JP3335492B2 - Thin film deposition equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a CVD (Chemical Vapo)
The present invention relates to a thin film deposition apparatus for forming various thin films on a substrate by a (r Deposition, chemical vapor deposition) method,
In particular, the present invention relates to improvement of a vaporizer and a reaction chamber constituting the deposition apparatus.

[0002]

2. Description of the Related Art In recent years, the integration of semiconductor memories and devices has been rapidly progressing. For example, in a dynamic random access memory (DRAM), the number of bits has been increased to four in three years.
It is a rapid pace of doubling. This is to achieve higher speed, lower power consumption, lower cost, and the like of the device. However, no matter how the degree of integration increases, DRA
The capacitor that is a component of M must have a certain capacitance. For this reason, it is necessary to reduce the thickness of the capacitor material. However, thinning of the conventionally used SiO ₂ material has already reached its limit. Therefore, a method of increasing the capacitance of a capacitor by changing the material to a material having a high dielectric constant has been attempted, and research for using a high dielectric constant material has recently attracted attention.

As the characteristics required for such a capacitor material, it is most important that the material has a high dielectric constant as described above and that the film can be made sufficiently thin, and that the leakage current is small. That is, it is necessary to use a high dielectric constant material, reduce the film thickness as much as possible, and minimize the leakage current. Generally, the film thickness is SiO ₂
It is a general development goal to make the equivalent film thickness less than 1 nm and to make the leak current density when applying 1.1 V less than the order of 10 ^-8 A / cm ² . From such a viewpoint, oxide-based dielectric films such as tantalum oxide, lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), strontium titanate, and barium titanate are formed by various film forming methods. Various studies have been conducted. Generally, in order to form a thin film on a capacitor electrode of a DRAM having a step, it is very advantageous in terms of process to form a film by a CVD method which has a good ability to adhere to an object having a complicated shape. However, at present, there is a serious problem that there is no CVD raw material having stable and good vaporization characteristics. This is mainly due to the use of β-diketone dipivaloylmethane (DP) which is frequently used as a raw material for CVD.
M) Due to the poor vaporization characteristics of the compound upon heating. Therefore, due to such drawbacks caused by the raw materials, a technique for forming a dielectric thin film having good performance and good production reproducibility has not yet been established.

Under such circumstances, the present inventors have proposed a CVD raw material which is obtained by dissolving a conventional solid raw material in an organic solvent called tetrahydrofuran (THF) and which has greatly improved vaporization property ( Japanese Patent Application No. 4-252836
issue). However, we have found that such CVD
Using a raw material, an attempt was made to fabricate a dielectric film using a conventional thin film deposition apparatus for a liquid raw material such as a SiO ₂ film manufacturing method (hereinafter, referred to as a liquid raw material CVD apparatus). It has been found that there are various problems on the device.

FIG. 23 shows a CV for a liquid material according to the prior art.
It is a schematic diagram which shows the schematic structure of D apparatus. Here, a solution in which Sr (DPM) ₂ as a solid material is dissolved in THF (tetrahydrofuran) is used as a liquid CVD material, and TTIP [Ti (OiC ₃ H ₇ ) ₄ ] and O use ₂ describes an example of forming a strontium titanate [SrTiO _3] film on the substrate. In FIG. 23, 1 is a dilution gas pipe, 2 is a dilution gas amount regulator, 3 is a connection pipe, 4 is a vaporizer, 5 is a liquid material container, and 6 is a liquid material supply device. And 18 is a pressure tube,
7 is a spray nozzle, 8 is a heater for a vaporizer, 9 is a throttle, 10 is a source gas transport pipe,
11 is a heater for a source gas transport pipe, 12 is a source gas supply hole, 13 is a reaction gas supply pipe, and 1
Reference numeral 4 denotes a heater for a reaction chamber, 15 denotes a reaction chamber, 16 denotes a heating stage, and 17 denotes a film forming substrate made of silicon or the like.

Next, the operation of the CVD apparatus shown in FIG. 23 will be described. After the vaporizer 4 is heated to a predetermined temperature of about 250 ° C. by the heater 8, the diluting inert gas is ejected from the periphery of the spray nozzle 7 into the vaporizer 4 at a constant flow rate by the diluent gas amount regulator 2. Here, when a liquid CVD material [Sr (DPM) ₂ / THF] is supplied at a constant flow rate from the liquid material supply device 6, the liquid CVD material flows around the edge portion of the spray nozzle 7 at a high speed with a high-speed dilution gas flow. Accordingly, the particles are roughly atomized, and collide with a wide area of the inner wall of the vaporizer 4 to be instantaneously vaporized. Vaporized gas is transported into the reaction chamber 15 through the raw material gas transport pipe 10, Ti raw material TTIP supplied by bubbling [Ti (O-i-C 3 H 7) 4] and an oxidizing gas (e.g., O _2, N ₂ O ). The mixed gas is introduced into the reaction chamber 15 maintained at a constant pressure,
By the CVD reaction on the surface of the substrate 17 heated by the
A T film [SrTiO ₃ ] is formed. Note that the mixed gas that has not contributed to the formation of the thin film is discharged to the outside via a vacuum pump from an exhaust unit (exhaust line).

[0007]

However, when a thin film is formed by using the above-described conventional CVD apparatus for a liquid source using such a CVD source, there are the following problems. (1) In order to supply the CVD source gas vaporized in the vaporizer kept at 250 ° C. to the reaction chamber without condensing and decomposing, the pipe from the vaporizer to the reaction chamber needs to be kept uniformly at 250 ° C. There is. Therefore, the pipe made of SUS tubes and valves is kept at 250 ° C. by a ribbon heater, but the heat dissipation from the ribbon heater to the outside air is large, so the thermal efficiency is poor, or the temperature uniformity in each part of the pipe is poor. There was a problem.

(2) The BST film obtained by the CVD method using a liquid raw material has a problem that it is difficult to obtain good reproducibility in composition and film quality due to deterioration of the raw material.
This is because there is no suitable in-situ monitoring system.

(3) The susceptor for supporting the substrate in the reaction chamber is conventionally made of C (carbon).
When a film is formed on about 0 substrates (wafers), the susceptor deteriorates due to oxidation of carbon, and the temperature of the substrate becomes non-uniform. However, there was a problem that the data changed.

(4) The temperature of the diffusion plate is determined by the amount of radiant heat from the heating stage and the amount of heat radiated to the cooling water on the gas head, but there is a problem that these cannot be freely controlled.

(5) The CVD source gas vaporized by the vaporizer is:
The film is mixed with the reaction gas and passes through the diffusion plate to form a film on the substrate.Reaction products that do not contribute to the film adhere to the reaction chamber walls, etc., resulting in foreign matter on the substrate. There was a problem that there is.

(6) The temperature at the bottom of the reaction chamber is relatively low, and reaction products that do not contribute to film formation tend to condense and adhere to the bottom. Then, there is a problem that foreign matter deposited on the bottom surface rises when the reaction chamber is evacuated or returned to the atmospheric pressure, and as a result, foreign matter may adhere to the substrate.

(7) Since the composition ratio of the CVD raw material which is vaporized by the vaporizer and sent into the reaction chamber is unstable, the composition ratio of the thin film formed on the substrate becomes unstable. there were.

(8) Since the liquid CVD raw material collides with the inner wall of the vaporizer and is vaporized, the raw material residue adheres to the inner wall of the vaporizer, and the powder of the adhered substance is scattered and mixed into the reaction chamber together with the raw material. There was a problem.

(9) When the raw material residue adheres to the inner wall of the vaporizer and becomes contaminated, there is a problem that it is inconvenient to clean the inner wall of the vaporizer.

The present invention relates to a conventional liquid material CVD apparatus,
In particular, the present invention has been made to solve the above-mentioned problems in a CVD apparatus using an organometallic compound, and stabilizes a vaporized CVD source during the vaporization of a liquid CVD source and during film formation. To prevent the generation of dust due to the condensation of the reaction product and the like, and to obtain a means capable of accurately forming a high-quality thin film with no composition deviation on the substrate. It is the purpose.

[0017]

In order to achieve the above object, a first aspect of the present invention is to provide a raw material container for holding a CVD raw material obtained by dissolving an organometallic complex in a solvent;
CVD having a liquid supply for supplying a constant amount of raw material, a vaporizer for heating and vaporizing the CVD raw material supplied from the liquid supply, and a reaction chamber for forming a thin film on a substrate using the vaporized CVD raw material In a thin film deposition apparatus by the method,
A mass spectrometer for detecting the concentration of the vaporized CVD raw material is provided, and a sampling section of the mass spectrometer is arranged facing a CVD raw material supply system between the vaporizer and the reaction chamber.

According to a second aspect of the present invention, there is provided a material container for holding a CVD material obtained by dissolving an organometallic complex in a solvent;
A liquid supply device for supplying a constant amount of the CVD material, a vaporizer for heating and vaporizing the CVD material supplied from the liquid supply device, and a reaction chamber for forming a thin film on a substrate using the vaporized CVD material. In the apparatus for depositing a thin film by the CVD method, a light absorption cell for detecting the concentration of a vaporized CVD material is provided, and a sampling unit of the light absorption cell faces a CVD material supply system between a vaporizer and a reaction chamber. It is characterized by being arranged.

According to a third aspect of the present invention, there is provided a material container for holding a CVD material obtained by dissolving an organometallic complex in a solvent,
A liquid supply device for supplying a constant amount of the CVD material, a vaporizer for heating and vaporizing the CVD material supplied from the liquid supply device, and a reaction chamber for forming a thin film on a substrate using the vaporized CVD material. An apparatus for depositing a thin film by a CVD method having an atomizing mechanism for atomizing a liquid CVD raw material supplied to a vaporizer is provided.

According to a fourth aspect of the present invention, there is provided a material container for holding a CVD material obtained by dissolving an organometallic complex in a solvent,
A liquid supply device for supplying a constant amount of the CVD material, a vaporizer for heating and vaporizing the CVD material supplied from the liquid supply device, and a reaction chamber for forming a thin film on a substrate using the vaporized CVD material. In the apparatus for depositing a thin film by the CVD method, the vaporizer is formed in a cylindrical shape,
It is characterized in that the CVD material is formed so as to be introduced in a tangential direction of the vaporizer.

According to a fifth aspect of the present invention, there is provided a raw material container for holding a CVD raw material obtained by dissolving an organometallic complex in a solvent,
A liquid supply device for supplying a constant amount of the CVD material, a vaporizer for heating and vaporizing the CVD material supplied from the liquid supply device, and a reaction chamber for forming a thin film on a substrate using the vaporized CVD material. In the apparatus for depositing a thin film by a CVD method, the vaporizer has a replaceable inner wall.

According to a sixth aspect of the present invention, there is provided a raw material container for holding a CVD raw material obtained by dissolving an organometallic complex in a solvent,
A liquid supply device for supplying a constant amount of the CVD material, a vaporizer for heating and vaporizing the CVD material supplied from the liquid supply device, and a reaction chamber for forming a thin film on a substrate using the vaporized CVD material. In a thin film deposition apparatus using a CVD method, a cleaning liquid supply system for supplying a cleaning liquid to a vaporizer and a cleaning mechanism for cleaning an inner wall of the vaporizer with the cleaning liquid without opening and closing the vaporizer are provided. I do.

According to a seventh aspect of the present invention, there is provided a material container for holding a CVD material obtained by dissolving an organometallic complex in a solvent,
A liquid supply device for supplying a constant amount of the CVD material, a vaporizer for heating and vaporizing the CVD material supplied from the liquid supply device, and a reaction chamber for forming a thin film on a substrate using the vaporized CVD material. In the apparatus for depositing a thin film by the CVD method, a cleaning mechanism for sputter etching cleaning the inner wall of the vaporizer without opening and closing the vaporizer is provided.

According to an eighth aspect of the present invention, in the thin film deposition apparatus according to the seventh aspect, the inner wall of the vaporizer and the upper plate of the vaporizer are coated with the same material as the thin film formed on the substrate. It is characterized by having been done.

According to a ninth aspect of the present invention, there is provided a raw material container for holding a liquid CVD raw material, a liquid supply device for supplying the CVD raw material in the raw material container to the vaporizing section in a liquid state, In a thin film deposition apparatus by a CVD method having a vaporizer for evaporating the supplied liquid CVD raw material to a high temperature and a reaction chamber for forming a thin film on a substrate using the vaporized CVD raw material, A box is provided,
A vaporizer and a pipe from the vaporizer to the reaction chamber are housed in the constant temperature box.

According to a tenth aspect of the present invention, in the thin film deposition apparatus according to the ninth aspect, a KBr window to which a high-temperature N ₂ gas is blown is provided in the reaction chamber, and the inside is formed in the reaction chamber. A film quality analysis system for irradiating infrared light from outside the reaction chamber to the thin film through the above KBr window and analyzing the film quality of the thin film by infrared absorption spectroscopy (FT-IR) analysis while forming the thin film is provided. It is characterized by.

According to an eleventh aspect of the present invention, in the thin film deposition apparatus according to the ninth aspect, a Be window through which high-temperature N ₂ gas is blown is provided in the reaction chamber, and the Be window is formed in the reaction chamber. The thin film is irradiated with X-rays from the outside of the reaction chamber through the Be window and the fluorescent X-rays (X
A film quality analysis system for analyzing the film quality of the thin film by RF) analysis is provided.

According to a twelfth aspect of the present invention, in the thin film deposition apparatus according to the ninth aspect, a quartz window through which high-temperature N ₂ gas is blown is provided in the reaction chamber, and the quartz window is formed in the reaction chamber. A film quality analysis system for irradiating polarized light from the outside of the reaction chamber to the thin film through the above quartz window and analyzing the film quality of the thin film by surface light absorption method (SPA) analysis while continuing to form the thin film is provided. It is characterized by.

According to a thirteenth aspect of the present invention, there is provided the thin film deposition apparatus according to the ninth aspect, wherein
Mass spectrometer for detecting the amount of decomposition products from CVD raw materials
(QMS) is provided.

According to a fourteenth aspect of the present invention, in the thin film deposition apparatus according to the ninth aspect, the susceptor for supporting the substrate is made of boron nitride (BN).

According to a fifteenth aspect of the present invention, in the thin film deposition apparatus according to the ninth aspect, a thermocouple for detecting a temperature of the substrate is arranged on an outer peripheral portion of a susceptor supporting the substrate. And

According to a sixteenth aspect of the present invention, in the thin film deposition apparatus according to the ninth aspect, a heater for controlling the temperature of the diffusion plate in the reaction chamber is provided.

A seventeenth aspect of the present invention is the thin film deposition apparatus according to the ninth aspect, wherein the inner wall of the reaction chamber has a double structure having a hollow portion, and a cooling medium for supplying a cooling medium to the hollow portion. Means are provided.

According to an eighteenth aspect of the present invention, in the thin film deposition apparatus according to the ninth aspect, the inner wall of the reaction chamber is made of Si.
It is characterized by being coated with O ₂ .

According to a nineteenth aspect of the present invention, in the thin film deposition apparatus according to the ninth aspect, the TEOS supply system for supplying TEOS into the reaction chamber by bubbling every time a predetermined number of thin films are formed. It is characterized by being provided.

According to a twentieth aspect of the present invention, in the thin film deposition apparatus according to the ninth aspect, the HF supply system for supplying HF into the reaction chamber by bubbling every time a predetermined number of thin films are formed. It is characterized by being provided.

According to a twenty-first aspect of the present invention, in the thin film deposition apparatus according to the ninth aspect, a replaceable dust-preventing mesh is provided at the bottom of the reaction chamber.

[0038]

According to the first aspect of the present invention, a CVD method is employed in which a mass spectrometer sends a vapor from a vaporizer into a reaction chamber during film formation.
The concentration of the raw material is constantly monitored, and the liquid composition (flow rate controller) can be automatically controlled to adjust the film composition ratio.

According to a second aspect of the present invention, a light absorbing cell
(FT-IR) constantly monitors the concentration of the CVD raw material fed into the reaction chamber from the vaporizer during film formation,
The liquid composition (flow rate controller) can be automatically controlled to adjust the film composition ratio.

According to the third aspect of the present invention, since the liquid CVD material is atomized before entering the vaporizer by the atomizing mechanism, uniform fine droplets are formed before the liquid CVD material enters the vaporizer. Becomes

According to the fourth aspect of the present invention, the vaporizer has a cylindrical shape, and the liquid CVD raw material is introduced in a tangential direction (circumferential direction) together with the carrier gas.
When the raw material is discharged in the direction of the central axis of the vaporizer, dusts such as vaporized residues adhere to the inner wall of the vaporizer.

According to the fifth aspect of the present invention, since the replaceable inner wall is provided in the vaporizer, it is possible to remove the deposits on the inner wall of the vaporizer by replacing the internal wall after the film formation is completed. it can.

According to the sixth aspect of the present invention, the cleaning liquid can be supplied into the vaporizer after the film formation is completed, and the inner wall can be cleaned without opening and closing the vaporizer.

According to the seventh aspect of the present invention, the inner wall of the vaporizer is sputter-etch-cleaned by providing a flat plate on the inner wall of the vaporizer and generating plasma after the film formation is completed. The inner wall can be cleaned without opening and closing the vaporizer.

According to the eighth aspect of the present invention, basically the same operation as in the seventh aspect occurs. Further, since the inner wall of the vaporizer and the upper plate of the vaporizer are coated with the same material as the thin film formed on the substrate, sputter etching cleaning is promoted.

According to the ninth aspect of the present invention, since the vaporizer and the piping from the vaporizer to the reaction chamber are all housed in the constant temperature box on the reaction chamber, the system is simplified and the thermal efficiency is reduced. Enhanced.

According to the tenth aspect of the present invention, basically, the same operation as in the ninth aspect occurs. Furthermore, the film quality during film formation was determined by infrared absorption spectroscopy (FT-IR) analysis.
Since the analysis is performed in tu, the film quality of the thin film can be monitored, and the film quality can be controlled during the film formation.

According to the eleventh aspect of the present invention, basically the same operation as in the ninth aspect occurs. Furthermore, since the film quality during film formation is analyzed in situ by X-ray fluorescence (XRF) analysis, the film quality of the thin film can be monitored,
The film quality can be controlled during the film formation.

According to the twelfth aspect of the present invention, basically, the same operation as in the ninth aspect occurs. Further, the quality of the film during the film formation is determined in situ by the surface light absorption method (SPA method) analysis.
Therefore, the quality of the thin film can be monitored, and the quality of the thin film can be controlled during the film formation.

According to the thirteenth aspect of the present invention, basically the same operation as in the ninth aspect is produced. Further, the mass spectrometer (QMS) provided in the exhaust unit is used to supply THF and Sr.
Since the amount of decomposition products from the CVD raw material such as (DPM) ₂ is detected (monitored), an abnormality in the raw material supply amount or the like is immediately detected.

According to the fourteenth aspect of the present invention, basically, the same operation as in the ninth aspect occurs. Further, since the susceptor conventionally made of C (carbon) is made of BN having high oxidation resistance, deterioration of the susceptor is suppressed.

According to the fifteenth aspect of the present invention, basically, the same operation as in the ninth aspect occurs. Further, since a thermocouple conventionally provided on the back surface of the heater is provided in the susceptor, temperature monitoring can be performed at a position close to the substrate.

According to the sixteenth aspect of the present invention, basically, the same operation as in the ninth aspect occurs. Furthermore, a heater is provided on the diffusion plate, and the temperature of the diffusion plate can be controlled, so that the temperature of the diffusion plate can be made to match the temperature of the vaporizer under any film forming conditions.

According to the seventeenth aspect of the present invention, basically, the same operation as in the ninth aspect occurs. Further, since the reaction chamber has a double wall, and a cooling medium is introduced into the inside of the reaction chamber, the reaction chamber wall is cooled, reaction products and the like are condensed on the reaction chamber wall, and dust generation is suppressed.

According to the eighteenth aspect of the present invention, basically, the same operation as in the ninth aspect occurs. Further, since the inner wall of the reaction chamber is covered with SiO ₂ , reaction products and the like are less likely to adhere to the inner wall of the reaction chamber, and generation of dust is suppressed.

According to the nineteenth aspect of the present invention, basically, the same operations as in the ninth aspect occur. Further, every time a predetermined number of thin film formations are performed, TE is formed by bubbling.
Since the OS is supplied into the reaction chamber, and thereby the inner wall of the reaction chamber is coated with SiO ₂ , reaction products and the like hardly adhere to the inner wall of the reaction chamber, and dust generation is suppressed.

According to the twentieth aspect of the present invention, basically, the same operations as in the ninth aspect occur. Further, each time a predetermined number of thin film formations are performed, HF is bubbled.
Is supplied into the reaction chamber, thereby cleaning the inner wall of the reaction chamber, thereby suppressing dust generation.

According to the twenty-first aspect of the present invention, basically, the same operation as in the ninth aspect occurs. Further, since a replaceable dust suppression mesh is provided at the bottom of the reaction chamber, dust generation is suppressed.

[0059]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. <First Embodiment> First, a first embodiment of the present invention will be specifically described with reference to the accompanying drawings. In the first embodiment,
Ba (DPM) ₂ , Sr (D
(Ba, Sr) TiO ₃ [BS] using a solution of PM) ₂ and TiO (DPM) ₂ dissolved in THF (tetrahydrofuran).
T] An example of forming a thin film on a substrate is shown. In addition, the description which overlaps with the above-mentioned conventional technology will be appropriately omitted.

FIG. 1 shows a CV according to a first embodiment of the present invention.
FIG. 1 is a schematic configuration diagram of a thin film deposition apparatus (CVD apparatus) by a D method. In FIG. 1, reference numeral 20 denotes a mass spectrometer provided with a sampling unit facing the source gas transport pipe 10 between the vaporizer 4 and the reaction chamber 15. Other configurations are the same as those of the conventional CVD apparatus shown in FIG.

Next, the operation of the CVD apparatus will be described. The procedure of film formation in this CVD apparatus is the same as in the prior art. Then, during the film formation, the CVD is vaporized by the vaporizer 4 and supplied to the reaction chamber 15 through the source gas transport pipe 10.
A part of the mixture of the raw material and the carrier gas is sampled and analyzed (monitored) by the mass spectrometer 20.
FIG. 8 shows an example of a signal obtained when _two molecules of Sr (DPM) of the Sr-based raw material are measured by a mass spectrometer. In the data shown in FIG. 8, the ratio between the signal intensity of the mass number m / z = 397 and the signal intensity of the carrier gas N ₂ (m / z = 28) or Ar (m / z = 40) whose absolute amount is known is obtained. The concentration of Sr can be calculated. Further, the concentrations of Ba and Ti can be calculated in the same manner. The mass flow controller of the liquid material supply device 6 is adjusted based on the Ba, Sr, and Ti concentrations calculated as described above, and a target flow rate of the CVD material is determined.

As described above, in the CVD apparatus according to the first embodiment, since the mass spectrometer 20 is provided in the pipe between the vaporizer 4 and the reaction chamber 15, the reaction chamber
Ba, Sr, and Ti concentrations in the CVD raw material supplied to the apparatus can be monitored. Thereby, the ratio of Ba, Sr, and Ti in the thin film (BST film) formed on the substrate can be stabilized.

<Second Embodiment> A second embodiment of the present invention will be specifically described below with reference to the accompanying drawings. In the second embodiment, a solid material Ba (DP
An example in which a BST thin film is formed using a solution in which M) ₂ , Sr (DPM) ₂ , and TiO (DPM) ₂ are dissolved in THF (tetrahydrofuran) will be described. In addition, the description which overlaps with the above-mentioned conventional technology will be appropriately omitted. FIG. 2 is a schematic configuration diagram of a CVD apparatus according to the second embodiment. In FIG.
Reference numeral 21 denotes a light source of an infrared absorption analysis (FT-IR) device, 22 to 25 are KBr windows, 26 is an infrared absorption tube, and 27 is an infrared ray emitted from the light source 21 of the FT-IR device. , and the the 28 and the 29 are in respectively spectrometer FT-IR apparatus and detectors 30-35 are off valve 36 supplies N ₂ gas in the infrared absorption tube 26 N ₂ gas supply Reference numeral 37 denotes an exhaust pipe for evacuating the infrared absorption pipe 26.

Next, the operation of the CVD apparatus will be described. First, the open / close valves 30 and 31 are closed. And
While the on-off valve 33 is closed, the on-off valve 34 is opened to evacuate the infrared absorption tube 26 from the exhaust pipe 37. After the evacuation is sufficiently performed, the open / close valve 34 is closed. Next, the on-off valves 32 and 35 are closed while the on-off valve 3 is closed.
By opening 0 and 31, the CVD raw material vaporized by the vaporizer 4 is introduced into the reaction chamber 15 through the infrared absorption tube 26. The infrared ray 27 emitted from the FT-IR light source 21 passes through the CVD raw material in the infrared absorption tube 26 and is detected by the spectroscope 28 and the detector 29. 9 (a) to 9 (c) show T
Ba (DPM) ₂ , Sr (DPM) ₂ , TiO (DPM) ₂
1 shows an example of an infrared absorption spectrum of a solution in which is dissolved. In FIG. 9, Ba (DPM) ₂ and Sr (DPM) ₂ are 145.
From the absorption peak at 0 cm ^-1 , TiO (DPM) ₂ was 1520 cm
^The molar concentration can be calculated from the absorption peak at ^-1 or 650 cm ^-1 , respectively. Further, the carrier gas N ₂
Considering the flow rate of Ba (DPM) ₂ , Sr (DPM) ₂ , Ti
The supply amount of O (DPM) ₂ can be calculated. The mass flow controller of the liquid material supply device 6 is adjusted based on the Ba, Sr, and Ti concentrations calculated as described above, and a target flow rate of the CVD material is determined. The infrared absorption tube 26 is heated and kept at the same temperature as the source gas transport tube 10. Further, in order to prevent fogging due to the adhesion of the raw material residue on the KBr windows 22 and 25, another single KBr windows 23 and 24 are provided inside these. K inside
Since the windows 23 and 24 made of Br have a higher temperature than the windows 22 and 25 made of KB on the outside, condensation of the CVD raw material vapor does not occur. When the measurement is completed, the open / close valve 34 is opened and the infrared absorption tube 26 is opened.
Is sufficiently evacuated, and the on-off valve 34 is closed while the on-off valve 33 is opened to introduce N ₂ into the infrared absorption tube 26. During normal film formation, the opening and closing valves 32 and 35 are opened while the opening and closing valves 30 and 31 are closed, and film formation is performed in the same procedure as in the related art.

As described above, in the CVD apparatus according to the second embodiment, since the infrared absorption tube 26 is provided between the vaporizer 4 and the reaction chamber 15, the infrared absorption analysis method is used.
During the film formation, the concentration of the CVD raw material supplied to the reaction chamber 15 can be monitored. This stabilizes the ratio of Ba, Sr, and Ti in the BST film.

<Third Embodiment> A third embodiment of the present invention will be specifically described below with reference to the accompanying drawings. FIG.
It is a schematic structure figure of a CVD device concerning a 3rd example. In FIG. 3, reference numeral 38 denotes a liquid material supply device 6 and a liquid material container 5.
And 7a is a pressure atomizing nozzle.

Next, the operation of the CVD apparatus will be described. For example, Ba (DP) supplied from the liquid material container 5
CVD raw material liquid comprising the M) ₂ from a solution dissolved in THF at a concentration of 0.1 mol / litter is pressurized to 2-5 atm by a compressor 38, nozzle pressure atomizing through a liquid material supply unit 6 It is atomized by 7a. The atomized liquid CVD raw material is easily heated and vaporized by the vaporizer 4 and introduced into the reaction chamber 15 without generating a residue.

As described above, in the CVD apparatus according to the third embodiment, since the liquid CVD raw material is atomized before being vaporized in the vaporizer 4, the residue generated in the vaporizer 4 can be reduced. Can be.

<Fourth Embodiment> Hereinafter, a fourth embodiment of the present invention will be described in detail with reference to the accompanying drawings. FIG.
It is a schematic structure figure around a vaporizer of a CVD device concerning a 4th example. In FIG. 4, reference numeral 39 denotes a cylindrical vaporizer, and reference numeral 40 denotes a liquid CVD device in a tangential direction (circumferential direction) of the cylinder.
A nozzle 41 for blowing the raw material and the carrier gas is provided. Reference numeral 41 denotes a raw material gas transport pipe for exhausting the CVD raw material gas from the central axis direction of the cylindrical vaporizer 39. 42 is the nozzle 4
CVD of liquid blown into the vaporizer 39 vigorously from 0
It is a mixed flow (swirl) of a raw material and a carrier gas.

Next, the operation of the CVD apparatus will be described. The CV of the liquid which is vigorously blown tangentially with the inert carrier gas into the vaporizer 39 from the nozzle 40
The D raw material is vaporized while flowing along the inner wall of the cylindrical vaporizer 39 by centrifugal force, and the vaporized CVD raw material vapor is sucked into the central exhaust pipe 41 and then introduced into the reaction chamber 15. At this time, even if dust or powder is generated in the vaporizer 4, they are attached to the inner wall of the vaporizer 39 by centrifugal force, and are prevented from entering the reaction chamber 15 from the central exhaust pipe 41.

As described above, in the CVD apparatus according to the fourth embodiment, the generated dust or powder adheres to the inner wall of the vaporizer, so that the generation of dust in the vaporizer 39 is suppressed, and Dust or powder is prevented from entering.

<Fifth Embodiment> Hereinafter, a fifth embodiment of the present invention will be described in detail with reference to the accompanying drawings. FIG.
It is a schematic structure figure of a CVD device concerning a 5th example. In FIG. 5, reference numeral 43 denotes a removable inner wall plate provided on the inner wall of the vaporizer 4.

Next, the operation of the CVD apparatus will be described. In this CVD apparatus, after the film formation, the upper half of the vaporizer 4 is removed, and the inner wall plate 43 is replaced. Thereby, the raw material residue attached to the inner wall of the vaporizer can be easily removed.

As described above, in the CVD apparatus according to the fifth embodiment, since the inside of the vaporizer can be easily purified by replacing the inner wall plate 43 after the film formation, the maintenance time is shortened and the throughput is increased.

<Sixth Embodiment> Hereinafter, a sixth embodiment of the present invention will be described in detail with reference to the accompanying drawings. FIG.
It is a schematic structure figure of a CVD device concerning a 6th example. In FIG. 6, reference numeral 44 denotes a cleaning liquid container for holding a cleaning liquid such as THF, for example, 45 denotes a pressure tube, and 46 to 48.
Is an opening / closing valve, and 49 is an exhaust pump for evacuating the vaporizer 4.

Next, the operation of the CVD apparatus will be described. In this CVD apparatus, after the film formation is completed, the open / close valve 47 is closed and the open / close valve 46 is opened, and the inside of the vaporizer 4 is evacuated by the exhaust pump 49 while the cleaning liquid is injected into the vaporizer 4. Thereby, the raw material residue adhering to the inner wall of the vaporizer is decomposed by the cleaning liquid, and is sucked out of the vaporizer by the exhaust pump 49.

As described above, in the CVD apparatus according to the sixth embodiment, the cleaning liquid is poured into the inside of the vaporizer after the film formation,
By evacuating with the exhaust pump 49, the inside of the vaporizer can be easily purified without opening and closing the vaporizer. It is also effective to use a hydrofluoric acid aqueous solution as the cleaning liquid. In this case, it is preferable to use a material having a strong acid resistance such as stainless steel or copper as the material of the vaporizer 4.

<Seventh Embodiment> Hereinafter, a seventh embodiment of the present invention will be described in detail with reference to the accompanying drawings. FIG.
It is a schematic structure figure around a vaporizer of a CVD device concerning a 7th example. In FIG. 7, 50 is a conductive vaporizer lower plate whose inner surface is coated with Ti, 51 is a vaporizer lower plate heater wrapped in an insulator for heating the vaporizer lower plate 50, 52 is a high-frequency power supply, 53 is a conductive vaporizer upper plate, 54 is a heater for the vaporizer upper plate whose inner surface is coated with Ti, 55 is a source gas transport pipe, and 56 is Reference numeral 57 denotes a heater for a source gas transport pipe, reference numeral 57 denotes a discharge gas supply pipe, reference numeral 58 denotes an exhaust pipe of the vaporizer 4, reference numeral 59 denotes a liquid source supply pipe, and reference numeral 60 denotes a liquid source supply pipe.
And 61 are insulator materials in which the pipes 57 to 59 are embedded.

Next, the operation of the CVD apparatus will be described. In this CVD apparatus, the exhaust pipe 58
After the interior of the vaporizer is sufficiently evacuated, the discharge gas is introduced from the discharge gas supply pipe 57, and the high frequency power supply 52 is turned on.
Set to N. Then, the vaporizer upper plate 53 and the vaporizer lower plate 5
Discharge using 0 as an electrode occurs, and plasma is generated.
Then, the raw material residue adhering to the inner wall of the vaporizer is removed by the sputtering by the plasma. At this time, since the inner surface of the vaporizer 4 is covered with Ti, there is no fear that a part of the inner wall becomes a contamination component of the BST film due to sputtering.

As described above, in the CVD apparatus according to the seventh embodiment, the inner wall of the vaporizer can be cleaned without opening / closing the vaporizer 4 by generating plasma after film formation and performing sputter etching. .

<Eighth Embodiment> Hereinafter, an eighth embodiment of the present invention will be described in detail with reference to the accompanying drawings. here,
Ba (DPM) ₂ , which is a solid material as a liquid CVD material,
Using a solution obtained by dissolving Sr (DPM) ₂ and TiO (DPM) ₂ in THF (tetrahydrofuran), forming a (Ba, Sr) TiO ₃ [BST] film on the substrate using O ₂ and N ₂ O. An example of coating will be described. In addition, the description which overlaps with the above-mentioned conventional technology will be appropriately omitted.

FIG. 10 is a schematic configuration diagram of a CVD apparatus according to the eighth embodiment. In FIG. 10, reference numeral 71 denotes a vent-side valve, 72 denotes a reaction chamber-side valve, 73 denotes a source gas vent line, 74 denotes a constant temperature box, 75 denotes a mixer, and 76 denotes a diffusion plate. , 77
Is a susceptor, 78 is a reflector, and 79 is a thermocouple.

Next, the operation of the CVD apparatus will be described. Conventionally, as shown in FIG. 23, for example, the vaporizer 4 is arranged around the reaction chamber 15. However, in the eighth embodiment, the vaporizer 4 is arranged at a constant temperature box 74 installed above the reaction chamber 15. And all the piping from the vaporizer 4 to the reaction chamber 15 is housed in a constant temperature box 74.
These pipes are heated by a ribbon heater, and the inner wall of the constant temperature box 74 is formed of a heat insulating material. Liquid CVD raw materials (Ba (DPM) ₂ , Sr
(DPM) ₂ , TiO (DPM) ₂ + THF) and carrier gas
(N ₂ gas) is supplied from the raw material gas transport pipe 10 to the vaporizer 4 and collides with a wide range of the inner wall of the vaporizer 4 and is instantaneously vaporized. First, the vaporized CVD source gas is allowed to flow to the vent side by opening the vent side valve 71 and closing the reaction chamber side valve 72. Thereafter, the vent valve 71 is changed to the closed state while the reaction chamber valve 7 is closed.
By changing 2 to the open state, the CVD source gas flows to the reaction chamber side. Thereby, the CVD source gas is supplied to the mixer 7.
5, mixed with an oxidizing gas (for example, O ₂ , N ₂ O) and heated on the surface of the film forming substrate 17 by the heating stage 16,
The formation of the BST film is started by the CVD reaction.

As described above, C according to the eighth embodiment
In the VD apparatus, since the vaporizer 4 and the piping from the vaporizer 4 to the reaction chamber 15 are all housed in the constant temperature box 74 on the reaction chamber, the liquid source vaporization system is simplified. Further, the temperature of the piping from the vaporizer 4 to the reaction chamber 15 can be relatively easily made uniform. Further, since the inner wall of the constant temperature box is formed of a heat insulating material, the amount of heat radiation from the ribbon heater is reduced, and the thermal efficiency is improved.

<Ninth Embodiment> Hereinafter, a ninth embodiment of the present invention will be described in detail with reference to a CVD apparatus shown in FIG. In FIG. 11, reference numeral 80 denotes an IR light source, 81 denotes a polarizer, 82 denotes IR light (p-polarized light), and 83 denotes IR light.
Reference numeral 84 denotes a window for transmitting IR light (KBr, etc.).
Reference numeral 85 denotes a purge N ₂ gas, and reference numeral 86 denotes a cover.

Next, the operation of the CVD apparatus will be described. Here, the surface formed by the incident light on the thin film surface during film formation and the normal line set at the light incident point on the thin film surface is called an incident surface, and the light oscillating in that surface is parallel polarized light ( (P wave). In the parallel polarized light, the electric vector of the incident light and that of the reflected light reinforce each other on the surface of the thin film, thereby generating a stationary vibration electric field perpendicular to the surface of the thin film. Then, the standing wave acts on the component molecules of the thin film, and the light is absorbed. Here, a purge N ₂ gas 85 flows between the inner wall of the reaction chamber and the cover 86, thereby preventing the CVD raw material gas and its decomposition products from adhering to the window 84. During the film formation, light absorption on the surface of the thin film is observed in-situ to monitor whether the film formation is performed with good reproducibility. Further, by estimating the film formation reaction mechanism, it is possible to control the film formation parameters and to form a higher quality BST film.

As described above, the C according to the ninth embodiment is
The VD system has a system that can analyze the film quality of the thin film in situ by infrared absorption spectroscopy (FT-IR) analysis during the film formation process, so that the film can be formed with high reproducibility. In addition, the film formation reaction mechanism can be estimated, and a higher quality BST film can be obtained by controlling the film formation parameters.

<Tenth Embodiment> Hereinafter, a tenth embodiment of the present invention will be described in detail with reference to a CVD apparatus shown in FIG. In FIG. 12, reference numeral 87 denotes an X-ray tube, 88 denotes continuous X-rays, 89 denotes characteristic X-rays of elements in the thin film, 90 denotes spectrally separated characteristic X-rays, and 91 denotes an X-ray window.
(Be etc.), 92 is a spectral crystal, 93 is a detector, and 94 is a goniometer.

Next, the operation of the CVD apparatus will be described. In this CVD apparatus, an X-ray tube 8 is placed on a thin film being formed.
When the continuous X-ray 88 generated in step 7 is irradiated, electrons in the K and L shells of the atoms in the thin film are repelled (photoelectric effect), and the repelled electrons are knocked out of the atoms. In this way, the atoms are excited. Electrons fall from the outer shell into the vacancy formed in the K or L shell, and return from the excited state to the steady state. At this time, the inner shell that created the vacancy with the outer shell
X-rays corresponding to the energy difference (K shell or L shell in this case) are irradiated. This is the characteristic X-ray 89 of the element in the thin film.
It is. Be or the like can be used for the X-ray window 91, and the spectral crystal 92 and the detector 93 in the goniometer 94 can be used.
The characteristic X-ray 90 is detected by adjusting the angle with
In-situ composition analysis is performed during film formation. When the composition analyzed in-situ is different from the target value, the supply amount of the raw material solution is adjusted.

As described above, in the CVD apparatus according to the tenth embodiment, during the film formation process, the XR
Since it has a system that can perform F analysis,
Film formation can be performed with good reproducibility, and a film formation reaction mechanism can be estimated. A BST film with higher quality can be obtained by controlling film formation parameters.

<Eleventh Embodiment> Hereinafter, an eleventh embodiment of the present invention will be described in detail with reference to a CVD apparatus shown in FIG. In FIG. 13, reference numeral 95 denotes a Xe lamp;
6 is p-polarized light, 97 is a synthetic quartz window, and 98 is a photodetector.

Next, the operation of the CVD apparatus will be described. Surface light absorption method used in this CVD apparatus
(Surface-Photo Absorption, SPA) is Brewster
At an incident angle close to the angle, light polarized in the plane of incidence (p-polarization) 96
Is applied to the surface of the thin film on which the film is being formed, and the intensity of the reflected light is monitored. The feature of the SPA method is that only the light intensity is monitored. Synthetic quartz is used as the material of the window 97, and a purge N ₂ gas 85 is supplied to the window 97 as in the case of the ninth embodiment, so that the raw material gas and decomposition products adhere to the window. Is prevented.

As described above, in the CVD apparatus according to the eleventh embodiment, the film composition is adjusted in-situ during the film formation process.
Because it has a system that can perform A analysis,
Film formation can be performed with good reproducibility, and a film formation reaction mechanism can be estimated. A BST film with higher quality can be obtained by controlling film formation parameters.

<Twelfth Embodiment> Hereinafter, a twelfth embodiment of the present invention will be described in detail with reference to a CVD apparatus shown in FIG. In FIG. 14, 99 is a mass spectrometer (QMS), and 100 is an orifice heater.

Next, the operation of the CVD apparatus will be described. In this CVD apparatus, a mass spectrometer 99 is installed between the exhaust part of the reaction chamber 15 and the exhaust rotary pump,
Analyze the decomposition products of exhaust gas. Orifice 100
Has a diameter of 0.3 mm, and the CVD source gas having a low temperature and a low vapor pressure is easily clogged by the orifice 100. Therefore, the orifice 10 is heated by the orifice heater.
0 is heated to 250 ° C. to prevent clogging.

As described above, in the CVD apparatus according to the twelfth embodiment, the source gas and decomposition products in the exhaust part during film formation can be analyzed in situ, so that the source gas is supplied with high reproducibility. It is possible to confirm whether or not the film formation is performed, and furthermore, it is possible to estimate the film formation reaction mechanism, so that film formation with good reproducibility can be performed, and a high quality BST film can be obtained by controlling the film formation parameters. .

<Thirteenth Embodiment> Hereinafter, a thirteenth embodiment of the present invention will be described in detail with reference to a CVD apparatus shown in FIG. In FIG. 15, reference numeral 101 denotes a BN susceptor.

Next, the operation of the CVD apparatus will be described. Conventionally, a BST film is formed on a substrate (wafer) placed on a C (carbon) susceptor. In this case, C is gradually oxidized and deteriorated in a high-temperature oxygen atmosphere. Therefore, the susceptor is made of BN (boron nitride) to increase the oxidation resistance and to prevent the deterioration. Also, while the thermal conductivity of C is 0.08 cal / cm · sec · ° C,
The thermal conductivity of BN is 0.06 cal / cm.sec..degree. C., and there is not much difference between them, so that the temperature distribution on the substrate is almost the same as the conventional one.

As described above, in the CVD apparatus according to the thirteenth embodiment, the susceptor 101 is made of BN having oxidation resistance and high thermal conductivity.
Is not deteriorated, and a stable and reproducible film is formed over a long period of time.

<Fourteenth Embodiment> Hereinafter, a fourteenth embodiment of the present invention will be described in detail with reference to a CVD apparatus shown in FIG. In FIG. 16, reference numeral 102 denotes a thermocouple installed on the susceptor 77.

Next, the operation of the CVD apparatus will be described. In a conventional CVD apparatus, temperature is measured by a thermocouple installed on the bottom of a heating stage, and heating to the heating stage is performed based on this signal. However, in this case, if the susceptor is made of C (carbon), the susceptor will deteriorate if left in a high-temperature oxygen atmosphere for a long period of time. The surface or substrate surface temperature will be different. Therefore, in the CVD apparatus according to the fourteenth embodiment, the installation location of the thermocouple 102 was changed to the outer peripheral portion of the susceptor 77.

As described above, in the CVD apparatus according to the fourteenth embodiment, the location of the thermocouple 102 is
7, the temperature can be monitored in a place close to the substrate 17, and a stable and reproducible film can be formed over a long period of time while always maintaining the same wafer temperature.

<Fifteenth Embodiment> Hereinafter, a fifteenth embodiment of the present invention will be described in detail with reference to a CVD apparatus shown in FIG. In FIG. 17, reference numeral 103 denotes a heater for a diffusion plate, and 104 denotes cooling water.

Next, the operation of the CVD apparatus will be described. In this CVD apparatus, the temperature of the diffusion plate 76 is determined by radiant heat from the heating stage 16 and heat radiation to the cooling water 104. Therefore, in order to replenish the supplied heat amount when the amount of radiated heat is small, heaters 103 for the diffuser plate are installed at four places around the diffuser plate 76. Therefore, the temperature of the diffusion plate 76 can be controlled under any film forming conditions.

As described above, in the CVD apparatus according to the fifteenth embodiment, since the heaters 103 for the diffusion plate are installed at four locations around the diffusion plate 76, the diffusion plate 76 The temperature can be controlled to the same temperature as the vaporizer 4 (for example, 250 ° C.).

<Sixteenth Embodiment> Hereinafter, a sixteenth embodiment of the present invention will be described in detail with reference to a CVD apparatus shown in FIG. In FIG. 18, reference numeral 105 denotes a cooling water outlet,
106 is a cooling water inlet, and 107 is cooling water.

Next, the operation of the CVD apparatus will be described. In this CVD apparatus, the inner wall of the reaction chamber 15 has a double structure, and the cooling water 10
7 is injected and discharged from the cooling water outlet 105. by this,
The temperature of the inner wall of the reaction chamber becomes lower than room temperature, and the raw material gas and the reaction product having a low vapor pressure condense on the inner wall of the reaction chamber. In addition, liquid nitrogen (77 ° K) or liquid helium (4 °
The vapor of K) may be used.

As described above, in the CVD apparatus according to the sixteenth embodiment, the inner wall of the reaction chamber has a double structure, and by cooling the inside thereof, the source gas and the reaction product having a low vapor pressure can be removed. , And the generation of dust and the like is suppressed, and a long-term stable continuous film formation becomes possible.

<Seventeenth Embodiment> Hereinafter, a seventeenth embodiment of the present invention will be described in detail with reference to a CVD apparatus shown in FIG. In FIG. 19, reference numeral 108 denotes a reaction chamber wall coated with SiO ₂ .

Next, the operation of the CVD apparatus will be described. The present inventors have found that BST film formation by a CVD method using a liquid raw material is dependent on the substrate material. In other words, there is a substrate material dependence such that the deposition rate of the CVD-BST film is lower on the surface of SiO ₂ than on the surface of Pt or Poly-Si. Therefore, the entire reaction chamber wall 108 was coated with SiO ₂ .

As described above, in the CVD apparatus according to the seventeenth embodiment, since the entire reaction chamber wall 108 is covered with SiO ₂ , the amount of deposits on the reaction chamber wall 108 is reduced and dust generation is suppressed. As a result, a stable and reproducible film can be formed over a long period of time.

<Eighteenth Embodiment> Hereinafter, an eighteenth embodiment of the present invention will be described in detail with reference to a CVD apparatus shown in FIG. In FIG. 20, reference numeral 109 denotes a nitrogen gas for bubbling, 110 denotes a TEOS bubbler, and 111 denotes an automatic pressure controller (Auto-Pressure-Controller, A).
PC), and 112 is a 120 ° C. heat keeping pipe.

Next, the operation of the CVD apparatus will be described. In this CVD apparatus, as in the case of the seventeenth embodiment, the inner wall of the reaction chamber is covered with SiO ₂ , thereby reducing the amount of deposits on the inner wall of the reaction chamber and suppressing the amount of dust generation. However, every time the BST film is formed, the source gas or its reaction product gradually adheres to SiO ₂ , and the surface S 2
Io ₂ will be covered. Therefore, every time about 60 films are formed, a nitrogen gas for bubbling 1 is supplied from the TEOS bubbler 110.
In step 09, TEOS is bubbled into the reaction chamber, and the inner wall of the reaction chamber is again covered with SiO ₂ . TEOS bubbler 110
The temperature of the pipe 112 is set to 120 ° C. or higher in order to prevent TEOS from condensing in the path from the reaction chamber 15 to the reaction chamber 15.

As described above, in the CVD apparatus according to the eighteenth embodiment, the TEOS
TEOS is bubbled into the reaction chamber by the bubbling nitrogen gas 109 from the bubbler 110, the inner wall of the reaction chamber is always covered with SiO ₂ , the amount of deposits on the inner wall of the reaction chamber is reduced, the amount of dust generation is suppressed, and long-term stability is achieved. This makes it possible to form a film with good reproducibility.

<Nineteenth Embodiment> Hereinafter, a nineteenth embodiment of the present invention will be described in detail with reference to a CVD apparatus shown in FIG. In FIG. 21, reference numeral 113 denotes an HF bubbler.

Next, the operation of the CVD apparatus will be described. In this CVD apparatus, every time about 60 films are formed, a nitrogen gas 109 for bubbling is supplied from the HF bubbler 113.
Bubbling HF into the reaction chamber to wash the inside of the reaction chamber.

As described above, in the CVD apparatus according to the nineteenth embodiment, the interior of the reaction chamber can be cleaned with HF, the amount of dust generated is suppressed, and a long-term stable reproducible composition is obtained. A membrane becomes possible.

<Twentieth Embodiment> A twentieth embodiment of the present invention will be specifically described below with reference to a CVD apparatus shown in FIG. In FIG. 22, reference numeral 114 denotes a dust generation suppression mesh.

Next, the operation of the CVD apparatus will be described. In this CVD apparatus, a dust suppression mesh 114 is provided at the bottom of the reaction chamber, and the gas flowing out to the exhaust part passes through the dust suppression mesh 114. Are mostly captured by the dust generation suppressing mesh 114. Further, the dust generation suppressing mesh 114 can be exchanged, and by exchanging every time when several tens of sheets are formed, it is possible to remove foreign matter that has conventionally accumulated in the exhaust part, and to reduce the amount of dust generation. it can.

As described above, in the CVD apparatus according to the twentieth embodiment, the mesh 11 for suppressing dust generation is provided at the bottom of the reaction chamber.
Since the number 4 is installed, by exchanging the film every time when several tens of films are formed, it is possible to remove the foreign matter conventionally accumulated in the exhaust part and reduce the amount of dust generation.

[0121]

According to the first aspect of the present invention, the concentration of the CVD raw material fed into the reaction chamber from the vaporizer during film formation is constantly monitored by the mass spectrometer. The film composition ratio can be adjusted by automatic control, and the composition ratio of the thin film is stabilized.

According to a second aspect of the present invention, a light absorbing cell
(FT-IR) constantly monitors the concentration of the CVD raw material sent from the vaporizer into the reaction chamber during film formation, so it is possible to automatically control the liquid feeder (flow rate controller) to adjust the film composition ratio. In addition, the composition ratio of the thin film is stabilized.

According to the third aspect of the present invention, the liquid CVD source is atomized before entering the vaporizer by the atomizing mechanism, so that the uniform fine droplets are formed before the liquid CVD source enters the vaporizer. And the amount of raw material residue on the inner wall of the vaporizer is reduced.

According to the fourth aspect of the present invention, the vaporizer is cylindrical, and the liquid CVD raw material is introduced in the tangential direction (circumferential direction) together with the carrier gas.
If the raw material is discharged in the direction of the central axis of the vaporizer, dust such as vaporized residue adheres to the inner wall of the vaporizer, thereby preventing the dust from entering the reaction chamber.

According to the fifth aspect of the present invention, since the replaceable inner wall is provided in the vaporizer, it is possible to remove the deposits on the inner wall of the vaporizer by replacing the inner wall after the film formation is completed. The removal of the deposits is facilitated.

According to the sixth aspect of the present invention, the cleaning liquid can be supplied into the vaporizer after the film formation is completed, and the inner wall thereof can be cleaned without opening and closing the vaporizer. Mixing into the reaction chamber is prevented.

According to the seventh aspect of the present invention, the inner wall of the vaporizer is sputter-etch-cleaned by providing a flat plate on the inner wall of the vaporizer and generating plasma after the film formation is completed. In addition, the inner wall of the vaporizer can be cleaned without opening and closing the vaporizer, thereby preventing foreign substances (contamination) from entering the reaction chamber.

According to the eighth aspect of the present invention, basically the same effects as in the seventh aspect can be obtained. Furthermore, since the inner wall of the vaporizer and the electrodes are coated with the same material as the thin film formed on the substrate, sputter etching cleaning is promoted.

According to the ninth aspect of the present invention, since the vaporizer and the piping from the vaporizer to the reaction chamber are all housed in the constant temperature box on the reaction chamber, the system is simplified and the thermal efficiency is reduced. Increased cost is reduced.

According to the tenth aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Further, the film quality during film formation is determined by infrared absorption spectroscopy (FT-IR) analysis.
Since the analysis is performed in situ, the quality of the thin film can be monitored, and the quality of the thin film can be controlled during the film formation, so that a high-quality thin film can be obtained.

According to the eleventh aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Furthermore, since the film quality during the film formation is analyzed in situ by X-ray fluorescence (XRF) analysis, the film quality of the thin film can be monitored, and the film quality can be controlled during the film formation. can get.

According to the twelfth aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Furthermore, the quality of the film during film formation was confirmed by the surface light absorption method (SPA method) analysis.
Since the analysis is performed in tu, the quality of the thin film can be monitored, and the quality of the thin film can be controlled during the film formation, so that a high-quality thin film can be obtained.

According to the thirteenth aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Further, the mass spectrometer (QMS) provided in the exhaust unit is used to obtain THF,
Detects the amount of decomposition products from CVD raw materials such as r (DPM) ₂
Since (monitoring) is performed, abnormality of the raw material supply amount or the like is immediately detected, and a high-quality thin film with good reproducibility is obtained.

According to the fourteenth aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Further, since the susceptor conventionally made of C (carbon) is made of BN having high oxidation resistance, deterioration of the susceptor is suppressed, and a stable and reproducible high-quality thin film can be obtained.

According to the fifteenth aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Furthermore, since the thermocouple previously installed on the back of the heater is provided inside the susceptor, temperature monitoring can be performed at a position close to the substrate, and a high-quality thin film with long-term stability and good reproducibility can be obtained. .

According to the sixteenth aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Further, a heater is provided on the diffusion plate, and the temperature of the diffusion plate can be controlled, so that the temperature of the diffusion plate can be made to match the temperature of the vaporizer under any film forming conditions, and high reproducibility can be obtained. A high quality thin film can be obtained.

According to the seventeenth aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Further, since the reaction chamber wall has a double structure and a cooling medium is introduced into the inside thereof, the reaction chamber wall is cooled, reaction products and the like are condensed on the reaction chamber wall, and generation of dust is suppressed. Long-term stable continuous film formation becomes possible.

According to the eighteenth aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Further, since the inner wall of the reaction chamber is coated with SiO ₂ , reaction products and the like hardly adhere to the inner wall of the reaction chamber, dust generation is suppressed, and a high-quality thin film that is stable over the long term and has good reproducibility can be obtained. .

According to the nineteenth aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Further, every time a predetermined number of thin film formations are performed, T
Since EOS is supplied into the reaction chamber and thereby the reaction chamber walls are coated with SiO ₂ , reaction products and the like hardly adhere to the reaction chamber walls, dust generation is suppressed, and long-term stable reproducibility is obtained. Good and high quality thin films can be obtained.

According to the twentieth aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Further, every time a predetermined number of thin film formations are performed, H
Since F is supplied into the reaction chamber and thereby the inside of the reaction chamber is washed, dust generation is suppressed, and a high-quality thin film that is stable over the long term and has high reproducibility can be obtained.

According to the twenty-first aspect of the present invention, basically the same effects as in the ninth aspect can be obtained. Further, since a replaceable dust-preventing mesh is provided at the bottom of the reaction chamber, dust is suppressed, and stable continuous film formation over a long period of time becomes possible.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 2 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 3 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 4 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 5 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 6 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 7 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 8 is a diagram showing an example of a result of analyzing a CVD raw material by a mass spectrometer.

FIG. 9 is a view showing an example of a measurement result of an infrared absorption spectrum of a CVD raw material.

FIG. 10 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 11 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 12 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 13 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 14 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 15 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 16 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 17 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 18 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 19 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 20 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 21 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 22 is a schematic configuration diagram of a CVD apparatus showing one embodiment of the present invention.

FIG. 23 is a schematic configuration diagram of a conventional liquid source CVD apparatus.

[Explanation of symbols]

1 dilution gas pipe, 2 dilution gas volume controller, 3 connection pipe,
4 vaporizer, 5 liquid raw material container, 6 liquid raw material feeder,
Reference Signs List 7 spray nozzle, 7a nozzle for pressure atomization, 8 heater, 9 throttle section, 10 source gas transport pipe, 11 heater, 12 source gas supply hole, 13 reaction gas supply pipe, 14 heater, 15 reaction chamber, 16 Heating stage, 17 film-forming substrate, 18 pressure tube, 20 mass spectrometer, 21 FT-IR light source, 22-25 KBr window,
26 infrared absorption tube, 27 infrared ray, 28 FT-IR
Spectrometer, 29 FT-IR detector, 30-35 open / close valve, 36 N ₂ gas supply pipe, 37 exhaust pipe, 38 compressor, 39 cylindrical vaporizer, 40 nozzle, 4
1 raw material gas transport pipe, 42 mixed flow of carrier gas and raw material, 43 inner wall plate, 44 cleaning liquid container, 45 pressurized pipe,
46-48 open / close valve, 49 exhaust pump, 50 carburetor lower plate, 51 heater, 52 high frequency power supply, 53
Upper plate of vaporizer, 54 Heater, 55 Source gas transport pipe, 56 Heater, 57 Discharge gas supply pipe, 58
Exhaust pipe, 59 liquid material supply pipe, 60-61 insulating material,
71 Vent side valve, 72 Reaction chamber side valve, 73
Vent line for raw material gas, 74 constant temperature box, 75
Mixer, 76 diffuser, 77 susceptor, 78 reflector, 79 thermocouple, 80 IR light source, 81 polarizer, 82 IR light (p-polarized), 83 IR light detector, 84
IR window (KBr, etc.), 85 Nitrogen gas for purge, 86
Cover, 87 X-ray tube, 88 continuous X-ray, 89 characteristic X-ray of element in thin film, 90 spectral X-ray, 91
X-ray window (Be etc.), 92 spectral crystal, 93 detector, 9
4 Goniometer, 95 Xe lamp, 96 p polarized light, 9
7 Synthetic quartz window, 98 photodetector, 99 mass spectrometer
(QMS), 100 Heater for orifice, 101
BN susceptor, 102 thermocouple, 103 heater for diffusion plate, 104 cooling water, 105 cooling water outlet, 106
Cooling water inlet, 107 cooling water, 108 reaction chamber wall, 1
09 Nitrogen gas for bubbling, 110 TEOS bubbler, 111 APC, 112 120 ° C heat insulation pipe, 11
3 HF, 114 Dust prevention mesh.

────────────────────────────────────────────────── ─── Continuation of the front page Examiner Koichi Kato (56) References JP-A-4-22126 (JP, A) JP-A-2-261529 (JP, A) JP-A-48-71399 (JP, A) JP-A-58-86719 (JP, A) JP-A-3-18016 (JP, A) JP-A-3-245524 (JP, A) JP-A-4-98784 (JP, A) JP-A-4-333570 ( JP, A) JP-A-4-354326 (JP, A) JP-A-5-136120 (JP, A) JP-A-5-90246 (JP, A) JP-A-5-291152 (JP, A) JP-A-6-102247 (JP, A) JP-A-6-291040 (JP, A) JP-A-6-310444 (JP, A) JP-A-7-94426 (JP, A) JP-A-6-346243 (JP) JP-A-6-349747 (JP, A) JP-A-8-508315 (JP, A) WO 94/21840 (WO, 1) (58) investigated the field (Int.Cl. ^7, DB name) H01L 21/31 C23C 16/18 C23C 16/52 H01L 21/205 H01L 21/316

Claims (2)

(57) [Claims] 1. A C obtained by dissolving an organometallic complex in a solvent.
A raw material container for holding the VD raw material, a liquid supply for supplying the CVD raw material in a fixed amount, and a CV supplied from the liquid supply
A vaporizer for heating and vaporizing the D raw material, and a vaporized CVD
An apparatus for depositing a thin film by a CVD method having a reaction chamber for forming a thin film on a substrate by using a raw material, wherein the vaporizer has a replaceable inner wall. 2. A compound obtained by dissolving an organometallic complex in a solvent.
A raw material container for holding the VD raw material, a liquid supply for supplying the CVD raw material in a fixed amount, and a CV supplied from the liquid supply
A vaporizer for heating and vaporizing the D raw material, and a vaporized CVD
In a thin film deposition apparatus by a CVD method having a reaction chamber for forming a thin film on a substrate using a raw material, a cleaning mechanism for sputter etching cleaning the inner wall of the vaporizer without opening and closing the vaporizer is provided. An apparatus for depositing a thin film, wherein the upper plate of the vaporizer is coated with the same material as the thin film formed on the substrate.