HH20

Claims (9)

[Claims] 1. A reaction vessel which is a space for forming a noble metal thin film on a predetermined substrate, a gas supply system for supplying a gas into the reaction vessel, a gas exhaust system for exhausting the gas,
A CVD apparatus provided with a heating mechanism for heating the substrate, wherein an inner wall of the reaction vessel is coated with a film that inhibits formation of a noble metal thin film. 2. A reaction container which is a space for forming a noble metal thin film on a predetermined substrate, a gas supply system for supplying a gas into the reaction container, a gas exhaust system for exhausting the gas,
A CVD apparatus provided with a heating mechanism for heating the substrate, wherein the inner wall of the reaction vessel is coated with a film having an incubation time for forming a noble metal thin film. 3. A reaction vessel which is a space for forming a noble metal thin film on a predetermined substrate, a gas supply system for supplying a gas into the reaction vessel, a gas exhaust system for exhausting the gas,
In a CVD apparatus provided with a heating mechanism for heating the substrate, the inner wall of the reaction vessel is made of W, Cu, Ti, Ta, Pt, or Si.
CVD characterized by being coated with a film made of any material of C, Si ₃ N ₄ , TiN, and Al ₂ O ₃ , a film made of a mixture containing any of them, or a multilayer film in which any one of the films is laminated. apparatus. 4. A reaction vessel which is a space for forming a noble metal thin film on a predetermined substrate, a gas supply system for supplying a gas into the reaction vessel, a gas exhaust system for exhausting the gas,
In a CVD apparatus provided with a heating mechanism for heating the substrate, W, Cu, Ti, Ta, Pt, SiC, Si ₃ N ₄ , Ti
A film coated with a film made of any material of N and Al ₂ O ₃ , a film made of a mixture containing any one of them, or a multilayer film formed by laminating any one of the films is placed inside the reaction vessel. CVD equipment. 5. A reaction vessel which is a space for forming a noble metal thin film on a predetermined substrate, a gas supply system for supplying a gas into the reaction vessel, a gas exhaust system for exhausting the gas,
In a CVD apparatus provided with a heating mechanism for heating the substrate, the CVD apparatus has a deposition barrier for suppressing deposits due to a film formation reaction on the inner wall of the reaction vessel, and the deposition barrier is removable. , And the surface is made of W, Cu, Ti, Ta, Pt,
CVD characterized by being coated with a film made of any material of SiC, Si ₃ N ₄ , TiN and Al ₂ O ₃ , a film made of a mixture containing any one of them, or a multilayer film in which any one of the films is laminated. apparatus. 6. The CVD apparatus according to claim 1, wherein said noble metal thin film is made of one of Ru, Ir, and Pt.
Alternatively, a CVD apparatus characterized by being a mixture, an oxide, or a compound thereof. 7. The CVD apparatus according to claim 1, wherein said coating film has a thickness of 0.1 μm or more and 10 μm or less. 8. A method for manufacturing a semiconductor device using a CVD apparatus according to claim 6, wherein a cyclopentadienyl complex is used as a CVD raw material. 9. A semiconductor device manufactured by using any one of the CVD devices according to claim 1.