JP2001085425A - Method of manufacturing dielectric film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate the need of a process for removing unwanted films formed on the rear surface of a substrate by making an electrostatic chuck usable by making a ferroelectric film formable at a substrate temperature of <=400 deg.C. SOLUTION: In a method for manufacturing dielectric film, an SrxBiy(Ta, Nb)2.0TizOw film 16, having a ferroelectric characteristic, is formed in such a way that a reaction gas is prepared by mixing together at least four kinds of organometallic compounds respectively selected from among a first group composed of organo-Bi compounds, a second group composed of organo-Sr compounds, a third group composed of organo-Ti compounds, and a fourth group composed of organo-Ta and organo-Nb compounds. After an oxidizing gas is mixed with the reaction gas, an oxidized film is formed on a substrate 10 maintained at <=400 deg.C by chemical vapor growth utilizing plasma energy, by introducing the mixed gas to a reaction chamber in which the substrate 10 is set up. Then the oxidized film is heat-treated in an oxidizing atmosphere.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a dielectric film, and more particularly, to a method for manufacturing a dielectric film used for a dielectric capacitor, for example.

[0002]

_2. Description of the Related Art Bismuth layered ferroelectric SrBi ₂ (T
a, Nb) ₂ O _{9 is produced} by metal organic chemical vapor deposition (hereinafter referred to as M
OCVD, MOCVD is Metal Organic Chemica
l In the case of manufacturing by the Vapor Deposition method, strontium (Sr), bismuth (Bi), tantalum (T
a) an organometallic raw material containing each element such as niobium (Nb) is mixed with oxygen together with a carrier gas, then introduced into a reaction chamber, and placed on a substrate heated to a temperature higher than 400 ° C. installed in the reaction chamber. SrBi using thermal decomposition reaction
A thermal CVD method for depositing ₂ (Ta, Nb) ₂ O ₉ has been used.

Incidentally, SrBi ₂ (T
a, Nb) ₂ O ₉ film is formed at a substrate temperature of 400
When the film is formed at a temperature of less than or equal to ° C., bismuth (Bi) hardly precipitates in the film, so that SrBi _{2 having} excellent electric characteristics is formed.
It was difficult to produce a (Ta, Nb) ₂ O ₉ film. Therefore, in the conventional thermal CVD method, the substrate temperature is set to 40
The temperature was higher than 0 ° C. The SrBi ₂ (Ta, Nb) ₂ O ₉ film formed at a substrate temperature of more than 400 ° C. and not more than 600 ° C. by a conventional thermal CVD method is 700 ° C. to 80 ° C.
By performing crystallization at a temperature of about 0 ° C., sufficient ferroelectric properties were obtained.

[0004]

However, in the prior art, it was difficult to fix the substrate by the electrostatic chuck because the substrate temperature had to be set to a temperature exceeding 400 ° C. Even when the electrostatic chuck is used in such a high temperature state, the chucking performance is reduced, so that the reaction gas flows around the back surface of the substrate, and the film is formed on the back surface of the substrate. Therefore, SrBi ₂ deposited on the back side of the substrate
In order to remove (Ta, Nb) ₂ O ₉ , an additional removal process was required, resulting in an increase in the number of steps. One of the objects of the present invention is to solve this problem.

In the prior art, it is necessary to perform a heat treatment at a temperature higher than 700 ° C. and about 800 ° C. or less in order to obtain good ferroelectric characteristics. This heat treatment is performed by SrBi ₂
A thermal load is applied to an electrode of a capacitor using (Ta, Nb) ₂ O ₉ as a dielectric film, which causes deterioration of electric resistance. Therefore, a technique for forming a ferroelectric film at a low temperature of at least 700 ° C. has been required. One of the objects of the present invention is to solve this problem.

[0006]

SUMMARY OF THE INVENTION The present invention is a method for manufacturing a dielectric film which has been made to solve the above-mentioned problems.

[0007] The first manufacturing method uses, for example, the chemical formula Bi (C
₆H_Five)_Three, Bi (o-C₇H₇)_Three, Bi (OC_TwoH
_Five)_Three, Bi (O-iC_ThreeH₇)_Three, Bi (O-tC_Four
H₉)_Three, Bi (O-tC_FiveH₁₁)_ThreeAnd Bi (TH
D)_Three[Hereinafter, THD is 2,2,6,6-tetramethyl
-3,5-heptanedione: C₁₁H₂₀O_TwoRepresents
A first group consisting of an organic bismuth compound
Chemical formula Sr (THD) _Two, Sr (THD)_TwoTetragri
M, Sr (Me_FiveC_Five)_Two2THF [Me is meth
And THF represents tetrahydrofuran.]
A second group of organic strontium compounds,
For example, the chemical formula Ti (i-OC_ThreeH₇)_Four, TiO (TH
D)_Two, Ti (THD)_Two(I-OC_ThreeH₇)_TwoRepresented by
And a third group of organic titanium compounds
The expression Ta (i-OC_ThreeH₇)_Five, Ta (i-OC_ThreeH₇)_Four
Organic tantalum compounds represented by THD and, for example, chemical
The formula Nb (i-OC_ThreeH₇)_Five, Nb (i-OC_ThreeH₇)_Four
A fourth group consisting of an organic niobium compound represented by THD
At least one organometallic compound from each group of
Generate a reaction gas that is selected and mixed to a predetermined composition,
Mixing the reaction gas with an oxidizing gas;
A substrate holding a mixed gas with a reactive gas at 400 ° C or lower is installed.
Use plasma energy by introducing it into the reaction chamber
Oxide film on the substrate by the chemical vapor deposition
Forming a film, and heat-treating the oxide film in an oxidizing gas.
And Sr_xBi_y(Ta, Nb)_2.0Ti_zO_w[Ta
However, 0.6 ≦ x ≦ 1.2, 1.7 ≦ y ≦ 2.5, 0 ≦
z ≦ 1.0, w = 9 ± d, 0 ≦ d ≦ 1]
And a process.

In the first manufacturing method, the first to fourth
A reaction gas is prepared by selecting at least one type of organometallic compound from each of the groups and mixing the mixture with a predetermined composition, and further mixing an oxidizing gas with the reaction gas. Is introduced into a reaction chamber in which a substrate holding a mixed gas of 400 ° C. or less is installed, and an oxide film is formed on the substrate by chemical vapor deposition using plasma energy. Low temperature, for example 200
° C. to 400 ° C. in _{Sr x Bi y (Ta, Nb} ) 2. 0 Ti
_An oxide film serving as a precursor of zO _w is formed. Therefore, the substrate can be fixedly placed using the electrostatic chuck. At this time, since the performance of the electrostatic chuck does not decrease, the reactive gas flows around the back surface of the substrate, and no film is formed on the back surface of the substrate. As explained above,
In the first manufacturing method, the problem relating to the electrostatic chuck is solved.

The above oxide film is formed, for example, at a temperature of 600.degree.
Heat treatment is performed in an oxidizing gas at 00 ° C. to obtain Sr _x Bi _y (T
_{a, Nb) 2.0 Ti z O} w film by forming, precursor is crystallized, excellent ferroelectric properties, for example 2Pr = 10~20μC / cm ² of about Sr _x Bi _{y
(Ta, Nb) 2.0 Ti z} O w film. For example, the substrate temperature Tsub is set to 25 by the first manufacturing method.
At 0 ° C., a SrBi ₂ Ta ₂ O ₉ film was formed to a thickness of 120 nm. Then, a capacitor was formed using the SrBi ₂ Ta ₂ O ₉ film, and the PV characteristics were examined. As a result, a favorable PV hysteresis loop as shown in FIG. 2 could be obtained. In FIG. 2, the vertical axis represents the polarization value (Po
larization) 2Pr, and the horizontal axis represents the applied voltage (Applied).
Voltage). Also, the polarization value 2Pr = 19.6 μC
/ Cm ² .

[0010] In a second manufacturing method, the organic metal compound constituting the reaction gas is converted into the first gas in the first manufacturing method.
Instead of selecting from the group ~ the fourth group of, for example, the formula Sr _{[Ta (O-C 2 H 5} ) 6 ] _2, Sr [Ta (O
-IC ₃ H _{7) 6] 2,} Sr [Nb (O-C
₂ H _{5) 6] 2} and Sr [Nb (O-iC
₃ H ₇ ) ₆ ] ₂ and the first and fourth groups used in the first manufacturing method.

The second manufacturing method is the same as the first manufacturing method except that the selected organometallic compound is different. Therefore, the second manufacturing method is also the first manufacturing method.
In the same manner as in the production method, a low temperature of 400 ° C. or less, for example, 20 ° C. by chemical vapor deposition using plasma energy.
Sr _x Bi _y (Ta, Nb) _2.0 Ti at 0 ° C. to 400 ° C.
_An oxide film serving as a precursor of zO _w is formed. Therefore, the substrate can be fixedly placed using the electrostatic chuck. At this time, since the performance of the electrostatic chuck does not decrease, the reactive gas flows around the back surface of the substrate, and no film is formed on the back surface of the substrate. As explained above,
In the second manufacturing method, the problem relating to the electrostatic chuck is solved.

The oxide film is formed, for example, at a temperature of 600 ° C. to 8
Heat treatment is performed in an oxidizing gas at 00 ° C. to obtain Sr _x Bi _y (T
_{a, Nb) 2.0 Ti z O} w film by forming, precursor is crystallized, excellent ferroelectric properties, for example 2Pr = 10~20μC / cm ² of about Sr _x Bi _{y
(Ta, Nb) 2.0 Ti z} O w film.

[0013] The third manufacturing method comprises at least one of each of the first to fourth groups shown in the first manufacturing method.
A step of generating a reaction gas obtained by selecting and mixing various kinds of organometallic compounds to a predetermined composition, and mixing the reaction gas with an oxidizing gas;
Sr _x Bi _y (Ta, Nb) is introduced onto the substrate by introducing it into a reaction chamber in which a substrate maintained at a temperature of 700 ° C. or lower is installed by chemical vapor deposition using plasma energy.
_2.0 Ti _z O _w [where 0.6 ≦ x ≦ 1.2, 1.
7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w = 9 ± d, 0 ≦ d
.Ltoreq.1]. Forming a film.

In the third manufacturing method, at least one type of organometallic compound is selected from each of the first to fourth groups shown in the first manufacturing method and mixed to a predetermined composition. After the reaction gas is generated and mixed with the oxidizing gas, the mixed gas with the oxidizing gas is
Sr _x Bi _y (Ta, Nb) is introduced into a reaction chamber in which a substrate maintained at a temperature of not less than 700 ° C. and not more than 700 ° C. is placed by chemical vapor deposition using plasma energy.
_{Since the 2.0} Ti _z O _w film is formed, the deposited S
_{r x Bi y (Ta, Nb} ) 2.0 Ti z O w film was crystallized, an excellent film ferroelectric characteristics. This film has a ferroelectric property of, for example, about ² Pr = 10 to 20 μC / cm ² .

As described above, Sr _x crystallized on a substrate by chemical vapor deposition utilizing plasma energy.
Bi _y (Ta, Nb) _2.0 Since Ti _z O _w film is formed directly, has been performed in the conventional process, performing a precursor film at a high 800 ° C. temperature below than 700 ° C. for crystallizing heat treatment It becomes unnecessary. Therefore, Sr _x Bi _y (Ta, Nb) _2.0 Ti _z formed by the third manufacturing method is used.
When a capacitor is formed using an O _w film, the thermal load on the electrode is reduced, and the electrical resistance of the electrode does not deteriorate. In addition, the upper electrode can be formed of a metal film having low heat resistance. As described above, in the third manufacturing method, the thermal load on the electrode is reduced.

[0016] In a fourth manufacturing method, the organic metal compound constituting the reaction gas is mixed with the first metal in the third manufacturing method.
Instead of selecting from the group of the above-mentioned fourth group, the chemical formula Sr
_{[Ta (O-C 2 H 5} ) 6 ] _2, Sr [Ta (O-iC
In ₃ H _{7) 6] 2,} Sr _{[Nb (O-C 2 H 5} ) 6 ] ₂ and Sr _{[Nb (O-iC 3 H 7} ) 6 ] above and the group represented by ₂ third production method It is characterized in that each is selected from the first group and the fourth group used (the first group and the fourth group used in the first manufacturing method).

The fourth manufacturing method is the same as the third manufacturing method except that the selected organometallic compound is different. Therefore, the fourth manufacturing method is also the third manufacturing method.
In the same manner as in the manufacturing method, Sr _x Bi _y (Ta, Nb) _2.0 Ti _z O having excellent crystallized ferroelectric properties is formed on the substrate.
_A film is formed. This film is, for example, 2Pr = 10-2
Ferroelectric characteristics of about 0 μC / cm ² can be obtained. As described above, Sr _x Bi _y (Ta, N) crystallized on a substrate by chemical vapor deposition using plasma energy.
b) Since the _2.0 Ti _z O _z film is directly formed, the conventional process for crystallizing the precursor film is not required.
Heat treatment performed at a temperature higher than 00 ° C. and equal to or lower than 800 ° C. becomes unnecessary. For this reason, the Sr formed by the fourth manufacturing method
_{x Bi y (Ta, Nb)} 2.0 using a Ti _z O _z film when forming a capacitor, thermal load is reduced according to the electrode, thereby preventing deteriorating the electrical resistance of the electrode. In addition, the upper electrode can be formed of a metal film having low heat resistance. As described above, in the fourth manufacturing method, the thermal load on the electrode is reduced.

The fifth manufacturing method comprises at least one of the first to fourth groups shown in the first manufacturing method.
A step of selecting a kind of organometallic compound and mixing and dissolving it in an organic solvent containing THF as a main component so as to have a predetermined composition ratio to form a mixed solution, and vaporizing the mixed solution to generate a reaction gas And introducing the reaction gas into a reaction chamber in which a substrate holding the reaction gas at 400 ° C. or lower is installed, and the reaction gas is decomposed by chemical vapor deposition using plasma energy to oxidize the substrate. Forming an object film, and heat treating the oxide film in an oxidizing gas,
_{Sr x Bi y (Ta, Nb} ) 2.0 Ti z O w [however, 0.6 ≦ x ≦ 1.2,1.7 ≦ y ≦ 2.5,0 ≦ z
≦ 1.0, w = 9 ± d, and 0 ≦ d ≦ 1].

In the fifth manufacturing method, at least one type of organometallic compound is selected from each of the first to fourth groups shown in the first manufacturing method, and THF is used as a main component. A mixed solution was produced by mixing and dissolving in an organic solvent having a predetermined composition ratio, a mixed gas was vaporized to generate a reaction gas, and a substrate holding the reaction gas at 400 ° C. or lower was installed. Since the oxide film is formed on the substrate by chemical vapor deposition using plasma energy after being introduced into the reaction chamber, Sr _x Bi _y at a low temperature of 400 ° C. or less, for example, 200 ° C. to 400 ° C. (Ta, Nb)
_An oxide film serving as a precursor of _2.0 Ti _z O _w is formed. Therefore, the substrate can be fixedly placed using the electrostatic chuck. At this time, since the performance of the electrostatic chuck does not decrease, the reactive gas flows around the back surface of the substrate, and no film is formed on the back surface of the substrate. As described above, the problem relating to the electrostatic chuck is solved in the fifth manufacturing method.

The oxide film is formed, for example, at a temperature of 600.degree.
Heat treatment is performed in an oxidizing gas at about 00 ° C. to obtain Sr _x B
i _y (Ta, Nb) by forming a _2.0 Ti _z O _w film, the precursor is crystallized, excellent ferroelectric properties,
For example, Sr _x B of about ² Pr = 10 to 20 μC / cm ²
_{i y (Ta, Nb) 2.0} Ti z O w film.

[0021] In a sixth production method, the organic metal compound constituting the reaction gas is mixed with the first metal in the first production method.
Instead of selecting from the group of the above-mentioned fourth group, the chemical formula Sr
_{[Ta (O-C 2 H 5} ) 6 ] _2, Sr [Ta (O-iC
In ₃ H _{7) 6] 2,} Sr _{[Nb (O-C 2 H 5} ) 6 ] ₂ and Sr _{[Nb (O-iC 3 H 7} ) 6 ] the group represented by ₂ in the first production method It is characterized in that each is selected from the first group and the fourth group used.

The sixth manufacturing method is the same as the fifth manufacturing method except that the selected organometallic compound is different. Therefore, the sixth manufacturing method is the same as the fifth manufacturing method.
In the same manner as in the production method, a low temperature of 400 ° C. or less, for example, 20 ° C. by chemical vapor deposition using plasma energy.
Sr _x Bi _y (Ta, Nb) _2.0 Ti at 0 ° C. to 400 ° C.
_An oxide film serving as a precursor of zO _w is formed. Therefore, the substrate can be fixedly placed using the electrostatic chuck. At this time, since the performance of the electrostatic chuck does not decrease, the reactive gas flows around the back surface of the substrate, and no film is formed on the back surface of the substrate. As explained above,
In the sixth manufacturing method, the problem relating to the electrostatic chuck is solved.

Then, the oxide film is formed, for example, at a temperature of 600.degree.
Heat treatment is performed in an oxidizing gas at 00 ° C. to obtain Sr _x Bi _y (T
_{a, Nb) 2.0 Ti z O} w film by forming, precursor is crystallized, excellent ferroelectric properties, for example 2Pr = 10~20μC / cm ² of about Sr _x Bi _{y
(Ta, Nb) 2.0 Ti z} O w film.

In a seventh manufacturing method, at least one type of organometallic compound is selected from each of the first to fourth groups shown in the first manufacturing method, and THF is used as a main component. A step of producing a mixed solution by mixing and dissolving in an organic solvent so as to have a predetermined composition ratio, a step of vaporizing the mixed solution to generate a reaction gas, and a step of mixing the reaction gas with an oxidizing gas And introducing a mixed gas with the oxidizing gas into a reaction chamber in which a substrate holding a temperature of 500 ° C. or more and 700 ° C. or less is installed, and Sr _x Bi _{y is} deposited on the substrate by chemical vapor deposition using plasma energy. (Ta, Nb)
_2.0 Ti _z O _w [where 0.6 ≦ x ≦ 1.2, 1.
7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w = 9 ± d, 0 ≦ d
≦ 1] to form a film.

In the seventh manufacturing method, at least one kind of organometallic compound is selected from each of the first to fourth groups shown in the first manufacturing method, and THF is used as a main component. A mixed solution is produced by mixing and dissolving in an organic solvent so as to have a predetermined composition ratio, and the mixed solution is vaporized to generate a reaction gas. After the reaction gas is mixed with an oxidizing gas, the oxidizing gas is mixed. Is introduced into a reaction chamber in which a substrate holding a temperature of 500 ° C. or more and 700 ° C. or less is placed, and Sr _x Bi _y (Ta, Nb) is deposited on the substrate by chemical vapor deposition using plasma energy. _2.0 Ti _z O _w
Since the film is formed, the formed Sr _x Bi _y (T
_{a, Nb) 2.0 Ti z O} w film was crystallized, an excellent film ferroelectric characteristics. This film is, for example, 2Pr = 1
Ferroelectric characteristics of about 0 to ²⁰ μC / cm ² can be obtained.

As described above, Sr _x crystallized on the substrate by chemical vapor deposition utilizing plasma energy.
Bi _y (Ta, Nb) _2.0 Since Ti _z O _w film is formed directly, has been performed in the conventional process, performing a precursor film at a high 800 ° C. temperature below than 700 ° C. for crystallizing heat treatment It becomes unnecessary. Therefore, the Sr _x Bi _y (Ta, Nb) _2.0 Ti _z formed by the seventh manufacturing method is used.
When a capacitor is formed using an O _w film, the thermal load on the electrode is reduced, and the electrical resistance of the electrode does not deteriorate. In addition, the upper electrode can be formed of a metal film having low heat resistance. As described above, in the seventh manufacturing method, the thermal load on the electrode is reduced.

In the eighth production method, instead of selecting the organometallic compound constituting the reaction gas from the first group to the fourth group in the first production method, the chemical formula Sr [T
_{a (O-C 2 H 5} ) 6 ] _2, Sr [Ta (O-iC ₃ H
₇ ) ₆ ] ₂ , Sr [Nb (O—C ₂ H ₅ ) ₆ ] ₂ and a group represented by Sr [Nb (O—iC ₃ H ₇ ) ₆ ] ₂ were used in the first production method. It is characterized in that each is selected from the first group and the fourth group.

In the eighth manufacturing method, only the selected organometallic compound is different, and the other steps are the same as in the seventh manufacturing method. Therefore, the eighth manufacturing method is also the seventh manufacturing method.
In the same manner as in the manufacturing method, Sr _x Bi _y (Ta, Nb) _2.0 Ti _z O having excellent crystallized ferroelectric properties is formed on the substrate.
_A film is formed. This film is, for example, 2Pr = 10-2
Ferroelectric characteristics of about 0 μC / cm ² can be obtained. As described above, Sr _x Bi _y (Ta, N) crystallized on a substrate by chemical vapor deposition using plasma energy.
b) Since the _2.0 Ti _z O _w film is directly formed, the conventional process for crystallizing the precursor film has been performed.
Heat treatment performed at a temperature higher than 00 ° C. and equal to or lower than 800 ° C. becomes unnecessary. Therefore, the Sr formed by the eighth manufacturing method
_{x Bi y (Ta, Nb)} 2.0 Ti z O w film using the case of forming a capacitor, thermal load is reduced according to the electrode, thereby preventing deteriorating the electrical resistance of the electrode. In addition, the upper electrode can be formed of a metal film having low heat resistance. As described above, in the eighth manufacturing method, the thermal load on the electrode is reduced.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One example of an embodiment according to a first manufacturing method of the present invention will be described with reference to a schematic sectional view of FIG.

As shown in FIG. 1, a silicon oxide film 12 is formed on a semiconductor substrate (for example, a silicon substrate) 11 to a thickness of, for example, 300 nm by, for example, a thermal oxidation method. Thereafter, a titanium (Ti) film 13 is formed to a thickness of, for example, 30 nm on the silicon oxide film 12 by, for example, sputtering, and then a platinum (Pt) film 14 is formed, for example, to a thickness of 200 nm.
The first electrode 15 is formed to a thickness of nm.

The substrate 10 formed as described above is provided, for example, in a reaction chamber (not shown) of a general high-frequency plasma CVD apparatus, and is 400 ° C. or lower, for example, 2 ° C.
It is mounted on a plasma discharge electrode (not shown) maintained at 00 ° C. to 400 ° C.

Next, the chemical formula Bi (C ₆ H ₅ ) ₃ , Bi
_{(O-C 7 H 7)} 3, Bi (O-C 2 H 5) 3, Bi (O
_{-IC 3 H 7) 3, Bi} (O-tC 4 H 9) 3, Bi
_{(O-tC 5 H 11)} 3 and Bi (THD) ₃ [hereinafter,
THD is 2,2,6,6-tetramethyl-3,5-heptanedione: C ₁₁ H ₂₀ O ₂ ], for example, Bi (o-C ₇
H ₇ ) ₃ was selected and, in a vaporized state, argon (Ar)
The gas is conveyed to a stage preceding the reaction chamber by a gas (for example, a supply flow rate is 200 cm ³ / min).

Further, the chemical formula Sr (THD)_Two, Sr (T
HD)_TwoTetraglyme, Sr (Me _FiveC_Five)_Two2THF
[Where Me represents a methyl group and THF is tetrahydro
An organic strontium compound represented by
From the second group consisting of, for example, Sr (THD)_TwoAnd select
In a vaporized state, an argon (Ar) gas [for example, a supply flow
220cm^Three/ Min] before the reaction chamber
Transport to

Further, the chemical formula Ti (i-OC ₃ H ₇ ) ₄ ,
TiO (THD) ₂ , Ti (THD) ₂ (i-OC ₃ H
₇₎ made of an organic titanium compound represented by the ₂ third example from the group of _{Ti (i-OC 3 H 7} ) 4 is selected, in vaporized state, argon (Ar) gas [e.g. supply flow rate is 30
cm ³ / min] to the preceding stage of the reaction chamber.

In addition, the chemical formula Ta (i-OC ₃ H ₇ ) ₅ ,
_{Ta (i-OC 3 H 7} ) 4 organic tantalum compound represented by the THD and chemical formula _{Nb (i-OC 3 H 7} ) 5, Nb
(I-OC ₃ H ₇₎ made of an organic niobium compound represented by ₄ THD fourth example from the group of _{Ta (i-OC 3 H 7} )
₅ is selected and transported to the previous stage of the reaction chamber by an argon (Ar) gas (for example, a supply flow rate of 50 cm ³ / min) in a vaporized state.

In the preceding stage of the reaction chamber, an oxygen (O ₂ ) [for example, when the supply flow rate is 50
0 cm ³ / min]. Then, the mixed gas is introduced into the reaction chamber. At that time, the temperature of the mixed gas until it is introduced into the reaction chamber is kept, for example, in the range of 150 ° C to 250 ° C. Further, the temperature of the gas diffusion nozzle of the introduction part is kept at, for example, 150 ° C. to 250 ° C. so that a uniform gas flow is generated in the reaction chamber when the gas is introduced into the reaction chamber. Then, the pressure of the mixed gas introduced into the reaction chamber is adjusted so as to be uniformly in the range of 1.33 Pa to 1.33 kPa, preferably 13.3 Pa to 400 Pa, and the input power of the high-frequency power is set to 0.5 W. / Cm ²
Plasma is discharged at a setting in the range of 10 to 10 W / cm ² , and a film is formed by chemical vapor deposition using the plasma energy. That is, the reaction gas is decomposed by the plasma energy, and the reaction gas is chemically vapor-grown to generate and deposit an oxide to form an oxide film (not shown).

The oxide film is made of Sr / (Ta + Nb),
Each of the atomic composition ratios represented by Bi / (Ta + Nb) and Ti / (Ta + Nb) is 0.6 ≦ 2Sr /
(Ta + Nb) ≦ 1.2, 1.7 ≦ 2Bi / (Ta + N
b) ≦ 2.8 and 0 ≦ 2Ti / (Ta + Nb) ≦ 1.
0 is satisfied. In this embodiment, since niobium (Nb) is not contained, Nb = 0, so that the oxide film has an atomic composition ratio of Sr / Ta, Bi / Ta, and Ti / Ta. Each is
0.6 ≦ 2Sr / Ta ≦ 1.2, 1.7 ≦ 2Bi / Ta
It suffices to satisfy the relationship of ≦ 2.8 and 0 ≦ 2Ti / Ta ≦ 1.0. If the above relations are not satisfied, Sr _x Bi having ferroelectric properties is used.
_y (Ta, Nb) _2.0 Ti _z O _w film cannot be obtained. Therefore, it is necessary to satisfy the above relationships.

Thereafter, the substrate is used as an oxidizing gas for 60 hours.
As a result of performing the heat treatment for 1 hour in an oxygen atmosphere at a normal pressure of 0 ° C. to 800 ° C., the oxide film is crystallized, for example, 20 μm.
The thickness of 0nm of _{Sr x Bi y Ta 2.0 Ti z} O w film 1
It became 6. Here, x, y, z, w, and d are 0.6 ≦
x ≦ 1.2, 1.7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w
= 9 ± d and 0 ≦ d ≦ 1.

Further, Sr _x B
i _y Ta _2.0 Ti _z O _w film 16 of platinum (Pt) on 1
The second electrode 17 is formed by depositing to a thickness of 00 nm.
Next, a heat treatment was performed for 1 hour in an oxygen atmosphere at 725 ° C., for example. After that, the first electrode 15, Sr _x Bi _y T
a _2.0 Ti _z O constitutes a capacitor in _w film 16 and the second electrode 17 was measured a P-V ^{hysteresis, 2Pr = 10μC / cm 2 ~20μC} / cm 2, 2
A value of Ec = 100 kV / cm to 150 kV / cm (Ec is a coercive electric field) was obtained.

In the first manufacturing method, the first to fourth
A reaction gas is prepared by selecting at least one type of organometallic compound from each of the groups and mixing the mixture with a predetermined composition, and further mixing an oxidizing gas with the reaction gas. Substrate 1 holding mixed gas of 400 ° C. or less
0 is introduced into a reaction chamber (not shown) in which an oxide film (not shown) is formed on the substrate 10 by chemical vapor deposition using plasma energy.
Sr at a low temperature of 400 ° C or less, for example, 200 ° C to 400 ° C.
_{x Bi y Ta 2.0 Ti z O} w oxide film serving as a precursor is formed. Therefore, when the substrate 10 is mounted on the electrostatic chuck, the performance of the electrostatic chuck does not decrease, so that the substrate 10 can be fixedly mounted. Further, the reactive gas does not flow around the back surface of the substrate 10 to form a film. Therefore, as in the conventional case, strontium (Sr) and bismuth (B
i), there is no need to add a process for removing tantalum (Ta) or the like, and the load of increasing the number of steps is reduced. As described above, in the first manufacturing method, the problem relating to the electrostatic chuck is solved.

Then, the oxide film is formed at a temperature of 600 ° C. to 800 ° C.
The precursor oxide film is crystallized by heat treatment in an oxidizing gas of 2Pr = 2Pr =
10-20 μC / cm ² , 2Ec = 100 kV / cm
Sr _x Bi _y Ta having a value of 150 kV / cm
_{A 2.0} Ti _z O _w film 16 is obtained.

Next, an example of an embodiment according to the second manufacturing method of the present invention will be described below.

On a semiconductor substrate (for example, a silicon substrate),
The silicon oxide film is, for example, 300
It is formed to a thickness of nm. After that, a titanium (Ti) film is formed to a thickness of, for example, 30 nm on the silicon oxide film by, for example, sputtering, and then a platinum (Pt) film is formed to a thickness of, for example, 200 nm, and the first electrode is formed. Form.

As described above, the substrate formed up to the first electrode is provided, for example, in a reaction chamber of a general high-frequency plasma CVD apparatus, and is 400 ° C. or less, for example, 20 ° C.
It is placed on a plasma discharge electrode maintained at 0 ° C. to 400 ° C.

Next, the chemical formula Bi (C ₆ H ₅ ) ₃ , Bi
_{(O-C 7 H 7)} 3, Bi (O-C 2 H 5) 3, Bi (O
_{-IC 3 H 7) 3, Bi} (O-tC 4 H 9) 3, Bi
_{(O-tC 5 H 11)} 3 and Bi (THD) first example from the group of Bi consisting of an organic bismuth compound represented by the ₃
(C ₆ H ₅ ) ₃ is selected, and in a vaporized state, an argon (Ar) gas [for example, a supply flow rate is 30 cm ³ / min]
To a stage preceding the reaction chamber.

In addition, the chemical formula Sr [Ta (OC_TwoH_Five)
₆]_Two, Sr [Ta (O-iC_ThreeH ₇)₆]_Two, Sr
[Nb (OC_TwoH_Five)₆]_TwoAnd Sr [Nb (O-
iC_ThreeH₇)₆]_TwoOrganic strontium-tan represented by
For example, Sr [Ta (O (O
-IC_ThreeH₇)₆]_TwoSelect and evaporate
Gon (Ar) gas [for example, the supply flow rate is 140 cm^Three/ M
in], and is conveyed to the preceding stage of the reaction chamber.

Further, the chemical formula Ti (i-OC ₃ H ₇ ) ₄ ,
TiO (THD) ₂ and Ti (THD) ₂ (i-OC
₃ H ₇₎ made of an organic titanium compound represented by the ₂ third example from the group of _{Ti (THD) 2 (i-} OC 3 H 7) 2 is selected, in vaporized state, argon (Ar) gas [e.g. At a supply flow rate of 30 cm ³ / min] to the preceding stage of the reaction chamber.

In the preceding stage of the reaction chamber,
Oxidizing gas is added to the reaction gas consisting of each organic metal and the carrier gas.
For example, oxygen (O_Two(For example, if the supply flow rate is 500
cm ^Three/ Min) mixing. Then, the mixed gas is
Introduce into the room. At that time, until the introduction into the reaction chamber
Keep the temperature of the mixed gas in the range of 150 ° C to 250 ° C, for example.
One. Furthermore, a uniform gas flow when introduced into the reaction chamber
Gas diffusion nozzle at the inlet so that
Is kept at, for example, 150 ° C. to 250 ° C. So
The pressure of the mixed gas introduced into the reaction chamber
1.33 Pa to 1.33 kPa, preferably within
Adjust to be in the range of 13.3 Pa to 400 Pa
At the same time, the input power of the high-frequency power is 0.5 W / cm^Two
-10W / cm^TwoSet the range to discharge the plasma
Chemical vapor deposition using the plasma energy
To form a film. In other words, the plasma energy
Decompose the reaction gas and make it grow by chemical vapor deposition
Is formed to form an oxide film.

The oxide film is made of Sr / (Ta + Nb),
Each of the atomic composition ratios represented by Bi / (Ta + Nb) and Ti / (Ta + Nb) is 0.6 ≦ 2Sr /
(Ta + Nb) ≦ 1.2, 1.7 ≦ 2Bi / (Ta + N
b) ≦ 2.8 and 0 ≦ 2Ti / (Ta + Nb) ≦ 1.
0 is satisfied. In this embodiment, since niobium (Nb) is not contained, Nb = 0, so that the oxide film has an atomic composition ratio of Sr / Ta, Bi / Ta, and Ti / Ta. Each is
0.6 ≦ 2Sr / Ta ≦ 1.2, 1.7 ≦ 2Bi / Ta
It suffices to satisfy the relationship of ≦ 2.8 and 0 ≦ 2Ti / Ta ≦ 1.0. If the above relations are not satisfied, Sr _x Bi having ferroelectric properties is used.
_y Ta _2.0 Ti _z O _w film can not be obtained. Therefore, it is necessary to satisfy the above relationships.

After that, the substrate is used as an oxidizing gas for 60 hours.
As a result of performing the heat treatment for 1 hour in an oxygen gas at a normal pressure of 0 ° C. to 800 ° C., the oxide film is crystallized, for example, 200 μm.
of nm thick Sr _x Bi _y Ta _2.0 became Ti _z O _w film. Here, x, y, z, w, and d are 0.6 ≦ x ≦
1.2, 1.7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w = 9
± d, 0 ≦ d ≦ 1.

Further, Sr _x B
_{i y Ta 2.0 Ti z O w} 100 platinum (Pt) on the film
Deposited to a thickness of nm to form a second electrode. Then
For example, heat treatment was performed in an oxygen atmosphere at 725 ° C. for one hour. After that, the first electrode, Sr _x Bi _y Ta _2.0 Ti
and a capacitor in _z O _w film and the second electrode, P-
When V hysteresis was measured, 2Pr = 10 μC /
cm ² -20 μC / cm ² , 2Ec = 100 kV / cm
A value of １５０150 kV / cm was obtained.

The second manufacturing method is the same as the first manufacturing method except that the selected organometallic compound is different. Therefore, the second manufacturing method is also the first manufacturing method.
In the same manner as in the production method, a low temperature of 400 ° C. or less, for example, 20 ° C. by chemical vapor deposition using plasma energy.
0 oxide film at ° C. to 400 ° C. is a precursor of _{Sr x Bi y Ta 2.0 Ti z} O w is formed. Therefore, when the substrate is mounted on the electrostatic chuck, the performance of the electrostatic chuck does not decrease, and the substrate can be fixedly mounted. Further, the reaction gas does not flow around the back surface of the substrate to form a film. Therefore, as in the prior art, strontium (Sr) and bismuth (B
i), there is no need to add a process for removing tantalum (Ta) or the like, and the load of increasing the number of steps is reduced. As described above, the problem related to the electrostatic chuck is solved in the second manufacturing method.

Then, the above oxide film is formed at a temperature of 600 to 800 ° C.
The precursor oxide film is crystallized by heat treatment in an oxidizing gas of 2Pr = 2Pr =
10-20 μC / cm ² , 2Ec = 100 kV / cm
Sr _x Bi _y Ta having a value of 150 kV / cm
_{A 2.0} Ti _z O _w film is obtained.

Next, an example of an embodiment according to the third manufacturing method of the present invention will be described below.

For example, iridium oxide (Ir) is deposited on a semiconductor substrate (eg, a silicon substrate) by sputtering.
After forming an O ₂ ) film to a thickness of, for example, 100 nm, an iridium (Ir) film is formed to a thickness of, for example, 100 nm to form a first electrode.

The substrate formed up to the first electrode as described above is provided, for example, in a reaction chamber of a general high-frequency plasma CVD apparatus, and is provided with a plasma discharge electrode maintained at 500 ° C. or more and 700 ° C. or less. Place on top.

Next, the chemical formula Bi (C ₆ H ₅ ) ₃ , Bi
_{(O-C 7 H 7)} 3, Bi (O-C 2 H 5) 3, Bi (O
_{-IC 3 H 7) 3, Bi} (O-tC 4 H 9) 3, Bi
_{(O-tC 5 H 11)} 3 and Bi (THD) first example from the group of Bi consisting of an organic bismuth compound represented by the ₃
(C ₆ H ₅ ) ₃ is selected, and in a vaporized state, an argon (Ar) gas [for example, the supply flow rate is 90 cm ³ / min]
To a stage preceding the reaction chamber.

Chemical formula Sr (THD) ₂ , Sr (THD)
₂ tetraglyme and Sr (Me ₅ C ₅ ) ₂ 2THF
[Where Me represents a methyl group and THF represents tetrahydrofuran] For example, Sr (THD) ₂ tetraglyme was selected from the second group of organic strontium compounds represented by the following formula, and argon (Ar) was vaporized. The gas is conveyed to the preceding stage of the reaction chamber by a gas (for example, the supply flow rate is 80 cm ³ / min).

Chemical formula Ti (i-OC_ThreeH₇)_Four, TiO
(THD)_TwoAnd Ti (THD)_Two (I-OC_ThreeH₇)
_TwoExample from the third group consisting of the organic titanium compound represented by
For example, Ti (THD)_Two(I-OC_ThreeH₇)_TwoAnd select
In a vaporized state, an argon (Ar) gas [for example, a supply flow
The amount is 30cm^Three/ Min] before the reaction chamber
Transport.

Chemical formula Ta (i-OC ₃ H ₇ ) ₅ , Ta
_{(I-OC 3 H 7)} 4 organic tantalum compound represented by the THD and chemical formula _{Nb (i-OC 3 H 7} ) 5, Nb (i
From the fourth group consisting of the organic niobium compound represented by —OC ₃ H ₇ ) ₄ THD, for example, Ta (i-OC ₃ H ₇ ) ₄ TH
D is selected and, in a vaporized state, transported to the preceding stage of the reaction chamber by an argon (Ar) gas (for example, a supply flow rate of 40 cm ³ / min).

In the preceding stage of the reaction chamber, for example, oxygen (O ₂ ) (for example, a supply flow rate of 500 cm ³ / min) is mixed as an oxidizing gas with a reaction gas composed of each of the conveyed organometallic compounds and a carrier gas. I do. Then, the mixed gas is introduced into the reaction chamber. At that time, the temperature of the mixed gas until it is introduced into the reaction chamber is kept, for example, in the range of 150 ° C to 250 ° C. Further, the temperature of the gas diffusion nozzle of the introduction part is kept at, for example, 150 ° C. to 250 ° C. so that a uniform gas flow is generated in the reaction chamber when the gas is introduced into the reaction chamber. Then, the pressure of the mixed gas introduced into the reaction chamber is adjusted so as to be uniformly in the range of 1.33 Pa to 1.33 kPa, preferably 13.3 Pa to 400 Pa, and the input power of the high frequency power is set to, for example, 1.
Plasma is discharged at a setting of 0 kW, and a film is formed by chemical vapor deposition using the plasma energy.
In other words, the reaction gas is decomposed by the plasma energy,
It is grown chemical vapor, for example to form a _{Sr x Bi y Ta 2.0 Ti z} O w film thickness of 100 nm. Here, x, y, z, w, and d are 0.6 ≦ x ≦ 1.2,
1.7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w = 9 ± d, 0
≦ d ≦ 1.

Further, Sr _x B
i _y Ta _2.0 Ti _z O _w film iridium (Ir) to form a second electrode is deposited to a thickness of 100nm on. Next, a heat treatment was performed for one hour in a normal pressure oxygen atmosphere at 600 ° C., for example. Then, the first electrode, Sr _x Bi _y Ta
_A capacitor was composed of the _2.0 Ti _z O _w film and the second electrode, and PV hysteresis was measured.
^{10μC / cm 2 ~20μC / cm 2} , 2Ec = 100
Values of kV / cm to 150 kV / cm were obtained.

In the third manufacturing method, the first group to the first group
At least one organometallic from each of the fourth group
Select to generate a reaction gas mixed with the specified composition
After mixing the oxidizing gas with the reaction gas,
Keep the mixed gas with the oxidizing gas at 500 ° C or more and 700 ° C or less.
Into the reaction chamber where the substrate
On the substrate by chemical vapor deposition using energy
To Sr_xBi_yTa_2.0 Ti_zO_wTo form a film
Thus, the film becomes a crystallized film. Crystallized in this way
Sr_xBi_yTa_2.0Ti_zO_wThe membrane is described above
As described above, both 2Pr and 2Ec have good values.
Shows that excellent ferroelectric properties have been obtained.
Was.

In this manufacturing method, a crystallized Sr _x Bi _y Ta _2.0 Ti _z O _w film is directly formed on a substrate by chemical vapor deposition using plasma energy. The heat treatment performed at a temperature higher than 700 ° C. and equal to or lower than 800 ° C. for crystallizing the precursor film, which is performed in the step (1), becomes unnecessary. Therefore, when forming a capacitor by using a _{Sr x Bi y Ta 2.0 Ti z} O w film formed in the third manufacturing method, the thermal load is reduced according to the first electrode, the electrical resistance of the electrode It does not deteriorate. In addition, the second electrode can be formed using a metal film having low heat resistance. As described above, in the third manufacturing method, the thermal load on the electrode is reduced.

Next, an example of an embodiment according to the fourth manufacturing method of the present invention will be described below.

An iridium oxide (Ir) is formed on a semiconductor substrate (eg, a silicon substrate) by, for example, sputtering.
After forming an O ₂ ) film to a thickness of, for example, 100 nm, an iridium (Ir) film is formed to a thickness of, for example, 100 nm to form a first electrode.

The substrate formed up to the first electrode as described above is provided, for example, in a reaction chamber of a general high-frequency plasma CVD apparatus, and is provided with a plasma discharge electrode maintained at 500 ° C. or more and 700 ° C. or less. Place on top.

Next, the chemical formula Bi (C ₆ H ₅ ) ₃ , Bi
_{(O-C 7 H 7)} 3, Bi (O-C 2 H 5) 3, Bi (O
_{-IC 3 H 7) 3, Bi} (O-tC 4 H 9) 3, Bi
_{(O-tC 5 H 11)} 3 and Bi (THD) first example from the group of Bi consisting of an organic bismuth compound represented by the ₃
(O-iC ₃ H ₇ ) ₃ is selected, and in a vaporized state, an argon (Ar) gas [for example, a supply flow rate of 90 cm ³ / mi
n] to the stage preceding the reaction chamber.

The chemical formula Sr [Ta (OC_TwoH_Five)
₆]_Two, Sr [Ta (O-iC_ThreeH ₇)₆]_TwoRepresented by
Organic strontium tantalum compound and chemical formula S
r [Nb (OC_TwoH_Five)₆]_Two, Sr [Nb (O-i
C_ThreeH₇)₆]_TwoOrganic strontium nio represented by
For example, Sr [Ta (O-
C_TwoH_Five)₆]_TwoSelect and vaporize the argon
(Ar) gas [for example, the supply flow rate is 80 cm^Three/ Min]
To a stage preceding the reaction chamber.

Further, the chemical formula Ti (i-OC ₃ H ₇ ) ₄ ,
TiO (THD) ₂ and Ti (THD) ₂ (i-OC
For example, Ti (i-OC ₃ H ₇ ) ₄ is selected from a third group consisting of the organic titanium compound represented by ₃ H ₇ ) ₂ , and in a vaporized state, argon (Ar) gas [for example, a supply flow rate of 30 cm ³ / min] to the preceding stage of the reaction chamber.

In the preceding stage of the reaction chamber, an oxygen (O ₂ ) (for example, when the supply flow rate is 50
(0 cm ³ / min). Then, the mixed gas is introduced into the reaction chamber. At that time, the temperature of the mixed gas until it is introduced into the reaction chamber is kept, for example, in the range of 150 ° C to 250 ° C. Further, the temperature of the gas diffusion nozzle of the introduction part is kept at, for example, 150 ° C. to 250 ° C. so that a uniform gas flow is generated in the reaction chamber when the gas is introduced into the reaction chamber. Then, the pressure of the mixed gas introduced into the reaction chamber is adjusted so as to be uniformly in the range of 1.33 Pa to 1.33 kPa, preferably 13.3 Pa to 400 Pa, and the input power of the high frequency power is set to, for example, 1. 0kW
And discharge the plasma, and perform film formation by chemical vapor deposition using the plasma energy. In other words, the reaction gas is decomposed by the plasma energy, and the reaction gas is chemically vapor-grown.
to form the _{r x Bi x Ta 2.0 Ti z} O w film. However,
x, y, z, w, d are 0.6 ≦ x ≦ 1.2, 1.7 ≦
y ≦ 2.5, 0 ≦ z ≦ 1.0, w = 9 ± d, 0 ≦ d ≦ 1
And

Further, by sputtering, Sr_xB
i_xTa_2.0Ti_zO_wIridium (Ir) on the film
Deposit to a thickness of 100 nm to form a second electrode. Next
For example, heat for 1 hour in a normal pressure oxygen atmosphere at 600 ° C.
Processing was performed. Thereafter, PV hysteresis was measured.
However, 2Pr = 10 μC / cm^Two~ 20μC / c
m ^Two2Ec = 100kV / cm-150kV / cm
Values were obtained.

In the fourth manufacturing method, the selected organic
Only the metal compound is different, and the step of forming the dielectric film is the third step.
It is the same as the manufacturing method. Therefore, the fourth manufacturing method
Also uses plasma energy as in the third manufacturing method
Sr on the substrate by chemical vapor deposition_xBi_x
Ta_2.0Ti_zO_wBy forming a film, the film
It becomes a crystallized film. Sr thus crystallized_x
Bi_xTa_2.0Ti_z O_wThe film has 2 Pr = 10 μC / c
m^Two~ 20μC / cm^Two2Ec = 100 kV / cm ~
Both 150kV / cm show good numerical value, excellent incentive
Electrical properties were obtained.

As described above, Sr _x crystallized on the substrate by chemical vapor deposition utilizing plasma energy.
Since a Bi _x Ta _2.0 Ti _z O _w film is directly formed,
The heat treatment performed at a temperature higher than 700 ° C. and lower than 800 ° C. for crystallizing the precursor film, which is performed in the conventional process, becomes unnecessary. Therefore, when forming a capacitor by using a _{Sr x Bi x Ta 2.0 Ti z} O w film formed in the fourth manufacturing method, the thermal load is reduced according to the electrodes, the electrical resistance of the first electrode It does not deteriorate. In addition, the second electrode can be formed using a metal film having low heat resistance. As described above, in the fourth manufacturing method, the thermal load on the electrode is reduced.

Next, a first embodiment according to the fifth manufacturing method of the present invention will be described below.

On a semiconductor substrate (for example, a silicon substrate)
The silicon oxide film is, for example, 300
It is formed to a thickness of nm. After that, a titanium (Ti) film is formed to a thickness of, for example, 30 nm on the silicon oxide film by, for example, sputtering, and then a platinum (Pt) film is formed to a thickness of, for example, 200 nm to form a first electrode. I do.

The substrate formed as described above is provided, for example, in a reaction chamber of a general high-frequency plasma CVD apparatus, and is provided on a plasma discharge electrode maintained at 400 ° C. or lower, for example, 200 ° C. to 400 ° C. Place on.

Next, the chemical formula Bi (C ₆ H ₅ ) ₃ , Bi
_{(O-C 7 H 7)} 3, Bi (O-C 2 H 5) 3, Bi (O
_{-IC 3 H 7) 3, Bi} (O-tC 4 H 9) 3, Bi
_{(O-tC 5 H 11)} 3 and Bi (THD) first example from the group of Bi consisting of an organic bismuth compound represented by the ₃
(C ₆ H ₅ ) ₃ is selected.

Chemical formula Sr (THD) ₂ , Sr (THD)
For example, Sr (THD) ₂ is selected from a second group consisting of an organic strontium compound represented by ₂ tetraglyme and Sr (Me ₅ C ₅ ) ₂ 2THF.

Chemical formula Ti (i-OC_ThreeH₇)_Four, TiO
(THD)_TwoAnd Ti (THD)_Two (I-OC_ThreeH₇)
_TwoExample from the third group consisting of the organic titanium compound represented by
For example, Ti (i-OC_ThreeH₇)_FourSelect

And the chemical formula Ta (i-OC ₃ H ₇ ) ₅ ,
_{Ta (i-OC 3 H 7} ) 4 organic tantalum compound represented by the THD and chemical formula _{Nb (i-OC 3 H 7} ) 5, Nb
(I-OC ₃ H ₇₎ made of an organic niobium compound represented by ₄ THD fourth example from the group of _{Ta (i-OC 3 H 7} )
₄ Select THD.

Then, each of the selected organic metals is replaced with THF.
Mix with organic solvent as main component so as to have a prescribed composition ratio
Dissolve to form a mixed solution. Here, the main focus is on THF.
Of THF (tetrahydrofuran) for organic solvent
Was. Next, this mixed solution is, for example, 150 ° C. to 250 ° C.
Vaporized in a vaporizer held in
You. Then, an argon (Ar) gas (for example,
Supply flow is 500cm^Three/ Min) before the reaction chamber
To supply. Therefore, oxygen gas (for example, when the supply flow rate is 500
cm^Three/ Min). And the mixed gas is
Introduce into the room. At that time, until the introduction into the reaction chamber
Keep the temperature of the mixed gas in the range of 150 ° C to 250 ° C, for example.
One. Furthermore, a uniform gas flow when introduced into the reaction chamber
Gas diffusion nozzle at the inlet so that
Is kept at, for example, 150 ° C. to 250 ° C. So
The pressure of the mixed gas introduced into the reaction chamber
1.33 Pa to 1.33 kPa, preferably within
Adjust to be in the range of 13.3 Pa to 400 Pa
At the same time, the input power of the high-frequency power is 0.5 W / cm ^Two
-10W / cm^TwoSet the range to discharge the plasma
Chemical vapor deposition using the plasma energy
To form a film. In other words, the plasma energy
Decompose the reaction gas and make it grow by chemical vapor deposition
Is formed to form an oxide film.

The oxide film is made of Sr / (Ta + Nb),
Each of the atomic composition ratios represented by Bi / (Ta + Nb) and Ti / (Ta + Nb) is 0.6 ≦ 2Sr /
(Ta + Nb) ≦ 1.2, 1.7 ≦ 2Bi / (Ta + N
b) ≦ 2.8 and 0 ≦ 2Ti / (Ta + Nb) ≦ 1.
0 is satisfied. In this embodiment, since niobium (Nb) is not contained, Nb = 0, so that the oxide film has an atomic composition ratio of Sr / Ta, Bi / Ta, and Ti / Ta. Each is
0.6 ≦ 2Sr / Ta ≦ 1.2, 1.7 ≦ 2Bi / Ta
It suffices to satisfy the relationship of ≦ 2.8 and 0 ≦ 2Ti / Ta ≦ 1.0. If the above relations are not satisfied, Sr _x Bi having ferroelectric properties is used.
_y (Ta, Nb) _2.0 Ti _z O _w film cannot be obtained. Therefore, it is necessary to satisfy the above relationships.

Thereafter, the above substrate is used as an oxidizing gas for 60 hours.
As a result of performing the heat treatment for 1 hour in an oxygen gas at a normal pressure of 0 ° C. to 800 ° C., the oxide film is crystallized, for example, 100
of nm thick Sr _x Bi _y Ta _2.0 became Ti _z O _w film. Here, x, y, z, w, and d are 0.6 ≦ x ≦
1.2, 1.7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w = 9
± d, 0 ≦ d ≦ 1.

Further, Sr _x B
_{i y Ta 2.0 Ti z O w} 100 platinum (Pt) on the film
Deposited to a thickness of nm to form a second electrode. Then
For example, heat treatment was performed in an oxygen atmosphere at 725 ° C. for one hour. After that, the first electrode, Sr _x Bi _y Ta _2.0 Ti
and a capacitor in _z O _w film and the second electrode, P-
When V hysteresis was measured, 2Pr = 10 μC /
cm ² -22 μC / cm ² , 2Ec = 100 kV / cm
A value of １５０150 kV / cm was obtained.

Next, the fifth method according to the fifth manufacturing method of the present invention will be described.
The second embodiment will be described below. This second embodiment
In the state, iridium oxide (I
rO _TwoA) forming a film with a thickness of, for example, 100 nm;
An iridium (Ir) film is formed to a thickness of, for example, 100 nm.
Thus, a first electrode is formed. Others are the first
In the same manner as described in the embodiment, Sr_xBi_yTa
_2.0Ti_zO_wA film is formed.

Then, by sputtering, Sr _x B
i _y Ta _2.0 Ti _z O _w film iridium (Ir) to form a second electrode is deposited to a thickness of 100nm on. Next, a heat treatment was performed for 1 hour in an oxygen atmosphere at 725 ° C., for example. Then, the first electrode, Sr _x Bi _y Ta
_A capacitor was composed of the _2.0 Ti _z O _w film and the second electrode, and PV hysteresis was measured.
^{10μC / cm 2 ~22μC / cm 2} , 2Ec = 100
Values of kV / cm to 150 kV / cm were obtained.

Next, a third embodiment according to the fifth manufacturing method of the present invention will be described below. In the third embodiment, an iridium oxide (IrO ₂ ) film is formed to a thickness of, for example, 100 nm by sputtering without forming the silicon oxide film described in the first embodiment, and further, the iridium (IrO ₂ ) film is formed. An Ir) film is formed to a thickness of, for example, 20 nm to form a first electrode.

The first group of organometallics, for example, Bi
(C ₆ H ₅ ) ₃ is selected and, for example, Sr (T
HD) ₂ and, for example, Ti (i-OC) from the third group.
₃ H ₇ ) ₄ and, for example, Ta (i-O) from the fourth group.
C ₃ H _{7) 4} THD and _{Nb (i-OC 3 H 7} ) 4 TH
D is selected. Otherwise, in the same manner as described in the first embodiment, Sr _x Bi _y (Ta, Nb)
Forming an oxide film that is a precursor of the _2.0 Ti _z O _w film,
By performing the same heat treatment as described in the first embodiment, Sr _x Bi _y (Ta, Nb) _2.0
A Ti _z O _w film is formed.

Then, by sputtering, Sr_xB
i_y(Ta, Nb)_2.0Ti_zO_w Platinum (Pt) on the film
Is deposited to a thickness of 100 nm to form a second electrode.
Then, for example, heat for 10 minutes in an oxygen atmosphere at 750 ° C.
Processing was performed. Then, the first electrode, Sr_xBi_y(T
a, Nb)_2.0Ti_zO_wCapacitor with membrane and second electrode
The P-V hysteresis was measured by configuring the Pashita.
2Pr = 10μC / cm^Two~ 25μC / cm^Two, 2
Ec = 100kV / cm ~ 250kV / cm
Good values were obtained.

In the fifth manufacturing method, the first group to the first group
At least one organometallic from each of the fourth group
And a predetermined composition in an organic solvent containing THF as a main component.
Mix and dissolve so as to obtain a mixed solution to obtain the mixed solution.
The reaction solution is vaporized to generate a reaction gas, and the reaction gas is
Introduced into the reaction chamber where the substrate maintained at 400 ° C or lower was installed
For chemical vapor deposition using plasma energy
Since an oxide film is formed on the substrate,
At a low temperature of 0 ° C. or lower, for example, 200 ° C. to 400 ° C., first,
In the second embodiment, Sr_xBi_yTa_2.0Ti_zO
_wAn oxide film serving as a precursor of is formed.
In state Sr_xBi_y(Ta, Nb)_2.0 Ti_zO_wBefore
An oxide film serving as a precursor is formed. Therefore, keep the substrate
When placed on the electric chuck, the capacity of the electrostatic chuck decreases.
Can be fixedly placed on the board.
Become. Also, the reaction gas wraps around the back surface of the substrate to form a film.
It will not be. Therefore, as before,
Strontium (Sr), bismuth (B
i), a process for removing tantalum (Ta), etc.
There is no need to add, and the burden of increasing the number of processes is reduced.
You. As described above, in the fifth manufacturing method, the electrostatic chip is used.
Problems related to jacks are solved.

Then, the above oxide film is formed at a temperature of 600 ° C. to 800 ° C.
Heat treatment in an oxidizing gas of
In the first and second embodiments, the oxide film is crystallized.
Pr = 10 μC / cm^Two~ 22μC / cm^Two, 2Ec =
Strong with a value of 100 kV / cm to 150 kV / cm
Sr with excellent dielectric properties_xBi_yTa_2.0Ti_zO_w film
Is obtained, and in the third embodiment, 2Pr = 10 μC / c
m^Two~ 25μC / cm^Two2Ec = 100 kV / cm ~
Excellent ferroelectric properties having a value of 250 kV / cm
Sr_xBi_y(Ta, Nb)_2.0Ti_zO_wMembrane obtained
It is.

Next, an example of an embodiment according to the sixth manufacturing method of the present invention will be described below.

For example, iridium oxide (Ir) is deposited on a semiconductor substrate (eg, a silicon substrate) by sputtering.
After forming an O ₂ ) film to a thickness of, for example, 100 nm, an iridium (Ir) film is formed to a thickness of, for example, 100 nm to form a first electrode.

The substrate formed up to the first electrode as described above is provided, for example, in a reaction chamber of a general high-frequency plasma CVD apparatus, and is 400 ° C. or less, for example, 200 ° C.
The substrate is placed on a plasma discharge electrode maintained at a temperature of from 400C to 400C.

Next, the chemical formula Bi (C ₆ H ₅ ) ₃ , Bi
_{(O-C 7 H 7)} 3, Bi (O-C 2 H 5) 3, Bi (O
_{-IC 3 H 7) 3, Bi} (O-tC 4 H 9) 3, Bi
_{(O-tC 5 H 11)} 3 and Bi (THD) first example from the group of Bi consisting of an organic bismuth compound represented by the ₃
(C ₆ H ₅ ) ₃ is selected.

Chemical formula Sr [Ta (OC
_TwoH_Five)₆]_Two, Sr [Ta (O-iC_ThreeH₇)₆]_Twoso
Organic strontium-tantalum compounds and chemical compounds represented
Formula Sr [Nb (OC_TwoH_Five)₆]_Two, Sr [Nb
(O-iC_ThreeH₇)₆]_TwoOrganic strontium represented by
For example, Sr [T
a (O-iC _ThreeH₇)₆]_TwoSelect

Chemical formula Ti (i-OC_ThreeH₇)_Four, TiO
(THD)_TwoAnd Ti (THD)_Two (I-OC_ThreeH₇)
_TwoExample from the third group consisting of the organic titanium compound represented by
For example, Ti (i-OC_ThreeH₇)_FourSelect

After that, according to the same method as described in the first embodiment of the fifth manufacturing method, each selected organic metal is dissolved in THF (tetrahydrofuran) to form a mixed solution. The solution is for example 150 ° C. to 25
It is vaporized in a vaporizer maintained at 0 ° C. to generate a reaction gas. Then, the reaction gas is transferred to argon (A
r) A gas (for example, a supply flow rate of 500 cm ³ / min) is supplied to the front stage of the reaction chamber. Therefore, an oxygen gas (for example, a supply flow rate of 500 cm ³ / min) is mixed, and the mixed gas is introduced into the reaction chamber while maintaining the mixed gas at, for example, 150 ° C to 250 ° C.

Then, in the first embodiment of the fifth manufacturing method,
In the same manner as described in the form,
Pressure of the introduced mixed gas uniformly in the reaction chamber is 1.3
3 Pa to 1.33 kPa, preferably 13.3 Pa to 4
Adjust to be in the range of 00 Pa
0.5 W / cm input power^Two-10W / cm ^Two
To discharge the plasma in the range of
The film is formed by chemical vapor deposition utilizing energy.
In other words, the reaction gas is decomposed by the plasma energy,
Oxidation by depositing and depositing oxides by chemical vapor deposition
An object film is formed.

The oxide film is made of Sr / (Ta + Nb),
Each of the atomic composition ratios represented by Bi / (Ta + Nb) and Ti / (Ta + Nb) is 0.6 ≦ 2Sr /
(Ta + Nb) ≦ 1.2, 1.7 ≦ 2Bi / (Ta + N
b) ≦ 2.8 and 0 ≦ 2Ti / (Ta + Nb) ≦ 1.
0 is satisfied. In this embodiment, since niobium (Nb) is not contained, Nb = 0, so that the oxide film has an atomic composition ratio of Sr / Ta, Bi / Ta, and Ti / Ta. Each is
0.6 ≦ 2Sr / Ta ≦ 1.2, 1.7 ≦ 2Bi / Ta
It suffices to satisfy the relationship of ≦ 2.8 and 0 ≦ 2Ti / Ta ≦ 1.0. If the above relations are not satisfied, Sr _x Bi having ferroelectric properties is used.
_y (Ta, Nb) _2.0 Ti _z O _w film cannot be obtained. Therefore, it is necessary to satisfy the above relationships.

Thereafter, the above substrate is used as an oxidizing gas for 60 hours.
As a result of performing the heat treatment for 1 hour in an oxygen gas at a normal pressure of 0 ° C. to 800 ° C., the oxide film is crystallized, for example, 100
of nm thick Sr _x Bi _y Ta _2.0 became Ti _z O _w film. Here, x, y, z, w, and d are 0.6 ≦ x ≦
1.2, 1.7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w = 9
± d, 0 ≦ d ≦ 1.

Further, by sputtering, Sr _x B
_{i y Ta 2.0 Ti z O w} 100 platinum (Pt) on the film
Deposited to a thickness of nm to form a second electrode. Then
For example, heat treatment was performed in an oxygen atmosphere at 725 ° C. for one hour. After that, the first electrode, Sr _x Bi _y Ta _2.0 Ti
and a capacitor in _z O _w film and the second electrode, P-
When V hysteresis was measured, 2Pr = 10 μC /
cm ² -22 μC / cm ² , 2Ec = 100 kV / cm
A value of １５０150 kV / cm was obtained.

The sixth manufacturing method is the same as the fifth manufacturing method except that the selected organometallic compound is different. Therefore, the sixth manufacturing method is the same as the fifth manufacturing method.
In the same manner as in the production method, a low temperature of 400 ° C. or less, for example, 20 ° C. by chemical vapor deposition using plasma energy.
0 oxide film at ° C. to 400 ° C. is a precursor of _{Sr x Bi y Ta 2.0 Ti z} O w is formed. Therefore, when the substrate is mounted on the electrostatic chuck, the performance of the electrostatic chuck does not decrease, and the substrate can be fixedly mounted. Further, the reaction gas does not flow around the back surface of the substrate to form a film. Therefore, as in the prior art, strontium (Sr) and bismuth (B
i), there is no need to add a process for removing tantalum (Ta) or the like, and the load of increasing the number of steps is reduced. As described above, the problem relating to the electrostatic chuck is solved in the sixth manufacturing method.

Then, the above oxide film is formed at a temperature of 600 ° C. to 800 ° C.
The precursor oxide film is crystallized by heat treatment in an oxidizing gas of ² Pr = 10 μC / cm ² -22
μC / cm ² , 2Ec = 100 kV / cm to 150 kV
/ Cm becomes excellent in ferroelectric characteristics having a value Sr _x Bi
_y Ta _2.0 Ti _z O _w film.

Next, an example of an embodiment according to the seventh manufacturing method of the present invention will be described below.

For example, iridium oxide (Ir) is deposited on a semiconductor substrate (eg, a silicon substrate) by sputtering.
An O ₂ ) film is formed to a thickness of, for example, 100 nm, and an iridium-ruthenium alloy (Ir _0.7 Ru _0.3 ) film is formed to a thickness of, for example, 100 nm to form a first electrode.

The substrate formed up to the first electrode as described above is provided, for example, in a reaction chamber of a general high-frequency plasma CVD apparatus, and is provided with a plasma discharge electrode maintained at 500 ° C. or more and 700 ° C. or less. Place on top.

Next, the chemical formula Bi (C ₆ H ₅ ) ₃ , Bi
_{(O-C 7 H 7)} 3, Bi (O-C 2 H 5) 3, Bi (O
_{-IC 3 H 7) 3, Bi} (O-tC 4 H 9) 3, Bi
_{(O-tC 5 H 11)} 3 and Bi (THD) first example from the group of Bi consisting of an organic bismuth compound represented by the _{3
(O-iC 3 H 7)} 3 selects.

Chemical formula Sr (THD) ₂ , Sr (THD)
For example, Sr (THD) ₂ is selected from a second group consisting of an organic strontium compound represented by ₂ tetraglyme and Sr (Me ₅ C ₅ ) ₂ 2THF.

Chemical formula Ti (i-OC_ThreeH₇)_Four, TiO
(THD)_TwoAnd Ti (THD)_Two (I-OC_ThreeH₇)
_TwoExample from the third group consisting of the organic titanium compound represented by
For example, Ti (i-OC_ThreeH₇)_FourSelect

And the chemical formula Ta (i-OC ₃ H ₇ ) ₅ ,
_{Ta (i-OC 3 H 7} ) 4 organic tantalum compound represented by the THD and chemical formula _{Nb (i-OC 3 H 7} ) 5, Nb
(I-OC ₃ H ₇₎ made of an organic niobium compound represented by ₄ THD fourth example from the group of _{Ta (i-OC 3 H 7} )
₄ Select THD.

Then, each of the selected organic metals is mixed and dissolved in an organic solvent mainly composed of THF so as to have a predetermined composition ratio to form a mixed solution. Here, THF (tetrahydrofuran) was used as an organic solvent mainly containing THF. Next, this mixed solution is, for example,
The reaction gas is vaporized in the vaporizer held in the reaction chamber. Then, it is supplied to the front stage of the reaction chamber together with an argon (Ar) gas (for example, a supply flow rate of 500 cm ³ / min) as a carrier gas. Therefore, oxygen gas (for example, when the supply flow rate is 500
cm ³ / min). Then, the mixed gas is introduced into the reaction chamber. At that time, the temperature of the mixed gas until it is introduced into the reaction chamber is kept, for example, in the range of 150 ° C to 250 ° C. Then, the pressure of the mixed gas introduced into the reaction chamber is adjusted so as to be uniformly within the range of 1.33 Pa to 1.33 kPa, preferably 13.3 Pa to 400 Pa, and the input power of the high-frequency power is set to 1 kPa, for example.
The plasma is discharged by setting to W, and a film is formed by chemical vapor deposition using the plasma energy. That is, the reaction gas is decomposed by the plasma energy, and the reaction gas is chemically vapor-grown to form Sr _x Bi _y Ta _2.0 Ti.
to form a _z O _w film.

Thereafter, the substrate was subjected to a heat treatment for 1 hour in an oxygen gas at a normal pressure of, for example, 600 ° C. as an oxidizing gas. As a result, for example, a crystallized Sr _x B having a thickness of 100 nm was obtained.
i _y Ta _2.0 Ti _z O _w film was obtained. Where x,
y, z, w, d are 0.6 ≦ x ≦ 1.2, 1.7 ≦ y ≦
2.5, 0 ≦ z ≦ 1.0, w = 9 ± d, and 0 ≦ d ≦ 1.

Further, Sr _x B
i _y Ta _2.0 Ti _z O _w film iridium ruthenium alloy (Ir _0.7 Ru _0.3) to form the second electrode is deposited to a thickness of 100nm on. Next, a heat treatment was performed in an oxygen atmosphere at, for example, 600 ° C. for 30 minutes. Thereafter, the first electrode, and a capacitor in _{Sr x Bi y Ta 2.0 Ti z} O w film and the second electrode was measured a P-V hysteresis, 2Pr = 5μC / cm ² ~18μC
/ Cm ² , 2Ec = 100 kV / cm to 200 kV / c
The value m was obtained.

In the seventh manufacturing method, the first to fourth
, At least one organometallic compound is selected from each of the groups, and they are adjusted to a predetermined composition ratio with TH.
F to form a mixed solution, vaporize the mixed solution to generate a reaction gas, and further mix an oxidizing gas with the reaction gas.
° C. or higher 700 ° C. was introduced into the reaction chamber was installed and the substrate holding below, by chemical vapor deposition using plasma _{energy, Sr x Bi y Ta 2. 0} Ti on the substrate
Since forming the _z O _w film, the film becomes a film crystallized. Sr _x Bi _y Ta thus crystallized
As described above, the _2.0 Ti _z O _w film exhibited favorable values for both 2Pr and 2Ec, indicating that ferroelectric properties were obtained.

In this manufacturing method, a crystallized Sr _x Bi _y Ta _2.0 Ti _z O _w film is directly formed on a substrate by chemical vapor deposition using plasma energy. The heat treatment performed at a temperature higher than 700 ° C. and equal to or lower than 800 ° C. for crystallizing the precursor film, which is performed in the step (1), becomes unnecessary. Therefore, when forming a capacitor by using a _{Sr x Bi y Ta 2.0 Ti z} O w film formed in the third manufacturing method, the thermal load is reduced according to the first electrode, the electrical resistance of the electrode It does not deteriorate. In addition, the second electrode can be formed using a metal film having low heat resistance. As described above, in the seventh manufacturing method, the thermal load on the electrode is reduced.

Next, an example of the embodiment according to the eighth manufacturing method of the present invention will be described below.

For example, iridium oxide (IrO) is deposited on a semiconductor substrate (eg, a silicon substrate) by sputtering.
₂ ) A film is formed to a thickness of, for example, 100 nm, and an iridium (Ir) film is formed to a thickness of, for example, 100 nm to form a first electrode.

The substrate formed as described above is provided, for example, in a reaction chamber of a general high-frequency plasma CVD apparatus, and is mounted on a plasma discharge electrode maintained at 500 ° C. or higher and 700 ° C. or lower. .

Next, the chemical formula Bi (C ₆ H ₅ ) ₃ , Bi
_{(O-C 7 H 7)} 3, Bi (O-C 2 H 5) 3, Bi (O
_{-IC 3 H 7) 3, Bi} (O-tC 4 H 9) 3, Bi
_{(O-tC 5 H 11)} 3 and Bi (THD) first example from the group of Bi consisting of an organic bismuth compound represented by the ₃
(C ₆ H ₅ ) ₃ is selected.

Further, the chemical formula Sr [Ta (OC_TwoH_Five)
₆]_Two, Sr [Ta (O-iC_ThreeH ₇)₆]_TwoRepresented by
Organic strontium tantalum compound and chemical formula S
r [Nb (OC_TwoH_Five)₆]_Two, Sr [Nb (O-i
C_ThreeH₇)₆]_TwoOrganic strontium nio represented by
For example, Sr [Ta (O-
iC_ThreeH₇)₆]_TwoSelect

The chemical formula Ti (i-OC ₃ H ₇ ) ₄ ,
TiO (THD) ₂ and Ti (THD) ₂ (i-OC
₃ H ₇₎ made of an organic titanium compound represented by the ₂ third example from the group of _{Ti (i-OC 3 H 7} ) 4 to select.

Thereafter, each of the selected organic metals is dissolved in THF (tetrahydrofuran) to form a mixed solution, and the mixed solution is vaporized in a vaporizer maintained at, for example, 150 ° C. to 250 ° C. to generate a reaction gas. I do. And that the argon of the reaction gas carrier gas (Ar) gas (e.g., supply flow rate is 500 cm ³ / min) was supplied to the front along with the reaction chamber, where the oxygen gas (e.g. supply flow rate is 500 cm ³
/ Min). The mixed gas is, for example, 150 ° C.
It is introduced into the reaction chamber while keeping it at ~ 250 ° C.

Then, the pressure of the mixed gas introduced into the reaction chamber is uniformly 1.33 Pa to 1.33 k in the reaction chamber.
Pa, preferably with adjusted to be in the range of 13.3Pa～400Pa, by setting the input power of the RF power in the range of 0.5W / cm ² ~10W / cm ² to discharge the plasma, the plasma energy The film is formed by chemical vapor deposition using the method. In other words, to decompose the reaction gas by the plasma energy, generates deposited it is grown chemical vapor with _{Sr x Bi y Ta 2.0 Ti z} O w.

Thereafter, a heat treatment is performed for 1 hour in an oxygen atmosphere at 600 ° C. and normal pressure, for example, to a crystallized 100 nm
_{Sr x Bi y Ta 2.0 Ti z} O w film thickness were obtained. Here, x, y, z, w, and d are 0.6 ≦ x ≦ 1.
2, 1.7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w = 9 ±
d, 0 ≦ d ≦ 1.

Further, Sr _x B
i _y Ta _2.0 Ti _z O _w film iridium (Ir) to form a second electrode is deposited to a thickness of 100nm on. Next, a heat treatment was performed in an oxygen atmosphere at, for example, 600 ° C. for one hour. Then, the first electrode, Sr _x Bi _y Ta
_A capacitor was composed of the _2.0 Ti _z O _w film and the second electrode, and PV hysteresis was measured.
^{= 10μC / cm 2 ~22μC / cm} 2, 2Ec = 10
Values of 0 kV / cm to 150 kV / cm were obtained.

In the eighth manufacturing method, the selected organic
Only the metal compound is different.
It is the same as the manufacturing method. Therefore, the eighth manufacturing method
Also uses plasma energy as in the seventh manufacturing method
Sr on the substrate by chemical vapor deposition_xBi_y
Ta_2.0Ti_zO_wBy forming a film, the film
It becomes a crystallized film. Sr thus crystallized_x
Bi_yTa_2.0Ti_z O_wThe film has 2 Pr = 10 μC / c
m^Two~ 22μC / cm^Two2Ec = 100 kV / cm ~
Both 150kV / cm show good numerical value, excellent incentive
Electrical properties were obtained.

As described above, Sr _x crystallized on the substrate by chemical vapor deposition utilizing plasma energy.
Since Bi _y Ta _2.0 Ti _z O _w film is formed directly,
The heat treatment performed at a temperature higher than 700 ° C. and lower than 800 ° C. for crystallizing the precursor film, which is performed in the conventional process, becomes unnecessary. Therefore, when forming a capacitor by using a _{Sr x Bi y Ta 2.0 Ti z} O w film formed in this eighth method of manufacturing a thermal load is reduced according to the electrodes, the electrical resistance of the first electrode It does not deteriorate. In addition, the second electrode can be formed using a metal film having low heat resistance. As described above, in the eighth manufacturing method, the thermal load on the electrode is reduced.

In each of the first to eighth embodiments, the organic titanium compound is used. However, the organic titanium compound may not be used. In that case, the formed film is an Sr _x Bi _y (Ta, Nb) _2.0 O _w film.

The following are examples of the electrodes that can be used in each of the first to eighth manufacturing methods.

One is a chemical formula Ir _a Pt _b Ru _c [where a, b, and c represent compositions in atomic%, and 0 ≦ a ≦ 10
0, 0 ≦ b ≦ 100, 0 ≦ c ≦ 100, a + b + c = 1
Satisfies the relationship of “00”.
In the case of such a metal electrode, an oxide layer of the metal electrode may be formed on the lower surface of the metal electrode in some cases.

One is the chemical formula Ir _a Pt _b Ru _c O
_d [where a, b, c, and d represent the composition in atomic%, and 0
≦ a ≦ 90, 0 ≦ b ≦ 90, 0 ≦ c ≦ 90, 0 ≦ d ≦ 1
0, a + b + c + d = 100 are satisfied), and an oxide electrode formed on this oxide electrode, the chemical formula Ir _a Pt _b Ru _c [where a, b, c
Represents the composition in atomic%, 0 ≦ a ≦ 100, 0 ≦ b ≦ 10
0, 0 ≦ c ≦ 100, and a + b + c = 100 are satisfied].

[0134]

As described above, according to the first, second, fifth, and sixth manufacturing methods of the present invention, a substrate holding a reaction gas comprising a desired organometallic compound at a temperature of 400.degree. An oxide film can be formed on a substrate by chemical vapor deposition using plasma energy after being introduced into the installed reaction chamber, and then heat treatment is performed in an oxidizing gas. Sr _x Bi _y (Ta, N
b) A _2.0 Ti _z O _w film can be formed. Since the film can be formed at 400 ° C. or lower, an electrostatic chuck can be used at the time of film formation. Therefore, the reaction gas does not flow to the back surface of the substrate, and a process for removing an unnecessary film attached to the back surface of the substrate as in the related art is not required, so that the number of steps can be reduced.

Third, Fourth, Seventh, and Eighth Manufacturing Methods of the Present Invention
According to the method, a reaction gas comprising a desired organometallic compound is
When a substrate held at 500 ° C or higher and 700 ° C or lower is installed,
Chemistry using plasma energy introduced into the reaction room
Crystallized on a substrate by selective vapor phase growth
Sr with excellent properties_xBi_y(Ta, Nb)_2.0Ti_zO_w
A film can be formed. Such Sr_xBi
_x(Ta, Nb)_2.0Ti_zO_wForm film directly on substrate
So we could go with the traditional process,
800 ° C. higher than 700 ° C. for crystallizing the precursor film
The heat treatment performed at the following temperatures becomes unnecessary. For this reason, Sr
_xBi_y(Ta, Nb)_2.0Ti_zO_w Using a membrane
When a paster is formed, the thermal load on the electrode is reduced.
In this case, it is possible to prevent deterioration of the electric resistance of the electrode. Ma
Metal film with low heat resistance_xBi_y(Ta, Nb)
_2.0Ti_zO_wIt is also possible to form electrodes on the film.
You.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of an embodiment according to the present invention.

FIG. 2 shows SrBi ₂ T formed by the manufacturing method of the present invention.
FIG. 4 is a PV characteristic diagram measured by forming a capacitor with an a ₂ O ₉ film.

[Explanation of symbols]

10 ... _{substrate, 16 ... Sr x Bi y Ta} 2.0 Ti z O w
film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01G 4/12 355

Claims (56)

[Claims] 1. A first group consisting of an organic bismuth compound
A second group consisting of an organic strontium compound; a third group consisting of an organic titanium compound; and a fourth group consisting of an organic tantalum compound and an organic niobium compound.
At least one organometallic compound from each of the groups
Generate reactant gas by selecting substances and mixing them to a specified composition
Mixing the reaction gas and the oxidizing gas;
By introducing a gas mixture with an oxidizing gas, the plasma energy
Oxidation on the substrate by chemical vapor deposition
Forming an object film; and heat-treating the oxide film in an oxidizing gas to form Sr._xBi
_y(Ta, Nb)_2.0 Ti_zO_w[However, 0.6 ≦ x
≦ 1.2, 1.7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w =
9 ± d, 0 ≦ d ≦ 1).
And a method for producing a dielectric film. 2. The method according to claim 1, wherein the first group has a chemical formula Bi (C
₆H_Five)_Three, Bi (o-C ₇H₇)_Three, Bi (OC_Two
H_Five)_Three, Bi (O-iC_ThreeH₇)_Three, Bi (O-tC
_FourH₉)_Three, Bi (O-tC_FiveH₁₁)_ThreeAnd Bi (T
HD)_Three[Hereinafter, THD is 2,2,6,6-tetramethyl
Ru-3,5-heptanedione: C₁₁H₂₀O_TwoRepresents
Characterized by being composed of an organic bismuth compound represented
A method for manufacturing a dielectric film according to claim 1. 3. The method according to claim 2, wherein the second group has the chemical formula Sr (THD)
_Two, Sr (THD) _TwoTetraglyme, Sr (Me
_FiveC_Five)_Two2THF [where Me represents a methyl group;
HF represents tetrahydrofuran].
2. The composition according to claim 1, wherein the composition comprises a rontium compound.
Manufacturing method of the above-mentioned dielectric film. 4. The third group has a chemical formula of Ti (i-OC
_{3 H 7) 4, TiO (} THD) 2, Ti (THD)
_{2 (i-OC 3 H 7} ) method for producing a dielectric film according to claim 1, characterized in that it consists of an organic titanium compound represented by _2. 5. The fourth group has a chemical formula Ta (i-OC
An organic tantalum compound represented by ₃ H ₇ ) ₅ , Ta (i-OC ₃ H ₇ ) ₄ THD, and Nb (i-OC ₃ H ₇ )
_{5, Nb (i-OC 3} H 7) 4 method for producing a dielectric film according to claim 1, characterized in that it consists of an organic niobium compound represented by THD. 6. The oxide film includes Sr / (Ta + Nb), Bi / (Ta + Nb) and T /
Each of the atomic composition ratios represented by i / (Ta + Nb) is 0.6 ≦ 2Sr / (Ta + Nb) ≦ 1.2, 1.7.
≦ 2Bi / (Ta + Nb) ≦ 2.8 and 0 ≦ 2Ti /
2. The method according to claim 1, wherein a relationship of (Ta + Nb) ≦ 1.0 is satisfied. 7. The film-forming surface of the substrate has a chemical formula Ir _a Pt _b Ru _c [where a, b, and c represent compositions in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0
≦ c ≦ 100, a + b + c = 100 is satisfied]. The method of manufacturing a dielectric film according to claim 1, wherein 8. The film-forming surface of the substrate has a chemical formula Ir _a Pt _b Ru _c O _d [where a, b, c,
d represents the composition in atomic%, 0 ≦ a ≦ 90, 0 ≦ b ≦ 9
0, 0 ≦ c ≦ 90, 0 ≦ d ≦ 10, a + b + c + d = 1
And an oxide electrode formed on the oxide electrode and having the chemical formula Ir _a P
t _b Ru _c [where a, b, and c represent the composition in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ c ≦ 10
0, a + b + c = 100 is satisfied], and a metal electrode represented by the following formula: is formed. 9. A first group consisting of an organic bismuth compound
And organic strontium-tantalum compound and organic strontium
A second group consisting of a niobium-niobium compound;
At least from each group of the third group consisting of
Select one kind of organometallic compound and mix it to the specified composition
Reacting gas and oxidizing gas.
Mixing step and installing the substrate held at 400 ° C or lower
Introducing a mixed gas with the oxidizing gas into the reaction chamber,
By chemical vapor deposition using plasma energy,
Forming an oxide film on the substrate; heat-treating the oxide film in an oxidizing gas;_xBi
_y(Ta, Nb)_2.0 Ti_zO_w[However, 0.6 ≦ x
≦ 1.2, 1.7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w =
9 ± d, 0 ≦ d ≦ 1]
A method for producing a dielectric film. 10. The first group has the chemical formula Bi (C ₆ H)
₅ ) ₃ , Bi (o-C ₇ H ₇ ) ₃ , Bi (OC
_{2 H 5) 3, Bi (} O-iC 3 H 7) 3, Bi (O-t
_{C 4 H 9) 3, Bi} (O-tC 5 H 11) 3, Bi (TH
D) ₃ [hereinafter, THD represents 2,2,6,6-tetramethyl-3,5-heptanedione: C ₁₁ H ₂₀ O ₂ ], and is characterized by comprising an organic bismuth compound. Item 10. The method for producing a dielectric film according to Item 9. 11. The second group has a chemical formula of Sr [Ta
(OC_TwoH_Five)₆] _Two, Sr [Ta (O-iC
_ThreeH₇)₆]_TwoOrganic strontium tantalum represented by
Compound and Sr [Nb (OC_TwoH_Five)₆]_Two,
Sr [Nb (O-iC _ThreeH₇)₆]_TwoOrganics represented by
Characterized by being composed of a trontium-niobium compound
A method for manufacturing a dielectric film according to claim 9. 12. The second group has a chemical formula Ti (i-O
C ₃ H ₇ ) ₄ , TiO (THD) ₂ , Ti (THD) ₂
(I-OC ₃ H ₇₎ method for producing a dielectric film according to claim 9, characterized in that it consists of an organic titanium compound represented by _2. 13. The oxide film according to claim 1, wherein Sr / (Ta + Nb), Bi / (Ta + Nb) and T /
Each of the atomic composition ratios represented by i / (Ta + Nb) is 0.6 ≦ 2Sr / (Ta + Nb) ≦ 1.2, 1.7.
≦ 2Bi / (Ta + Nb) ≦ 2.8 and 0 ≦ 2Ti /
The method according to claim 9, wherein a relationship of (Ta + Nb) ≦ 1.0 is satisfied. 14. The film-forming surface of the substrate has a chemical formula Ir _a Pt _b Ru _c [where a, b, and c represent compositions in atomic% and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0
≦ c ≦ 100, a + b + c = 100 is satisfied]. The method of manufacturing a dielectric film according to claim 9, wherein 15. The film-forming surface of the substrate has a chemical formula Ir _a Pt _b Ru _c O _d [where a, b, c,
d represents the composition in atomic%, 0 ≦ a ≦ 90, 0 ≦ b ≦ 9
0, 0 ≦ c ≦ 90, 0 ≦ d ≦ 10, a + b + c + d = 1
And an oxide electrode formed on the oxide electrode and having the chemical formula Ir _a P
t _b Ru _c [where a, b, and c represent the composition in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ c ≦ 10
0, a + b + c = 100 is satisfied], and a metal electrode represented by the following formula: is formed. 16. A first group consisting of an organic bismuth compound, a second group consisting of an organic strontium compound, a third group consisting of an organic titanium compound, and a fourth group consisting of an organic tantalum compound and an organic niobium compound. Generating a reaction gas by selecting at least one type of organometallic compound from each of the groups and mixing the mixture with a predetermined composition, and mixing the reaction gas with an oxidizing gas; A mixed gas with the oxidizing gas is introduced into a reaction chamber in which a substrate maintained at a temperature of not more than 0 ° C. is placed, and Sr _x Bi _y (Ta, Nb) is formed on the substrate by chemical vapor deposition using plasma energy. _2.0 Ti _z O _w
[However, 0.6 ≦ x ≦ 1.2, 1.7 ≦ y ≦ 2.5,
0 ≦ z ≦ 1.0, w = 9 ± d, and 0 ≦ d ≦ 1). Forming a film. 17. The method according to claim 17, wherein the first group has the formula Bi (C₆H
_Five)_Three, Bi (o-C₇H₇)_Three, Bi (OC
_TwoH_Five)_Three, Bi (O-iC_ThreeH₇)_Three, Bi (Ot
C_FourH₉)_Three, Bi (O-tC_FiveH₁₁)_ThreeAnd Bi
(THD)_Three[Hereinafter, THD is 2,2,6,6-tetra
Methyl-3,5-heptanedione: C₁₁H₂₀O _TwoThe table
Characterized by the organic bismuth compound represented by
The method for producing a dielectric film according to claim 16, wherein 18. The second group comprises a compound represented by the chemical formula Sr (TH
D) ₂ , Sr (THD) ₂ tetraglyme, Sr (Me ₅
C ₅ ) _{2 2} THF [where Me represents a methyl group;
F represents tetrahydrofuran.] The method according to claim 16, wherein the organic strontium compound is represented by the following formula: 19. The third group has a chemical formula Ti (i-O
C ₃ H ₇ ) ₄ , TiO (THD) ₂ , Ti (THD) ₂
(I-OC ₃ H ₇₎ method for producing a dielectric film according to claim 16, wherein the formed of an organic titanium compound represented by _2. 20. The fourth group comprises a compound of the formula Ta (i-O
_{C 3 H 7) 5, Ta} (i-OC 3 H 7) organic tantalum compound represented by the ₄ THD, and Nb (i-OC
_{3 H 7) 5, Nb (} i-OC 3 H 7) 4 claim 1, characterized in that it consists of an organic niobium compound represented by THD
7. The method for producing a dielectric film according to item 6. 21. A film-forming surface of the substrate having a chemical formula Ir _a Pt _b Ru _c [where a, b, and c represent compositions in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ b ≦ 100.
≦ c ≦ 100, a + b + c = 100 is satisfied]. The method of manufacturing a dielectric film according to claim 16, wherein 22. The film forming surface of the substrate has the formula Ir _a Pt _b Ru _c O _d [However, a, b, c,
d represents the composition in atomic%, 0 ≦ a ≦ 90, 0 ≦ b ≦ 9
0, 0 ≦ c ≦ 90, 0 ≦ d ≦ 10, a + b + c + d = 1
And an oxide electrode formed on the oxide electrode and having the chemical formula Ir _a P
t _b Ru _c [where a, b, and c represent the composition in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ c ≦ 10
0, a + b + c = 100 is satisfied). The method of manufacturing a dielectric film according to claim 16, wherein: 23. Each group of a first group consisting of an organic bismuth compound, a second group consisting of an organic strontium-tantalum compound and an organic strontium-niobium compound, and a third group consisting of an organic titanium compound Generating a reaction gas by mixing at least one type of organometallic compound to a predetermined composition, and mixing the reaction gas with an oxidizing gas; A mixed gas with the oxidizing gas is introduced into the installed reaction chamber, and Sr _x Bi _y (Ta, Nb) _2.0 Ti _z O _{w is} deposited on the substrate by chemical vapor deposition using plasma energy.
[However, 0.6 ≦ x ≦ 1.2, 1.7 ≦ y ≦ 2.5,
0 ≦ z ≦ 1.0, w = 9 ± d, and 0 ≦ d ≦ 1). Forming a film. 24. The first group has a chemical formula Bi (C ₆ H
₅ ) ₃ , Bi (o-C ₇ H ₇ ) ₃ , Bi (OC
_{2 H 5) 3, Bi (} O-iC 3 H 7) 3, Bi (O-t
_{C 4 H 9) 3, Bi} (O-tC 5 H 11) 3, Bi (TH
D) ₃ [hereinafter, THD represents 2,2,6,6-tetramethyl-3,5-heptanedione: C ₁₁ H ₂₀ O ₂ ], and is characterized by comprising an organic bismuth compound. Item 24. The method for producing a dielectric film according to Item 23. 25. The second group comprises a compound of the formula Sr [Ta
(OC_TwoH_Five)₆] _Two, Sr [Ta (O-iC
_ThreeH₇)₆]_TwoOrganic strontium tantalum represented by
Compound and Sr [Nb (OC_TwoH_Five)₆]_Two,
Sr [Nb (O-iC _ThreeH₇)₆]_TwoOrganics represented by
Characterized by being composed of a trontium-niobium compound
A method for manufacturing a dielectric film according to claim 23. 26. The second group comprises a compound of the formula Ti (i-O
C ₃ H ₇ ) ₄ , TiO (THD) ₂ , Ti (THD) ₂
(I-OC ₃ H ₇₎ method for producing a dielectric film according to claim 23, wherein a formed of an organic titanium compound represented by _2. 27. The film-forming surface of the substrate has a chemical formula Ir _a Pt _b Ru _c [where a, b, and c represent compositions in atomic% and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ b ≦ 100.
≦ c ≦ 100, a + b + c = 100 is satisfied]. The method of manufacturing a dielectric film according to claim 23, wherein: 28. The film-forming surface of the substrate has a chemical formula Ir _a Pt _b Ru _c O _d [where a, b, c,
d represents the composition in atomic%, 0 ≦ a ≦ 90, 0 ≦ b ≦ 9
0, 0 ≦ c ≦ 90, 0 ≦ d ≦ 10, a + b + c + d = 1
And an oxide electrode formed on the oxide electrode and having the chemical formula Ir _a P
t _b Ru _c [where a, b, and c represent the composition in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ c ≦ 10
0, a + b + c = 100 is satisfied], and a metal electrode represented by the following formula: is formed. 29. A first group consisting of an organic bismuth compound
A second group consisting of an organic strontium compound, a third group consisting of an organic titanium compound, and an organic tantalum compound and an organic niobium compound.
At least one kind of organic gold from each of the fourth group
Select a genus compound and place it in an organic solvent whose main component is THF.
Mix and dissolve so as to have a fixed composition ratio to form a mixed solution
Evaporating the mixed solution to generate a reaction gas; and installing the substrate maintained at 400 ° C. or lower in a reaction chamber where
Introduce reaction gas and use plasma energy
By decomposing the reaction gas by chemical vapor deposition,
Forming an oxide film on the substrate; heat-treating the oxide film in an oxidizing gas;_xBi
_y(Ta, Nb)_2.0 Ti_zO_w[However, 0.6 ≦ x
≦ 1.2, 1.7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w =
9 ± d, 0 ≦ d ≦ 1).
And a method for producing a dielectric film. 30. The first group comprises a compound of the formula Bi (C ₆ H
₅ ) ₃ , Bi (o-C ₇ H ₇ ) ₃ , Bi (OC ₂ H ₅ )
₃ , Bi (O-iC ₃ H ₇ ) ₃ , Bi (O-tC
₄ H ₉ ) ₃ , Bi (O-tC ₅ H ₁₁ ) ₃ and Bi (T
HD) ₃ [hereinafter, THD represents 2,2,6,6-tetramethyl-3,5-heptanedione: C ₁₁ H ₂₀ O ₂ ]. Item 30. The method for producing a dielectric film according to Item 29. 31. The second group comprises a compound of the formula Sr (TH
D) ₂ , Sr (THD) ₂ tetraglyme, Sr (Me ₅
C ₅ ) _{2 2} THF [where Me represents a methyl group;
F represents tetrahydrofuran.] The method according to claim 29, wherein the organic strontium compound is represented by the following formula: 32. The third group comprises a compound of the formula Ti (i-O
C ₃ H ₇ ) ₄ , TiO (THD) ₂ , Ti (THD) ₂
(I-OC ₃ H ₇₎ method for producing a dielectric film according to claim 29, wherein the formed of an organic titanium compound represented by _2. 33. The fourth group comprises a compound of the formula Ta (i-O
_{C 3 H 7) 5, Ta} (i-OC 3 H 7) organic tantalum compound represented by the ₄ THD, and _{Nb (i-OC 3 H 7} )
_{5, Nb (i-OC 3} H 7) 4 method for producing a dielectric film according to claim 29, wherein the formed of an organic niobium compound represented by THD. 34. The oxide film comprises: Sr / (Ta + Nb), Bi / (Ta + Nb),
Each of the atomic composition ratios represented by i / (Ta + Nb) is 0.6 ≦ 2Sr / (Ta + Nb) ≦ 1.2, 1.7.
≦ 2Bi / (Ta + Nb) ≦ 2.8 and 0 ≦ 2Ti
30. The method of manufacturing a dielectric film according to claim 29, wherein a relationship of /(Ta+Nb)≦1.0 is satisfied. 35. A film-forming surface of the substrate, which has a chemical formula Ir _a Pt _b Ru _c [where a, b, and c represent compositions in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ b ≦ 100.
≦ c ≦ 100, a + b + c = 100 is satisfied]. The method of manufacturing a dielectric film according to claim 29, wherein: 36. A film-forming surface of the substrate according to the present invention, wherein Ir _a Pt _b Ru _c O _d [where a, b, c,
d represents the composition in atomic%, 0 ≦ a ≦ 90, 0 ≦ b ≦ 9
0, 0 ≦ c ≦ 90, 0 ≦ d ≦ 10, a + b + c + d = 1
And an oxide electrode formed on the oxide electrode and having the chemical formula Ir _a P
t _b Ru _c [where a, b, and c represent the composition in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ c ≦ 10
0, a + b + c = 100 is satisfied], and a metal electrode represented by the following formula: is formed. 37. A first group consisting of an organic bismuth compound
And organic strontium-tantalum compound and organic strontium
A small group from each of the second group consisting of the niobium-niobium compound and the third group consisting of the organotitanium compound.
At least one kind of organometallic compound is selected and THF is mainly used.
Mix and dissolve in the organic solvent used as the component so that the specified composition ratio is obtained.
Dissolving to generate a mixed solution; evaporating the mixed solution to generate a reaction gas; and setting the substrate maintained at 400 ° C. or lower in a reaction chamber in which a substrate is installed.
Introduce reaction gas and use plasma energy
By decomposing the reaction gas by chemical vapor deposition,
Forming an oxide film on the substrate; heat-treating the oxide film in an oxidizing gas;_xBi
_y(Ta, Nb)_2.0 Ti_zO_w[However, 0.6 ≦ x
≦ 1.2, 1.7 ≦ y ≦ 2.5, 0 ≦ z ≦ 1.0, w =
9 ± d, 0 ≦ d ≦ 1).
And a method for producing a dielectric film. 38. The first group comprises a compound of the formula Bi (C ₆ H
₅ ) ₃ , Bi (o-C ₇ H ₇ ) ₃ , Bi (OC ₂ H ₅ )
₃ , Bi (O-iC ₃ H ₇ ) ₃ , Bi (O-tC
_{4 H 9) 3, Bi (} O-tC 5 H 11) 3, Bi (TH
D) ₃ [hereinafter, THD represents 2,2,6,6-tetramethyl-3,5-heptanedione: C ₁₁ H ₂₀ O ₂ ], and is characterized by comprising an organic bismuth compound. Item 38. The method for producing a dielectric film according to Item 37. 39. The second group has a chemical formula of Sr [Ta
(OC_TwoH_Five)₆] _Two, Sr [Ta (O-iC
_ThreeH₇)₆]_TwoOrganic strontium tantalum represented by
Compound and Sr [Nb (OC_TwoH_Five)₆]_Two,
Sr [Nb (O-iC _ThreeH₇)₆]_TwoOrganics represented by
Characterized by being composed of a trontium-niobium compound
A method for manufacturing a dielectric film according to claim 37. 40. The second group comprises a compound of the formula Ti (i-O
C ₃ H ₇ ) ₄ , TiO (THD) ₂ , Ti (THD) ₂
(I-OC ₃ H ₇₎ method for producing a dielectric film according to claim 37, wherein a formed of an organic titanium compound represented by _2. 41. The oxide film is composed of Sr / (Ta + Nb), Bi / (Ta + Nb) and T / (Ta + Nb).
Each of the atomic composition ratios represented by i / (Ta + Nb) is 0.6 ≦ 2Sr / (Ta + Nb) ≦ 1.2, 1.7.
≦ 2Bi / (Ta + Nb) ≦ 2.8 and 0 ≦ 2Ti
The method for producing a dielectric film according to claim 37, wherein a relationship of /(Ta+Nb)≦1.0 is satisfied. 42. A film-forming surface of the substrate has a chemical formula Ir _a Pt _b Ru _c [where a, b, and c represent compositions in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ b ≦ 100.
≦ c ≦ 100, a + b + c = 100 is satisfied]. The method of manufacturing a dielectric film according to claim 37, wherein 43. The film-forming surface of the substrate has a chemical formula Ir _a Pt _b Ru _c O _d [where a, b, c,
d represents the composition in atomic%, 0 ≦ a ≦ 90, 0 ≦ b ≦ 9
0, 0 ≦ c ≦ 90, 0 ≦ d ≦ 10, a + b + c + d = 1
And an oxide electrode formed on the oxide electrode and having the chemical formula Ir _a P
t _b Ru _c [where represents a, b, c is a composition in atomic%, 0 ≦ a ≦ 100,0 ≦ b ≦ 100,0 ≦ c ≦ 10
0, a + b + c = 100 is satisfied). The method of manufacturing a dielectric film according to claim 37, wherein: 44. A first group consisting of an organic bismuth compound, a second group consisting of an organic strontium compound, a third group consisting of an organic titanium compound, and a fourth group consisting of an organic tantalum compound and an organic niobium compound. A step of selecting at least one kind of organometallic compound from each of the groups and mixing and dissolving it in an organic solvent containing THF as a main component so as to have a predetermined composition ratio, and forming a mixed solution; A step of vaporizing the solution to generate a reaction gas; a step of mixing the reaction gas with an oxidizing gas; and a mixed gas of the oxidizing gas in a reaction chamber in which a substrate held at 500 ° C. or more and 700 ° C. or less is installed. And Sr _x Bi _y (Ta, Nb) _2.0 Ti _z O _{w is formed} on the substrate by chemical vapor deposition using plasma energy.
[However, 0.6 ≦ x ≦ 1.2, 1.7 ≦ y ≦ 2.5,
0 ≦ z ≦ 1.0, w = 9 ± d, and 0 ≦ d ≦ 1). Forming a film. 45. The first group comprises a compound of the formula Bi (C ₆ H
₅ ) ₃ , Bi (o-C ₇ H ₇ ) ₃ , Bi (OC ₂ H ₅ )
₃ , Bi (O-iC ₃ H ₇ ) ₃ , Bi (O-tC
₄ H ₉ ) ₃ , Bi (O-tC ₅ H ₁₁ ) ₃ and Bi (T
HD) ₃ [hereinafter, THD represents 2,2,6,6-tetramethyl-3,5-heptanedione: C ₁₁ H ₂₀ O ₂ ]. Item 44. The method for producing a dielectric film according to Item 44. 46. The second group has a chemical formula Sr (TH
D) ₂ , Sr (THD) ₂ tetraglyme, Sr (Me ₅
C ₅ ) _{2 2} THF [where Me represents a methyl group;
F represents tetrahydrofuran.] The method according to claim 44, wherein the organic strontium compound is represented by the following formula: 47. The third group comprises a compound of the formula Ti (i-O
C ₃ H ₇ ) ₄ , TiO (THD) ₂ , Ti (THD) ₂
(I-OC ₃ H ₇₎ method for producing a dielectric film according to claim 44, wherein a formed of an organic titanium compound represented by _2. 48. The fourth group comprises a compound of the formula Ta (i-O
_{C 3 H 7) 5, Ta} (i-OC 3 H 7) organic tantalum compound represented by the ₄ THD, and _{Nb (i-OC 3 H 7} )
_{5, Nb (i-OC 3} H 7) 4 method for producing a dielectric film according to claim 44, wherein a formed of an organic niobium compound represented by THD. 49. The film-forming surface of the substrate has a chemical formula Ir _a Pt _b Ru _c [where a, b, and c represent compositions in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ b ≦ 100.
≦ c ≦ 100, a + b + c = 100 is satisfied]. The method of manufacturing a dielectric film according to claim 44, wherein 50. A film forming surface of the substrate, wherein a chemical formula Ir _a Pt _b Ru _c O _d [where a, b, c,
d represents the composition in atomic%, 0 ≦ a ≦ 90, 0 ≦ b ≦ 9
0, 0 ≦ c ≦ 90, 0 ≦ d ≦ 10, a + b + c + d = 1
And an oxide electrode formed on the oxide electrode and having the chemical formula Ir _a P
t _b Ru _c [where a, b, and c represent the composition in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ c ≦ 10
0, a + b + c = 100 is satisfied], and a metal electrode represented by the following formula: is formed. 51. Each of a first group consisting of an organic bismuth compound, a second group consisting of an organic strontium-tantalum compound and an organic strontium-niobium compound, and a third group consisting of an organic titanium compound A step of selecting at least one kind of organometallic compound and mixing and dissolving it in an organic solvent mainly containing THF so as to have a predetermined composition ratio to form a mixed solution; and evaporating the mixed solution to form a reaction gas. Generating a mixed gas with the oxidizing gas; introducing a mixed gas with the oxidizing gas into a reaction chamber in which a substrate held at 500 ° C. or higher and 700 ° C. or lower is installed; Sr _z Bi _y (Ta, Nb) _2.0 Ti _z O _{w is} deposited on the substrate by chemical vapor deposition using the method.
[However, 0.6 ≦ x ≦ 1.2, 1.7 ≦ y ≦ 2.5,
0 ≦ z ≦ 1.0, w = 9 ± d, and 0 ≦ d ≦ 1). Forming a film. 52. The first group comprises a compound of the formula Bi (C ₆ H
₅ ) ₃ , Bi (o-C ₇ H ₇ ) ₃ , Bi (OC ₂ H ₅ )
₃ , Bi (O-iC ₃ H ₇ ) ₃ , Bi (O-tC
_{4 H 9) 3, Bi (} O-tC 5 H 11) 3, Bi (TH
D) ₃ [hereinafter, THD represents 2,2,6,6-tetramethyl-3,5-heptanedione: C ₁₁ H ₂₀ O ₂ ], and is characterized by comprising an organic bismuth compound. Item 51. The method for producing a dielectric film according to Item 51. 53. The second group comprises a compound represented by the chemical formula Sr [Ta
(OC_TwoH_Five)₆] _Two, Sr [Ta (O-iC
_ThreeH₇)₆]_TwoOrganic strontium tantalum represented by
Compound and Sr [Nb (OC_TwoH_Five)₆]_Two,
Sr [Nb (O-iC _ThreeH₇)₆]_TwoOrganics represented by
Characterized by being composed of a trontium-niobium compound
A method for manufacturing a dielectric film according to claim 51. 54. The second group comprises a compound of the formula Ti (i-O
C ₃ H ₇ ) ₄ , TiO (THD) ₂ , Ti (THD) ₂
(I-OC ₃ H ₇₎ method for producing a dielectric film according to claim 51, wherein a formed of an organic titanium compound represented by _2. 55. The film-forming surface of the substrate has a chemical formula Ir _a Pt _b Ru _c [where a, b, and c represent compositions in atomic%, and 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0
≦ c ≦ 100, a + b + c = 100 are satisfied]. The method of manufacturing a dielectric film according to claim 51, wherein 56. A film forming surface of the substrate, wherein a chemical formula Ir _a Pt _b Ru _c O _d [where a, b, c,
d represents the composition in atomic%, 0 ≦ a ≦ 90, 0 ≦ b ≦ 9
0, 0 ≦ c ≦ 90, 0 ≦ d ≦ 10, a + b + c + d = 1
And an oxide electrode formed on the oxide electrode and having the chemical formula Ir _a P
t _b Ru _c [where represents a, b, c is a composition in atomic%, 0 ≦ a ≦ 100,0 ≦ b ≦ 100,0 ≦ c ≦ 10
0, a + b + c = 100 is satisfied], and the metal electrode represented by the following formula: is formed.