JP2002033460A - Semiconductor device and manufacturing method thereof - Google Patents

Abstract

(57) [Summary] A spontaneous polarization sufficiently appears in a ferroelectric film or a high-dielectric film constituting a capacitive insulating film by applying a tensile stress to a capacitive element. Improve device characteristics. SOLUTION: After a capacitive element including a capacitive lower electrode 104, a capacitive insulating film 105 and a capacitive upper electrode 106 is formed on an insulating film 103 on a semiconductor substrate 100, a silicon oxide film 111 is formed so as to cover the capacitive element. Form. next,
After depositing an ozone TEOS film 107 as a protective film on the silicon oxide film 111 by an ozone TEOS method,
Heat treatment is performed on the ozone TEOS film 107. Next, the lower metal wiring 10 is formed on the ozone TEOS film 107.
After the formation of 8, an interlayer insulating film 109 is deposited on the lower metal wiring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device having a capacitance element having a dielectric film having a high dielectric constant (hereinafter, referred to as a high dielectric film) or a capacitance insulating film made of a ferroelectric film. It relates to the manufacturing method.

[0002]

2. Description of the Related Art In recent years, consumer electronic devices have become more sophisticated with the trend toward higher speed and lower power consumption of microcomputers and the like. 2. Description of the Related Art The miniaturization of semiconductor elements constituting a semiconductor device is rapidly progressing.

In a semiconductor device having a capacitance element, a high dielectric film or a ferroelectric film is used as a capacitance insulating film constituting the capacitance element, instead of a conventionally used silicon oxide film or silicon nitride film. Techniques using membranes have been widely studied.

Further, research and development on ferroelectric films having spontaneous polarization characteristics have been actively conducted with the aim of putting a nonvolatile RAM capable of operating at a low voltage and writing or reading at a high speed to practical use.

Therefore, in order to realize a semiconductor device satisfying these requirements, a high integration of the semiconductor device can be realized without deteriorating the characteristics of a capacitor having a capacitor insulating film made of a high dielectric film or a ferroelectric film. It is important to develop a method to achieve this.

Hereinafter, a conventional method of manufacturing a semiconductor device will be described with reference to FIGS.

First, as shown in FIG. 18A, after an element isolation region 11 and a gate electrode 12 of an FET are formed on a semiconductor substrate 10, an FET is formed on the surface of the semiconductor substrate 10.
(Not shown) and the like are formed.
Next, after depositing an insulating film 13 over the entire surface of the element isolation region 11 and the gate electrode 12, a capacitor lower electrode 14 made of a platinum film or the like is formed above the element isolation region 11 on the insulating film 13. A capacitor insulating film 15 made of a high dielectric film or a ferroelectric film and a capacitor upper electrode 16 made of a platinum film or the like are formed. In addition, a capacitive element is configured by the capacitive lower electrode 14, the capacitive insulating film 15, and the capacitive upper electrode 16.

Next, as shown in FIG. 18B, a protective film 17 made of a non-doped silicon oxide film is deposited so as to cover the capacitive element.

Next, as shown in FIG. 1C, after the protective film 17 is flattened, etch back is performed to reduce the thickness of the protective film 17, and then the source region of the transistor in the insulating film 13 and A contact hole is formed above the drain region, and a contact hole is formed above the capacitor upper electrode 17 in the protective film 17.

Next, on the insulating film 13 and the protective film 17,
After depositing a metal film made of a titanium film or an aluminum film so that the contact holes are buried, the metal film is patterned to form a lower metal wiring 18, and thereafter, a heat treatment is performed on the lower metal wiring 18. Apply.

By the way, in order to prevent disconnection of the metal wiring 18 in the lower layer, the thickness of the protective film 17 before the etch back is performed as shown in FIG. 16 is required to be about 600 nm, and 800 nm above the edge of the capacitive insulating film 15.
m or more is required.

Next, as shown in FIG. 18D, an interlayer insulating film 19 is formed over the entire surface so as to cover the metal wiring 18 in the lower layer.
After depositing, although not shown, the interlayer insulating film 19
An upper metal wiring connected to the lower metal wiring 18 through the via is formed thereon.

[0013]

As described above, since the protective film formed on the capacitive element is made of a non-doped silicon oxide film, hydrogen gas generated as a reaction product constitutes the capacitive insulating film. Since a reducing action is exerted on the interface between the ferroelectric film or the high dielectric film and the upper electrode of the capacitor,
Adhesion between the capacitor insulating film and the capacitor upper electrode is reduced. Therefore, there is a problem that the capacitor upper electrode is peeled off.

Further, under the influence of the generated hydrogen gas,
There is also a problem that the ferroelectric film or the high-dielectric film constituting the capacitive insulating film is deteriorated, and the characteristics of the capacitive element are reduced.

Further, since the protective film is made of a non-doped silicon oxide film, the stress applied to the capacitive element is small and the stress tends to be compressive. Therefore, the ferroelectric film or the high dielectric There is a problem that spontaneous polarization does not sufficiently appear in the body film and the capacitor does not have good characteristics.

Further, since the protection film is made of a non-doped silicon oxide film, the flatness of the protection film cannot be sufficiently obtained, so that the inclination angle of a portion of the protection film corresponding to the edge of the capacitive insulating film becomes large. Would. For this reason, there is a problem that the metal wiring in the lower layer is disconnected at a portion corresponding to the edge of the capacitive insulating film in the protective film. On the other hand, if the thickness of the metal film is increased in order to prevent disconnection of the lower metal wiring, the metal film of the lower layer is left unetched on the side of the capacitance insulating film in the metal film, and the lower metal wiring becomes The problem of short-circuiting occurs. In order to satisfactorily form the lower metal wiring on the protective film, the inclination angle of the portion of the protective film corresponding to the edge of the capacitive insulating film is preferably 60 degrees or less.

However, when the thickness of the protective film is increased,
Although the flatness of the protective film is improved, it is not preferable to increase the thickness of the protective film because the aspect ratio of a contact hole formed in the protective film increases.

As described above, there are various problems in a semiconductor device having a capacitor having a capacitor insulating film made of a high dielectric film or a ferroelectric film. It is an object of the present invention to apply a stress so that spontaneous polarization sufficiently appears in a ferroelectric film or a high-dielectric film constituting a capacitor insulating film, thereby improving characteristics of the capacitor.

[0019]

In order to achieve the above object, a semiconductor device according to the present invention comprises a capacitor lower electrode, a high dielectric film or a ferroelectric film formed sequentially on a semiconductor substrate. A capacitance element including a capacitance insulating film and a capacitance upper electrode, a protection film including an ozone TEOS film formed to cover the capacitance element, and a wiring layer formed on the protection film;
An interlayer insulating film formed so as to cover the wiring layer.

According to the semiconductor device of the present invention, as the protective film, the ozone TEO formed so as to cover the capacitance element.
Since the S film is provided and the ozone TEOS film has a tensile stress, the spontaneous polarization sufficiently appears in the high-dielectric film or the ferroelectric film that constitutes the capacitance element. The characteristics of the capacitor are improved.

In the semiconductor device according to the present invention, the ozone TEOS film is formed by the first ozone TEOS method having a relatively low ozone concentration, and a lower ozone TEOS film having a relatively large amount of water in the film and an ozone TEOS film. It is preferable to include an upper ozone TEOS film formed by the second ozone TEOS method having a relatively high concentration and having relatively low moisture in the film.

In this case, since the lower ozone TEOS film covering the capacitive element is formed by the first ozone TEOS method having a relatively low ozone concentration, it has good film quality without defects such as voids. At the same time, since the film has a large amount of water, the adhesion to the underlying film is improved. Further, since the upper ozone TEOS film is formed by the second ozone TEOS method in which the ozone concentration is relatively high, moisture in the film is reduced, so that a tensile stress is applied to the capacitance insulating film of the capacitor. Therefore, the spontaneous polarization characteristics of the capacitive insulating film are improved, and the characteristics of the capacitive element are improved.

In the semiconductor device according to the present invention, the ozone TEOS film has a lower ozone TEOS film and an upper ozone TOS film.
When an EOS film is used, a silicon-containing insulating film formed by plasma CVD is preferably provided between the upper ozone TEOS film and the wiring layer.

In this manner, the silicon-containing insulating film formed by plasma CVD has a high ability to inhibit the diffusion of moisture, and thus blocks the moisture in the underlying ozone TEOS film without diffusing it to the capacitive insulating film. A capacitor with excellent uniformity can be obtained.

In the semiconductor device according to the present invention, the ozone TEOS film has a lower ozone TEOS film and an upper ozone TOS film.
When an EOS film is used, the thickness of the upper ozone TEOS film is preferably 0.3 nm or more and 0.6 nm or less.

By doing so, the upper ozone TEOS
Since the stress of the film can be optimized, the characteristics of the capacitor are improved.

Preferably, the semiconductor device according to the present invention includes a silicon-containing insulating film formed by plasma CVD between the capacitor and the ozone TEOS film.

In this manner, the silicon-containing insulating film formed by plasma CVD has a high ability to prevent the diffusion of water, so that the water in the ozone TEOS film is blocked without diffusing to the capacitance insulating film, so that the uniformity is obtained. This makes it possible to obtain a capacitive element having excellent characteristics.

In the semiconductor device according to the present invention, when a silicon-containing insulating film formed by plasma CVD is provided between the capacitive element and the ozone TEOS film, the silicon-containing insulating film has a refractive index of 1.65 or less. It is preferable that the silicon oxynitride film has a ratio.

In this way, the silicon oxynitride film having a refractive index of 1.65 or less has a very high moisture diffusion inhibiting ability. For this reason, moisture in the ozone TEOS film does not diffuse into the capacitor insulating film, so that a capacitor element having extremely excellent uniformity can be obtained.

The semiconductor device according to the present invention preferably includes a hydrophobic primer layer between the capacitor and the ozone TEOS film.

In this manner, the ozone TEOS film becomes
Since it is formed on the hydrophobic primer layer, it grows well and has excellent step coverage, thereby improving the insulating property and flatness of the ozone TEOS film.

In the semiconductor device according to the present invention, a silicon oxide film containing no impurity or containing at least one of boron and phosphorus and having a thickness of 150 nm or less is provided between the capacitor and the ozone TEOS film. Preferably, it is provided.

In this way, the ozone TEOS film becomes
Since it is formed on a silicon oxide film that has no dependency on the base and has excellent conformability with the ozone TEOS film, a base film made of a different material such as a capacitor element and an insulating film is formed under the ozone TEOS film. Even if it exists, it grows well without being affected by the underlying film, so that the thickness of the insulating film including the silicon oxide film and the ozone TEOS film becomes uniform. Therefore, a semiconductor device including a capacitor with excellent stability and long life can be realized.

In the semiconductor device according to the present invention, it is preferable that a silicon nitride layer is formed on the surface of the ozone TEOS film.

In this case, since the silicon nitride layer has a high ability to inhibit the diffusion of moisture, even if the ozone TEOS film is exposed to the air for a long time, the moisture in the atmosphere is reduced to the ozone TOS.
Since diffusion to the capacitor insulating film via the EOS film can be prevented, a capacitor element having excellent uniformity can be obtained.

The semiconductor device according to the present invention comprises an ozone TEO.
It is preferable to provide a silicon-containing insulating film formed by plasma CVD between the S film and the wiring layer.

In this case, since the silicon-containing insulating film formed by plasma CVD has a high ability to inhibit the diffusion of moisture, even if the ozone TEOS film is exposed to the air for a long time, the moisture in the air is reduced. Since it is possible to prevent a situation in which the capacitor is diffused into the capacitor insulating film via the ozone TEOS film, a capacitor having excellent uniformity can be obtained.

In the semiconductor device according to the present invention, the thickness of the ozone TEOS film is 0.3 nm or more and 0.6 nm or more.
The following is preferred.

This makes it possible to optimize the stress of the ozone TEOS film, thereby improving the characteristics of the capacitor.

The method of manufacturing a semiconductor device according to the present invention comprises the steps of forming a capacitor element comprising a capacitor lower electrode, a capacitor insulating film made of a high dielectric film or a ferroelectric film, and a capacitor upper electrode on a semiconductor substrate. And ozone TE so as to cover the capacitive element.
The method includes a step of forming a protective film made of an OS film, a step of forming a wiring layer on the protective film, and a step of forming an interlayer insulating film so as to cover the wiring layer.

According to the method of manufacturing a semiconductor device of the present invention, the method includes the step of forming a protective film made of an ozone TEOS film so as to cover a capacitance element, and the ozone TEOS film has a tensile stress. In addition, since spontaneous polarization sufficiently appears in the capacitor insulating film made of the high dielectric film or the ferroelectric film constituting the capacitor, the characteristics of the capacitor are improved.

In the method of manufacturing a semiconductor device according to the present invention, the step of forming a protective film includes the steps of:
Forming a lower ozone TEOS film by a first ozone TEOS method having a relatively low ozone concentration; and forming an upper layer by a second ozone TEOS method having a relatively high ozone concentration on the lower ozone TEOS film. And forming a TEOS film of ozone.

In this case, since the lower ozone TEOS film covering the capacitive element is formed by the first ozone TEOS method having a relatively low ozone concentration, it has good film quality without defects such as voids. At the same time, since the film has a large amount of water, the adhesion to the interlayer insulating film is improved. Further, since the upper ozone TEOS film is formed by the second ozone TEOS method in which the ozone concentration is relatively high, moisture in the film is reduced, so that stress applied to the capacitor insulating film of the capacitor is increased. Therefore, the spontaneous polarization characteristics of the capacitive insulating film are improved, and the characteristics of the capacitive element are improved. Therefore, a semiconductor device including a highly reliable capacitor can be manufactured.

The step of forming the protective film is the first ozone T
In the case of including the EOS method and the second ozone TEOS method, the first method
Ozone concentration in the ozone TEOS method is 25 g / m ³
In addition, the ozone concentration in the second ozone TEOS method is preferably 130 g / m ³ or more.

By doing so, the first ozone TEOS
Since the first ozone TEOS film formed by the method is excellent in self-reflow properties, defects such as defects do not occur in the first ozone TEOS film, so that a first ozone TEOS film having good film quality can be obtained. Also, the second ozone TE
The second ozone TEOS film formed by the OS method can give a sufficient stress to the capacitor insulating film of the capacitor, and the second ozone TEOS film due to the low moisture content.
Cracks can be prevented from occurring in the OS film during heat treatment.

The step of forming the protective film is the first ozone T
In the case of including the EOS method and the second ozone TEOS method, the first method
The ozone TEOS method is performed under the condition that the value of (ozone flow rate / TEOS flow rate) is 3 or less, and the second ozone TEOS method is (ozone flow rate / TEOS flow rate).
Is preferably performed under the condition that the value is 15 or more.

By doing so, the first ozone TEOS
Since the first ozone TEOS film formed by the method is excellent in self-reflow properties, defects such as defects do not occur in the first ozone TEOS film, so that a first ozone TEOS film having good film quality can be obtained. Also, the second ozone TE
The second ozone TEOS film formed by the OS method can give a sufficient stress to the capacitor insulating film of the capacitor, and the second ozone TEOS film due to the low moisture content.
Cracks can be prevented from occurring in the OS film during heat treatment.

In this case, the second ozone TEOS film is
× 10^ThreeN / cm^Two~ 3.5 × 10 ^FourN / cm^TwoTen of
It is preferable to have a sail stress.

In this manner, the ozone TEOS film becomes
Since sufficient stress can be applied to the capacitor insulating film of the capacitor, the spontaneous polarization characteristics of the capacitor insulating film are improved, so that the characteristics of the capacitor are improved.

In the method of manufacturing a semiconductor device according to the present invention, a step of forming a silicon-containing insulating film so as to cover the capacitive element by plasma CVD is provided between the step of forming the capacitive element and the step of forming the protective film. Preferably, the step of forming a protective film preferably includes the step of forming an ozone TEOS film on the silicon-containing insulating film.

In this case, since the silicon-containing insulating film formed by plasma CVD has a high ability to prevent the diffusion of water, the silicon-containing insulating film blocks the water in the ozone TEOS film without diffusing it to the capacitive insulating film, so that the uniformity is obtained. This makes it possible to obtain a capacitive element having excellent characteristics.

When the method for manufacturing a semiconductor device according to the present invention includes the step of forming a silicon-containing insulating film so as to cover a capacitive element by plasma CVD, the step of forming the silicon-containing insulating film includes It is preferable to include a step of performing a plasma treatment on the surface of the substrate.

In this case, since the surface of the silicon-containing insulating film has irregularities, the ability of the silicon-containing insulating film to prevent moisture diffusion is improved.

In this case, the plasma processing is performed by using N ₂ gas and N ₂ gas.
It is preferable that the sputter etching is performed using a plasma including a gas containing at least one of H ₃ gas, N ₂ O gas, O ₂ gas, Ar gas, Cl ₂ gas and C ₂ F ₆ gas.

This makes it possible to reliably form irregularities on the surface of the silicon-containing insulating film.

In the case where the method for manufacturing a semiconductor device according to the present invention includes the step of forming a silicon-containing insulating film so as to cover the capacitive element by plasma CVD, the step of forming the silicon-containing insulating film includes the step of: To perform a plasma treatment on the surface of the silicon-containing insulating film to form a silicon nitride layer.

In this case, since the silicon nitride layer has a high ability to inhibit the diffusion of moisture, the diffusion of moisture from the ozone TEOS film to the capacitance insulating film or the ozone TEO of moisture in the atmosphere is performed.
Diffusion into the S film can be prevented.

In this case, the plasma processing is performed by a plasma CV
It is preferable to perform the process without exposing the silicon-containing insulating film formed by D to the atmosphere.

In this case, since the silicon-containing insulating film is continuously subjected to plasma processing without being exposed to the air, the thickness of the silicon nitride layer increases, and the silicon nitride layer has an ability to prevent moisture diffusion. It will be even higher.

The method of manufacturing a semiconductor device according to the present invention includes a step of forming a hydrophobic primer layer so as to cover the capacitive element, between the step of forming the capacitive element and the step of forming the protective film, The step of forming the protective film is performed by using ozone TEO.
It is preferable to include a step of forming the S film on the primer layer.

In this manner, the ozone TEOS film becomes
Since it is formed on the hydrophobic primer layer, it grows well and has excellent step coverage, thereby improving the insulating property and flatness of the ozone TEOS film.

In the method of manufacturing a semiconductor device according to the present invention, when a step of forming a hydrophobic primer layer so as to cover a capacitive element is provided, the step of forming a primer layer uses hexamethyldisilazane. It is preferred to do so.

In this way, a primer layer having hydrophobicity can be reliably formed.

In the method of manufacturing a semiconductor device according to the present invention, between the step of forming a capacitive element and the step of forming a protective film, no impurities are contained or boron or phosphorus is contained so as to cover the capacitive element. 150 nm including at least one of
Preferably, the method includes a step of forming a silicon oxide film having the following thickness, and the step of forming the protective film preferably includes a step of forming an ozone TEOS film on the silicon oxide film.

In this way, the ozone TEOS film becomes
Since it is formed on a silicon oxide film that has no dependency on the base and has excellent conformability with the ozone TEOS film, a base film made of a different material such as a capacitor element and an insulating film is formed under the ozone TEOS film. Even if it exists, it grows well without being affected by the underlying film, so that the thickness of the insulating film including the silicon oxide film and the ozone TEOS film becomes uniform. Therefore, a semiconductor device including a capacitor with excellent stability and long life can be manufactured.

In the method of manufacturing a semiconductor device according to the present invention, the step of forming a protective film includes a step of performing a plasma treatment on the surface of the ozone TEOS film to form a silicon nitride layer on the surface of the ozone TEOS film. It is preferred to include.

In this case, since the silicon nitride layer has a high ability to inhibit the diffusion of moisture, even if the ozone TEOS film is exposed to the air for a long time, the moisture in the atmosphere is reduced to the ozone TOS.
Since diffusion to the capacitor insulating film via the EOS film can be prevented, a capacitor element having excellent uniformity can be obtained.

In the method of manufacturing a semiconductor device according to the present invention, the step of forming a protective film and the step of forming a wiring layer are performed between
Preferably, the method includes a step of forming a silicon-containing insulating film on the protective film by plasma CVD, and the step of forming the wiring layer preferably includes a step of forming the wiring layer on the silicon-containing insulating film.

In this manner, the silicon-containing insulating film formed by the plasma CVD has a high ability to inhibit the diffusion of moisture, so that even if the ozone TEOS film is exposed to the air for a long time, the moisture in the air may be reduced. Can be prevented from diffusing into the capacitor insulating film via the ozone TEOS film, so that a capacitor element having excellent uniformity can be obtained.

In the case where the method of manufacturing a semiconductor device according to the present invention includes a step of forming a silicon-containing insulating film on a protective film by plasma CVD, the step of forming the silicon-containing insulating film includes It is preferable to include a step of performing a plasma treatment on the surface of the substrate.

In this way, the unevenness is formed on the surface of the silicon-containing insulating film, so that the capability of the silicon-containing insulating film to diffuse moisture can be improved.

In this case, the plasma processing is performed with N ₂ gas and N ₂ gas.
It is preferable that the sputter etching is performed using a plasma including a gas containing at least one of H ₃ gas, N ₂ O gas, O ₂ gas, Ar gas, Cl ₂ gas and C ₂ F ₆ gas.

In this way, irregularities can be reliably formed on the surface of the silicon-containing insulating film.

In the case where the method of manufacturing a semiconductor device according to the present invention includes a step of forming a silicon-containing insulating film on a protective film by plasma CVD, the step of forming the silicon-containing insulating film includes To perform a plasma treatment on the surface of the silicon-containing insulating film to form a silicon nitride layer.

In this case, since the silicon nitride layer has a high ability to inhibit the diffusion of moisture, even if the ozone TEOS film is exposed to the air for a long time, the moisture in the atmosphere is reduced to the ozone TOS.
Since the situation of diffusion into the capacitor insulating film via the EOS film can be further prevented, a capacitor element with more excellent uniformity can be obtained.

In this case, the plasma processing is performed by a plasma CV
It is preferable to perform the process without exposing the silicon-containing insulating film formed by D to the atmosphere.

In this case, the silicon-containing insulating film is continuously plasma-treated without being exposed to the air, so that the thickness of the silicon nitride layer is increased. It will be even higher.

In the method of manufacturing a semiconductor device according to the present invention, the step of forming the protective film preferably includes a step of performing a heat treatment on the ozone TEOS film.

In this way, the stress of the ozone TEOS film can be increased and the density of the ozone TEOS film can be increased, so that the characteristics of the capacitor can be further improved.

In this case, the heat treatment is performed at 500 ° C. to 650 ° C.
It is preferred to be carried out at a temperature of

As described above, by performing the heat treatment at a temperature of 500 ° C. to 650 ° C., the stress of the ozone TEOS film can be surely increased and the ozone TEOS film can be surely densified.

In this case, the heat treatment is preferably performed in an atmosphere containing oxygen gas.

In this case, sufficient oxygen is supplied to the capacitive insulating film forming the capacitive element, so that the characteristics of the capacitive element are improved.

In the method for manufacturing a semiconductor device according to the present invention, the ozone TEOS film has an ozone concentration of 130 g / m ^3.
It is preferably formed by the ozone TEOS method described above.

In this way, the ozone TEOS film can give a sufficient stress to the capacitance insulating film of the capacitor, and also prevents the ozone TEOS film from cracking during heat treatment due to the low moisture content. it can.

In the method of manufacturing a semiconductor device according to the present invention, the ozone TEOS film is preferably formed by an ozone TEOS method in which the value of (ozone flow rate / TEOS flow rate) is 15 or more.

In this way, the ozone TEOS film can give a sufficient stress to the capacitive insulating film of the capacitor, and also prevents the ozone TEOS film from cracking during heat treatment due to the low moisture content. it can.

In the method for manufacturing a semiconductor device according to the present invention,
And the ozone TEOS film is 5 × 10 ^ThreeN / cm^Two~ 3.
5 × 10^FourN / cm^TwoHave a tensile stress of
Preferably.

In this way, the ozone TEOS film becomes
Since sufficient stress can be applied to the capacitor insulating film of the capacitor, the spontaneous polarization characteristics of the capacitor insulating film are improved, so that the characteristics of the capacitor are improved.

In the method of manufacturing a semiconductor device according to the present invention, the ozone TEOS film is preferably formed at a film forming temperature of 400 ° C. to 450 ° C.

In this manner, the stress of the ozone TEOS film can be increased and the ozone TEOS film can be made dense, so that the characteristics of the capacitor can be further improved.

In the method of manufacturing a semiconductor device according to the present invention, the ozone TEOS film is formed by using a primer agent and ozone TEOS.
It is preferably formed using a mixed source obtained by mixing a liquid.

In this way, a hydrophobic ozone TEOS film can be formed without increasing the number of processes. Further, since the volatilization of the primer agent can be suppressed, defects in the plasma TEOS film can be reduced, and the step coverage of the ozone TEOS film can be improved to improve the insulating property and flatness of the ozone TEOS film. it can.

[0095]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS (First Embodiment) A semiconductor device according to a first embodiment of the present invention and a method for manufacturing the same will be described below with reference to FIGS.

First, as shown in FIG. 1A, after an element isolation region 101 and a gate electrode 102 of an FET are formed on a semiconductor substrate 100, an impurity diffusion layer of the FET (shown in FIG. Are omitted), and thereafter, the element isolation region 101 and the gate electrode 102 are formed.
An insulating film 103 is deposited over the entire surface.

Next, a capacitor lower electrode 104, a capacitor insulating film 105 made of a high dielectric film or a high dielectric film, and a capacitor upper electrode 106 are formed on the insulating film 103 above the element isolation region 102. Note that a capacitance element is constituted by the capacitance lower electrode 104, the capacitance insulating film 105, and the capacitance upper electrode 106.

The capacitance lower electrode 104 and the capacitance upper electrode 10
As 6, a single-layer film composed of platinum, iridium, palladium, ruthenium or an alloy of two or more of these, or a laminated film composed of two or more films of a platinum film, an iridium film, a palladium film, and a ruthenium film After depositing a metal film by sputtering, the metal film can be patterned.

As the capacitor insulating film 105, a high dielectric film or a ferroelectric film containing strontium, bismuth, tantalum or the like as a main component can be used.

Next, as shown in FIG.
03, containing at least one of boron and phosphorus so as to cover the capacitive element.
After forming a silicon oxide film 111 having a thickness of 0 nm or less, the silicon oxide film 111 is formed by an ozone TEOS method.
An ozone TEOS film 107 as a protective film is deposited on the substrate. As described above, the ozone TEOS film 10 is formed on the capacitive element.
When 7 is formed, a tensile stress is applied to the capacitive element, so that spontaneous polarization sufficiently appears in the capacitive insulating film 105 made of a high dielectric film or a ferroelectric film, so that the characteristics of the capacitive element are improved.

Next, with respect to the ozone TEOS film 107,
The heat treatment is performed at a temperature of 500 ° C. to 650 ° C. in an oxygen atmosphere, for example, at a temperature of 600 ° C. for about 1 hour. Thus, when the heat treatment is performed on the ozone TEOS film 107, the stress of the ozone TEOS film 107 can be increased and the ozone TEOS film 10
7 can be made denser. Further, when the heat treatment is performed in an oxygen atmosphere, a sufficient amount of oxygen is supplied to the capacitor insulating film 105, so that the characteristics of the capacitor are improved. Note that the oxygen atmosphere in which the heat treatment is performed may be an atmosphere of an oxygen gas or an atmosphere of a mixed gas of an oxygen gas and another gas.

As described above, the ozone TE is placed on the capacitive element.
When the OS film 107 is formed, a tensile stress is applied to the capacitor, so that spontaneous polarization sufficiently appears in the capacitor insulating film 105 made of a high dielectric film or a ferroelectric film, and thus the characteristics of the capacitor are improved.

By the way, in order to favorably generate spontaneous polarization in the capacitor insulating film 105, it is necessary to use ozone TEOS after heat treatment.
The stress of the film 107 is preferably a tensile stress (tensile stress) of 5 × 10 ³ N / cm ² or more and 3.5 × 10 ⁴ N / cm ² or less. If the ozone TEOS film 107 after the heat treatment has a tensile stress within this range, the spontaneous polarization characteristics of the capacitance insulating film 105 are improved, so that the characteristics of the capacitance element are improved.

The thickness of the ozone TEOS film 107 is preferably in the range of 0.3 μm to 0.6 μm. If the thickness of the ozone TEOS film 107 is less than 0.3 μm, the flatness required for the protective film cannot be obtained, so the metal film deposited on the ozone TEOS film 107 is patterned to form a metal wiring layer. When etching is performed, there is a possibility that etching residue and the like may occur. When the thickness of the ozone TEOS film 107 exceeds 0.6 μm, the total thickness of the insulating film 103 and the ozone TEOS film 107 increases,
The aspect ratio of the contact hole formed in the insulating film 103 and the ozone TEOS film 107 becomes high.

The concentration of ozone in the ozone TEOS method (in this specification, the concentration of oxygen gas including ozone gas is referred to as the concentration of ozone for convenience) is as follows.
130 g / m ³ or more is preferable, and 150 g / m ³ or more is more preferable. Ozone concentration 130g / m
If it is ³ or more, sufficient stress can be applied to the capacitor insulating film 105, and the occurrence of cracks in the ozone film 107 during heat treatment due to the low moisture content can be prevented. Note that the upper limit of the ozone concentration is ozone TE
What is necessary is just to be in the range where the OS film 107 grows.

In order to set the concentration of ozone in the ozone TEOS method to 130 g / m ³ or more, (ozone flow rate /
The value of TEOS may be set to 15 or more.

The ozone TEOS method for forming the ozone TEOS film 107 is preferably performed in a temperature range of 400 to 450 ° C. This way,
The stress of the ozone TEOS film 107 can be increased, and the quality of the ozone TEOS film 107 can be increased.

Next, as shown in FIG.
EOS film 107, silicon oxide film 111 and insulating film 10
3 and a contact hole of a capacitive element in the ozone TEOS film 107 and the silicon oxide film 111, and then a titanium film, a titanium nitride film,
A metal film composed of a laminated film of an aluminum film and a titanium nitride film is deposited, and thereafter, the metal film is patterned to form a lower metal wiring 108. Note that the lower metal wiring 108 is subjected to 400
Heat treatment is performed at a temperature of 30 ° C. for 30 minutes to make the lower metal wiring 108 denser and lower in stress.

Next, as shown in FIG. 1D, an interlayer insulating film 109 made of, for example, a silicon nitride film is deposited on the lower metal wiring 108 by a plasma CVD method. However, an upper metal wiring is formed on the interlayer insulating film 109.

According to the first embodiment, the silicon oxide film 111 which has no dependency on the underlayer and is excellent in conformity with the ozone TEOS film 107 is formed on the insulating film 103 so as to cover the capacitance element. Even if a base film made of a different material such as a capacitor element and an insulating film 103 exists under the film 107, the ozone TEOS film 107
Grows well without being affected by the underlying film. Therefore, the silicon oxide film 111 and the ozone TEOS film 1
In addition, since the thickness of the insulating film is adjusted to be uniform, the capacitance element is excellent in stability and long life.

(Second Embodiment) Hereinafter, a semiconductor device and a method of manufacturing the same according to a second embodiment of the present invention will be described.
This will be described with reference to FIGS. 2 (a) to 2 (c) and 3 (a) to 3 (c).

First, as shown in FIG. 2A, after an element isolation region 101 and a gate electrode 102 of an FET are formed on a semiconductor substrate 100, an impurity diffusion layer of the FET (shown in FIG. Are omitted), and thereafter, the element isolation region 101 and the gate electrode 102 are formed.
An insulating film 103 is deposited over the entire surface.

Next, on the insulating film 103 and above the element isolation region 102, a capacitive element comprising a capacitive lower electrode 104, a high dielectric film or a capacitive insulating film 105 composed of a high dielectric film and a capacitive upper electrode 106 is formed. Form.

Next, as shown in FIG. 2B, a first silicon-containing insulating film (hereinafter, referred to as a silicon oxide film) made of a silicon oxide film or the like is formed on the insulating film 103 by a plasma CVD method so as to cover the capacitive element. After the formation of the first plasma silicon insulating film 112, the first plasma silicon insulating film 112 is subjected to a first plasma treatment,
A first surface treatment layer 112a is formed on a surface of the first plasma silicon insulating film 112. The first surface treatment layer 1
12a will be described later.

Next, as shown in FIG.
The first plasma silicon insulating film 112 is formed by the EOS method.
After depositing an ozone TEOS film 107 as a protective film thereon, the ozone TEOS film 107 is subjected to a heat treatment at a temperature of 500 ° C. to 650 ° C. in an oxygen atmosphere for about 1 hour.

Next, as shown in FIG. 3A, a second silicon-containing insulating film (hereinafter referred to as a second insulating film) made of a silicon oxide film or the like is entirely formed on the ozone TEOS film 107 by a plasma CVD method. After forming the 113, a second plasma process is performed on the second plasma silicon insulating film 113,
A second surface treatment layer 113a is formed on the surface of the second plasma silicon insulating film 113. The second surface treatment layer 1
13a will be described later.

Next, as shown in FIG. 3B, the second plasma silicon insulating film 113, the ozone TEOS film 10
7. First plasma silicon insulating film 112 and insulating film 1
03, a contact hole of a capacitor is formed in the second plasma silicon insulating film 113, the ozone TEOS film 107, and the first plasma silicon insulating film 112, and then a second plasma silicon insulating film is formed. A titanium film over the entire surface of the film 113,
A metal film composed of a laminated film of a titanium nitride film, an aluminum film, and a titanium nitride film is deposited, and thereafter, the metal film is patterned to form a lower metal wiring 108.

Next, as shown in FIG. 3C, an interlayer insulating film 109 made of, for example, a silicon nitride film is deposited on the lower metal wiring 108 by a plasma CVD method. However, an upper metal wiring is formed on the interlayer insulating film 109.

According to the second embodiment, after forming the first plasma silicon insulating film 112 having a high water diffusion preventing ability on the insulating film 103 so as to cover the capacitive element, the first plasma silicon insulating film 112 is formed. Plasma T on insulating film 112
Since the EOS film 107 is deposited, the first plasma silicon insulating film 112 blocks moisture in the ozone TEOS film 107 without diffusing to the capacitor insulating film 105, so that a capacitor element with excellent uniformity can be obtained. .

According to the second embodiment, the ozone T
Since the second plasma silicon insulating film 113 having a high moisture diffusion inhibiting ability is formed over the entire surface of the EOS film 107, even if the ozone TEOS film 107 is exposed to the air for a long time, The moisture in the ozone TEOS film 10
7 can be prevented from diffusing into the capacitor insulating film 105 via the gate electrode 7, so that a capacitor element having excellent uniformity can be obtained.

Incidentally, as the first plasma processing,
It is preferable that the sputter etching is performed using a plasma including a gas containing at least one of N ₂ gas, NH ₃ gas, N ₂ O gas, O ₂ gas, Ar gas, Cl ₂ gas and C ₂ F ₆ gas. .

In this way, the first surface treatment layer 112a composed of the uneven portion having a height of several tens nm is formed on the surface of the first plasma silicon insulating film 112.
The ability of the first plasma silicon insulating film 112 to prevent diffusion of moisture is improved.

As the first plasma processing, N ₂
Preferably, the nitriding treatment is performed by using a plasma composed of a gas containing at least one of a gas, an NH ₃ gas and an N ₂ O gas.

In this manner, the first surface treatment layer 112a made of a silicon nitride layer having a high moisture diffusion inhibiting ability is formed on the surface of the first plasma silicon insulating film 112. Capacitive insulating film 1
Diffusion of moisture into ozone 05 or ozone TEOS of atmospheric moisture
Diffusion into the film 107 can be further prevented.

In this case, the first plasma treatment is preferably performed without exposing first plasma silicon insulating film 112 formed by plasma CVD to the atmosphere. By doing so, the first plasma silicon insulating film 112 is continuously plasma-treated without being exposed to the air, so that the thickness of the first surface treatment layer 112a (silicon nitride layer) increases. , First surface treatment layer 1
The water diffusion inhibiting ability of 12a is further enhanced.

As the second plasma processing, N ₂ gas,
NH ₃ gas, N ₂ O gas, O ₂ gas, Ar gas, Cl ₂
It is preferable that the sputter etching is performed using a plasma composed of a gas containing at least one of a gas and a C ₂ F ₆ gas.

In this way, the second surface treatment layer 113a composed of the concave and convex portions having a height of several tens nm is formed on the surface of the second plasma silicon insulating film 113.
The ability of the second plasma silicon insulating film 113 to prevent diffusion of moisture is improved.

As the second plasma processing, N ₂
Preferably, the nitriding treatment is performed by using a plasma composed of a gas containing at least one of a gas, an NH ₃ gas and an N ₂ O gas.

Thus, the second surface treatment layer 113a made of a silicon nitride layer having a high moisture diffusion inhibiting ability is formed on the surface of the second plasma silicon insulating film 113, so that the ozone TEOS film 107 is formed. Even when exposed to the air for a long time, the situation in which the moisture in the air diffuses into the capacitor insulating film 105 via the ozone TEOS film 107 can be further prevented, so that a capacitor element with more excellent uniformity can be obtained. be able to.

In this case, the second plasma treatment is preferably performed without exposing second plasma silicon insulating film 113 formed by plasma CVD to the atmosphere. In this case, the second plasma silicon insulating film 113 is continuously plasma-treated without being exposed to the air, so that the thickness of the second surface treatment layer 113a (silicon nitride layer) increases. , Second surface treatment layer 1
13a has a higher moisture diffusion inhibiting ability.

The first or second plasma silicon insulating films 112 and 113 have a refractive index n of 1.65.
It is preferable to use a silicon oxynitride film (SiON) film described below. The reason is that a silicon oxynitride film having a refractive index of 1.65 or less has an extremely high ability to prevent diffusion of moisture. Therefore, the first plasma silicon insulating film 1
12 prevents the moisture in the ozone TEOS film 107 from diffusing into the capacitor insulating film 105, so that a capacitor element with extremely excellent uniformity can be obtained. Further, the second plasma silicon insulating film 113 is formed of an ozone TEOS film 107.
Is exposed to the air for a long time, moisture in the air passes through the ozone TEOS film 107 and the capacitance insulating film 1
Since the diffusion to the element 05 is prevented, a capacitor element having excellent uniformity can be obtained.

First or second plasma silicon insulating film 1
It is preferable that the film thicknesses of the layers 12 and 113 be 200 nm or less. When the thickness of the first plasma silicon insulating film 112 exceeds 200 nm, the stress applied to the capacitor insulating film 105 becomes too large, and the characteristics of the capacitor may be deteriorated. Also, the second plasma silicon insulating film 1
If the film thickness of the second plasma silicon insulating film 13 exceeds 200 nm, the flatness of the second plasma silicon insulating film 113 cannot be secured, and the metal film deposited on the second plasma silicon insulating film 113 is patterned to form a lower metal layer. When the wiring 108 is formed, there is a possibility that the metal film may be left unetched.

(Third Embodiment) Hereinafter, a semiconductor device and a method of manufacturing the same according to a third embodiment of the present invention will be described.
This will be described with reference to FIGS.

First, as shown in FIG. 4A, after an element isolation region 101 and a gate electrode 102 of an FET are formed on a semiconductor substrate 100, an impurity diffusion layer of the FET (not shown) is formed on the surface of the semiconductor substrate 100. Are omitted), and thereafter, the element isolation region 101 and the gate electrode 102 are formed.
An insulating film 103 is deposited over the entire surface.

Next, on the insulating film 103 and above the element isolation region 102, a capacitive element comprising a capacitive lower electrode 104, a high dielectric film or a capacitive insulating film 105 composed of a high dielectric film and a capacitive upper electrode 106 is formed. Form.

Next, as shown in FIG.
Hexamethyldisilazane is supplied on the substrate 03 to form a hydrophobic primer layer 114 having a thickness of about 2 to 5 nm so as to cover the capacitor.
Ozone TEOS as a protective film on the primer layer 114
A film 107 is deposited.

Next, as shown in FIG.
A contact hole for the FET is formed in the EOS film 107, the primer layer 114, and the insulating film 103, and the ozone T
After forming a contact hole of a capacitive element in the EOS film 107 and the primer layer 114, a metal film including a laminated film of a titanium film, a titanium nitride film, an aluminum film, and a titanium nitride film is entirely formed on the ozone TEOS film 107. And then patterning the metal film,
A lower metal wiring 108 is formed.

Next, as shown in FIG. 4D, an interlayer insulating film 109 made of, for example, a silicon nitride film is deposited on the lower metal wiring 108 by a plasma CVD method. However, an upper metal wiring is formed on the interlayer insulating film 109.

According to the third embodiment, ozone TEOS
Since the film 107 is formed on the hydrophobic primer layer 114 and grows well, the film 107 has excellent step coverage. Accordingly, the step coverage of the ozone TEOS film 114 formed on the capacitor is improved, so that the insulation and flatness of the ozone TEOS film 107 are improved.

(Fourth Embodiment) Hereinafter, a semiconductor device and a method of manufacturing the same according to a fourth embodiment of the present invention will be described.
This will be described with reference to FIGS.

First, as shown in FIG. 5A, after an element isolation region 101 and a gate electrode 102 of an FET are formed on a semiconductor substrate 100, an impurity diffusion layer of the FET (shown in FIG. Are omitted), and thereafter, the element isolation region 101 and the gate electrode 102 are formed.
An insulating film 103 is deposited over the entire surface.

Next, on the insulating film 103 and above the element isolation region 102, a capacitive element comprising a capacitive lower electrode 104, a high dielectric film or a capacitive insulating film 105 composed of a high dielectric film and a capacitive upper electrode 106 is formed. Form.

Next, as shown in FIG.
Ozone T containing 5% by weight of primer solution
After supplying an EOS liquid source to deposit an ozone TEOS film 107 as a protective film having hydrophobicity on the insulating film 103, the ozone TEOS film 107 is subjected to N ₂ gas, NH ₃ gas and N ₂ gas. A plasma nitridation process is performed using a plasma including at least one of O 2 gas to form a silicon nitride layer 115 on the surface of the ozone TEOS film 107.

Next, as shown in FIG.
After forming a contact hole of the FET in the EOS film 107 and the insulating film 103, and forming a contact hole of the capacitor in the ozone TEOS film 107, the ozone TEO is formed.
By depositing a metal film composed of a laminated film of a titanium film, a titanium nitride film, an aluminum film and a titanium nitride film over the entire surface of the S film 107, and then patterning the metal film, a lower metal wiring is formed. 108 is formed.

Next, as shown in FIG. 5D, an interlayer insulating film 109 made of, for example, a silicon nitride film is deposited on the lower metal wiring 108 by a plasma CVD method. However, an upper metal wiring is formed on the interlayer insulating film 109.

According to the fourth embodiment, the ozone TEOS film 107 having hydrophobicity is processed by supplying the ozone TEOS liquid source containing the primer liquid to deposit the ozone TEOS film 107 on the insulating film 103. It can be formed without increasing the number of layers. In addition, since the volatilization of the primer agent can be suppressed, defects in the plasma TEOS film 107 can be reduced, and the step coverage of the ozone TEOS film 107 can be improved to improve the ozone TEOS film.
The insulating property and flatness of the OS film 107 can be improved.

Further, since the silicon nitride layer 115 formed on the surface of the ozone TEOS film 107 has a high ability to prevent the diffusion of moisture, even if the ozone TEOS film 107 is exposed to the air for a long time, Of water is ozone TEOS
Since diffusion to the capacitor insulating film 105 via the film 107 can be prevented, a capacitor element with excellent uniformity can be obtained.

(Fifth Embodiment) Hereinafter, a semiconductor device and a method of manufacturing the same according to a fifth embodiment of the present invention will be described.
This will be described with reference to FIGS.

First, as shown in FIG. 6A, after an element isolation region 101 and a gate electrode 102 of an FET are formed on a semiconductor substrate 100, an impurity diffusion layer of the FET (not shown) is formed on the surface of the semiconductor substrate 100. Are omitted), and thereafter, the element isolation region 101 and the gate electrode 102 are formed.
An insulating film 103 is deposited over the entire surface.

Next, on the insulating film 103 and above the element isolation region 102, a capacitive element comprising a capacitive lower electrode 104, a high dielectric film or a capacitive insulating film 105 composed of a high dielectric film and a capacitive upper electrode 106 is formed. Form.

Next, as shown in FIG.
03, containing at least one of boron and phosphorus so as to cover the capacitive element.
After forming a silicon oxide film 111 having a thickness of 0 nm or less, a first ozone TEOS having a relatively low ozone concentration is formed.
A lower ozone TEOS film 107a having a relatively high moisture content in the film is grown on the silicon oxide film 111 by a method, and then a second ozone T having a relatively high ozone concentration is formed.
By the EOS method, an upper ozone TEOS film 107b having relatively less moisture in the film is grown on the lower ozone TEOS film 107a.

Next, the lower and upper ozone TEOS films 1
07a and 107b in an oxygen atmosphere.
Heat treatment is performed at a temperature of 0 ° C. to 650 ° C. for about 1 hour. When the heat treatment is performed in this manner, the upper ozone TEO
The stress of the S film 107b can be increased, and the film quality of the upper ozone TEOS film 107b can be made dense. Further, when the heat treatment is performed in an oxygen atmosphere, a sufficient amount of oxygen is supplied to the capacitor insulating film 105, so that the characteristics of the capacitor are improved. Note that the oxygen atmosphere in which the heat treatment is performed may be an atmosphere of an oxygen gas or an atmosphere of a mixed gas of an oxygen gas and another gas.

As described above, since the lower ozone TEOS film 107a covering the capacitive element is formed by the first ozone TEOS method having a relatively low ozone concentration, it does not have defects such as voids and is excellent. The film quality and the amount of moisture in the film are high, so that the adhesion to the insulating film 103 is improved.

The upper ozone TEOS film 107b
Is formed by the second ozone TEOS method in which the ozone concentration is relatively high, so that the moisture in the film is reduced.
Stress applied to the capacitor insulating film 105 of the capacitor increases. For this reason, the spontaneous polarization characteristics of the capacitor insulating film 105 are improved, so that the characteristics of the capacitor are improved.

By the way, the spontaneous spontaneous spontaneous
In order to generate polarization, the upper layer of ozone T after heat treatment is used.
The stress of the EOS film 107b is 5 × 10^ThreeN /
cm ^TwoAbove and 3.5 × 10^FourN / cm^TwoThe following tensor
It is preferably an il stress (tensile stress). heat
The upper ozone TEOS film 107b after the treatment is within this range.
Of the capacitor insulating film 10
5 improves the spontaneous polarization characteristics, thereby improving the characteristics of the capacitive element.
Up.

The thickness of the upper ozone TEOS film 107b is preferably in the range of 0.3 μm to 0.6 μm. If the thickness of the upper ozone TEOS film 107a is less than 0.3 μm, the flatness required for the protective film cannot be obtained.
When a metal film deposited on the substrate is patterned to form a metal wiring layer, there is a possibility that etching residue or the like may occur.

The concentration of ozone in the first ozone TEOS method may be 25 g / m ³ or less, and is 20 g / m ³ or less.
/ M ³ or less. If the ozone concentration is 25 g / m ³ or less, the lower ozone TEOS film 1
07a's self-reflow properties, lower ozone TE
No defect such as a defect occurs in the OS film 107a. Note that the lower limit of the ozone concentration is as follows.
What is necessary is just to be in the range where 7a grows.

In order to set the ozone concentration in the first ozone TEOS method to 25 g / m ³ or less, the value of (ozone flow rate / TEOS flow rate) may be set to 3 or less.

The concentration of ozone in the second ozone TEOS method may be 130 g / m ³ or more.
More preferably, it is 0 g / m ³ or more. If the ozone concentration is 130 g / m ³ or more, the upper ozone TEOS
The film 107b can give sufficient stress to the capacitor insulating film 105, and can prevent a crack from being generated in the upper ozone TEOS film 107b during the heat treatment due to the low moisture content. Note that the upper limit of the ozone concentration may be within a range in which the upper ozone TEOS film 107b grows.

In order to set the ozone concentration in the second ozone TEOS method to 130 g / m ³ or more, the value of (ozone flow rate / TEOS flow rate) may be set to 15 or more.

Incidentally, the second ozone TEOS method is 40
It is preferable to form a film in a temperature range of 0 to 450 ° C. By doing so, the stress of the upper ozone TEOS film 107b can be increased, and the film quality of the upper ozone TEOS film 107b can be made dense.

Next, as shown in FIG. 6C, contact holes of the FET are formed in the lower and upper ozone TEOS films 107a and 107b, the silicon oxide film 111 and the insulating film 103, and the lower and upper ozone layers are formed. TEO
After forming a contact hole of a capacitor in the S films 107a and 107b and the silicon oxide film 111, a titanium film, a titanium nitride film, an aluminum film, and a nitride film are formed over the entire lower and upper ozone TEOS films 107a and 107b. A metal film made of a laminated film of a titanium film is deposited, and thereafter, the metal film is patterned to form a lower metal wiring 108. Note that the lower metal wiring 108 is heated at a temperature of 400 ° C. in a nitrogen atmosphere at a temperature of 30 ° C.
A minute heat treatment is performed to densify the metal wiring 108 and reduce stress.

Next, as shown in FIG. 6D, an interlayer insulating film 109 made of, for example, a silicon nitride film is deposited on the lower metal wiring 108 by a plasma CVD method. However, an upper metal wiring is formed on the interlayer insulating film 109.

According to the fifth embodiment, the silicon oxide film 111 which has no dependence on the underlying layer and has excellent conformability to the ozone TEOS film is formed on the insulating film 103 so as to cover the capacitor element. Even if a base film made of a different material such as a capacitor element and an insulating film 103 exists under the TEOS film 107a, the lower ozone TEOS film 1
07a grows well without being affected by the underlying film. Therefore, the thickness of the insulating film including the silicon oxide film 111 and the lower and upper ozone TEOS films 107a and 107b becomes uniform, so that the capacitance element is excellent in stability and long life.

FIG. 11 shows the relationship between the stress of the protective film and the amount of remanent polarization of the ferroelectric film constituting the capacitive insulating film. In FIG. 11, ● shows the case of a conventional example using a non-doped silicon oxide film (NSG film) as the protective film, and ○ shows the lower and upper ozone TEs as the protective film.
The case of the fifth embodiment using OS films 107a and 107b is shown. As can be seen from FIG. 11, in the conventional example, the capacitance insulating film is subjected to the compressive stress, so that the amount of residual polarization is small, but in the fifth embodiment, the capacitance insulating film is subjected to the tensile stress. , The amount of remanent polarization increases.

FIGS. 12A and 12B show the relationship between the magnitude and frequency of leakage current between the lower metal wiring 108 and the capacitor. FIG. 12A shows the insulating film. A non-doped silicon oxide film (NSG film)
FIG. 12B shows a case in which a lower metal wiring is formed on the silicon oxide film (conventional example). FIG. 12B shows the lower and upper ozone TEOS films on the insulating film 103 via the silicon oxide film 111. This is a case in which 107a and 107b are deposited and a lower metal wiring 108 is formed on the lower and upper ozone TEOS films 107a and 107b (fifth embodiment). The frequency of non-defective products having a leakage current value of 0.01 nA is slightly more than 70% in the conventional example, but is 100% in the fifth embodiment.

FIG. 13 shows the conventional example and the fifth embodiment (in the case of a stress of 5 × 10 ³ N / cm ² and 3.5 × 10 ³ N / cm ² ).
At 10 ⁴ For N / cm ² stress) and the residual polarization of the ferroelectric film constituting the capacitive insulating film (indicated by ●)
And the withstand voltage (shown by ○) of the capacitive element having the capacitive insulating film. As can be seen from FIG. 13, according to the fifth embodiment, the amount of remanent polarization is 8 to 1 compared to the conventional example.
About 0 μC / cm ² , and withstand voltage of 5
About 7V.

(Sixth Embodiment) Hereinafter, a semiconductor device and a method of manufacturing the same according to a sixth embodiment of the present invention will be described.
This will be described with reference to FIGS. 7A to 7C and FIGS. 8A to 8C.

First, as shown in FIG. 7A, after an element isolation region 101 and a gate electrode 102 of an FET are formed on a semiconductor substrate 100, an impurity diffusion layer of the FET (not shown) is formed on the surface of the semiconductor substrate 100. Are omitted), and thereafter, the element isolation region 101 and the gate electrode 102 are formed.
An insulating film 103 is deposited over the entire surface.

Next, on the insulating film 103 and above the element isolation region 102, a capacitive element composed of a capacitive lower electrode 104, a high dielectric film or a capacitive insulating film 105 composed of a high dielectric film and a capacitive upper electrode 106 is formed. Form.

Next, as shown in FIG. 7B, a first silicon-containing insulating film (hereinafter, referred to as a silicon oxide film) made of a silicon oxide film or the like is formed on the insulating film 103 by plasma CVD so as to cover the capacitive element. After the formation of the first plasma silicon insulating film 112, the first plasma silicon insulating film 112 is subjected to a first plasma treatment,
A first surface treatment layer 112a is formed on a surface of the first plasma silicon insulating film 112.

Next, as shown in FIG. 7 (c), the first ozone concentration is relatively low by the first ozone TEOS method.
A lower ozone TEOS film 107a having a relatively high moisture content in the film is grown on the plasma silicon insulating film 112, and then a second ozone T having a relatively high ozone concentration is formed.
By the EOS method, an upper ozone TEOS film 107b having relatively less moisture in the film is grown on the lower ozone TEOS film 107a. Thereafter, heat treatment is performed on the lower and upper ozone TEOS films 107a and 107b at a temperature of 500 ° C. to 650 ° C. for about 1 hour in an oxygen atmosphere to increase the stress of the upper ozone TEOS film 107b. And the upper ozone TEOS film 1
07b is made denser, and a sufficient amount of oxygen is supplied to the capacitor insulating film 105.

Next, as shown in FIG. 8A, a second silicon-containing insulating film (hereinafter, referred to as a silicon oxide film) made of a silicon oxide film or the like is entirely formed on the upper ozone TEOS film 107b by a plasma CVD method. After forming the 113, a second plasma process is performed on the second plasma silicon insulating film 113 to form a second plasma silicon insulating film 113 on the surface of the second plasma silicon insulating film 113. 2
Of the surface treatment layer 113a is formed.

The first or second plasma processing is performed by using N ₂ gas, NH ₃ gas, N ₂ O gas, O ₂ gas, Ar gas,
If the sputter etching is performed using plasma composed of a gas containing at least one of l ₂ gas and C ₂ F ₆ gas, the first or second plasma silicon insulating film 112
The first or second plasma silicon insulating films 112 and 113 are formed of uneven portions having a height of several tens nm on the surface of
A surface treatment layer for improving the water diffusion inhibiting ability of the above can be formed.

In addition, the first or second plasma processing is performed by N
_{If the} nitriding process is performed using plasma composed of a gas containing at least one of two gases, NH ₃ gas and N ₂ O gas, the first or second plasma silicon insulating film 112
A surface treatment layer 112a made of a silicon nitride layer having a high moisture diffusion inhibiting ability can be formed on the surface of the substrate 113.

Next, as shown in FIG. 8B, the second plasma silicon insulating film 113 and the lower and upper ozone T
The contact holes of the FET are formed in the EOS films 107a and 107b, the first plasma silicon insulating film 112 and the insulating film 103, and the second plasma silicon insulating film 113 and the lower and upper ozone TEOS films 107a and 107a are formed.
07b and the first plasma silicon insulating film 112, a contact hole of a capacitor is formed, and then a titanium film is formed over the entire surface of the second plasma silicon insulating film 113.
A metal film composed of a laminated film of a titanium nitride film, an aluminum film, and a titanium nitride film is deposited, and thereafter, the metal film is patterned to form a lower metal wiring 108.

Next, as shown in FIG. 8C, an interlayer insulating film 109 made of, for example, a silicon nitride film is deposited on the lower metal wiring 108 by a plasma CVD method. However, an upper metal wiring is formed on the interlayer insulating film 109.

According to the sixth embodiment, similarly to the fifth embodiment, the ozone TEOS film is formed by the lower ozone TEOS film 107a formed by the first ozone TEOS method having a relatively low ozone concentration and the ozone TEOS film 107a. Upper ozone T formed by the second ozone TEOS method having a relatively high concentration
The lower layer of the ozone TEOS film 107a has good film quality without defects such as vacancies, and has a large amount of moisture in the film. And the upper layer ozone T
Since the EOS film 107b has less moisture in the film, the stress applied to the capacitor insulating film 105 of the capacitor increases. For this reason, the spontaneous polarization characteristics of the capacitor insulating film 105 are improved, so that the characteristics of the capacitor are improved.

Further, according to the sixth embodiment, similarly to the second embodiment, the first plasma silicon insulating film 112 having a high capability of preventing diffusion of moisture is formed on the insulating film 103 so as to cover the capacitive element. After the formation, the first and second plasma silicon insulating films 112 are deposited on the first plasma silicon insulating film 112 to deposit the lower and upper plasma TEOS films 107a and 107b.
The moisture inside the films 107a and 107b is
Blocking is performed without diffusion to the maximum, so that a capacitor element having excellent uniformity can be obtained.

Further, according to the sixth embodiment, similarly to the second embodiment, the lower and upper ozone TEOS films 107 are formed.
In order to form a second plasma silicon insulating film 113 having a high moisture diffusion inhibiting ability over the entire surface of the first and second ozone TEOS films 107a and 107b,
Even if 7b is exposed to the air for a long time, the moisture in the air causes the lower and upper ozone TEOS films 107a, 107
Since diffusion to the capacitor insulating film 105 via the “b” can be prevented, a capacitor element having excellent uniformity can be obtained.

FIG. 14 shows a case where a non-doped silicon oxide film (NSG film) is deposited on an insulating film and a lower metal wiring is formed on the silicon oxide film (conventional example). On the lower and upper ozone TEOS films 107a and 107b are deposited via a silicon oxide film 111, and the lower and upper ozone TEOS films 107a and 107b are deposited.
7b is formed on the lower metal wiring 108 (6th
2) and (3) the residual polarization amount (indicated by ●) of the ferroelectric film constituting the capacitive insulating film and the dielectric strength voltage (indicated by ○) of the capacitive element having the capacitive insulating film. Figure 1
As can be seen from FIG. 4, according to the sixth embodiment, the amount of remanent polarization is improved by about 10 μC / cm ² and the withstand voltage is improved by about 5 V as compared with the conventional example.

FIG. 15 shows the case where the first and second plasma silicon insulating films 112 and 113 are provided (indicated by ●).
And the first and second plasma silicon insulating films 112, 1
13 shows the relationship between the number of days left and the amount of remanent polarization in the case where No. 13 is not provided. As can be seen from FIG.
First and second plasma silicon insulating films 112 and 113
, The amount of remanent polarization hardly changes even after standing for 10 days.

(Seventh Embodiment) Hereinafter, a semiconductor device and a method of manufacturing the same according to a seventh embodiment of the present invention will be described.
This will be described with reference to FIGS.

First, as shown in FIG. 9A, after an element isolation region 101 and a gate electrode 102 of an FET are formed on a semiconductor substrate 100, an impurity diffusion layer of the FET (not shown) is formed on the surface of the semiconductor substrate 100. Are omitted), and thereafter, the element isolation region 101 and the gate electrode 102 are formed.
An insulating film 103 is deposited over the entire surface.

Next, on the insulating film 103 and above the element isolation region 102, a capacitive element comprising a capacitive lower electrode 104, a high dielectric film or a capacitive insulating film 105 composed of a high dielectric film and a capacitive upper electrode 106 is formed. Form.

Next, as shown in FIG.
03, containing at least one of boron and phosphorus so as to cover the capacitive element.
After a silicon oxide film 111 having a thickness of 0 nm or less is formed, hexamethyldisilazane is supplied on the silicon oxide film 111 so that about 2 to 2
A hydrophobic primer layer 114 having a thickness of 5 nm is formed.

Next, a lower ozone TEOS film 107a having a relatively large amount of moisture in the film is grown on the primer layer 114 by a first ozone TEOS method having a relatively low ozone concentration. The lower ozone TEOS film 107 by the second ozone TEOS method having a relatively high
The upper layer ozone TE, in which the moisture in the film is relatively low, on top of a
The OS film 107b is grown. After that, the lower and upper ozone TEOS films 107a and 107b are subjected to a heat treatment at a temperature of 500 ° C. to 650 ° C. for about 1 hour in an oxygen atmosphere, thereby obtaining an upper ozone TEOS film 107.
b increases the stress and the upper layer of ozone TEO
In addition to making the film quality of the S film 107b dense, the capacitance insulating film 1
Supply 05 with a sufficient amount of oxygen.

Next, as shown in FIG. 9C, the lower and upper ozone TEOS films 107a and 107b, the primer layer 114, the silicon oxide film 111 and the insulating film 103
After forming a contact hole of ET and forming a contact hole of a capacitive element in the lower and upper ozone TEOS films 107a and 107b, the primer layer 114 and the silicon oxide film 111, an upper ozone TEOS film 10 is formed.
A metal film composed of a laminated film of a titanium film, a titanium nitride film, an aluminum film, and a titanium nitride film is deposited over the entire surface of the metal wiring 7b, and then the metal film is patterned to form a lower metal wiring 108. Form.

Next, as shown in FIG. 9D, an interlayer insulating film 109 made of, for example, a silicon nitride film is deposited on the lower metal wiring 108 by a plasma CVD method. However, an upper metal wiring is formed on the interlayer insulating film 109.

According to the seventh embodiment, as in the fifth embodiment, the ozone TEOS film is formed by the lower ozone TEOS film 107a formed by the first ozone TEOS method having a relatively low ozone concentration and the ozone TEOS film 107a. Upper ozone T formed by the second ozone TEOS method having a relatively high concentration
The lower layer of the ozone TEOS film 107a has good film quality without defects such as vacancies, and has a large amount of moisture in the film. And the upper layer ozone T
Since the EOS film 107b has less moisture in the film, the stress applied to the capacitor insulating film 105 of the capacitor increases. For this reason, the spontaneous polarization characteristics of the capacitor insulating film 105 are improved, so that the characteristics of the capacitor are improved.

Further, according to the seventh embodiment, the insulating film 1
On the silicon oxide film 111, a silicon oxide film 111, which has no dependency on the underlayer and has excellent conformability to the ozone TEOS film, is formed so as to cover the capacitance element, and a hydrophobic primer layer 114 is formed on the silicon oxide film 111. Then, on the primer layer 114, the lower and upper ozone TEOS films 107 are formed.
a and 107b were deposited, so that the lower and upper ozone T
The step coverage of the EOS films 107a, 107b is improved, and the lower and upper ozone TEOS films 107a, 107b,
07b has improved insulating properties and flatness, as well as the silicon oxide film 111, and the lower and upper ozone TEOS films 107.
Since the thickness of the insulating film including the layers a and 107b becomes uniform, the capacitor element is excellent in stability and long life.

FIGS. 16A and 16B show the relationship between the magnitude and frequency of leakage current between the lower metal wiring 108 and the capacitor. FIG. 16A shows the insulating film. 10
3 and a lower and upper ozone TEOS film 107 having a thickness of 600 nm through a silicon oxide film 111.
a and 107b are deposited, and the lower and upper layers of ozone TEO are deposited.
FIG. 16B shows a case where a lower metal wiring 108 is formed on the S films 107a and 107b. FIG. 16B shows a case where the silicon oxide film 111 and the hydrophobic primer layer 1 are formed on the insulating film 103.
14, the lower and upper ozone TEOS films 107a and 107b having a thickness of 600 nm are deposited, and the lower metal wiring 108 is formed on the lower and upper ozone TEOS films 107a and 107b. Embodiment 7). According to the seventh embodiment, the frequency of non-defective products having a leakage current value of 0.01 nA is 100%.

(Eighth Embodiment) Hereinafter, a semiconductor device and a method of manufacturing the same according to an eighth embodiment of the present invention will be described.
This will be described with reference to FIGS.

First, as shown in FIG. 10A, after an element isolation region 101 and an FET gate electrode 102 are formed on a semiconductor substrate 100, an impurity diffusion layer of the FET (shown in FIG. Are omitted), and thereafter, the element isolation region 101 and the gate electrode 10 are formed.
An insulating film 103 is deposited on the entire surface of the substrate 2.

Next, on the insulating film 103 and above the element isolation region 102, a capacitive element comprising a capacitive lower electrode 104, a high dielectric film or a capacitive insulating film 105 composed of a high dielectric film and a capacitive upper electrode 106 is formed. Form.

Next, as shown in FIG. 10B, on the insulating film 103, no impurities are contained or at least one of boron and phosphorus is contained so as to cover the capacitor.
A silicon oxide film 111 having a thickness of 50 nm or less is formed. Next, a first ozone TEOS liquid source containing 5% by weight of a primer liquid and having a relatively low ozone concentration is supplied onto the silicon oxide film 111 to form a silicon oxide film 1.
11 is a lower layer of ozone TE on which moisture in the film is relatively high.
After forming the OS film 107a, the second ozone TEOS containing 5% by weight of the primer liquid and having a relatively high ozone concentration
By supplying a liquid source, the lower ozone TEOS film 107
The upper layer ozone TE, in which the moisture in the film is relatively low, on top of a
An OS film 107b is formed.

Next, as shown in FIG. 10C, contact holes for the FET are formed in the lower and upper ozone TEOS films 107a and 107b, the silicon oxide film 111, and the insulating film 103, and the lower and upper ozone layers are formed. TE
OS films 107a and 107b and silicon oxide film 111
After forming a contact hole of a capacitive element, a metal film composed of a laminated film of a titanium film, a titanium nitride film, an aluminum film and a titanium nitride film is formed over the entire surface of the lower and upper ozone TEOS films 107a and 107b. By depositing, and then patterning the metal film, a lower metal wiring 108 is formed. Note that the lower metal wiring 108 is heated at a temperature of 400 ° C. in a nitrogen atmosphere at 30 ° C.
A minute heat treatment is performed to densify the metal wiring 108 and reduce stress.

Next, as shown in FIG. 10D, an interlayer insulating film 109 made of, for example, a silicon nitride film is deposited on the lower metal wiring 108 by a plasma CVD method. However, an upper metal wiring is formed on the interlayer insulating film 109.

According to the eighth embodiment, two kinds of ozone TEOS liquid sources containing a primer liquid and having different ozone concentrations are supplied, and the lower ozone TEOS film 107a and the lower ozone TEOS film 107a having a relatively large amount of water in the film are supplied. In order to form the upper ozone TEOS film 107b in which the water content is relatively small, the lower and upper ozone TEOS each having hydrophobicity are formed.
The films 107a and 107b can be formed without increasing the number of processes.

FIGS. 17A and 17B show the relationship between the magnitude and frequency of leakage current between the lower metal wiring 108 and the capacitor. FIG. 17A shows the insulating film. 10
3 and a lower and upper ozone TEOS film 107 having a thickness of 600 nm through a silicon oxide film 111.
a and 107b are deposited, and the lower and upper layers of ozone TEO are deposited.
FIG. 17B shows a case in which a lower metal wiring 108 is formed on the S films 107a and 107b. FIG. 17B shows a case where the silicon oxide film 111 and the hydrophobic primer layer 1 are formed on the insulating film 103.
14, the lower and upper ozone TEOS films 107a and 107b having a thickness of 600 nm are deposited, and the lower metal wiring 108 is formed on the lower and upper ozone TEOS films 107a and 107b. Eighth Embodiment). According to the eighth embodiment, the frequency of non-defective products having a leakage current value of 0.01 nA is 100%.

In the first to eighth embodiments, the lower metal wiring 108 is formed of a laminated film of a titanium film, a titanium nitride film, an aluminum film, and a titanium nitride film. It may be formed by a stacked film of a film and an aluminum film, or a stacked film of a titanium film, an aluminum film, and a titanium tungsten film.

[0202]

According to the semiconductor device and the method of manufacturing the same according to the present invention, the capacitive element is covered with the protective film made of the ozone TEOS film having a tensile stress, so that the high dielectric film or the ferroelectric film constituting the capacitive element is formed. Since spontaneous polarization sufficiently appears in the capacitive insulating film made of the body film, the characteristics of the capacitive element are improved.

[Brief description of the drawings]

FIGS. 1A to 1D are cross-sectional views illustrating respective steps of a method for manufacturing a semiconductor device according to a first embodiment.

FIGS. 2A to 2C are cross-sectional views illustrating respective steps of a method for manufacturing a semiconductor device according to a second embodiment.

FIGS. 3A to 3C are cross-sectional views illustrating respective steps of a method for manufacturing a semiconductor device according to a second embodiment.

FIGS. 4A to 4D are cross-sectional views illustrating respective steps of a method for manufacturing a semiconductor device according to a third embodiment.

FIGS. 5A to 5D are cross-sectional views illustrating respective steps of a method for manufacturing a semiconductor device according to a fourth embodiment.

FIGS. 6A to 6D are cross-sectional views illustrating respective steps of a method for manufacturing a semiconductor device according to a fifth embodiment.

FIGS. 7A to 7C are cross-sectional views illustrating respective steps of a method for manufacturing a semiconductor device according to a sixth embodiment.

FIGS. 8A to 8C are cross-sectional views illustrating respective steps of a method for manufacturing a semiconductor device according to a sixth embodiment.

FIGS. 9A to 9D are cross-sectional views illustrating respective steps of a method for manufacturing a semiconductor device according to a seventh embodiment.

FIGS. 10A to 10D are cross-sectional views illustrating steps of a method of manufacturing a semiconductor device according to an eighth embodiment.

FIG. 11 is a characteristic diagram showing the relationship between the stress of the protective film and the amount of remanent polarization of the ferroelectric film forming the capacitive insulating film.

FIGS. 12A and 12B are comparative characteristic diagrams showing the relationship between the magnitude of leakage current and the frequency of occurrence between a lower metal wiring and a capacitor.

FIG. 13 is a characteristic diagram showing a residual polarization amount of a ferroelectric film constituting a capacitance insulating film and a dielectric strength voltage of a capacitance element having the capacitance insulating film in the conventional example and the fifth embodiment.

FIG. 14 is a characteristic diagram showing the amount of remanent polarization of a ferroelectric film constituting a capacitive insulating film and the withstand voltage of a capacitive element having the capacitive insulating film in the conventional example and the sixth embodiment.

FIG. 15 is a characteristic diagram showing the relationship between the number of days left and the amount of remanent polarization when the first and second plasma silicon insulating films are provided and when they are not provided in the sixth embodiment.

FIGS. 16 (a) and (b) are comparative characteristic diagrams showing the relationship between the magnitude of leakage current and the frequency of occurrence between a lower metal wiring and a capacitor.

FIGS. 17A and 17B are comparative characteristic diagrams showing the relationship between the magnitude of leakage current between a lower metal wiring and a capacitor and the frequency of occurrence thereof. FIGS.

FIGS. 18A to 18D are cross-sectional views illustrating respective steps of a conventional method for manufacturing a semiconductor device.

[Explanation of symbols]

 REFERENCE SIGNS LIST 100 semiconductor substrate 101 element isolation region 102 gate electrode 103 insulating film 104 capacitor lower electrode 105 capacitor insulating film 106 capacitor upper electrode 107 ozone TEOS film 107a lower ozone TEOS film 107b upper ozone TEOS film 108 lower metal wiring 109 interlayer insulating film 111 silicon oxide film 112 first plasma silicon insulating film 112a first surface treatment layer 113 second plasma silicon insulation film 113a second surface treatment layer 114 primer layer 115 silicon nitride layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/318 H01L 27/10 444B (72) Inventor Yuji Judai 1-1, Yukicho, Takatsuki-shi, Osaka Matsushita Electronics Corporation F term (reference) 4K030 AA06 AA14 BA35 BA40 BA44 DA08 DA09 FA01 JA06 KA30 LA02 5F058 BA04 BA07 BA10 BA20 BD02 BD03 BD09 BD15 BF07 BF25 BF29 BF73 BF74 BH03 BJ01 BJ02 5F083 JA02 JA05 JA06 JA06 JA40 NA08 PR22 PR33

Claims (38)

[Claims] A capacitor formed of a capacitor lower electrode, a capacitor insulating film made of a high dielectric film or a ferroelectric film, and a capacitor upper electrode formed sequentially on a semiconductor substrate; and a capacitor formed so as to cover the capacitor. A semiconductor device comprising: a protective film made of an ozone TEOS film; a wiring layer formed on the protective film; and an interlayer insulating film formed to cover the wiring layer. 2. The ozone TEOS film is formed by a first ozone TEOS method having a relatively low ozone concentration,
A lower ozone TEOS film having a relatively high moisture content in the film,
2. The semiconductor device according to claim 1, comprising an upper ozone TEOS film formed by a second ozone TEOS method having a relatively high ozone concentration and having a relatively low moisture content in the film. 3. The semiconductor device according to claim 2, further comprising a silicon-containing insulating film formed by plasma CVD between said upper ozone TEOS film and said wiring layer. 4. The thickness of the upper ozone TEOS film is:
3. The semiconductor device according to claim 2, wherein the thickness is not less than 0.3 nm and not more than 0.6 nm. 5. The semiconductor device according to claim 1, further comprising a silicon-containing insulating film formed by plasma CVD between the capacitor and the ozone TEOS film. 6. The semiconductor device according to claim 5, wherein said silicon-containing insulating film is a silicon oxynitride film having a refractive index of 1.65 or less. 7. The semiconductor device according to claim 1, further comprising a hydrophobic primer layer between said capacitance element and said ozone TEOS film. 8. A silicon oxide film containing no impurity or containing at least one of boron and phosphorus and having a thickness of 150 nm or less is provided between the capacitor and the ozone TEOS film. The semiconductor device according to claim 1, wherein: 9. A silicon nitride layer is formed on a surface of the ozone TEOS film.
3. The semiconductor device according to claim 1. 10. The semiconductor device according to claim 1, further comprising a silicon-containing insulating film formed by plasma CVD between the ozone TEOS film and the wiring layer. 11. The ozone TEOS film has a thickness of 0.1 mm.
The semiconductor device according to claim 1, wherein the thickness is not less than 3 nm and not more than 0.6 nm. 12. A step of forming, on a semiconductor substrate, a capacitive element composed of a capacitive lower electrode, a capacitive insulating film composed of a high dielectric film or a ferroelectric film, and a capacitive upper electrode, and ozone covering the capacitive element. Forming a protective film made of a TEOS film; forming a wiring layer on the protective film; and forming an interlayer insulating film so as to cover the wiring layer. A method for manufacturing a semiconductor device. 13. The step of forming the protective film includes: forming a lower ozone TEOS film by a first ozone TEOS method having a relatively low ozone concentration so as to cover the capacitive element; 13. The method of manufacturing a semiconductor device according to claim 12, further comprising: forming an upper ozone TEOS film on the ozone TEOS film by a second ozone TEOS method having a relatively high ozone concentration. 14. The ozone concentration in the first ozone TEOS method is 25 g / m ³ or less, and the second ozone
Ozone concentration in the TEOS method of ozone is 130 g / m
14. The method according to claim 13, wherein the number is ^three or more. 15. The first ozone TEOS method is performed under the condition that the value of (ozone flow rate / TEOS flow rate) is 3 or less, and the second ozone TEOS method is performed by (ozone flow rate / TEOS flow rate). 14. The method according to claim 13, wherein the value of (flow rate) is 15 or more. 16. The ozone TEOS film of the upper layer is 5 ×
14. It has a tensile stress of 10 ³ N / cm ^{2 to} 3.5 × 10 ⁴ N / cm ^2.
13. The method for manufacturing a semiconductor device according to item 5. 17. A method according to claim 17, further comprising a step of forming a silicon-containing insulating film by plasma CVD so as to cover the capacitive element, between the step of forming the capacitive element and the step of forming the protective film. 13. The method according to claim 12, wherein the forming includes a step of forming the ozone TEOS film on the silicon-containing insulating film. 18. The method according to claim 17, wherein the step of forming the silicon-containing insulating film includes a step of performing a plasma treatment on a surface of the silicon-containing insulating film. 19. The plasma processing includes N ₂ gas, NH
₃ gas, N ₂ O gas, O ₂ gas, claim, characterized in that Ar gas, a sputter etching carried out by using plasma of a gas containing at least one of Cl ₂ gas and C ₂ F ₆ gas 18 13. The method for manufacturing a semiconductor device according to item 5. 20. The step of forming the silicon-containing insulating film includes a step of performing a plasma treatment on the silicon-containing insulating film to form a silicon nitride layer on a surface of the silicon-containing insulating film. Claim 17
13. The method for manufacturing a semiconductor device according to item 5. 21. The plasma processing according to claim 19, wherein the plasma processing is plasma CVD.
21. The method of manufacturing a semiconductor device according to claim 20, wherein the method is performed without exposing the silicon-containing insulating film formed by the above to the atmosphere. 22. A step of forming a hydrophobic primer layer so as to cover the capacitance element between the step of forming the capacitance element and the step of forming the protection film, wherein the protection film is formed. The method according to claim 12, wherein the step includes forming the ozone TEOS film on the primer layer. 23. The method according to claim 22, wherein the step of forming the primer layer is performed using hexamethyldisilazane. 24. Between the step of forming the capacitive element and the step of forming the protective film, do not include impurities or include at least one of boron and phosphorus so as to cover the capacitive element. Forming a silicon oxide film having a thickness of 150 nm or less, wherein forming the protective film includes forming the ozone TEOS film on the silicon oxide film. 13. The method for manufacturing a semiconductor device according to item 12. 25. The step of forming the protective film includes a step of performing a plasma treatment on a surface of the ozone TEOS film to form a silicon nitride layer on a surface of the ozone TEOS film. A method for manufacturing a semiconductor device according to claim 12. 26. A step of forming a silicon-containing insulating film on the protective film by plasma CVD between the step of forming the protective film and the step of forming the wiring layer, wherein forming the wiring layer 13. The method according to claim 12, wherein the step of forming includes a step of forming the wiring layer on the silicon-containing insulating film. 27. The method according to claim 26, wherein the step of forming the silicon-containing insulating film includes a step of performing a plasma treatment on a surface of the silicon-containing insulating film. 28. The plasma processing includes N ₂ gas, NH
28. Sputter etching performed by using plasma comprising a gas containing at least one of _three gases, N ₂ O gas, O ₂ gas, Ar gas, Cl ₂ gas and C ₂ F ₆ gas. 13. The method for manufacturing a semiconductor device according to item 5. 29. The step of forming the silicon-containing insulating film includes a step of performing a plasma treatment on the silicon-containing insulating film to form a silicon nitride layer on a surface of the silicon-containing insulating film. Claim 26
13. The method for manufacturing a semiconductor device according to item 5. 30. The plasma processing, comprising:
30. The method of manufacturing a semiconductor device according to claim 29, wherein the method is performed without exposing the silicon-containing insulating film formed by the above to the atmosphere. 31. The method according to claim 12, wherein forming the protective film includes performing a heat treatment on the ozone TEOS film. 32. The method according to claim 31, wherein the heat treatment is performed at a temperature of 500 ° C. to 650 ° C. 33. The method according to claim 31, wherein the heat treatment is performed in an atmosphere containing oxygen gas. 34. The method according to claim 12, wherein the ozone TEOS film is formed by an ozone TEOS method having an ozone concentration of 130 g / m ³ or more. 35. The ozone TEOS film, wherein the value of (flow rate of ozone / flow rate of TEOS) is 15 or more.
13. The method according to claim 12, wherein the first electrode is formed by an EOS method.
13. The method for manufacturing a semiconductor device according to item 5. 36. The ozone TEOS film has a size of 5 × 10 ^3.
The method according to claim 12, wherein the semiconductor device has a tensile stress of N / cm ^{2 to} 3.5 × 10 ⁴ N / cm ² . 37. The ozone TEOS film has a temperature of 400 ° C.
The method according to claim 12, wherein the semiconductor device is formed at a deposition temperature of 450 ° C. 38. The method according to claim 12, wherein the ozone TEOS film is formed using a mixed source obtained by mixing a primer agent and an ozone TEOS liquid.