JPH1066823A - Vapor phase chemical vapor deposition apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly efficient germanium membrane solar cell by reducing impurities in a membrane to 1ppm or less by supplying high purity germanium gas with impurity content of 1ppm or less. SOLUTION: In a vapor phase chemical vapor deposition apparatus consisting of a gas supply line, a reaction chamber and vacuum exhaust equipment, a plurality of a vacuum exhaust equipments consisting of the vacuum exhaust equipment directly connected to the reaction chamber and a vacuum exhaust equipment of a separate system diffrerent therefrom are provided and, at the same time, an adsorbent packed cylinder for removing impurities contained in gas is provided and branch lines are provided at the outlet of the packed cylinder and one of them is the line connected to the reaction chamber through a gas mass flow rate controller to supply a membrane forming gas and the other one line is the adsorbent regenerating line connected to the vacuum exhaust equipment of the separate system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an electronic device product using a thin film formed in a reaction chamber by a chemical vapor deposition method. More specifically,
By installing an adsorption device (adsorbent-filled cylinder) that removes impurities contained in the gas, a thin film is formed with a clean gas, and regeneration of the adsorption device can be performed without flowing impurities into the reaction chamber. The present invention relates to a chemical vapor deposition apparatus.

[0002]

2. Description of the Related Art Electronic devices using silicon semiconductors are used in many current electronic products. These electronic devices cover a very wide range of fields, such as diodes, transistors, solar cells, and TFTs. In addition, silicon semiconductors can also be classified based on their material aspects such as crystalline, polycrystalline, and amorphous. In addition to these products, products using surface coatings such as reflectors and transparent materials are also widespread in products using thin films, and are extremely diverse.

[0003] Among them, monosilane gas, which is important in the semiconductor industry, has reached an industrially sufficient level in terms of its impurity reduction, and there is no problem in practical use. However, the amount of other gases used is limited, and there are still some industrially insufficient control of impurities.

On the other hand, there is a germanium-based semiconductor like a silicon semiconductor, and a germanium gas is usually used to form this germanium-based semiconductor thin film. On the other hand, the germanium semiconductor has a band gap of 1.1 eV for crystalline silicon and a band gap of 0.6 eV for crystalline germanium, and is developed into various fields due to the difference in the band gap.

A typical example of an electronic device using germanium is an amorphous solar cell.
1.7-1.8 eV optical band gap of amorphous silicon
It is. Therefore, a solar cell using only an amorphous silicon thin film shows the maximum sensitivity at around 500 nm, and its wavelength sensitivity ranges from 350 nm to around 800 nm.

On the other hand, in a solar cell using a silicon-germanium amorphous alloy thin film, which is an alloy of germanium and silicon, the optical band gap is reduced in accordance with the proportion of germanium, and the optical band gap is reduced. The sensitivity of long-wavelength light increases with a decrease.

Therefore, by forming a tandem-type solar cell in which an amorphous silicon thin film having excellent short-wavelength sensitivity and an amorphous silicon germanium thin film having excellent long-wavelength sensitivity are connected in series, a wide range of wavelengths can be obtained. Therefore, it should be possible to obtain a high current value and, consequently, to form a solar cell with high conversion efficiency. Therefore, there is an increasing demand for germane gas for forming a silicon germanium thin film.

[0008]

However, the amorphous silicon germanium thin film generally has a higher defect density than the amorphous silicon thin film, so that carriers generated by light irradiation can be effectively taken out. There was a problem that it would not be possible. There is a problem that the quality of the silicon germanium thin film decreases as the ratio of germanium increases, and solving this problem has been a problem for forming a highly efficient solar cell.

This is a problem due to the semiconductor of germanium, and at the same time, the silicon germanium semiconductor thin film itself contains more impurities such as oxygen than the silicon semiconductor thin film. It has become clear. Then, in addition to the impurity gas generated inside the thin film formation chamber for performing the film formation, the present inventors have found that the germane gas itself may have the impurity. It was recognized that.

Here, if a thin film can be formed using germane gas containing no impurities, a high quality silicon germanium semiconductor thin film should be formed.
Furthermore, these things are the same for other gases, and in order to improve the quality of the thin film, it is very important to improve the quality of the source gas for forming the thin film. Things come into view.

Then, when germane gas used for forming a thin film was introduced into a thin film forming chamber equipped with a quadrupole mass spectrometer, an analysis result corresponding to the mass could be obtained. Using this quadrupole mass spectrometer, from the results of analysis from mass 1 to 60, apart from mass 1 considered to be a hydrogen peak and mass near mass 36 considered to be a germane double peak, Only peaks corresponding to mass 18 assumed to be water were observed. On the other hand, it was confirmed that the peak of mass 18 was 5 times as high as the mass spectrometry result (background) measured without flowing any gas. Thus 1000
It was confirmed that the water content was close to ppm.

As described above, in a germanium-based thin film formed using germanium gas containing impurities, impurities are taken into the thin film in accordance with the amount of impurities contained in germanium gas. We have found that in order to form a high quality germanium-based thin film, it is necessary to improve the purity of germane gas introduced into the thin film forming apparatus.

[0013] However, at present, the purchased germane gas is usually used as it is in the existing piping as it is, and it has not been involved in the problem of the purity of the supplied germane gas. Therefore, it was a problem to be solved to construct a system capable of supplying high-purity germane gas.

[0014]

According to the present invention, there is provided (1) a vapor-phase chemical vapor deposition apparatus comprising a gas supply line, a reaction chamber, and a vacuum exhaust system, wherein a vacuum exhaust system directly connected to the reaction chamber is provided. At the same time as having a plurality of vacuum evacuation equipment consisting of a system vacuum evacuation equipment, an adsorbent filling cylinder for removing impurities contained in the gas, and a branch line at the outlet of the filling cylinder, One line is a line for supplying a thin film forming gas connected to the reaction chamber via a gas mass flow controller, and the other one line is connected to the other vacuum evacuation equipment. A vapor-phase chemical vapor deposition apparatus characterized in that it is a line for regenerating adsorbents, (2) the filling cylinder has a double-pipe structure,
At the same time, the lower tube has a structure in which the inner tube sealed with a porous sintered body protrudes from the bottom of the tube to the outside of the tube, and the outer ring is filled with an adsorbent. Vapor phase chemical vapor deposition apparatus according to (1), wherein (3)
The filling cylinder can be cooled to -80 ° C or less,
It has a structure that can be heated to 400 ° C or higher, and the gas that has passed through this cylinder during cooling is supplied to a gas mass flow controller, and is supplied to another vacuum exhaust system during heating. (4) The gas-phase chemical vapor deposition apparatus according to (1), wherein the adsorbent is composed of a synthetic zeolite having a pore diameter of 4 mm or less. Is a gas-phase chemical vapor deposition apparatus according to any one of (1) to (4), which contains germane gas, and (6) a vapor-phase chemical vapor deposition apparatus described in (5), which is used by removing water in germane gas to 1 ppm or less. It is a phase chemical vapor deposition apparatus.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows a schematic diagram of a vapor phase chemical vapor deposition apparatus for carrying out the present invention. The vapor phase chemical vapor deposition apparatus includes a thin film forming chamber 10 and a germane gas supply system. A substrate 11 is set in the thin film forming chamber 10, and a thin film is formed on the substrate. The substrate is placed on the substrate holder 12, and the germane gas supplied from the germane gas supply system is decomposed into film-forming species,
It is formed on a substrate.

In FIG. 1, a plasma CVD method using a plasma formed between the electrode 13 and the substrate holder 12 is used to decompose the germane gas. However, as a method for decomposing germane gas, there is a method using heat (thermal CVD method), light (optical CVD method), or the like.

Further, a partial pressure vacuum gauge 14 is attached to the thin film forming chamber 10 so that components of germane gas and impurity gas can be divided and measured and quantified for each mass.

The germane gas supplied to the thin film forming chamber 10 and remaining without being consumed in the thin film forming chamber is evacuated by an exhaust system 15 for the thin film forming chamber.

The gas supply system for supplying germane gas includes an adsorbent filling cylinder 21, a gas line for a thin film forming chamber, and a regeneration gas line 24.

The gas line 23 for the thin film formation chamber is composed of a plurality of gas switching valves 28 and a gas flow controller 25 for the thin film formation chamber. The operation of adjusting the gas flow rate of the source gas and supplying it to the thin film formation chamber is performed.

Similarly, the regeneration gas line includes a plurality of gas switching valves 28 and a regeneration gas flow controller 26. The gas line is for use during regeneration of the adsorbent, and helium, neon,
An inert gas such as argon is supplied. The carrier gas passes through a plurality of gas switching valves and a regeneration gas flow controller, flows into the regeneration vacuum exhaust system 27, and is exhausted out of the system.

As described above, when the raw material gas has passed through the adsorbent-filled cylinder, impurities are removed to the thin film forming chamber, and the purified gas is deposited using the gas line for the thin film forming chamber. When the adsorbent supplied to the formation chamber and regenerated in the adsorbent-filled cylinder is to be regenerated, a regeneration gas line is used while passing the carrier gas. This cutting of the line is performed by the valve 28.

Furthermore, it is desirable that the adsorbent-filled cylinder is cooled when the raw material gas passes through and is supplied to the thin film forming chamber. The cooling method is performed by a general temperature controller. In the case of a low temperature such as −80 ° C., it is general to use alcohol or the like into which dry ice has been charged. When used at around 0 ° C., it may be performed with ice water.

On the other hand, the cylinder filled with the adsorbent is heated to 15
By evacuating and flowing a carrier gas such as helium at a temperature of 0 ° C. or more, the gas adsorbed on the adsorbent can be completely desorbed and regenerated. The degree of vacuum at this time is desirably 1 × 10 ⁻² Torr or less.
More desirably, the pressure is set to 1 × 10 ⁻³ Torr or less.

The desorption may be performed while flowing a carrier gas such as helium at a temperature of 150 ° C. or higher, but the effect is obtained by performing the desorption while performing vacuum evacuation. High desorption can be performed.

As described above, since there is a cycle in which the low temperature and the high temperature are alternately repeated, it is possible to continuously use while performing adsorption and desorption alternately.

Cylinder filled with adsorbent (adsorbent filled cylinder) 21
Is installed immediately before the branch point between the gas line for the thin film formation chamber and the gas line for regeneration. And this adsorbent filled cylinder
It is necessary to have equipment for purifying the raw material gas and the adsorbent.

The adsorbent to be filled in the adsorbent-filled cylinder is made of synthetic zeolite having a pore diameter of 4 mm or less, and these are supplied as molecular sieves (manufactured by Showa Union Co., Ltd.) as trade names. Things.

In order to be applied to the present invention as a molecular sieve, it must be determined in consideration of the molecular diameter of germane gas. Since the molecular diameter of the germane gas molecule is about 4.8 °, the pore size of the synthetic zeolite needs to be smaller than about 4.8 °.

At the same time, the molecular diameter of the water molecule is 2.8 °, and the pore diameter needs to be large enough to capture the water molecule. Furthermore, it is necessary to determine the molecular sieve to be used in consideration of the fact that the molecular diameter of oxygen is 3.0 ° and the molecular diameter of nitrogen is 2.8 °.

The molecular sieves have a pore size of 3 mm.
And molecular sieves 3A and molecular sieves 4A, respectively, which can be used for this purpose.

It is preferable to use molecular sieves 3A in order to remove only water in the germane gas, and it is preferable to use molecular sieves 4A in order to remove oxygen and nitrogen. Thus, it is preferable to appropriately select an adsorbent according to the purpose.

FIG. 2 shows a sectional structural view of the adsorbent-filled cylinder.
It was shown to. Tube body 31 must withstand vacuum
At the same time, from -80 ° C to at least 400 ° C
Have the strength to withstand temperature changes when heated
Is required and must be made of metal such as SUS or Al
Is preferred. For vacuum, the leak rate is 10 ^-9
It is preferably at most Torr / sec. This is 0.1T
When flowing gas under orrr pressure conditions, 10^-7
Keeping the amount of impurities below Torr below
The amount of impurities such as oxygen, nitrogen and water
This is a favorable requirement to keep it below 1 ppm.
You.

In order to maintain the above conditions, it is preferable that the inside of the cylinder is sufficiently polished by electrolytic polishing.

Two tubes are connected to the tube, and a short tube
32 is connected to the top of the absorbent-filled tube, and a longer tube 33 is inserted down to the bottom of the tube. These tubes are preferably made of metal such as SUS or Al as in the case of the main body, and are preferably electrolytically polished. Furthermore, a sintered body 32 made of porous glass is provided at the end of each tube.
a and 33a are attached. This is intended to prevent the powder of the adsorbent to be filled from diffusing into the gas line.

This cylinder has a screw-type cap 34 at the top.
The adsorbent can be filled in the tube by removing the cap. Preferably, this cap also withstands vacuum sufficiently and in the range of -80 ° C to at least 400 ° C.
For this purpose, it is preferable to use a metal gasket or the like. VCR connector and I
Must be joined by FC flange.

It is possible to cope with various changes in the composition of the filled adsorbent depending on the type of these adsorbents. Further, adsorbent-filled cylinders filled with different adsorbents may be arranged in series as shown in FIG.

Since the cylinder filled with the adsorbent is installed before the gas mass flow controller, the pressure difference inside the cylinder during supply of the raw material gas does not become large, and is at most about 10 Torr. Therefore, the source gas can pass through the adsorber for a sufficient time, which is sufficient for impurities to be adsorbed and removed.

The length of the adsorption layer depends on the supply rate of the raw material gas,
It is determined by the relationship with the cross-sectional area of the adsorption layer. In general, the flow rate of a source gas by a chemical vapor deposition method is a standard state (1 at.
m, 0 ° C) and sccm (stand
ard cc per minutes) unit. Further, when the cross-sectional area of the adsorption layer is represented by cm ² , when the Vsccm source gas is represented by the adsorption cross-sectional area Scm ² , the speed becomes V / S [c
m / minutes].

More specifically, when a source gas of 10 sccm flows through an adsorption layer having a cross-sectional area of 10 cm ² , the flow rate becomes 1 [cm / minutes].

It is desirable that the temperature of the adsorbent-filled cylinder can be adjusted from a low temperature to a high temperature by controlling it with a temperature control system. Specifically, from -80 ° C to 4
Desirably, it can be used in a temperature range of 00 ° C.

By cooling the adsorbent-filled cylinder, the adsorbing capacity of the filled adsorbent can be increased.
The adsorption capacity varies depending on the type of adsorbent,
Generally, by keeping the temperature low, the adsorption capacity can be increased. It is shown to be effective for the adsorption and removal of carbonaceous compounds, nitrogen and oxygen in addition to moisture.

Further, the boiling point of germane gas is -88.4.
° C, and the vapor pressure at −82 ° C. is 0.5 kg / cm ² -G.
As long as the operation is performed under the pressure condition of / cm ² -G, the germane gas does not liquefy and can be handled as a gas, and it is considered that no inconvenience in operation occurs.

[0044]

【Example】

[Embodiment 1] Hereinafter, the present invention will be described based on Embodiment 1. In Example 1, the results obtained by using the thin film forming apparatus shown in FIG. 1 will be described. The determination of the impurity concentration of germane gas was performed using a partial pressure vacuum gauge 14 connected to the thin film forming chamber main body 10 shown in FIG. The partial pressure gauge used in the examples is a QIG-
066, which can measure the pressure of gas molecules corresponding to mass 1 to mass 66.

First, the concentration of gas existing in the thin film forming chamber was measured without flowing germane gas. As a result, the overall pressure was 5.68 × 10 ⁻⁷ Torr. On the other hand, the partial pressure corresponding to the mass number 18 is 2.56 × 1
0 ^-8 Torr.

As the adsorbent, 50 cc of synthetic zeolite having a pore size of 4 ° is used by filling it into the adsorbent filling cylinder 21, and helium gas is flowed as a carrier gas at a temperature of 210 ° C. Regeneration was performed in advance.
At this time, the vacuum evacuation system 27 for regeneration was used for 20 hours while evacuating.

Germanic gas was supplied at 1 sccm. The germane gas is supplied to the thin film forming chamber via the adsorbent-filled cylinder. As the adsorbent, 50 cc of synthetic zeolite having a pore size of 4 ° was used by filling the adsorbent-filled cylinder, and ethanol was frozen with dry ice and cooled to -30 ° C.

The volume of the thin film forming chamber was 20 l, and the combination of a turbo molecular pump having a pumping speed of 300 l / s and a rotary pump of 200 m ³ / min was used for the vacuum evacuation system 15 for the thin film forming chamber. . As previously mentioned,
In the state where 1 sccm of Germanic gas is supplied, 2 ×
It showed a pressure of 10 ^-4 Torr. In this state, the partial pressure at a mass number of 18 was 2.56 × 10 ⁻⁸ Torr, which was exactly the same value as when no gas was flowed.

That is, it was found that when synthetic zeolite having a pore diameter of 4 ° was used, the water concentration in the germane gas became 1 ppm or less by passing through the adsorbent-filled cylinder.

[Comparative Example 1] In Comparative Example 1, [FIG. 1]
The results obtained by using the thin film forming apparatus shown in FIG.
Also in this Comparative Example 1, the determination of the impurity concentration of the germane gas was performed using the partial pressure vacuum gauge 14 connected to the thin film forming chamber main body 10 shown in FIG.

First, the concentration of gas existing in the thin film forming chamber was measured without flowing germane gas. As a result, the overall pressure was 5.34 × 10 ⁻⁷ Torr. On the other hand, the partial pressure corresponding to mass number 18 is 2.32 × 1
0 ^-8 Torr.

Further, in Comparative Example 1, 1 sccm of germane gas was supplied. The germane gas is supplied to the thin film forming chamber without passing through the adsorbent-filled cylinder. The pressure of 2 × 10 ⁻⁴ Torr was shown in a state where 1 sccm of the germane gas was supplied. In this state, the partial pressure of mass number 18 was 2.43 × 10 ⁻⁷ Torr.

As a result, about 100
It was found that it contained 0 ppm of water. Conversely, according to this comparative example, it was found that the water concentration could be reduced to 1 ppm or less by passing through the adsorbent-filled cylinder.

Example 2 Hereinafter, a method of regenerating a filler in the present invention will be described. In addition, in Example 2, the result performed using the thin film forming apparatus shown in FIG. 1 is shown. As the adsorbent, 50 cc of synthetic zeolite having a pore diameter of 4 mm was used by filling the adsorbent-filled cylinder with 50 cc, and 5 l of germane gas was passed at a total flow rate. , The partial pressure of mass number 18 increased to 4.78 × 10 ⁻⁸ Torr.

Then, the adsorbent-filled cylinder was heated at a temperature of 210.degree.
Allowed to flow for hours. At this time, the evacuation system for regeneration 27
, While performing vacuum evacuation.

After 20 hours, the adsorbent-filled cylinder is gradually cooled, and ethanol is frozen with dry ice.
Used after cooling. In this state, the pressure in the thin film forming apparatus and the partial pressure of water were measured by flowing 1 sccm of Germanic gas. The total pressure was 5 × 10 ⁻⁴ Torr, and the partial pressure of mass 18 was measured. Is 4.23 × 10
^-8 Torr.

Then, the adsorbent-filled cylinder was filled with Germanic gas for 1 hour.
After flowing through 0 sccm, the total pressure inside the thin film forming chamber was 5 ×
A pressure of 10 ⁻⁴ Torr was shown, and a partial pressure of mass number 18 was 4.23 × 10 ⁻⁸ Torr, which was exactly the same value as when no gas was flowed.

Therefore, it was confirmed that the regeneration of the adsorbent was completely performed.

[Embodiment 3] In Embodiment 3, [FIG. 1]
This is an example in which a thin-film solar cell as shown in FIG. 1 is formed. The structure of the solar cell formed after exposure to oxygen plasma is pi
It was an n-type. Using germane gas supplied to the thin film formation chamber through the adsorbent-filled cylinder, the raw material gas supplied after mixing with monosilane gas was supplied to the thin film formation chamber to form an amorphous silicon germanium thin film. At this time, the flow rate of the germane gas is 1 sccm, and the flow rate of the monosilane gas is 10 sccm.

The amorphous silicon germanium thin film used for the formation was formed by forming a tin oxide thin film as a transparent conductive film 42 on a glass substrate 41, and formed on a p-layer 43 formed. The i of the solar cell shown in FIG.
This is one in which the layer 44 is formed.

Thereafter, an n-layer 45 was formed, and a metal electrode was formed as the back electrode 46, whereby a single-cell solar cell having an amorphous silicon germanium thin film in the i-layer was formed.

When the current-voltage characteristics of this solar cell were measured, the short-circuit photocurrent was 21 mA / cm ² ,
The fill factors were 0.68 V and 0.64, respectively, and the conversion efficiency was 9.1%.

[Comparative Example 2] In Comparative Example 2, [FIG. 4]
A thin-film solar cell as shown in
The mixture was supplied to the thin film forming chamber without flowing through the adsorbent-filled cylinder (that is, without removing impurities such as moisture).

Before forming a thin film in advance, when the pressure in the system and the partial pressure of water were measured without flowing germane gas, the total pressure was 5.34 × 10 ⁻⁷ Torr. On the other hand, the partial pressure of mass number 18 corresponding to water is 4.32.
× 10 ^-8 Torr.

Further, when germanium gas was supplied at 10 sccm and supplied to the thin film forming chamber without passing through the adsorbent-filled cylinder, the pressure in the thin film forming chamber was 5 × 10 ⁻⁴ Torr and the mass number was 18 Is 4. 43 × 10 ⁻⁷ Torr. This indicates that germane gas contains water equivalent to 1000 ppm.

As described above, using the germane gas supplied to the thin film forming chamber without flowing through the adsorbent-filled cylinder, the raw material gas supplied after mixing with the monosilane gas is supplied to the thin film forming chamber, and the amorphous silicon germanium is supplied. A thin film was formed. At this time, the flow rate of the germane gas is 1 sccm, and the flow rate of the monosilane gas is 10 sccm.

The amorphous silicon-germanium thin film used for the formation was formed by forming a tin oxide thin film as a transparent conductive film on a glass substrate, and formed on a p-layer formed. 4] is obtained by forming an i-layer of the solar cell shown in FIG.

Thereafter, an n-layer was formed and a metal electrode was formed, thereby forming a single-cell solar cell having an amorphous silicon-germanium thin film in the i-layer.

When the current-voltage characteristics of this solar cell were measured, the short-circuit photocurrent was 21 mA / cm ² ,
The fill factors were 0.66 V and 0.56, respectively, and the conversion efficiency was 7.8%.

[0070]

According to the present invention, the water content of germane gas can be reduced to 1 ppm or less, and a solar cell can be formed with high efficiency by using the germane gas to form a solar cell. .

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a gas phase chemical vapor deposition apparatus having an adsorbent filled cylinder for gas purification according to the present invention.

FIG. 2 is an explanatory view showing the structure of an adsorbent-filled cylinder.

FIG. 3 is an explanatory view showing a state in which adsorbent-filled cylinders are connected in series.

FIG. 4 is an explanatory view showing a configuration of a thin-film solar cell used in the present invention.

[Explanation of symbols]

 10 Thin film formation room 11 Substrate 12 Substrate holder 13 Electrode 14 Partial pressure gauge 15 Vacuum exhaust system for thin film formation room 21 Adsorbent filling cylinder 22 Temperature control system 23 Gas line for thin film formation room 24 Regeneration gas line 25 For film formation room Gas flow controller 26 Gas flow controller for regeneration 27 Vacuum exhaust system for regeneration 28 Gas switching valve 31 Adsorbent filled cylinder body 32 Short pipe (gas inlet side) 32a Sintered body (gas inlet side) 33 Long pipe (gas outlet) Side) 33a Sintered body (gas outlet side) 34 Cap 41 Glass substrate 42 Transparent conductive film 43 P layer 44 i layer 45 n layer 46 Back electrode

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location H01L 21/205

Claims (6)

[Claims] 1. A gas-phase chemical vapor deposition apparatus comprising a gas supply line, a reaction chamber, and a vacuum exhaust system, wherein a plurality of vacuum systems comprising a vacuum exhaust system directly connected to the reaction chamber and a vacuum exhaust system of another system different from the vacuum exhaust system. At the same time as having an exhaust system, an adsorbent-filled cylinder for removing impurities contained in the gas is provided, and at the outlet of the filled cylinder, a branch line is provided,
One line is a line for supplying a thin film forming gas connected to the reaction chamber via a gas mass flow controller, and the other one line is connected to the other vacuum evacuation equipment. Vapor-phase chemical vapor deposition apparatus, characterized in that the adsorbent regeneration line is used. 2. A structure in which a filling cylinder has a double-pipe structure, and an inner pipe whose lower opening is sealed by a porous sintered body protrudes from the lower part of the cylinder to the outside of the cylinder. 2. The vapor-phase chemical vapor deposition apparatus according to claim 1, wherein the outer ring portion is filled with an adsorbent. 3. The filling cylinder has a structure capable of cooling to -80 ° C. or less and heating to 400 ° C. or more, and gas passing through the cylinder during cooling is supplied to a gas mass flow controller. 2. The vapor phase chemical vapor deposition apparatus according to claim 1, wherein the apparatus is supplied to another system of evacuation equipment during heating. 4. The vapor-phase chemical vapor deposition apparatus according to claim 1, wherein the adsorbent comprises a synthetic zeolite having a pore diameter of 4 mm or less. 5. The chemical vapor deposition apparatus according to claim 1, wherein the gas contains germane gas. 6. The vapor phase chemical vapor deposition apparatus according to claim 5, wherein water in the germane gas is removed to 1 ppm or less.