JP2000040675A - Manufacture of semiconductor device and semiconductor device manufactured thereby - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a semiconductor device and a manufacturing method of the semiconductor device for adjusting a composition ratio of high m.p. metal silicide film on a surface of a silicon material in a CVD method and eliminating a difference in composition ratios and film characteristics in CVD chambers when a plurality of CVD chambers are used. SOLUTION: Tungsten hexafluoride (WF6) and dichlorosilane(DCS) are reacted in a CVD method on the surface of a polysilicon film doped in a water and a tungsten silicide (WSix) film a little rich in tungsten in generated. In this case, the dichlorosilane(DCS) only is carried in the reactive chamber for a given time, and the tungsten silicide (WSix) film rich in silicon is obtained by adjusted to a target component ratio of Si/W=2.6±0.1. Then, a difference in composition ratios and film characteristics of the tungsten silicide (WSix) film formed in each one-water processing chamber can be eliminated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a semiconductor device in which a refractory metal silicide film is formed on the surface of a silicon material, and a semiconductor device using the method.
More specifically, the composition ratio and film characteristics of the refractory metal silicide film formed by the CVD (Chemical Vapor Deposition) method are changed to reduce the difference between the refractory metal silicide films formed in a plurality of reaction chambers. The present invention relates to a method for manufacturing a semiconductor device to be solved and a semiconductor device using the method.

[0002]

2. Description of the Related Art As the density of LSIs (Large Scale Integrated Circuits) has increased, the wiring width and wiring length have been reduced.
This makes signal propagation at high speed difficult. In contrast, refractory metal silicides, such as tungsten silicide, have an order of magnitude lower specific resistance than the heavily doped polycrystalline silicon used for the gate electrodes and gate wiring, thus reducing signal delay due to resistance. In addition to being able to suppress it, acid treatment is possible, and a good insulating film is formed on its surface in an oxidizing atmosphere, so it is widely used for gate electrodes and gate wiring. Essential for high-density, high-speed devices.

[0003] eg, DRAM as polycide gate of the insulated gate field effect transistor in (dynamic random access memory), tungsten silicide on the surface of the polycrystalline silicon film doped with phosphorus (P) (WSi _X) film Is formed, tungsten hexafluoride (WF ₆ ) and dichlorosilane (SiH ₂₎
Cl ₂ ) as a source gas in many cases. When the film composition becomes Si-rich, the film becomes silicon and has good adhesion to polycrystalline silicon. When the film becomes W-rich, the film becomes metal and the specific resistance decreases, and the film is formed thereon. Adhesion to the metal electrode is improved. Therefore, S in WSi _X film to form
Control of the i / W composition ratio has become an important technology.

Recently, for example, 20
Instead of setting up to 30 wafers in a boat and processing them all at once, one wafer at a time in the reaction chamber (CV
A single-wafer CVD apparatus that performs processing in the (D chamber) is adopted. FIG. 8 is a plan view showing a single-wafer CVD apparatus 10 as an example. That is, the single-wafer CVD apparatus 10 has a left cassette chamber 1 and a right cassette chamber 2 on both sides of the loader chamber 3 at the lower side of FIG. The wafer w is taken in and out by the operation. Loader room 3
The transfer chamber 6 is provided with the load lock chambers 5 and 5 ′ therebetween, and a left CVD chamber 7, a center CVD chamber 8, and a right CVD chamber 9 are disposed with the transfer chamber 6 as a center. .
Then, the wafer w is transferred by the transfer robot 11 in the transfer chamber 6.
Is put in and out.

[0005]

The above-mentioned single-wafer CVD apparatus 10 is used to form a C gas containing tungsten hexafluoride (WF ₆ ) and dichlorosilane (SiH ₂ Cl ₂ ) as source gases.
The VD method, when forming a tungsten silicide (WSi _X) film on the surface of the doped polycrystalline silicon film on the wafer, the left CVD chamber 7, Center CVD chamber 8,
It is often found to cause inter-chamber differential characteristics of WSi _X film formed in each of the right CVD chamber 9. This difference between the chambers is caused by the single-wafer CVD apparatus 10,
This is due to a subtle difference that occurs when components are assembled in the components 8 and 9, and is a problem that cannot be solved by the conventional film forming technology. In the case where the composition ratio Si / W of WSi _X film formed is obtained slightly deviates from the target value set, WSi _X film WF ₆ and SiH ₂ Cl ₂ (hereinafter the raw material gas during the formation of, abbreviated as DCS It is difficult to adjust the deviation and adjust it to the target value only by changing the flow ratio with the target value.

The present invention has been made in view of the above-mentioned problems, and has a CV
In manufacturing a semiconductor device by introducing a high-melting metal fluoride and a silane compound as a raw material gas into one or more CVD chambers in the D apparatus and reacting them, forming a high-melting metal silicide film on the surface of a silicon material, When the composition of the refractory metal silicide film is formed slightly metal-rich, the composition ratio and characteristics of the formed refractory metal silicide film are changed, and the composition of the refractory metal silicide film formed in a plurality of CVD chambers It is an object of the present invention to provide a method of manufacturing a semiconductor device that eliminates differences in characteristics between chambers, and a semiconductor device using the method.

[0007] Regarding the control of the composition of the tungsten silicide film, examples of the "method of manufacturing a semiconductor device" disclosed in JP-A-63-120419 include silane (Si).
H ₄₎ and tungsten silicide (WSi _X) film by CVD method using a WF ₆ as a source gas is formed by the following method. That is, at the beginning of the reaction,
The tungsten silicide formed by reducing the flow ratio of WF _{6 to} H ₄ is made Si-rich, and the composition ratio is x
= 3.0 or more, and thereafter, WF _{6 with} respect to SiH ₄
Is gradually increased, and the tungsten silicide to be formed is made W-rich, and the composition ratio is set to about x = 2.4.

[0008] The "chemical vapor deposition method" disclosed in Japanese Patent Application Laid-Open No. 6-163426 discloses the conventional SiH ₄ and WF.
Than methods using the _6, since towards the CVD method using the DCS and WF ₆ as a raw material gas can be grown with good coverage WSi _X at a high temperature, as a method of using the DCS currently is employed However, the WSi _x film formed by the method using DCS has a large distribution of the Si / W composition ratio, and even if the gas flow ratio and the gas flow are devised and attempted to improve, only unsatisfactory results can be obtained. For the purpose of maintaining a desired Si / W composition ratio and reducing the width of the in-plane distribution of the Si / W composition ratio, DCS is introduced into the growth chamber at a constant flow rate, and WF ₆ is introduced therein. A method of intermittent introduction is disclosed. In the example and the conventional example, the Si / W composition ratio was kept constant, and the in-plane distribution of the Si / W composition ratio was ± 5% in the conventional example, but was improved to ± 3% in the example. And it is effective in that respect. In this case, there is no mention of the distribution of the Si / W composition ratio in the film thickness direction.

[0009]

Means for Solving the Problems The above-mentioned problem is solved by the constitutions of claim 1 and claim 6. To solve the problem, the method of manufacturing a semiconductor device according to claim 1 is as follows.
A high-melting metal fluoride and a silane compound are introduced as raw material gases into one or more reaction chambers of a CVD (chemical vapor deposition) apparatus, that is, a CVD chamber, and reacted to form a high-melting metal silicide film on the surface of a silicon material. In the method of manufacturing a semiconductor device to be formed, when the composition of the refractory metal silicide film is formed to be slightly rich in metal, it is formed by introducing a silane compound subsequently for a time set according to the composition. This is a method for manufacturing a semiconductor device in which the composition ratio and characteristics of a high melting point metal silicide film are changed to eliminate differences between the composition ratios and film characteristics of the high melting point metal silicide films formed in a plurality of reaction chambers. The semiconductor device manufactured by such a method has small characteristic variations, stabilizes the manufacturing process, and improves the productivity.

According to a sixth aspect of the present invention, a high-melting metal fluoride as a raw material gas and a silane compound are introduced into one or a plurality of reaction chambers of a CVD (chemical vapor deposition) apparatus, that is, a CVD chamber and reacted. In a semiconductor device manufactured by forming a refractory metal silicide film on the surface of a silicon material, when the composition of the refractory metal silicide film is formed to be slightly metal-rich, then the silane compound is changed to the above composition. By introducing a time set according to the above, the composition ratio and characteristics of the formed refractory metal silicide film are changed, and the composition ratio and film characteristics of the refractory metal silicide film formed in a plurality of CVD chambers are changed. This is a semiconductor device manufactured by eliminating differences between rooms. Semiconductor devices manufactured by such a method have small characteristic variations and high reliability.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a semiconductor device according to an embodiment of the present invention and a method for manufacturing the same will be described.

According to the method of manufacturing a semiconductor device of the present invention, for example, tungsten silicide is used as a gate electrode or a gate wiring in an insulated gate field effect transistor.
When forming a silicide film of a refractory metal selected based on the melting point or specific resistance of molybdenum silicide, tantalum silicide, or titanium silicide, when the composition of the film is formed slightly rich in metal, the resulting high In order to adjust the composition ratio of the melting point metal silicide film or to eliminate the difference in composition ratio and film characteristics between a plurality of CVD chambers when the film is formed by a single wafer CVD apparatus, a high melting point metal silicide is used. After forming the film, CV
This is a method in which a silane-based compound gas is introduced into the chamber D when it is set according to the above composition.

[0013] For example, taking the case of forming a tungsten silicide film as an example, the a and silane compound into the CVD chamber tungsten hexafluoride (WF ₆₎ by introducing a raw material gas reaction of tungsten silicide (WSi _x) film After the formation, the gas of the silane-based compound is further
By introducing into the D chamber, i.e. the ratio of the silicon in the WSi _x film formed slightly tungsten-rich (Si) and tungsten (W) by the post-flow of DCS, i.e. the Si / W composition ratio While approaching the target value, the WSi
_This is to equalize electrical characteristics, in-plane uniformity, and other film characteristics generated between a plurality of CVD chambers when _x is formed. When forming a molybdenum silicide film, molybdenum hexafluoride (MoF ₆ ) is used as a source gas of molybdenum. When forming a tantalum silicide film, a tantalum pentafluoride (TaF ₅ ) or titanium silicide film is formed. In that case, titanium tetrafluoride is used.

Adjustment of the composition of the gaseous silane compound introduced into the formation of the refractory metal silicide film and the silicide film after the film formation, the composition ratio of the silicide films formed in a plurality of CVD chambers, and the film characteristics Examples of gaseous silane compounds used for DCS post-flow for eliminating and equalizing differences between chambers include silane (SiH ₄ ), monochlorosilane (SiH ₃ Cl), and dichlorosilane (SiH ₂ Cl).
₂ ), trichlorosilane (SiHCl ₃ ), and tetrachlorosilane (SiCl ₄ ). Of these, those having the most suitable reactivity are selected and used.

It is convenient to carry out post-flow using a silane-based compound while maintaining the temperature and pressure at the time of forming the refractory metal silicide film. Of course, these may be changed. The post flow is performed in a temperature range of about 500 ° C. or more and 700 ° C. or less, and the pressure at that time is generally in a range of 0.2 × 10 ⁻² Pa or more and 3 × 10 ⁻² Pa or less. However, the present invention is not limited to these. Since the post-flow time varies depending on the type and composition ratio of the refractory metal silicide, the type of the silane compound to be post-flowed, and the temperature of the post-flow, it cannot be determined unconditionally. Is set.

[0016]

EXAMPLE A single-wafer CV shown in FIG. 8 was applied to the surface of a polycrystalline silicon film doped with P (phosphorus) on a wafer.
For tungsten silicide (WSi _x) film is slightly tungsten Rich was formed using the D device 10 is subjected to a post-flow of the silane compound, Si / W
The composition ratio approaches the target value and the single wafer CVD apparatus 1
The method of manufacturing a semiconductor device according to the present invention and the semiconductor device using the same will be described in detail with reference to an example in which film characteristics generated between the three CVD chambers at 0 are equalized.

Table 1 shows that tungsten hexafluoride (WF ₆ )
And the process of the tungsten silicide (WSi _x) film formed to a dichlorosilane (SiH ₂ Cl ₂₎ as a raw material gas for the process of the post-flow of DCS following the film formation (dichlorosilane), the conditions of each step It is a table shown.

[0018]

[Table 1]

The steps in Table 1 will be described. Step 1 is a step for starting the film formation of the single wafer type CVD apparatus 10 and is evacuated by a vacuum exhaust system to a high degree of vacuum.
Heating for raising the temperature of each of the CVD chambers 7, 8, 9 at a temperature of 00 ° C. is started. At the same time, 2 sccm of argon gas Ar (3) was used as backside gas (BSG).
(The number of cc of gas in a standard state per minute). Step 2 is to supply 200 sc of argon gas Ar (1) which is a carrier of WF ₆ introduced in the subsequent steps.
cm, argon gas Ar which is a carrier of DCS
This is a preflow step for causing (2) to flow at a flow rate of 150 sccm, and is discharged out of the system together with Ar (3) at 30 sccm without being introduced into the CVD chambers 7, 8, and 9. That is, the five seconds in step 2 is the time required for the mass flow controller (MFC) controlling the flow rate in each line to reach a steady state.

In step 3, Ar (1), Ar (1)
(2) Ar (3) is introduced into the CVD chambers 7, 8, and 9 and the pressure is maintained at 93.3 Pa, but after 70 seconds, the CVD chambers 7, 8, and 9 are heated to a predetermined 595 ° C. To reach. Step 4 is a DCS pre-flow step that is flowed for nucleation in a subsequent step.
Flow at a flow rate of sccm for 60 seconds. Step 5 is a step of pre-flowing WF ₆ at a flow rate of 1.0 sccm. After being discharged out of the system together with DCS, Ar (1), Ar (2), and Ar (3), WF ₆ , D
CS and each Ar are returned to the CVD chambers 7, 8, and 9 and flowed for 20 seconds. WSi _x molecule formed during this time a large number of nuclei adhere to the polycrystalline silicon film doped is formed.

[0021] Step 7 is a step of pre-flow to increase the flow rate of WF ₆ to 3.6sccm to form a WSi _x film, DCS that has been reduced the flow rate to 100sccm, Ar (1), Ar (2 ), Ar (3)
Is discharged out of the system together with W
F ₆ , DCS, and each Ar are returned to the CVD chambers 7, 8, and 9,
The time is set according to the thickness of the film to be formed,
i _x film is formed. In the conditions in the present embodiment,
The growth rate of the WSi _x film was 0.12μm / min.

[0022] formation of WSi _x film is completed, stop the WF ₆ at subsequent step 9, Ar (1), Ar
(2) DCS is post-flowed together with Ar (3). The post-flow time depends on the Si / W obtained by trial.
Achievement of the target value of the composition ratio is determined by the uniformity of the WSi _x film formed by the CVD chamber 7,8,9. That is, step 9 is a step constituting a main part of the method for manufacturing a semiconductor device of the present invention. Then, in step 10, the heating is stopped and the DCS is stopped, and Ar
(1), only Ar (2) and Ar (3) are flowed and CVD
The chambers 7, 8, and 9 are purged, and all gases are stopped in step 11, whereby the CVD chambers 7, 8, and 9 are purged.
The inside of 9 returns to a high vacuum and is maintained at a temperature of 200 ° C.

(Embodiment 1) For the purpose of forming a polycide gate of a DRAM, a single-wafer CVD apparatus 1 shown in FIG.
Using the 0, in accordance with step in Table 1 above, but to form a WSi _x film on the surface of the doped polycrystalline silicon film on the wafer, Step 9 for Si / W composition ratio of the WSi _x film The effect of DCS post flow was studied. That is, the time post-flow of DCS as 5 seconds, to measure the thickness direction of the Si / W composition ratio of the WSi _x film by Rutherford backscattering spectrometry, Figure 1 and the results
It was shown to.

FIG. 1 is a diagram showing the Si / W composition ratio in the thickness direction when DCS is post-flowed for 5 seconds. In other words, the horizontal axis is the thickness of the WSi _x film from the surface of the polycrystalline silicon film doped, the vertical axis represents the Si / W composition ratio. The symbol “△” in the figure indicates the left CV of the single wafer CVD apparatus 10.
D chamber 7, ○ mark center CVD chamber 8, □ mark is a measure of the WSi _x film in the right CVD chamber 9. In addition,
As conditions during WSi _x film is shown in Table 1, the temperature 59
5 ° C., pressure 93.3 Pa, WF ₆ flow rate 3.6 sccm,
The DCS flow rate was 100 sccm, and after the WF ₆ was stopped, the temperature and the pressure were further maintained and the DCS flow rate was 1
Post-flow was performed at 00 sccm for 5 seconds.

[0025] As seen in FIG. 1, when the 5 seconds DCS post-flow, as the closer to the surface of the WSi _x film from the interface between the polycrystalline silicon film, Si / W composition ratio is larger, That is, it is Si-rich, and the overall Si / W composition ratio is the target value of Si / W = 2.6 ±
It is slightly lower than 0.1 and W-rich. In addition, the left CVD chamber 7 indicated by a triangle was particularly rich in W, and it was recognized that there was a difference between the CVD chambers. Note that the target composition ratio S
i / W = 2.6 ± 0.1 is a value set since balance of adhesion to the specific resistance and the polycrystalline silicon film of WSi _x film is good.

(Embodiment 2) Based on the results of Embodiment 1,
When changing the time of the DCS post-flow, WSi _X
We examined how the film properties of the film changed. 3 is a stress, FIG. 4 is a specific resistance, FIG. 5 is a surface resistance (sheet resistance), FIG. 6 is a film thickness, and FIG.
It is a figure which shows the change when the time of S post flow is taken on the horizontal axis.

The characteristics of each film were measured as follows. * Stress (× E9Pa): For wafer being formed of WSi _X film was calculated by multiplying the elastic modulus on the degree of warpage resulting from a change in the reflection of light before and after the DCS post-flow. * Specific resistance (μΩcm): Determined as surface resistance × thickness. If the specific resistance is constant, that is, if the film quality is constant, the surface resistance decreases as the film thickness increases,
Information about the film quality can be obtained from the value. * Surface resistance (Ω / □): determined by the four probe method. * Film thickness (nm): Determined by the fluorescent X-ray method. * Plane uniformity (%): three times the standard deviation σ of the surface resistance in 49 places of WSi _X film surface, i.e., showed a 3σ a percentage of the mean value of the surface resistance.

As can be seen in FIG. 3, the stress is DCS
The time of the post-flow is reduced with the longer, suggesting that the WSi _X film is gradually changed to Si-rich. Further, FIG. 4, as seen in FIG. 5, the specific resistance and surface resistance are increased as the time of the DCS post-flow becomes longer, which also WSi _X
It is assumed that the film has changed to Si-rich. No change is detected in the film thickness except for the initial stage of the left CVD chamber 9. The tendency of WSi _X film changes the Si-rich becomes gradually from a number of seconds 10 seconds position of the DCS post-flow, to stabilize it exceeds 15 seconds. When the DCS post flow exceeds 10 seconds, the stress, specific resistance, and surface resistance of the left CVD chamber 7 of the single-wafer CVD apparatus 10 and the center C
The difference between the CVD chambers of the VD chamber 8 and the right CVD chamber 9 is reduced, and the in-plane uniformity as viewed from the surface resistance is improved. Around these reasons, by applying a DSC post-flow, by reacting with Si is incorporated into the WSi _X film, WSi _X film changes from W-rich composition to the Si-rich composition is more than 10 seconds The reaction seems to be gradually saturated.

[0029] (Example 3) DCS Since the composition of WSi _X film by post-flow is presumed to be altered in Si-rich, in order to check it, DSC post flow was 5 seconds in Example 1 About samples prepared exactly as except for using 15 seconds, likewise by Rutherford backscattering spectrometry, in the thickness direction of the WSi _X film Si
/ W composition ratio was measured. The result is as shown in FIG.

As a result of setting the DSC post flow for 15 seconds, the Si / W composition ratio was higher than that of FIG. 1 in the case of Example 1, and in addition, the target Si / W composition ratio = 2.6 ± 0.1 was obtained. In particular, in the left CVD chamber 7, the Si / W composition ratio increases from the middle to the surface of the film thickness, and the difference between the left, center, and right CVD chambers is eliminated. The effect of increasing the time is recognized.

The method of manufacturing a semiconductor device according to the embodiment of the present invention and the semiconductor device according to the method are configured and operated as described above. Of course, the present invention is not limited to this.
Various modifications are possible based on the technical idea of the present invention.

For example, in this embodiment, an example has been described in which the post-flow time of the DCS is set to 15 seconds.
The optimum time for the post-flow of S differs depending on the type and composition ratio of the refractory metal silicide to be formed, the temperature at the time of the post-flow, or the CVD apparatus used, and cannot be determined unconditionally. The optimal post-flow time is set for each case by trial.

Further in the present embodiment has been described by way of P (phosphorus) doped n-type polycrystalline silicon film as the silicon material to form a WSi _x film, of course, the polycrystalline silicon film is As (boron ), Sb (antimony) or the like as a dopant. In addition, B (boron)
Or the like may be a p-type polycrystalline silicon film using the dopant as a dopant, or may be a doped single crystal silicon film.

In this embodiment, the CV of the three chambers is used.
WSi _x using a single-wafer CVD apparatus 10 having a D chamber
Although the case where a film is formed has been exemplified, the method of manufacturing a semiconductor device of the present invention and the semiconductor device using the method have four or more C chambers.
The present invention is also applied to a case where a single-wafer CVD apparatus having a VD chamber is used or a case where a single-chamber CVD apparatus is used.

In this embodiment, argon (Ar) is used as the carrier gas for WF ₆ , the carrier gas for DCS, and the backside gas (BSG). However, helium (He), neon ( Ne)
Can be used.

[0036]

The semiconductor device and the method of manufacturing the same according to the present invention are implemented in the above-described embodiment, and have the following effects.

According to the first aspect of the present invention, it is possible to manufacture a semiconductor device having a small variation in the composition ratio and film characteristics of the refractory metal silicide film, thereby stabilizing the manufacturing process.
Productivity can be improved.

According to the second aspect of the present invention, a semiconductor device can be manufactured by selecting a high-melting-point metal silicide film having a melting point, a specific resistance and the like that are suitable for the purpose.

According to the third aspect of the present invention, a semiconductor device can be manufactured by selecting the most preferable gaseous silicon compound for adjusting the composition ratio of the silicide film to be formed and for equalizing the film characteristics.

According to the fourth aspect of the present invention, a semiconductor device having a gate electrode and a gate wiring suitable for high-speed signal propagation can be manufactured.

According to the fifth aspect of the present invention, it is possible to manufacture a semiconductor device having a tungsten silicide film that is balanced in film characteristics such as adhesion to a silicon material and specific resistance.

In the semiconductor device according to the sixth aspect of the present invention, the composition ratio of the silicide film and the characteristics of the silicide film are small in variation and high in reliability.

A semiconductor device according to a seventh aspect of the present invention has a refractory metal silicide film whose characteristics such as melting point and specific resistance are selected.

The semiconductor device according to the eighth aspect of the present invention has a refractory metal silicide film most appropriately adjusted in composition ratio and equalized in film characteristics.

According to a ninth aspect of the present invention, there is provided a semiconductor device having a refractory metal silicide film capable of forming a gate electrode and a gate wiring suitable for high-speed signal propagation.

The semiconductor device according to the tenth aspect of the present invention has a tungsten silicide film in which characteristics such as adhesion to a silicon material and specific resistance are balanced.

[Brief description of the drawings]

FIG. 1 is a diagram showing a Si / W composition ratio in a thickness direction of a tungsten silicide film when a post flow of dichlorosilane is set to 5 seconds.

FIG. 2 is a view similar to FIG. 1 when the post-flow of dichlorosilane is 15 seconds.

FIG. 3 is a diagram showing the relationship between the number of seconds of post flow and stress.

FIG. 4 is a diagram showing the relationship between the number of seconds of post-flow and the specific resistance.

FIG. 5 is a diagram showing the relationship between the number of seconds of post flow and the surface resistance.

FIG. 6 is a diagram showing the relationship between the number of seconds of post-flow and the film thickness.

FIG. 7 is a diagram showing a relationship between the number of seconds of post-flow and in-plane uniformity.

FIG. 8 is a schematic plan view of an example of a single-wafer CVD apparatus.

[Explanation of symbols]

7 left CVD chamber, 8 center CVD chamber, 9 right CVD chamber, 10 single wafer CVD apparatus.

Claims (10)

[Claims] 1. A refractory metal fluoride and a silane compound are introduced as raw material gases into one or a plurality of reaction chambers in a CVD (chemical vapor deposition) apparatus and allowed to react with each other. In the method of manufacturing a semiconductor device for forming a film, when the composition of the refractory metal silicide film is formed slightly metal-rich, by subsequently introducing the silane compound for a time set according to the composition, The composition ratio and characteristics of the formed high melting point metal silicide film are changed to eliminate a difference between the composition ratio and the film characteristics of the high melting point metal silicide film formed in the plurality of reaction chambers. Semiconductor device manufacturing method. 2. The method according to claim 1, wherein the refractory metal silicide film to be formed is any one of a group consisting of tungsten silicide, molybdenum silicide, tantalum silicide, and titanium silicide. Of manufacturing a semiconductor device. 3. The method according to claim 1, wherein the silane compound subsequently introduced after the formation of the refractory metal silicide film is at least one or two or more selected from the group consisting of silane, monochlorosilane, dichlorosilane, trichlorosilane, and tetrachlorosilane. 2. The method of manufacturing a semiconductor device according to claim 1, wherein the mixture is a mixture of the following. 4. The method according to claim 1, wherein the silicon material is a polycrystalline silicon film doped with phosphorus. 5. The high melting point metal fluoride is tungsten hexafluoride, the silane compound is dichlorosilane, and the composition ratio of the formed tungsten silicide film is silicon (Si) / tungsten (W) = 2. 0.6 ±
2. The method according to claim 1, wherein the adjustment is performed within a range of 0.1. 6. A refractory metal fluoride and a silane compound as source gases are introduced into one or a plurality of reaction chambers in a CVD (chemical vapor deposition) apparatus and reacted to form a refractory metal silicide on the surface of a silicon material. In a semiconductor device manufactured by forming a film, when the composition of the refractory metal silicide film is formed to be slightly metal-rich, by subsequently introducing the silane compound for a time set according to the composition, The high melting point metal silicide film is formed by changing the composition ratio and characteristics of the formed high melting point metal silicide film to eliminate the difference between the composition ratio and the film characteristics of the high melting point metal silicide film formed in the plurality of reaction chambers. A semiconductor device, comprising: 7. The film according to claim 6, wherein the refractory metal silicide film formed is any one of a group consisting of tungsten silicide, molybdenum silicide, tantalum silicide, and titanium silicide. Semiconductor device. 8. The method according to claim 8, wherein the silane compound subsequently introduced after the formation of the refractory metal silicide film is at least one or more of a group consisting of silane, monochlorosilane, dichlorosilane, trichlorosilane, and tetrachlorosilane. The semiconductor device according to claim 6, wherein the semiconductor device is a mixture of: 9. The semiconductor device according to claim 6, wherein said silicon material is a polycrystalline silicon film doped with phosphorus. 10. The refractory metal fluoride is tungsten hexafluoride, the silane compound is dichlorosilane, and the composition ratio of the formed tungsten silicide film is silicon (Si) / tungsten (W) = 2. 0.6 ±
7. The semiconductor device according to claim 6, wherein the value is within a range of 0.1.