JP2003324096A - Method for manufacturing semiconductor device and film forming processor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technology for forming a ferroelectric film by the MOCVD method for mass-production of a semiconductor device having the ferroelectric film. <P>SOLUTION: An exhaust system of an MOCVD device is provided with a decomposition cylinder for decomposing a residual organic solvent by catalytic reaction and a dust collector for collecting granular discharges. The temperature of the decomposition cylinder is set to a temperature so that catalytic reaction is generated in the decomposition room but lower than the film formation temperature of the ferroelectric film in a film formation room. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to the manufacture of semiconductor devices, and more particularly to the manufacture of non-volatile semiconductor devices having a ferroelectric film.

Semiconductor memory devices such as so-called DRAMs and SRAMs are widely used as high-speed main memory devices in information processing devices such as computers, but these are volatile memory devices and are stored when the power is turned off. The information given will be lost. On the other hand, a non-volatile magnetic disk device has been conventionally used as a large capacity auxiliary storage device for storing programs and data.

However, the magnetic disk device is large and mechanically fragile, consumes a large amount of power, and has a drawback that the access speed for reading and writing information is slow. On the other hand, recently, as a non-volatile auxiliary storage device, an EEP that stores information in the form of charges in a floating gate electrode
ROM or flash memory is often used. In particular, since a flash memory has a cell structure similar to that of a DRAM, it can be easily formed with a large integration density and is expected as a large-capacity storage device comparable to a magnetic disk device.

On the other hand, in an EEPROM or a flash memory, information is written by injecting hot electrons into a floating gate electrode through a tunnel insulating film, so that it takes a long time to write the information.
Further, there has been a problem that the tunnel insulating film is deteriorated when information is repeatedly written and erased. If the tunnel insulating film deteriorates, the writing or erasing operation becomes unstable.

On the other hand, information is taken as the spontaneous polarization of the ferroelectric film.
Ferroelectric memory device (hereinafter referred to as FeRAM)
Is proposed. In such FeRAM, individual memory
As in the case of DRAM, the memory cell transistor is a single
Dielectric in the memory cell capacitor consisting of MOSFET
The body film is made of PZT (Pb (Zr, Ti) O₃) Or PL
ZT ((Pb, La) (Zr, Ti) O₃),Moreover
SBT (SrBi₂Ta ₂O₃), Etc.
It is possible to integrate with high integration density.
It In addition, FeRAM is a ferroelectric capacitor when an electric field is applied.
Hot writing is used to control
EEPROM or FLA made by injecting lectron
Writing speed is 1000 times faster than Shure memory
It becomes faster and the power consumption is reduced to about 1/10.
It has the advantageous characteristics that Further tunnel oxide film
Since it does not need to be used, it has a long lifespan.
It is considered that the number of times of rewriting of 100,000 times can be secured.

[0006]

2. Description of the Related Art Conventionally, a ferroelectric film used for such an FeRAM is formed by a sol-gel method or a sputtering method. However, as semiconductor devices are miniaturized, these conventional methods provide coverage of fine steps. Is expected to be difficult. Under such circumstances, the CVD method is considered to be an indispensable technique as a technique for forming a ferroelectric film used in the next-generation FeRAM. In particular, when forming a ferroelectric film, it is necessary to supply a raw material containing a metal element such as Pb, Zr, or Ti. Therefore, the CVD method is different from the MOCVD method using an organometallic raw material of these metal elements. I have no choice.

FIG. 1 shows a conventional MOCVD of a ferroelectric film.
1 shows a schematic configuration of an MOCVD apparatus 10 used for film formation by the method.

Referring to FIG. 1, in the MOCVD apparatus 10, Pb (DPM) ₂ from the raw material containers 12 ₁ , 12 ₂ and 12 _{3 is} removed.
(Lead bis (dipivaloylmethanate)), Zr (DMH
D) ₄ (zirconium tetrakis (dimethyl heptadionate), Ti (O-iPr) ₂ (DPM) ₂ (titanium (diisoproxy) (dipivaloyl methanate)) and other solid organic metal raw materials such as THF (tetrahydrofuran) Liquid raw material obtained by dissolving in the organic solvent of
2, and the metal-organic vapor phase raw material formed by vaporization in the vaporizer 12 is supplied to the gas mixer 13 via the raw material gas supply line 12A. The gas mixer 1
The metal-organic vapor phase raw material supplied to No. 3 is the gas line 13A.
The mixed gas thus formed is supplied to the film forming chamber 11 holding the substrate W to be processed on the susceptor 11A from a shower head (not shown). . The organometallic vapor phase raw material introduced into the film forming chamber 11 is thermally decomposed on the surface of the substrate to be processed W, and as a result, a ferroelectric film such as PZT is formed on the surface of the substrate to be processed W. .

The film forming chamber 11 is connected to a vacuum pump 14 via an exhaust line 11B, and as a result, a reaction product generated as a result of thermal decomposition of the metal-organic vapor phase raw material in the film forming chamber 11, Alternatively, the unreacted organometallic raw material that has not been thermally decomposed is exhausted from the exhaust line 11B together with the organic solvent component. Further, the vaporizer 12 includes a vacuum pump 14, a valve 12 b and a bypass line 12.
When the film is not formed in the film forming chamber 11 by being connected by B, the metal-organic vapor phase raw material formed in the vaporizer 12 is exhausted through the valve 12b and the bypass line 12B.

The bypass line 12B joins with the exhaust line 11B on the upstream side of the vacuum pump 14, and a cold trap 15 is provided between the bypass line 12B and the vacuum pump 14 at the joining position.
Is provided to capture the unreacted organometallic raw material exhausted through the exhaust line 11B or 12B. Further, on the downstream side of the vacuum pump 14, an abatement device 16 for removing the organic solvent is provided.

In the MOCVD apparatus 10 of FIG. 1, a pipe 1 between the vaporizer 12 and the cold trap 15 is provided.
2A, 12B and the valves 12a, 12b are overheated by the heating jacket 17 to avoid precipitation of the organic metal raw material.

[0012]

The MOCVD apparatus 10 of FIG. 1 is used for research on a ferroelectric film.

However, when attempting to mass-produce semiconductor devices having a ferroelectric film using the MOCVD apparatus 10 as described above, various problems occur.

FIG. 2 shows the structure of the cold trap 15 used in the MOCVD apparatus 10 of FIG.

Referring to FIG. 2, the cold trap 15
A large number of cells in which exhaust gas sequentially flows are formed in the exhaust gas. However, when the organic metal raw material that is solid at room temperature as described above is used, the organic metal raw material is deposited and solidified near the inlet of the cold trap 15. The exhaust system will not function. This is a very serious problem especially in a mass production process using a large amount of raw material. Especially when this problem occurs in the process using Pb such as the formation of the PZT film, the P
b is discharged to the environment, causing serious environmental pollution.

Therefore, the present invention has solved the above problems.
It is a general object to provide a new and useful film forming method and film forming apparatus.

A more specific object of the present invention is to provide a film forming method and a film forming apparatus by a MOCVD method for a ferroelectric film using an organometallic material, which can be used in a mass production process.

[0018]

The present invention solves the above-mentioned problems.
A method of manufacturing a semiconductor device, comprising: supplying a film forming gas containing an organometallic raw material and an oxidizing gas to a film forming chamber, and depositing a ferroelectric film on a surface of a substrate to be processed held in the film forming chamber. Then, the step of depositing the ferroelectric film includes a step of detoxifying exhaust gas exhausted from the film forming chamber in a catalyst processing device provided in an exhaust system coupled to the film forming chamber, The detoxification step is performed by maintaining the catalyst processing device at a temperature at which a catalytic reaction of an organic solvent component contained in the film forming gas occurs, but lower than the film forming processing temperature in the film forming chamber. This is solved by a semiconductor device manufacturing method characterized by being executed.

According to the present invention, when the unreacted film forming gas discharged from the film forming chamber is decomposed in the catalyst processing apparatus,
By setting the temperature of the catalyst treatment device to a temperature at which the catalytic reaction of the organic solvent component contained in the film-forming gas occurs, the organic solvent contained in the film-forming gas can be decomposed and rendered harmless. it can. Further, by setting the temperature of the catalyst treatment device lower than the film formation treatment temperature, decomposition and precipitation of the unreacted organometallic raw material in the catalyst treatment device is suppressed, and a semiconductor device having a ferroelectric film such as FeRAM is provided. Even when it is used in a process using a large amount of organic metal raw material such as the mass production process, the malfunction of the abatement device can be avoided.

For example, the temperature of the catalyst treatment device is set to 3
By holding at a temperature of 00 to 450 ° C., Pb (DPM) ₂ , Zr as the organometallic raw material is stored in the film forming chamber.
Even when (DMHD) ₄ , Ti (O-iPr) ₂ (DPM) ₂ is supplied to form a PZT film, Ba (THD)
₂ , Sr (THD) ₂ , Ti (O-iPr) ₂ (DPM) ₂
Is supplied to form a BST film, Sr
(THD) ₂ and Ru (EtCP) ₂ to supply SRO
Even when the film is formed, it is possible to avoid the malfunction of the abatement device. At that time, the temperature fluctuation of the catalyst treatment device is 1
It is preferable to suppress the temperature to 00 ° C or lower.

Further, the temperature of the catalyst treatment device is set to 300 to 4
By maintaining the temperature at 00 ° C., Sr [Ta (O-Et) ₆ ] ₂ and Bi as the organometallic raw material are stored in the film forming chamber.
Even when the SBO film is formed by supplying (ph) ₃ , it is possible to avoid the malfunction of the harm removing device.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION [First Embodiment] FIG. 3 shows the overall structure of a MOCVD film forming apparatus 20 according to an embodiment of the present invention. However, in FIG. 3, parts corresponding to the parts described previously are designated by the same reference numerals, and a description thereof will be omitted.

Referring to FIG. 3, in this embodiment, the cold trap 15 of FIG. 1 is removed, and the abatement device 16 is
It is replaced by the abatement device 26 in which the disassembling cylinder 26A and the dust collecting device 26B are connected. Further, in this embodiment, the exhaust system piping is covered by the heating jacket 17 up to the front of the abatement device 26, including the vacuum pump 14.

FIG. 4 shows the structure of the disassembling cylinder 26A.

Referring to FIG. 4, the decomposition cylinder 26A has a cylindrical main body filled with a porous precious metal catalyst 26a, and when the organic solvent component in the exhaust gas passes through the decomposition cylinder 26A. Decomposed into water and carbon dioxide. Further, the decomposition tube 26A is provided with a heat exchanger 26R for accelerating the catalytic reaction, and by driving the heat exchanger 26R, the temperature of the catalyst 26a causes the catalytic reaction, The temperature is typically set to 300 ° C. or higher.

As a result of the catalytic reaction in the decomposition cylinder 26A, the unreacted organometallic raw material exhausted from the film forming chamber 11 is decomposed, and particles such as PbO, ZrO ₂ or TiO ₂ are generated. Therefore, in this embodiment, the disassembling cylinder 26A
A large-capacity dust collecting device 26B is connected to the downstream side of the so as to capture the discharged particles. The dust collector 26B
As the, a commercially available product can be used.

FIG. 5 shows Pb (DPM) as the raw material of Pb, Zr and Ti held in the raw material containers 12 ₁ , 12 ₂ and 12 ₃ in the MOCVD apparatus 20 of FIGS.
₂ , Zr (DMHD) ₄ and Ti (O-iPr) ₂ (D
PM) ₂ is dissolved in a THF solvent, and the liquid raw materials are vaporized at a temperature of 190 ° C. in a vaporizer 13 to produce PZ on a 6-inch Si wafer.
The number of deposited films and the abatement device 2 when a T film is deposited
The relationship with the pressure loss in 6 is shown. However, in the experiment of FIG. 5, the film forming pressure in the film forming chamber 11 was set to 667 Pa, the piping temperature of the source gas supply line 12A was set to 220 ° C., and the temperature of the oxygen gas in the line 13A was set to 200 ° C.
And the deposition of the PZT film is performed at 580 ° C. The pressure loss is defined as the pressure difference between the inlet and the outlet of the abatement device 26.

In the experiment of FIG. 5, the temperature of the decomposition cylinder 26A was not intentionally controlled, and as a result, a temperature distribution of 450 to 600 ° C. was generated in the decomposition cylinder 26A during the experiment. There is.

Referring to FIG. 5, the pressure loss in the abatement device 26 is about 4 until about 1000 substrates are processed.
It is almost constant at 00 mmH ₂ O, but rises sharply when it exceeds this value, and 800 mmH ₂ O is reached when 1500 sheets are processed.
You can see that If the pressure loss is further increased, abnormal back pressure occurs in the vacuum pump 14, so the experiment is terminated.

On the other hand, FIG. 6 shows the MOCV of FIGS.
In the D device 20, the results are shown under the same conditions as in FIG. 5, except that the temperature of the decomposition tube 26A is controlled in the range of 300 to 400 ° C. by controlling the heat exchanger 26R.

As shown in FIG. 6, the disassembling cylinder 26 is
When the temperature of A is controlled in the range of 300 to 400 ° C., the abatement device 2 is removed even when 1000 wafers are processed.
The pressure loss at 6 is only about 250 mmH ₂ O,
300m even when 1,500 wafers are processed
It is only about mH ₂ O. That is, by controlling the temperature of the decomposition cylinder 26A in this manner, the MOC of FIGS.
It will be appreciated that the VD apparatus 20 can be used to process large numbers of substrates.

Regarding the PZT film obtained in the experiment of FIG.
When the film thickness was measured at 9 points on the surface of the substrate, it was confirmed that the variation in the film thickness was ± 5 nm or less for the 120 nm film. Further, 10 wafers were continuously processed under the conditions of FIG. 6, and the Pb composition [Pb /
(Zr + Ti)] and Zr composition [Zr / (Zr + T
i)] was obtained, which were 1.14 ± 0.05 and 0.45 ± 0.05, respectively, and it was found that the PZT film was formed with good reproducibility. The above results are summarized in Table 1 below.

[0033]

[Table 1] Further, in the experiment of FIG. 6, the exhaust gas discharged from the decomposition tube 26A was inspected by the THF detector tube, and it was confirmed that the THF concentration in the exhaust gas was below the detection limit.

Further, the PZT formed in this way
When the number of particles deposited on the wafer for the film was measured by a particle counter, it was confirmed that the number of particles of 0.2 μm or less was 100 or less.

As described above, in the experiment of FIG.
The reason why the pressure loss of the abatement device 26 increases when the PZT film is deposited without controlling the temperature of 6A is that the unreacted organometallic raw material discharged from the film forming chamber 11
It is considered that this is because the temperature distribution generated in 6A decomposes particularly in a high temperature portion, and the precipitate blocks the gas passage inside the decomposition cylinder 26A. On the other hand, the temperature distribution in the decomposition cylinder 26A is uniform, and is lower than the film formation temperature of the PZT film (580 ° C. in this case), preferably 300 to 400.
When the temperature is controlled in the range of ° C, such decomposition of the organic metal material does not occur, only the organic solvent such as THF is decomposed, and the problem of clogging in the decomposition cylinder 26A as shown in Fig. 5 does not occur. it is conceivable that.

Therefore, in this embodiment, PZT is used.
When the film is formed, the temperature of the decomposition cylinder 26A is made uniform and the PZ
By setting the temperature lower than the film forming temperature of the T film, the disassembling cylinder 26
Solve the problem of clogging in A.

FIG. 7 shows the relationship between the film forming temperature and the film forming speed in the film forming process of the PZT film executed in the film forming chamber 11 of the MOCVD apparatus 20 of FIGS.

Referring to FIG. 7, it is understood that when the film forming temperature, that is, the substrate temperature becomes lower than 450 ° C., the film forming rate of the PZT film sharply decreases. From this, the above MOC
In the film formation process of the PZT film by the VD method, the film formation temperature is 45
It is preferable that the temperature is 0 ° C. or higher, and correspondingly, it is necessary to set the temperature of the decomposition tube 26A to less than 450 ° C. The range of 300 to 400 ° C. described above satisfies this condition.

Therefore, the present invention is not limited to the formation of PZT films.
Not used, for example Ba (THD)₂, Sr (T
HD)₂And Ti (O-iPr)₂(DPM)₂Supply
When forming a BST film by using Sr (THD)₂and
Ru (EtCp)₂SRO (Sr
RuO₃) When forming a film, Sr [Ta (O-E
t)₆] ₂And Bi (ph)₃SB by supplying and
T (SrBi₂(Ta, Nb)₂O₉) When forming a film
Is also effective. BST film formation is typically at 500 ° C.
The SBT film formation is typically performed at a substrate temperature of 400
Substrate temperature of ℃, SRO film formation is typical
At a substrate temperature of 600 ° C.

Therefore, when using these raw materials, the temperature of the decomposition cylinder 26A is set to be lower than the substrate temperature in the temperature range where the catalytic reaction occurs.
A large number of wafers can be continuously processed.

In this embodiment, the disassembling cylinder 2
Unreacted organometallic raw material upon decomposition of organic solvent in 6A
Also decomposes, resulting in PbO and Z as described above.
rO ₂Or TiO₂Particles such as are generated, but this time
In the experiment, these particles were clogged in the disassembly tube 26A.
It was confirmed that there is no risk of damage. This is this
Particles clogged in the cold trap 15 of FIG.
This is because it does not form a highly viscous droplet that causes
To be [Second Embodiment] Next, using the MOCVD apparatus shown in FIGS.
Also, the manufacturing process of the FeRAM according to the second embodiment of the present invention will be described.
explain.

FIG. 8 shows the FeR according to the second embodiment of the present invention.
The structure of AM30 is shown.

Referring to FIG. 8, the FeRAM 30 has Si having an element region defined by an element isolation structure 30A.
A gate electrode 33 formed on the substrate 31 and corresponding to the active region on the Si substrate 31 via a gate insulating film 32, and the Si substrate 31 on both sides of the gate electrode 33. Source and drain diffusion regions 31A and 31B formed therein are formed.

Further, an interlayer insulating film 34 is formed on the Si substrate 31, and a conductive plug 34A electrically connected to one diffusion region 31A is buried in the interlayer insulating film 34. There is. Further, a bit line BL electrically connected to the diffusion region 31A via the plug 34A is formed on the interlayer insulating film 34.

An interlayer insulating film 35 is further formed on the interlayer insulating film 34 on which the bit line BL is formed. The interlayer insulating film 35 penetrates the interlayer insulating film 34 and the other diffusion region 31B. Conductive plug 35 electrically connected to
B is embedded.

A lower capacitor electrode 36 having a structure in which a barrier metal layer and a lower electrode layer are sequentially stacked is formed on the interlayer insulating film 35 in which the conductive plug 35B is embedded. In the lower capacitor electrode 36, the lower electrode layer is composed of an Ir layer or a Pt layer. When a Pt layer is used as the lower electrode layer, an Ir layer is formed as a barrier metal layer, and an IrOx layer, for example, is formed as an adhesion layer on the Ir layer. The Pt lower electrode layer is formed on the IrOx layer thus formed. On the other hand, when the lower electrode layer is an Ir layer, the lower capacitor electrode 36 is composed of a single Ir layer. FIG. 8 shows a case where an Ir layer is used as the lower capacitor electrode 36.

PZ is formed on the lower capacitor electrode 36.
A capacitor dielectric film 37 made of T is formed,
An upper capacitor electrode 38 made of Pt, Ir, or IrOx is formed on the capacitor dielectric film 37. The lower capacitor electrode 36, the ferroelectric capacitor dielectric film 37 and the upper capacitor electrode 38 are
This constitutes a ferroelectric capacitor of FeRAM.

Next, a manufacturing process of the FeRAM of FIG. 8 will be described with reference to FIGS. 9 (A) to 12 (H).

Referring to FIG. 9A, the Si substrate 3
The element isolation structure 30A is formed in 1 by, for example, a shallow trench method to define an element region.

Then, on the element region defined by the element isolation structure 30A, the gate electrode 33 formed via the gate insulating film 32 and the gate are formed in the same manner as in the usual MOS transistor formation method. Diffusion regions 31 formed in the Si substrate 31 on both sides of the electrode 33.
A and 31B are formed to form a memory cell transistor of FeRAM.

Next, in the step of FIG. 9B, a silicon oxide film is deposited on the Si substrate 31 on which the memory cell transistors are formed by, for example, the CVD method to form the interlayer insulating film 34. Further, the surface of the interlayer insulating film 34 thus formed is polished by CMP (Chemical Mechanical Polishing) or the like to flatten the surface of the interlayer insulating film 34.

Further, in the step of FIG. 9B, the interlayer insulating film 34 is formed by the lithography technique and the etching technique.
Contact hole 34a reaching the diffusion region 31A
And the interlayer insulating film 3 is formed in the step of FIG.
A tungsten (W) film is deposited on the surface 4 by a sputtering method or the like so as to fill the contact hole 34a, and then polished by a CMP method until the surface of the interlayer insulating film 34 is exposed. As a result, the contact hole 34
A conductive plug 34A embedded in a is formed in a state of being electrically connected to the diffusion region 31A.

In the step of FIG. 9C, a W film is further deposited on the interlayer insulating film 34 by a sputtering method or the like, and is patterned by a lithography technique and an etching technique. A bit line BL connected to the diffusion region 31A via the sex plug 34A is formed.

Next, in the step of FIG. 10D, for example, C is formed on the interlayer insulating film 34 on which the bit BL line is formed.
A silicon oxide film is deposited by the VD method to form another interlayer insulating film 35. Further, a contact hole 35b penetrating the underlying interlayer insulating film 34 and reaching the diffusion region 31B is formed in the interlayer insulating film 35 by the lithography technique and the etching technique.

Further, in the step of FIG. 10E, after depositing a W film on the interlayer insulating film 35 by, for example, a sputtering method or the like, polishing is performed by a CMP method until the surface of the interlayer insulating film 35 is exposed, and a contact is made. Conductive plug 3 filling hole 35b and electrically connected to diffusion region 31B
5B is formed.

In the step of FIG. 10E, the barrier metal forming the lower capacitor electrode 36 and the lower electrode layer 360 are further deposited on the interlayer insulating film 35 by the sputtering method.

Next, in the step of FIG. 11F, the MOCVD apparatus 20 of FIG. 3 is used to form Pb (DPM) ₂ , Zr (DMHD) ₄ , Ti (iPr) on the lower electrode layer 360.
MOCV using organic metal raw materials such as (O) ₂ (DPM) ₂
The PZT film 370 is formed by the D method. At that time, in the present embodiment, the decomposition cylinder 26A of the MOCVD apparatus is
The temperature is controlled at 450 ° C., preferably at a temperature of 300 to 400 ° C., to suppress precipitation due to decomposition of the organometallic raw material in the decomposition cylinder 26A.

Further, in the step of FIG. 11G, a Pt, Ir, or IrOz film is deposited on the PZT film 370 by a sputtering method, and the upper electrode layer 380 is formed.
To form.

Finally, in the step of FIG. 12H, the films 360 to 360 are formed by lithography and etching techniques.
The lower capacitor electrode 36, the ferroelectric capacitor insulating film 37 and the upper capacitor electrode 37 are formed by patterning 380 to obtain the structure described above with reference to FIG.

As described above, according to this embodiment, the MOCV
The D method makes it possible to continuously mass-produce semiconductor devices having a ferroelectric film such as FeRAM.

Although the present invention has been described with reference to the preferred embodiments, the present invention is not limited to the above embodiments, and various modifications and changes can be made within the scope of the claims. .

(Supplementary Note 1) A step of supplying a film forming gas containing an organometallic material and an oxidizing gas to the film forming chamber to deposit a ferroelectric film on the surface of the substrate to be processed held in the film forming chamber. In the method for manufacturing a semiconductor device including the step of depositing the ferroelectric film, the exhaust gas exhausted from the film forming chamber is provided in an exhaust system coupled to the film forming chamber. Including the step of detoxifying, the step of detoxifying the catalyst treatment device, such that the catalytic reaction of the organic solvent component contained in the film forming gas occurs, but more than the film forming processing temperature in the film forming chamber. A method for manufacturing a semiconductor device, which is carried out by maintaining a low temperature.

(Supplementary Note 2) The catalyst treatment device is 300
Appendix 1 characterized in that it is maintained at a temperature of ~ 450 ° C
A method for manufacturing a semiconductor device as described above.

(Supplementary Note 3) The temperature of the catalyst treatment device is
3. The method for manufacturing a semiconductor device according to appendix 2, wherein the method is maintained constant within a range of 100 ° C. or lower.

(Supplementary Note 4) In the film forming chamber, Pb (DPM) ₂ , Zr (DMHD) ₄ ,
Ti (O-iPr) ₂ (DPM) ₂ is supplied, The manufacturing method of the semiconductor device as described in any one of Claims 1-3 characterized by the above-mentioned.

(Supplementary Note 5) In the film forming chamber, as the organometallic raw material, Ba (THD) ₂ , Sr (THD) ₂ , T
i (O-iPr) ₂ (DPM) ₂ is supplied, The manufacturing method of the semiconductor device as described in any one of Additional remarks 1-3 characterized by the above-mentioned.

(Supplementary Note 6) Sr (THD) ₂ and Ru (EtC) are used as the organometallic raw materials in the film forming chamber.
P) ₂ is supplied, The manufacturing method of the semiconductor device as described in any one of appendixes 1-3 characterized by the above-mentioned.

(Supplementary Note 7) The catalyst treatment device is 300
The temperature is maintained at 400 to 400 ° C., and Sr [Ta (O-Et) ₆ ] ₂ and Bi are used as the organometallic raw materials in the film forming chamber.
(Ph) ₃ and Supplementary notes 1 to 3 characterized in that
9. The method for manufacturing a semiconductor device according to claim 1.

(Supplementary Note 8) A step of evacuating the film forming chamber by an exhaust system, and a film forming gas containing an organometallic raw material and an oxidizing gas were supplied to the film forming chamber and kept in the film forming chamber. A film forming method comprising a step of depositing a ferroelectric film on a surface of a substrate to be processed, wherein exhaust gas exhausted from the film forming chamber is catalytically reacted by a catalyst processing device provided in the exhaust system. Including the step of detoxifying, the step of detoxifying the catalyst treatment device, such that the catalytic reaction of the organic solvent component contained in the film forming gas occurs, but more than the film forming processing temperature in the film forming chamber. A film forming method, which is performed by maintaining a low temperature.

(Supplementary Note 9) The catalyst treatment device is 300
Note 8 characterized in that it is maintained at a temperature of ~ 450 ° C
The film forming method described.

(Supplementary Note 10) The film forming method according to Supplementary Note 9, wherein the temperature of the catalyst treatment device is kept constant within a range of 100 ° C. or lower.

(Supplementary Note 11) In the film forming chamber, Pb (DPM) ₂ , Zr (DMH) are used as the organic metal raw material.
D) ₄ , Ti (O-iPr) ₂ (DPM) ₂ is supplied, The film-forming method as described in any one of Additional notes 8-10 characterized by the above-mentioned.

(Supplementary Note 12) In the film forming chamber, Ba (THD) ₂ , Sr (THD) ₂ ,
Ti (O-iPr) ₂ (DPM) ₂ is supplied, The film-forming method in any one of Additional notes 8-10 characterized by the above-mentioned.

(Supplementary Note 13) Sr (THD) ₂ and Ru (EtC) are used as the organometallic raw materials in the film forming chamber.
P) ₂ is supplied, The film-forming method as described in any one of appendixes 8-10 characterized by the above-mentioned.

(Supplementary Note 14) The catalyst treatment device comprises
The temperature is maintained at 0 to 400 ° C., and Sr [Ta (O-Et) ₆ ] ₂ and B are used as the organometallic raw materials in the film forming chamber.
Supplementary note 8 characterized in that i (ph) ₃ is supplied.
10. The film forming method according to any one of 10.

(Supplementary Note 15) A film forming chamber, a raw material supply system for supplying a film forming gas containing an organometallic raw material to the film forming chamber, an oxidizing gas supply system for supplying an oxidizing gas to the film forming chamber, An exhaust system for exhausting the film forming chamber, the exhaust system being provided on an exhaust pump and a downstream side of the exhaust pump for decomposing a film forming gas exhausted from the film forming chamber by a catalytic reaction. And a catalyst treatment device which is maintained at a temperature lower than the film formation treatment temperature in the film formation chamber, such that a catalytic reaction of the film formation gas occurs. A film forming processing apparatus.

(Additional remark 16) The film removal processing apparatus according to additional remark 15, wherein the abatement device further comprises a dust collector on the downstream side of the catalyst processing device.

(Additional remark 17) The portion of the exhaust system from the film forming chamber to the abatement device is kept at a temperature higher than the crystallization temperature. Film processing equipment.

[0079]

According to the present invention, when the unreacted film-forming gas discharged from the film-forming chamber is decomposed in the catalyst-processing apparatus, the temperature of the catalyst-processing apparatus is set to the level of organic gas contained in the film-forming gas. By setting the temperature at which the catalytic reaction of the solvent component occurs, the organic solvent contained in the film-forming gas is decomposed,
It can be made harmless. Further, by setting the temperature of the catalyst treatment device lower than the film formation treatment temperature, decomposition and precipitation of the unreacted organometallic raw material in the catalyst treatment device is suppressed, and a semiconductor device having a ferroelectric film such as FeRAM is provided. Even when it is used in a process using a large amount of organic metal raw material such as the mass production process, the malfunction of the abatement device can be avoided.

[Brief description of drawings]

FIG. 1 is a diagram showing a configuration of a MOCVD apparatus used for MOCVD deposition of a conventional ferroelectric film.

FIG. 2 is a diagram illustrating a configuration of a cold trap used in the MOCVD apparatus of FIG. 1 and its problems.

FIG. 3 is a diagram showing a configuration of an MOCVD apparatus according to an embodiment of the present invention.

FIG. 4 is a diagram showing a configuration of a disassembling cylinder used in FIG.

FIG. 5 is a diagram illustrating an example of the present invention.

FIG. 6 is another diagram for explaining the embodiment of the present invention.

FIG. 7 is still another diagram for explaining the embodiment of the present invention.

FIG. 8 is a diagram showing a structure of an FeRAM according to a second embodiment of the present invention.

9A to 9C are views (No. 1) showing a manufacturing process of the FeRAM in FIG.

10 (D) to (E) are views (No. 2) showing a manufacturing process of the FeRAM of FIG. 8.

11 (F) to (G) are views showing a manufacturing process of the FeRAM in FIG. 8 (No. 3).

12H is a view (No. 4) showing the manufacturing process of the FeRAM in FIG. 8; FIG.

[Explanation of symbols]

10, 20 MOCVD apparatus 11 film forming chamber 11A susceptor 11B exhaust line 12 vaporizer 12 ₁ , 12 ₂ , 12 ₃ raw material container 12A raw material gas supply line 12B bypass lines 12a, 12b valve 13 gas mixer 13A oxidizing gas line 14 vacuum pump 15 Cold Trap 16, 26 Harmful Equipment 17 Heating Jacket 26A Decomposition Cylinder 26a Catalyst 30 FeRAM 30A Element Isolation Structure 31 Si Substrates 31A, 31B Diffusion Region 32 Gate Insulation Film 33 Gate Electrodes 34, 35 Interlayer Insulation Film 36 Lower Capacitor Electrode 37 Strong Dielectric capacitor insulating film 38 Upper capacitor electrode 360 Lower electrode layer 370 Ferroelectric film 380 Upper electrode layer

Continued front page    F term (reference) 5F045 AA04 AB31 AD08 AD09 AD10                       AE21 AF10 BB16 DC61 EE02                       EE05 EG01 EG07                 5F083 FR02 JA14 JA15 JA17 JA38                       JA43 JA45 MA06 MA17 MA19                       NA01 NA08 PR21 PR33

Claims (10)

[Claims] 1. A semiconductor including a step of supplying a film forming gas containing an organometallic raw material and an oxidizing gas to a film forming chamber to deposit a ferroelectric film on a surface of a substrate to be processed held in the film forming chamber. A method of manufacturing an apparatus, wherein the step of depositing the ferroelectric film renders exhaust gas exhausted from the film forming chamber harmless in a catalyst processing device provided in an exhaust system coupled to the film forming chamber. The step of detoxifying, the catalyst treatment device, such that a catalytic reaction of the organic solvent component contained in the film forming gas occurs,
However, the method for manufacturing a semiconductor device is performed by maintaining the temperature at a temperature lower than the film forming processing temperature in the film forming chamber. 2. The catalyst treatment device is 300 to 450 ° C.
The method for manufacturing a semiconductor device according to claim 1, wherein the temperature is maintained at the temperature. 3. The temperature of the catalyst treatment device is kept constant within a range of 100 ° C. or lower.
A method for manufacturing a semiconductor device as described above. 4. The organometallic raw material is used in the film forming chamber.
Pb (DPM) ₂, Zr (DMHD)_Four, Ti (O-
iPr)₂(DPM)₂Contracts characterized in that
Manufacturing of the semiconductor device according to any one of claims 1 to 3.
Build method. 5. The organometallic raw material is provided in the film forming chamber.
And Ba (THD) ₂, Sr (THD)₂, Ti (O-i
Pr)₂(DPM)₂Claims characterized in that
Manufacturing the semiconductor device according to any one of items 1 to 3.
Method. 6. The organometallic raw material is used in the film forming chamber.
Sr (THD) ₂And Ru (EtCP)₂Supplied by
Any one of claims 1 to 3 characterized in that
A method of manufacturing a semiconductor device according to the item. 7. The catalyst treatment device is 300 to 400 ° C.
The temperature of the film is kept at a temperature of Sr [Ta (O-Et) ₆ ] ₂ and Bi (ph) _{3 in the} film forming chamber.
Is supplied, among claims 1 to 3,
A method for manufacturing a semiconductor device according to any one of claims. 8. A film forming chamber, a raw material supply system for supplying a film forming gas containing an organometallic raw material to the film forming chamber, an oxidizing gas supply system for supplying an oxidizing gas to the film forming chamber, and the film forming process. An exhaust system for exhausting the chamber, the exhaust system comprising an exhaust pump, and a catalyst treatment device provided on the downstream side of the exhaust pump for decomposing a film forming gas exhausted from the film forming chamber by a catalytic reaction. The catalyst processing device is maintained at a temperature at which a catalytic reaction of the film forming gas occurs but lower than the film forming processing temperature in the film forming chamber. Membrane processing equipment. 9. The film forming processing apparatus according to claim 8, wherein the detoxifying apparatus further includes a dust collecting apparatus provided downstream of the catalyst processing apparatus. 10. The exhaust system according to claim 7, wherein a portion from the film forming chamber to the abatement device is kept at a temperature higher than the crystallization temperature. Membrane processing equipment.