JPH0629314A - Semiconductor device and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide a semiconductor device in which boundary characteristics between a gate insulating film and a silicon substrate are improved without decreasing a capacity of a gate oxide film, without increasing a thickness of an insulating film and without deterioration of insulation of a MOS transistor and a MOS capacitor, etc. CONSTITUTION:A semiconductor device comprises a silicon substrate 101, a gate oxide film 103 formed on the substrate, and a gate electrode 106 formed on the film 103 in such a manner that nitrogen atoms are doped in at least one of the substrate 101 and the electrode 106 and the film 103.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device and a method of manufacturing the same, and more particularly to a semiconductor device having improved interface characteristics between a semiconductor substrate and a gate oxide film and a method of manufacturing the same.

[0002]

2. Description of the Related Art A MOS transistor is one of the main elements constituting a semiconductor device. There is an interface state at the interface between the semiconductor substrate of this transistor and the gate insulating film, which changes the threshold voltage, reduces the mobility of carriers in the surface inversion layer, and It was a factor that increased the leak current. As a method of reducing the interface state, a method of terminating a dangling bond, which is a physical substance of the interface state, with a fluorine atom is known. This method is, for example,
E-Transaction on Electron Device, Vol. 36, pp. 879-887 (1989) (IE
EE. Transactions on Electron Device, vol 36, No
5, pp879-887 (1989)).

On the other hand, as a technique for introducing nitrogen into the interface between the substrate and the oxide film, there is a nitriding technique using N ₂ O gas.
This technique is described, for example, in Proceedings of Solid State Devices and Materials Conference, pp. 159-162 (1990) (Extended
Abstracts of the 22ndConference on Solid Sta
te Devices and Materials, pp159-162 (1990))
It is described in. However, there is no report that the interface state is reduced by introducing nitrogen.

[0004]

In order to achieve high integration of the LSI, it is necessary to increase the capacitance per unit area by thinning the gate insulating film of the transistor.
However, when the interface state reduction method using fluorine is used as in the above-mentioned conventional technique, there is a problem that the capacitance of the gate insulating film is reduced and the design of the MOS transistor becomes difficult. Further, when the amount of fluorine introduced is large, the interface state increases conversely, so that there is a problem that the optimum range is narrow.

An object of the present invention is to provide a semiconductor device in which the interface state is reduced with good controllability and without reducing the capacitance of the insulating film, and a method for manufacturing the same.

[0006]

The semiconductor device of the present invention comprises:
A semiconductor substrate, an insulating film formed on the semiconductor substrate, and an electrode formed on the semiconductor substrate, and at least one of the semiconductor substrate and the electrode and a region in which nitrogen atoms are introduced into the insulating film. Further, fluorine atoms may be present together with nitrogen atoms at the insulating film, the interface between the semiconductor substrate and the insulating film, and the interface between the insulating film and the electrode.

[0007] These atoms are often introduced so as to have a concentration distribution peak in the depth direction of the semiconductor substrate.
When the peak of the concentration distribution of nitrogen atoms is present in the semiconductor substrate, the peak concentration is 1 × 10 ¹⁸ cm ³ or more, 1 × 10
It is preferably ²¹ cm to ³ or less. When there are no fluorine atoms in the insulating film but only nitrogen atoms and the peak of the concentration distribution is in the insulating film, the peak concentration is 1
It is preferably × 10 ¹⁸ cm ³ or more and 1 × 10 ²² cm ³ or less. Since a thin film having a thickness of 2 nm to 20 nm is often used as the insulating film, the peak concentration and the concentration of nitrogen atoms are almost the same. When fluorine atoms are present together with nitrogen atoms in the insulating film and the concentration distribution peaks in the insulating film, the concentrations of nitrogen atoms and fluorine atoms are both 1 × 1.
It is preferably 0 ¹⁸ cm ³ or more and 1 × 10 ²¹ cm ³ or less.

In such a semiconductor device, an insulating film is formed on a semiconductor substrate, an electrode is formed on the insulating film, and nitrogen atoms are introduced into the electrode, or nitrogen atoms are introduced into the insulating film or the semiconductor substrate through the electrode. Can be manufactured. When a fluorine atom is present together with a nitrogen atom, the fluorine atom can be similarly introduced into the insulating film through the electrode.

It is preferable to introduce these by ion implantation. At this time, for example, if the average projected range of nitrogen ions is set in the insulating film, most of the nitrogen ions are present in the insulating film. It is also possible to move these atoms to a portion other than the insulating film by heat treating the insulating film after the ion implantation. By such a method, nitrogen atoms and fluorine atoms can be made to exist in desired portions of the semiconductor device.

[0010]

The reduction of the interface state in the semiconductor device of the present invention is considered to be a result of atomic nitrogen terminating the dangling bond at the interface between the semiconductor substrate and the gate insulating film, but its mechanism has not been clarified. .

[0011]

Embodiments of the present invention will now be described in detail with reference to the drawings. Example 1 A first example will be described with reference to FIGS. FIG. 1 is a schematic sectional view of a MOS capacitor showing an embodiment of the present invention. As shown in the figure, after the element isolation oxide film 102 is selectively formed on the n-type silicon substrate 101 having a plane resistance (100) and a specific resistance of 10 Ω · cm using a normal manufacturing process, the temperature is set to 850. 8 ° C in steam atmosphere
A silicon oxide film to be the gate oxide film 103 having a thickness of 10 nm is formed (FIG. 1A). Then, phosphorus (P) is formed on the gate oxide film 103 so that the film thickness after formation is 100 nm.
A silicon film 104 is formed while doping. At this time, the formation temperature is 525 ° C., and the P concentration is 1 × 10 ²⁰ cm to ³
Is. After that, nitrogen ion implantation is performed with an implantation energy of 45 keV. Most of the implanted nitrogen is present in the gate oxide film. The driving amount is 1 × 10 ¹³ ~
It was changed within the range of 1 × 10 ¹⁶ cm ² Then 100
By performing heat treatment at 900 ° C. for 30 minutes in a% nitrogen atmosphere, ion implantation damage is recovered and P in the silicon film 104 is activated (FIG. 1B). The nitrogen atoms after this annealing are present in the electrode, the oxide film and the substrate, and the nitrogen atom concentration peak at this time is in the oxide film, and the peak concentration is 1 × 10 ¹⁸ to 1 × 10 ²² cm 2. ~ ³ .

A resist 106 is formed on the silicon film 104.
After applying and patterning, the resist 106
Is used as a mask to pattern the silicon film 104 (FIG. 1C). After that, the resist 106 is removed,
The silicon film is used as the gate electrode 107 (FIG. 1
(D)). Finally, in a 100% hydrogen atmosphere, 450 ℃
Heat treatment for 30 minutes. Thereafter, a protective film, wiring, etc. are formed as usual to complete a semiconductor device.

The capacitance-voltage of the MOS capacitor thus produced was measured, and the interface state density was calculated from the result. FIG. 2 shows the relationship between the nitrogen implantation amount and the interface state density in the midgap. It can be seen that the interface state density decreases as the nitrogen implantation amount increases. It is considered that this is because the implanted nitrogen atoms terminate the dangling bonds at the interface between the gate oxide film and the silicon substrate. In addition, in this example, no increase in the interface level with the increase in the amount of introduction, which is seen in the case of fluorine, is seen, and it is understood that the process controllability is excellent.

Further, FIG. 3 shows the relationship between the implantation amount and the change in oxide film capacitance. Here, for comparison, the results of a sample in which a conventional fluorine ion implantation is performed instead of the nitrogen ion implantation described in the above-mentioned sample preparation method (also referred to as a conventional method in the figure) are also shown. From the figure, it is understood that in the case of nitrogen implantation, the oxide film capacitance hardly decreases even if the implantation amount increases. The change in oxide film thickness at this time is shown in FIG. From the figure, it can be seen that the oxide film thickness hardly increases in the present invention. In addition, the gate oxide film 10
FIG. 5 shows the result of examining the gate oxide film insulating property after implantation of nitrogen ions by using the electric field strength (critical electric field strength) when the current density flowing in 3 is 1 μA / cm ² .
According to this, in the 1 × 10 ¹⁶ cm ~ nitrogen ion implantation amount of ^2, it can be seen that insulating gate oxide film is improved.

In this embodiment, the heat treatment after ion implantation was performed at 900 ° C., but 600 ° C. or higher 1
The same effect was obtained when performed at 200 ° C. or lower. When the temperature was lower than 600 ° C., the silicon film 104 was not crystallized, so that conductivity was not obtained and the silicon capacitor did not function as a MOS capacitor. Further, if the temperature exceeds 1200 ° C., the gate insulating film is deteriorated, which is not preferable. Also, when a similar experiment is performed using a p-type silicon substrate,
The same effect as that of this example was obtained. Furthermore, when the same experiment was performed using substrates having substrate plane orientations of (110) and (111), the same effect as that of this example was obtained. In addition, even when the silicon substrates having the plane orientations of (100), (110) or (111) and the inclination angles of 10 ° or less were used, the same effect as that of this example was obtained.

Second Embodiment A second embodiment will be described with reference to FIGS. 1 and 6. By the same process as in Example 1, the (100) plane orientation P
After selectively forming an element isolation oxide film 102 on a silicon substrate 101, a silicon oxide film to be a gate oxide film 103 having a film thickness of 8 nm is formed in a 100% O ₂ atmosphere at a temperature of 850 ° C. (FIG. a)). Next, a silicon film 104 to be an electrode was formed on the gate oxide film while doping phosphorus (P) so that the film thickness after formation was 100 nm. At this time, the P concentration is 1 × 10 ²⁰ cm ~ ³ . After that, with the implantation energy of 25 keV, nitrogen ions 105
Ion implantation was performed. At this time, most of the implanted ions are present in the electrode. The driving amount is 1 each
It is × 10 ¹⁴ to 1 × 10 ¹⁶ cm to ² . Then 100%
By performing heat treatment at 900 ° C. for 30 minutes in a nitrogen atmosphere, ion implantation damage recovery and silicon film 1
The activation of P of 04 was attempted (FIG. 1 (b)). The nitrogen atoms after this annealing are mainly present in the electrode and the oxide film, and the nitrogen atom concentration peaks at this time are in the electrode and the oxide film, and the peak concentration is 1 × 10 ¹⁸ to 1 × 10 5. ²² cm
~ ³ . A resist 106 is applied on the silicon film 104 and patterned, and then the silicon film 104 is patterned using the resist 106 as a mask (FIG. 1C). After that, the resist 106 is removed,
The silicon film is used as the gate electrode 107. (Fig. 1
(D)). Finally, in a 100% hydrogen atmosphere, 450 ℃
After heat treatment for 30 minutes, the semiconductor device is completed in the same manner as in Example 1.

The interface state density of this sample obtained from the capacitance-voltage measurement results is shown in FIG. It can be seen that the interface state can be reduced as compared with the sample without nitrogen implantation.
Moreover, the capacity was not reduced and the oxide film thickness was not increased.
Furthermore, the insulation did not deteriorate. Also, when the same experiment was performed using an n-type silicon substrate, the same effect as this example was obtained. Furthermore, when the same experiment was performed using substrates having substrate plane orientations of (110) and (111), the same effect as that of this example was obtained. In addition, the plane orientation is (100), (110) or (11
Even when each of the silicon substrates whose inclination angle from 1) was within 10 ° was used, the same effect as this example was obtained.

Third Embodiment A third embodiment will be described with reference to FIGS. 1 and 7. By the same process as in Example 1, the (100) plane orientation P
An element isolation oxide film 102 was selectively formed on the silicon substrate 101. Then, a silicon oxide film to be the gate oxide film 103 having a film thickness of 8 nm is formed in a 100% O ₂ atmosphere at a temperature of 850 ° C. (FIG. 1A). Next, a silicon film 10 to be an electrode is formed on the gate oxide film while doping phosphorus (P) so that the film thickness after formation is 100 nm.
4 was formed. At this time, the P concentration is 1 × 10 ²⁰ cm ~ ³ . After that, the nitrogen ions 105 were ion-implanted at an implantation energy of 160 keV. At this time, most of the implanted ions are present in the substrate. The implantation amount is 1 × 10 ¹⁴ cm- ² .

Then, in a 100% nitrogen atmosphere, 900
By performing a heat treatment at 30 ° C. for 30 minutes, recovery of ion implantation damage and activation of P in the silicon film 104 were achieved (FIG. 1B). The nitrogen atoms after this annealing are present in the oxide film and the substrate, and the nitrogen atom concentration peak at this time is near the interface between the oxide film and the substrate, and the peak concentration is 1 × 10 ¹⁸ to 1 × 10 ²¹ cm 2. ~ ³ . A resist 106 is applied on the silicon film 104 and patterned, and then the silicon film 104 is patterned using the resist 106 as a mask (FIG. 1C). afterwards,
The resist 106 is removed and the silicon film is used as the gate electrode 107. (FIG. 1 (d)). Finally, heat treatment is performed at 450 ° C. for 30 minutes in a 100% hydrogen atmosphere, and the semiconductor device is completed in the same manner as in Example 1.

The interface state density of this sample obtained from the capacitance-voltage measurement results is shown in FIG. It can be seen that the interface state can be reduced as compared with the sample without nitrogen implantation.
Moreover, no decrease in oxide film capacity and no increase in film thickness were observed. Also, the insulation did not deteriorate. Further, when the gate oxidation was performed at a temperature of 900 ° C. in a 1% oxygen atmosphere in nitrogen, the same effect as this example was obtained. The interface state densities when the plane orientation of the silicon substrate is (100) and (111) are also shown in FIG. In addition, a similar experiment
The same effect as that of the present example was obtained both when using the type silicon substrate and when using the substrate having the substrate surface orientation of (110). Also, the plane orientation is (1
The tilt angle from 00), (110) or (111) is 1
Even when the silicon substrates each having an angle of 0 ° or less were used, the same effect as that of this example was obtained.

Fourth Embodiment A fourth embodiment will be described with reference to FIGS. By the same process as in Example 1, the (100) plane orientation P
An element isolation oxide film 102 was selectively formed on the silicon substrate 101. Then, a silicon oxide film to be the gate oxide film 103 having a film thickness of 8 nm is formed in a 100% O ₂ atmosphere at a temperature of 850 ° C. (FIG. 1A). Next, on the gate oxide film, a silicon film 10 to be an electrode is formed while doping phosphorus (P) so that the film thickness after formation is 100 nm.
4 was formed. At this time, the P concentration is 1 × 10 ²⁰ cm ~ ³ . Then, nitrogen ions and fluorine ions 105 were ion-implanted at an implantation energy of 45 keV. At this time, most of the implanted ions are present in the gate oxide film. The driving amount is 1 × 10 ¹⁴ , 1 respectively.
It is × 10 ¹⁵ cm to ² (Fig. 1 (b)). Then 100
By performing heat treatment at 900 ° C. for 30 minutes in a nitrogen atmosphere, recovery of ion implantation damage and activation of P in the silicon film 104 were achieved. A resist 106 is applied on the silicon film 104 and patterned, and then the silicon film 104 is patterned using the resist 106 as a mask (FIG. 1C). Then resist 1
06 to remove the silicon film 104 from the gate electrode 1
07. (FIG. 1 (d)). Finally, heat treatment was performed at 450 ° C. for 30 minutes in a 100% hydrogen atmosphere.
A semiconductor device is completed in the same manner as in Example 1. The interface state density obtained from the capacitance-voltage measurement result at this time is shown in FIG.
Shown in. It can be seen that the interface state can be reduced as compared with the sample without nitrogen implantation. Moreover, the capacity was not reduced and the oxide film thickness was not increased. Also, the insulation did not deteriorate.

The nitrogen atoms after the annealing are present in the electrode, the oxide film and the substrate, and the fluorine atoms are present in the oxide film, and the concentration distributions of the nitrogen atoms and the fluorine atoms are both oxidized. There is a peak in the film, and the peak concentration is SI
Each measured by MS measurement is 1 × 10 ¹⁸ cm ~ ³ or more 1
It was × 10 ²¹ cm ³ or less. Next, the same experiment was conducted by setting the implantation energy of nitrogen ions to 25 keV while keeping the implantation energy of fluorine ions as above. Most of the implanted nitrogen ions exist in the electrode, and also exist in the electrode and the oxide film after annealing.
The concentration distribution has a peak in the electrode, and the peak concentration is 1
It was not less than × 10 ¹⁸ cm ^{-3 and not} more than 1 × 10 ²¹ cm ^-3 . The fluorine atom was the same as above. Also at this time, the same effect as that of the above-mentioned embodiment was obtained.

The implantation energy of fluorine ions is the same as above, and the implantation energy of nitrogen ions is 1
A similar experiment was conducted with the setting of 60 keV. Most of the implanted nitrogen ions exist in the substrate, and also exist in the oxide film and the substrate after annealing, and the concentration distribution has a peak near the interface between the oxide film and the substrate, and the peak concentration is 1 ×.
It was 10 ¹⁸ cm ³ or more and 1 × 10 ²¹ cm ³ or less. The fluorine atom was the same as above. Also in this case, the same effect as that of this embodiment was obtained.

Furthermore, when the implantation energy of fluorine ions is set to 25 keV and the implantation energy of nitrogen ions is set to three types of 25, 45, and 160 keV, and a similar experiment is performed, many of the implanted fluorine ions are gate-oxidized It exists in the film and also exists in the gate oxide film after annealing. The concentration distribution of fluorine atoms after annealing has a peak at at least one of the interface between the electrode and the oxide film or the interface between the oxide film and the substrate. Regarding the nitrogen atom, the implantation energies of the above-mentioned respective examples are 25, 45 and 160 k.
As in the case of eV, the concentration distribution of nitrogen atoms after annealing in each case has peaks in the electrodes, in the oxide film, and near the interface between the oxide film and the substrate, as described above. The peak concentration of these fluorine atoms and nitrogen atoms is 1 × 10
^{It was 18} cm ³ or more and 1 × 10 ²¹ cm ³ or less. Also in this case, the same effect as that of the present embodiment was obtained.

Also, when the same experiment was performed using an n-type silicon substrate, the same effect as that of this embodiment was obtained. Furthermore, a similar experiment was conducted with a substrate plane orientation of (110),
The same effect as that of this example was obtained when the process was performed using the substrate of (111). Also, the plane orientation is (1
The tilt angle from 00), (110) or (111) is 1
Even when the silicon substrates each having an angle of 0 ° or less were used, the same effect as that of this example was obtained.

[0026]

When nitrogen atoms are introduced into the semiconductor substrate, at least one of the electrodes, and the insulating film, the introduced nitrogen atoms terminate the dangling bond at the interface between the insulating film and the semiconductor substrate, so that the interface level is increased. Is reduced and the interface characteristics of the semiconductor device are improved. At this time, the capacity of the insulating film is not decreased and the insulating film thickness is not increased. In addition, the insulation does not deteriorate or improves. The same applies when a fluorine atom is introduced together with a nitrogen atom.

[Brief description of drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device of the present invention.

FIG. 2 is a diagram showing a relationship between a nitrogen implantation amount and an interface state density.

FIG. 3 is a diagram showing a relationship between a nitrogen implantation amount and a change in oxide film capacity (based on a sample without implantation).

FIG. 4 is a diagram showing a relationship between a nitrogen implantation amount and a change in oxide film thickness (based on a sample without implantation).

FIG. 5 is a diagram showing a relationship between a nitrogen implantation amount and a critical electric field strength.

FIG. 6 is a diagram showing a relationship between an implantation amount and an interface state density.

FIG. 7 is a diagram showing the effect of reducing the interface state of the semiconductor device of the present invention.

FIG. 8 is a diagram showing the effect of reducing the interface state of the semiconductor device of the present invention.

[Explanation of symbols]

 101 Silicon substrate 102 Element isolation oxide film 103 Gate oxide film 104 Silicon film 105 Ion 106 Gate electrode

Claims (23)

[Claims] 1. A semiconductor device having a semiconductor substrate, an insulating film formed on the semiconductor substrate, and an electrode formed on the insulating film. At least one of the semiconductor substrate and the electrode, and the insulating film. Is a semiconductor device having a region into which nitrogen atoms are introduced. 2. The semiconductor device according to claim 1, wherein the semiconductor substrate has a region into which nitrogen atoms are introduced, and has a peak of concentration distribution of nitrogen atoms in a depth direction of the semiconductor substrate. Peak concentration is 1 × 10 ¹⁸ cm ~ ³ or more 1 × 1
A semiconductor device having a size of 0 ²¹ cm to ³ or less. 3. The semiconductor device according to claim 1, wherein the concentration of nitrogen atoms in the region of the insulating film into which nitrogen atoms are introduced is 1 × 10 ¹⁸ cm ³ or more and 1 × 10 ²² cm ³ or less. A semiconductor device characterized by: 4. The semiconductor device according to claim 1, wherein a tilt angle of a plane orientation of the semiconductor substrate is within ± 10 ° from a (100) plane orientation or ± from a (111) plane orientation. Within 10 ° or ± 10 from (110) plane orientation
A semiconductor device characterized by being within °. 5. A semiconductor device having a semiconductor substrate, an insulating film formed on the semiconductor substrate, and an electrode formed on the insulating film, wherein nitrogen atoms and fluorine atoms are introduced into the insulating film. A semiconductor device having a region in which nitrogen atoms are introduced into at least one of the semiconductor substrate and the electrode. 6. The semiconductor device according to claim 5, wherein the concentration of nitrogen atoms and fluorine atoms in the region of the insulating film introduced with nitrogen atoms and fluorine atoms is 1 × 10 ¹⁸ c.
A semiconductor device having a size of m ³ or more and 1 × 10 ²¹ cm ³ or less. 7. The semiconductor device according to claim 5, wherein the inclination angle of the plane orientation of the semiconductor substrate is within ± 10 ° from the (100) plane orientation or ± 10 from the (111) plane orientation.
A semiconductor device, which is within ° or within ± 10 degrees from the (110) plane orientation. 8. A semiconductor device according to claim 1, wherein an insulating film is formed on a semiconductor substrate, an electrode is formed on the insulating film, and nitrogen atoms are introduced into at least the electrode. A method of manufacturing a semiconductor device, which comprises forming the semiconductor device. 9. The method according to claim 1, wherein an insulating film is formed on a semiconductor substrate, an electrode is formed on the insulating film, and nitrogen atoms are introduced into at least the insulating film through the electrode. 1. A method for manufacturing a semiconductor device, comprising forming the semiconductor device according to claim 1. 10. The method according to claim 1, wherein an insulating film is formed on a semiconductor substrate, an electrode is formed on the insulating film, and nitrogen atoms are introduced into at least the semiconductor substrate through the electrode. 1. A method for manufacturing a semiconductor device, comprising forming the semiconductor device according to claim 1. 11. The method of manufacturing a semiconductor device according to claim 8, wherein the introduction of the nitrogen atom is performed by ion implantation in which an average projection range of nitrogen ions is set in the electrode. Production method. 12. The method of manufacturing a semiconductor device according to claim 9, wherein the introduction of the nitrogen atoms is performed by ion implantation in which the average projected range of nitrogen ions is set in the insulating film. Manufacturing method. 13. The method of manufacturing a semiconductor device according to claim 10, wherein the introduction of the nitrogen atoms is performed by ion implantation in which the average projected range of nitrogen ions is set in the semiconductor substrate. Manufacturing method. 14. The method of manufacturing a semiconductor device according to claim 11, wherein the insulating film is heat-treated after the ion implantation. 15. The method of manufacturing a semiconductor device according to claim 14, wherein the heat treatment is performed in a range of 600 ° C. to 1200 ° C. 16. A first step of forming an insulating film on a semiconductor substrate, a second step of forming an electrode on the insulating film, and introduction of nitrogen atoms into at least the electrode, and to the electrode or the electrode. 8. A method of manufacturing a semiconductor device, comprising forming the semiconductor device according to claim 5 through a third step of performing introduction of fluorine atoms into the insulating film in a desired order through. 17. A first step of forming an insulating film on a semiconductor substrate, a second step of forming an electrode on the insulating film, and introducing at least nitrogen atoms into the insulating film through the electrode,
6. The third step of introducing fluorine atoms into the insulating film to the electrode or through the electrode in a desired order,
7. A method of manufacturing a semiconductor device, comprising forming the semiconductor device according to any one of items 1 to 7. 18. A first step of forming an insulating film on a semiconductor substrate, a second step of forming an electrode on the insulating film, and introduction of nitrogen atoms into at least the semiconductor substrate through the electrode, and the electrode. 9. A semiconductor device according to claim 5, wherein the semiconductor device is formed by a third step of performing introduction of fluorine atoms into the insulating film in the desired order through or through the electrode. Manufacturing method. 19. The method of manufacturing a semiconductor device according to claim 16, wherein the introduction of the nitrogen atom is performed by ion implantation in which an average projected range of nitrogen ions is set in the electrode, and the introduction of the fluorine atom is performed. A method for manufacturing a semiconductor device, characterized in that the average projected range of fluorine ions is performed by ion implantation set in the electrode or in the insulating film. 20. The method of manufacturing a semiconductor device according to claim 17, wherein the nitrogen atoms are introduced by ion implantation in which an average projected range of nitrogen ions is set in the insulating film, and the fluorine atoms are introduced. A method for manufacturing a semiconductor device, wherein the average projected range of fluorine ions is performed by ion implantation set in the electrode or the insulating film. 21. The method of manufacturing a semiconductor device according to claim 18, wherein the introduction of the nitrogen atom is performed by ion implantation in which an average projected range of nitrogen ions is set in the semiconductor substrate, and the introduction of the fluorine atom is performed. A method for manufacturing a semiconductor device, wherein the average projected range of fluorine ions is performed by ion implantation set in the electrode or the insulating film. 22. The method of manufacturing a semiconductor device according to claim 19, further comprising a fourth step of heat-treating the insulating film after the third step. Manufacturing method. 23. The method of manufacturing a semiconductor device according to claim 22, wherein the heat treatment is performed in a range of 600 ° C. to 1200 ° C.