JP2003273102A - Methods for forming metal oxide film and manufacturing capacitative element and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain good leakage current characteristics for a capacitative element by avoiding oxygen deficiency in a metal oxide film formed as a dielectric film, and effectively separating organic components from a film-forming liquid material. <P>SOLUTION: H<SB>2</SB>O is positively produced in a process of forming the metal oxide film on a film-forming face. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a metal oxide film, a method for producing a capacitive element using a metal oxide film as a dielectric film, and a method for producing a semiconductor device having a metal oxide film.

[0002]

2. Description of the Related Art DRAM (Dynamic Random Access Memo)
A silicon nitride film (Si ₃ N ₄ ) or silicon oxide (SiO ₂ ) has been conventionally used as a dielectric film for a capacitive element of various LSIs including ry). In recent years, with the high integration of semiconductor devices, the area occupied by the capacitive element in the semiconductor device is also decreasing.

On the other hand, in order to maintain the insulation resistance and the reliability as a memory, it is required that the capacitance value be rather increased. In order to secure the capacitance value while limiting the occupied area of the capacitive element, it is effective to use a material having higher dielectric properties as the dielectric film forming the capacitive element. As such a high dielectric film, a tantalum oxide (Ta ₂ O ₅ ) thin film has been developed in recent years.

The relative permittivity of each material is shown below. _{SiO 2: 3.9 Si 3 N 4} : 7 Ta 2 O 5: 25

As a method of manufacturing such a tantalum oxide thin film having a high relative dielectric constant, a sputtering method or a CVD method is used.
(Chemical vapor deposition) method, sol-gel method and the like have been developed, but in recent years, especially MOCVD (Metal Organic Chemical Vapor Deposition) method has been used.

A CVD apparatus for carrying out this MOCVD method uses an organic metal compound or a liquid obtained by dissolving it in a solvent as a film forming material. Such an organometallic compound material and a liquid obtained by dissolving it in a solvent are collectively referred to as a liquid material hereinafter. As the liquid material, for example, the most commonly used pentaethoxy tantalum (PE
T; Ta (OC ₂ H ₅ ) ₅ ) is an example.

When forming a tantalum oxide thin film by the MOCVD method, pentaethoxytantalum and a gas such as oxygen as an oxygen supply source are simultaneously introduced into the reaction chamber into which the substrate to be processed is inserted, and the thin film is formed by a mixed gas. Forming.

[0008]

A capacitance element using a tantalum oxide thin film having a large relative permittivity as a dielectric film can realize a high capacitance, but on the other hand, has electrical characteristics such as leakage current characteristics and dielectric strength characteristics. I have the problem of not being enough.

It has been pointed out that one of the reasons why the leak current characteristic and the dielectric strength characteristic are not sufficient is that when an organic metal compound is used as a film forming material, organic components such as carbon remain in the thin film.

Another factor is that it is generally difficult to form the composition ratio of oxygen (0) and tantalum (Ta) in the tantalum oxide thin film in a stoichiometric state, and oxygen is insufficient. Are listed.

Further, the organic component remaining in the tantalum oxide thin film deprives oxygen in the tantalum oxide thin film when various heat treatments are performed in the subsequent LSI manufacturing process,
For example, they are released from the film in the form of CO or CO ₂ . As a result, there is a drawback that oxygen in the tantalum oxide thin film is further deficient and the deterioration of leak current characteristics and dielectric strength characteristics further progresses.

Therefore, in order to improve the leakage current characteristic and the withstand voltage characteristic, generally, after forming the tantalum oxide thin film, the oxidation treatment for improving the film quality is performed. For example, techniques such as high-temperature annealing treatment in an oxygen atmosphere, oxygen plasma treatment, or annealing treatment in an atmosphere containing ozone (O ₃ ) gas irradiated with ultraviolet rays are known.

However, these oxidation treatments are usually performed at 500 ° C.
Under the above conditions, the effect of improving the film quality of the tantalum oxide thin film is exhibited. Therefore, it becomes impossible to form the capacitive element after the wiring forming process using the Al material.

As described above, since the maximum temperature for forming the capacitive element is defined by this oxidation treatment, although the electrical characteristics are improved, there is a problem that the step of forming the capacitive element in the semiconductor manufacturing process is restricted. Further, productivity may be deteriorated due to an increase in the number of LSI manufacturing steps, and a burden such as the need for dedicated equipment may be accompanied, which may lead to higher costs.

In order to solve the above problems, in order to obtain a good leak current characteristic as a capacitive element, the organic component in the liquid material is effectively released in the process of forming the tantalum oxide thin film which is the dielectric film. Required to do.

[0016]

In order to solve the above-mentioned problems, in the present invention, in the process of forming a metal oxide film on the film formation surface, during the formation of the metal oxide film, H ₂ O is positively generated.

Further, the present invention uses a mixed gas containing an organometallic compound material, oxygen or a compound gas containing oxygen, and hydrogen or a compound gas containing hydrogen in the process of forming the above-mentioned metal oxide film. , H ₂ O.

Furthermore, in the present invention, the above-mentioned metal oxide film is formed by a chemical vapor deposition method. Further, according to the present invention, the above-mentioned metal oxide film is formed by a plasma chemical vapor deposition method.

Further, according to the present invention, a tantalum oxide film is formed as a metal oxide film by using a material containing tantalum as the organometallic compound material. Furthermore, in the present invention, pentaethoxytantalum is used as the organometallic compound material.

Further, according to the present invention, the flow rate ratio of oxygen O _{2 as a} material for forming a metal oxide film to pentaethoxy tantalum as an organometallic compound material is 10 to 50 in terms of molar flow rate.

Further, according to the present invention, after the formation of the above-mentioned metal oxide film, a moisture removal treatment for removing moisture in the metal oxide film is performed. Further, in the present invention, as the moisture removal treatment, a heat treatment is performed at a temperature equal to or higher than the film formation temperature after the metal oxide film is formed. Further, in the present invention, plasma irradiation is performed as the moisture removal process.

Furthermore, the present invention provides the formation of a metal oxide film,
The water removal process is performed in the same device. Further, the present invention is
When forming the metal oxide film, the step of forming a film having a thickness effective for the moisture removal treatment and the step of performing the water removal treatment are repeated to form the metal oxide film having a target thickness.

[0023] As described above, in the present invention, when forming the metal oxide film, which generates a positively H ₂ O, by doing so, H ₂ generated during the film formation O is decomposed to form a metal oxide film with good quality.

Particularly, in forming the film, a mixed gas containing an organometallic compound material, oxygen or a compound gas containing oxygen, and hydrogen or a compound gas containing hydrogen is used to generate H ₂ O.
By generating the metal oxide film, the organic components in the formed metal oxide film can be efficiently released, the lack of oxygen in the metal oxide film can be avoided, and the metal oxide film can be formed with good characteristics. Can be membrane.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following examples, and various other material configurations can be adopted. Needless to say.

In the present embodiment, the present invention is applied to the case where a metal oxide film, particularly a tantalum oxide film, is formed as a capacitive insulating film of a semiconductor device having a capacitive element. An example of forming a film by the plasma CVD method is shown.

In this example, a metal oxide film is formed as a capacitive insulating film of a semiconductor device. In particular, a tantalum oxide film is provided and each layer including the tantalum oxide film is formed by plasma CVD. Filmed

FIG. 1 shows an example of the structure of the plasma CVD apparatus 1, and in this case, an example using a helicon wave plasma source is shown. This plasma CVD apparatus 1 is
It has a helicon wave plasma generation source 2 and a reaction vessel 4 communicating with a bell jar 3 made of quartz or the like for generating the plasma.

Inside the reaction vessel 4, such as a semiconductor wafer,
A substrate 5 having a film formation surface is placed, and a susceptor 6 provided with a heater for heating the substrate 5 to a required temperature is arranged. The reaction vessel 4 is provided with a gas introduction port 7 for introducing a process gas, and is exhausted from an exhaust port 8 by an exhaust means (not shown), and the inside of the reaction vessel 4 is exhausted by a pressure regulator (not shown). The degree of vacuum is adjusted to a desired degree.

In the process source 2, a helicon antenna 9 is arranged around the bell jar 3, and the helicon antenna 9 has a radio frequency (RF) oscillator 10 to 18.56 MH.
RF power of z is applied through the impedance matching means 11.

Further, the inner coil 1 is provided near the bell jar 3.
2A and the outer coil 12B are wound. These coils 12A and 12B have direct current (D
C) are supplied from the DC power supplies 13A and 13B through the current control means 14A and 14B, respectively, to form magnetic fields, and the current values and their ratios are adjusted to draw out plasma generated in the bell jar 3 by helicon wave propagation. At the same time, the plasma uniformity in the vicinity of the substrate 5 is adjusted by the interaction with the magnetic field generated by the magnetic field generating means 15 which is a permanent magnet or an electromagnet installed on the side surface of the reaction container 4.

In the present embodiment, the plasma CVD apparatus 1 having this structure uses a gas species to be supplied as an organometallic compound material to form a metal oxide film by MOCVD, and in particular pentaethoxytantalum (hereinafter referred to as PET).
Was used to form a tantalum oxide thin film as a capacitive insulating film of the capacitive element in the DRAM described above by the MOCVD method.

Although not shown in FIG. 1, PET is vaporized by being compressed with a gas for pressurization inside the liquid material container and then extruded, then controlled to a desired flow rate by a liquid flow meter, and further heated to a desired temperature. Sent to the machine, liquid material in this case PE
It is introduced from the gas inlet 7 into the above-mentioned reaction vessel 4 together with a gas for vaporizing T and further improving the transportation efficiency. An inert gas is generally used as the pressurizing gas and the transporting gas, but the condition is that it does not react with the liquid material PET,
Alternatively, a gas is selected that does not dissolve in the liquid material, in other words, does not deteriorate the liquid material. In addition, at this time, all the transportation piping paths from the vaporizer to the reaction container 4 are heated by a heating means such as a tape heater so that the vaporized liquid material is not reliquefied.

Here, the hydrolyzability of PET will be described. FIG. 2 shows the molecular structure of PET. Usually, the reaction of removing organic components with a material that becomes an oxidation source, such as oxygen,
As shown in FIG. 3, oxygen reacts with carbon, or oxygen reacts with hydrogen to form CO, HO, and the like, and they are released.

On the other hand, in the reaction with H ₂ O, as shown in FIG. 4, the bond between oxygen and carbon of the alkoxyl group constituting PET is cut, the oxygen of PET is terminated by hydrogen, and the ethyl group is Terminate with a hydroxyl group. By this reaction, by using H ₂ O, that is, by positively generating H ₂ O, PE
By forming a tantalum oxide thin film from T, PE
It can be seen that the organic component of T can be efficiently released.

On the other hand, the properties of other liquid materials used as the CVD film forming material will be described below.
Many liquid materials are in a liquid state even at room temperature and atmospheric pressure, and many of them hydrolyze when they come into contact with air, and their reactivity varies depending on each material.

For example, when a silicon oxide thin film is formed by CVD, tetraethoxysilane (TEOS; Si (OC ₂ H ₅ ) ₄ ) which is widely used as a film forming material is a typical compound whose hydrolysis is slow. is there.

However, as described above, PET is known as a representative of highly reactive compounds, and in the present invention, it is possible to form a high-quality tantalum oxide thin film by utilizing such properties. Is something that can be done. In other words, the present invention focuses on the fact that PET is a material that is highly hydrolyzable, and is able to form a better quality tantalum oxide thin film.

Prior to the formation of the metal oxide film, the present inventors changed the gas flow rate ratio at the time of forming the tantalum oxide thin film with the mixed gas of PET and oxygen by the above-mentioned plasma CVD apparatus. Then, the current leakage characteristic of the deposited tantalum oxide thin film, in this case, the withstand voltage dependency was examined.

In this example, a tantalum oxide thin film was formed as a capacitive insulating film of a capacitive element, a DC component voltage (V) was applied to the electrode layer, and a leak current density (I) was measured.

There is a region where the leak current density does not increase to a certain value with respect to a change in the applied voltage, and then enters the region of so-called Pool-Frenkel current. Since the voltage immediately before this is a region in which the LSI can be stably used, the breakdown voltage of this measurement is defined as the voltage before the Pool-Frenkel current flows. The result is shown in FIG.

As can be seen from FIG. 5, oxygen O ₂ gas and P
When the flow rate ratio with the ET gas decreases, the withstand voltage of the leakage current tends to improve, and the molar ratio [O ₂ / Ta (OC
₂ H ₅ ) ₅ ] shows that when [O ₂ / Ta (OC ₂ H ₅ ) ₅ ] ≦ 50, superiority appears.

Further, particles generated during film formation,
Molar ratio [O₂/ Ta (OC₂H_Five) _Five] To measure the relationship with
did. The result is shown in FIG. As you can see from Figure 6,
Molar flow ratio [O₂/ Ta (OC₂H_Five)_Five] Less than 10
When, the amount of particles generated increases and
It turns out that it is difficult to form a film. Therefore, the above
The molar ratio is 10 ≦ [O₂/ Ta (OC₂H_Five)_Five] By doing so, good film formation can be performed.
I understand.

Further, as a result of analyzing this tantalum oxide thin film, the molar flow rate ratio [O ₂ / Ta of O ₂ gas and PET gas]
It was found that a large amount of H ₂ O remaining in the film was contained under the condition that (OC ₂ H ₅ ) ₅ ] was small. From the result, it was found that the oxygen introduced at the same time as hydrogen contained in PET reacted during the reaction to form H ₂ O, which promoted the hydrolysis, so that the organic component in the tantalum oxide thin film was efficiently released. Conceivable.

From the above, the molar flow ratio [O ₂ / Ta (OC ₂ H ₅ ) ₅ ] of oxygen and PET is 10 or more and 5 as a condition for forming the tantalum oxide thin film in the plasma CVD method.
Good results are obtained when the value is 0 or less.

During the formation of the tantalum oxide thin film, H
₂The reaction that produces O is the hydrogen in PET and the introduced acid.
In addition to reacting with elementary gas, for example, H₂+ O₂Or H
₂O ₂Can be promoted by using.

FIG. 7 shows a case where the metal oxide film thus formed is used as a capacitive insulating film of a capacitive element of a semiconductor device.
This will be described with reference to the schematic enlarged sectional view of FIG. In this example, the case of application to a capacitive element of DRAM is shown.

In FIG. 7, reference numeral 31 denotes a p-type substrate made of silicon or the like, on which a p-type substrate is formed by selective oxidation.
A thick element isolation region 32 is formed in a region other than the transistor region, and an electrode layer 34 on the fixed potential side, for example, which constitutes a capacitive element is formed on the thick element isolation region 32 via the capacitive insulating film 33 made of the above-described tantalum oxide thin film.

Reference numeral 35 is an insulating layer made of silicon oxide or the like, 3
Reference numeral 6 denotes a gate insulating film, and the gate electrode 37 and the impurity regions 39 on both sides thereof form a switching MOS transistor. Reference numeral 38 indicates an electrode layer for word lines made of, for example, polysilicon. Reference numeral 40 is an insulating layer made of thick silicon oxide or the like, and an electrode layer 41 made of Al or the like on the bit line side is formed in a predetermined pattern. 42 indicates a protective film.

In such a structure, the above-described tantalum oxide thin film is used as the capacitive insulating film of the capacitive element in the plasma CV.
By forming the film while positively generating H ₂ O by the D method, it was possible to obtain a film having excellent leakage current characteristics and dielectric strength characteristics.

As described above, in the present invention, organic gold is used.
Efficiently removes organic components from metal materials to form metal oxide film
H method₂O is positively generated to form the film
It has been explained that doing is effective. But Naga
On the other hand, during the film formation reaction, H ₂Forming O
This moisture may remain in the film and deteriorate the leak current characteristics.
It is considered to have potential. As a countermeasure against this, the present invention
In, the metal oxide film was formed by the method described above.
After that, by removing the water taken in the membrane,
Further, the film quality can be improved.

As a method, by maintaining the substrate temperature at 100 ° C. or higher, the proportion of residual water can be considerably reduced. The higher the substrate temperature is, the lower the residual water content becomes, but the upper limit temperature is naturally limited due to the influence on the lower electrode material and other elements. For example, in the case of a substrate on which Al has already been formed for use as a lower electrode or other wiring, the upper limit temperature is 450 ° C., more preferably 400 ° C.
By setting the temperature to be ° C, it is possible to avoid the influence on the Al wiring and other elements. By such moisture removal treatment by heating, it is possible to avoid deterioration of leak current characteristics due to residual moisture in the tantalum oxide thin film.

Further, even when plasma irradiation is performed as the moisture removal treatment, the moisture can be activated or the substrate temperature can be raised to effectively reduce the proportion of residual moisture in the film.

In addition, in order to efficiently perform the above moisture removal treatment, the formation of the metal oxide film and the above moisture removal treatment are alternately performed to form the target metal oxide film. As a result, a metal oxide film having a low residual water content and a good film quality can be reliably formed without depending on the film thickness of the metal oxide film.

In the above embodiment, PET is used.
Although an example in which good film quality can be obtained when a tantalum oxide thin film is formed by using as a film forming material, the present invention forms a metal oxide film by using a liquid material rich in hydrolysis. It goes without saying that it can be applied to various cases. For example, as an organic metal material, in addition to PET, Ta (OC
_{H 3) 5, Ta (OC} 3 H 7) 5, Ta (OC 4 H 9)
₅ , Ta (OC ₂ H ₅ ) ₄ (OCHCH ₂ N (CH ₃ )
By using ₂ ) or the like, a metal oxide film having excellent characteristics can be formed.

[0056]

As described above, according to the present invention, H ₂ O is positively generated when the metal oxide film is formed. By doing so, the H ₂ O is generated during the film formation. H ₂ O is decomposed to form a metal oxide film with good quality.

In particular, in forming the film, an organometallic compound
Material, oxygen or oxygen-containing compound gas, hydrogen or water
Aggressive by using a mixed gas containing a compound gas containing element
To H ₂Oxidation to form a film of metal oxide
The organic components in the film can be removed efficiently, and metal
Good characteristics by avoiding lack of oxygen in the oxide film
With this, a metal oxide film can be formed.

When the tantalum oxide thin film is formed, P
By applying the present invention when a film is formed by the plasma CVD method using ET, oxygen deficiency in the film can be reduced, and the concentration of impurities such as residual carbon can be surely reduced. By applying it when forming a tantalum oxide thin film as a capacitive insulating film, the leakage current characteristics can be significantly improved, the characteristics of the capacitive element can be improved, and a semiconductor device having a capacitive element can be provided with good characteristics. Can be manufactured.

Further, after the metal oxide film is formed, a moisture removal treatment is performed to surely reduce the proportion of water remaining in the film, and to form a metal oxide film having more excellent leak current characteristics. be able to.

[Brief description of drawings]

FIG. 1 is a configuration diagram of an example of a plasma processing apparatus.

FIG. 2 is a diagram showing a molecular structure of pentaethoxytantalum (PET).

FIG. 3 is an explanatory diagram of a reaction between pentaethoxy tantalum (PET) and oxygen gas.

FIG. 4 is an explanatory diagram of a reaction between pentaethoxy tantalum (PET) and H ₂ O.

FIG. 5 is a diagram showing a relationship of a withstand voltage characteristic of leak current with respect to a molar flow rate ratio of O ₂ gas and pentaethoxy tantalum gas.

FIG. 6 is a diagram showing the relationship between the amount of particles generated and the molar flow ratio of O ₂ gas and pentaethoxytantalum gas.

FIG. 7 is a schematic enlarged cross-sectional view of an example of a semiconductor device.

[Explanation of symbols]

1 plasma processing apparatus, 2 plasma source, 3 bell jar, 4 reaction vessel, 5 substrate, 6 susceptor, 7
Gas inlet, 8 exhaust, 9 helicon antenna, 1
0 high frequency oscillator, 11 impedance matching means, 1
2A inner coil, 12B outer coil, 13A DC
Power supply, 13B DC power supply, 14A current control means, 14
B current control means, 15 magnetic field generation means, 31 substrate,
32 element isolation region, 33 capacitance insulating film, 34 electrode layer, 35 insulating layer, 36 gate insulating film, 37 gate electrode, 38 electrode layer, 39 impurity region, 40 insulating layer, 41 electrode layer, 42 protective film

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Ken Adachi             6-735 Kita-Shinagawa, Shinagawa-ku, Tokyo Soni             -Inside the corporation (72) Inventor Tetsuya Komoto             3-19-2 Minamirokugo, Ota-ku, Tokyo Stocks             Company CV Research F term (reference) 5F038 AC03 AC05 AC09 AC15 AC18                       DF05 EZ20                 5F058 BA01 BA11 BC03 BC20 BF07                       BF27 BF29 BF39 BF80 BG01                       BH01 BH16                 5F083 AD21 JA06 NA08

Claims (36)

[Claims] 1. A process for forming a metal oxide film on a film-forming surface.
By the way, H ₂Characterized by producing O
A method for forming a metal oxide film. 2. In the process of forming the metal oxide film, a mixed gas containing an organometallic compound material, oxygen or a compound gas containing oxygen, and hydrogen or a compound gas containing hydrogen is used to generate H ₂ O. The method for forming a metal oxide film according to claim 1, wherein the metal oxide film is formed. 3. The method for forming a metal oxide film according to claim 1 or 2, wherein the film formation of the metal oxide film is performed by a chemical vapor deposition method. 4. The method for forming a metal oxide film according to claim 1, 2 or 3, wherein the film formation of the metal oxide film is performed by a plasma chemical vapor deposition method. 5. The tantalum oxide film is formed as the metal oxide film by using a material containing tantalum as the organometallic compound material.
A method for forming a metal oxide film according to item 1. 6. The method for forming a metal oxide film according to claim 2, wherein pentaethoxytantalum is used as the organometallic compound material. 7. A flow rate ratio of oxygen O ₂ which is a material in the formation of the metal oxide film and pentaethoxy tantalum as the organometallic compound material is 10 or more and 50 in terms of molar flow rate.
The method for forming a metal oxide film according to claim 6, wherein: 8. The method of claim 1, 2, 3, 4, 5, 6 or 7, wherein after the formation of the metal oxide film, a moisture removal process for removing moisture in the metal oxide film is performed. A method for forming a metal oxide film according to item 1. 9. The method for depositing a metal oxide film according to claim 8, wherein, as the moisture removal treatment, a heat treatment is performed at a temperature equal to or higher than a deposition temperature after depositing the metal oxide film. 10. The method for forming a metal oxide film according to claim 8, wherein plasma irradiation is performed as the moisture removal process. 11. The method for forming a metal oxide film according to claim 8, wherein the film formation of the metal oxide film and the water removal treatment are performed in the same apparatus. 12. In forming the metal oxide film, the step of forming a film having a thickness effective for the moisture removal treatment and the step of performing the moisture removal treatment are repeated to obtain the object of the metal oxide film. The method for forming a metal oxide film according to claim 8, 9, 10 or 11, wherein the film is formed to a film thickness. 13. A method of manufacturing a capacitive element using a metal oxide film as a capacitive insulating film, wherein H ₂ O is positively generated in the process of forming the metal oxide film on the film formation surface. And a method for manufacturing a capacitive element. 14. A mixed gas containing an organometallic compound material, oxygen or a compound gas containing oxygen, and hydrogen or a compound gas containing hydrogen is used to form H ₂ O in the process of forming the metal oxide film. 14. The method for manufacturing a capacitive element according to claim 13, wherein the manufacturing method is as follows. 15. The method of manufacturing a capacitive element according to claim 13, wherein the metal oxide film is formed by a chemical vapor deposition method. 16. The method for manufacturing a capacitive element according to claim 13, 14 or 15, wherein the metal oxide film is formed by a plasma chemical vapor deposition method. 17. The capacitance element according to claim 14, wherein a tantalum oxide film is formed as the metal oxide film by using a material containing tantalum as the organometallic compound material. Production method. 18. The method of manufacturing a capacitive element according to claim 14, 15, 16 or 17, wherein pentaethoxytantalum is used as the organometallic compound material. 19. A flow rate ratio of oxygen O _{2 as a} material for forming the metal oxide film to pentaethoxy tantalum as the organometallic compound material is 10 or more and 5 as a molar flow rate ratio.
19. The method of manufacturing a capacitive element according to claim 18, wherein the capacitance is 0 or less. 20. The moisture desorption treatment for desorbing moisture in the metal oxide film is performed after the metal oxide film is formed, according to any one of claims 13, 14, 15, 16, and 17.
18. The method for manufacturing the capacitive element according to 18 or 19. 21. The method of manufacturing a capacitive element according to claim 20, wherein, as the moisture removal treatment, a heat treatment is performed at a temperature equal to or higher than a film formation temperature after the metal oxide film is formed. 22. The method of manufacturing a capacitive element according to claim 20, wherein plasma irradiation is performed as the moisture removal treatment. 23. The method of manufacturing a capacitive element according to claim 20, 21 or 22, wherein the film formation of the metal oxide film and the moisture removal process are performed in the same apparatus. 24. When forming the metal oxide film, the step of forming a film having a thickness effective for the moisture removal treatment and the step of performing the moisture removal treatment are repeated to obtain the object of the metal oxide film. The method for manufacturing a capacitive element according to claim 20, 21, 22, or 23, characterized in that a film having a film thickness is formed. 25. A method of manufacturing a semiconductor device having a metal oxide film, wherein H ₂ O is positively generated in the process of forming the metal oxide film on the film formation surface. Of manufacturing a semiconductor device. 26. In the process of forming the metal oxide film, H ₂ O is prepared by using a mixed gas containing an organometallic compound material, oxygen or a compound gas containing oxygen, and hydrogen or a compound gas containing hydrogen. 26. The method for manufacturing a semiconductor device according to claim 25, wherein: 27. The method of manufacturing a semiconductor device according to claim 25, wherein the metal oxide film is formed by a chemical vapor deposition method. 28. The method of manufacturing a semiconductor device according to claim 25, 26 or 27, wherein the metal oxide film is formed by a plasma chemical vapor deposition method. 29. The semiconductor device according to claim 26, wherein the tantalum oxide film is formed as the metal oxide film by using a material containing tantalum as the organometallic compound material. Production method. 30. The method of manufacturing a semiconductor device according to claim 26, 27, 28 or 29, wherein pentaethoxytantalum is used as the organometallic compound material. 31. A flow rate ratio of oxygen O _{2 as a} material for forming the metal oxide film and pentaethoxy tantalum as the organometallic compound material is 10 or more and 5 as a molar flow rate ratio.
31. The method for manufacturing a semiconductor device according to claim 30, wherein the number is 0 or less. 32. The moisture removal treatment for removing moisture in the metal oxide film is performed after the formation of the metal oxide film, according to any one of claims 25, 26, 27, 28 and 29.
30. The method for manufacturing a semiconductor device according to 30 or 31. 33. The method of manufacturing a semiconductor device according to claim 32, wherein, as the moisture removal process, a heat treatment is performed at a temperature equal to or higher than a film formation temperature after the metal oxide film is formed. 34. The method of manufacturing a semiconductor device according to claim 32, wherein plasma irradiation is performed as the moisture removal process. 35. The method of manufacturing a semiconductor device according to claim 32, 33 or 34, wherein the film formation of the metal oxide film and the moisture removal treatment are performed in the same device. 36. When forming the metal oxide film, the step of forming a film having a thickness effective for the moisture removal treatment and the step of performing the moisture removal treatment are repeated to obtain the object of the metal oxide film. The method for manufacturing a semiconductor device according to claim 32, 33, 34 or 35, characterized in that a film having a film thickness is formed.