KR100902526B1 - A method for recovering cvd source materials and a method therefor - Google Patents

Abstract

The present invention provides a recovery apparatus and a recovery method capable of efficiently collecting and recovering unreacted CVD source materials in CVD exhaust gas without clogging.

(Solution) A filter device is provided between the CVD device and the exhaust pump, and the filter in the filter device contains 50% by weight or more of acrylonitrile units and 0.1 to 6.0 mmol / g of ionic groups. A CVD source material recovery apparatus comprising an aggregate of fibers formed of an acrylonitrile-based polymer and having a porosity of 70 to 99% of the filter.

CVD source material

Description

CD source material recovery system and recovery method {A METHOD FOR RECOVERING CVD SOURCE MATERIALS AND A METHOD THEREFOR}

1 is a schematic diagram of a CVD source material recovery apparatus of the present invention.

FIG. 2 is a schematic view showing the structure of the filter device in FIG. 1. FIG.

3 is a schematic view showing the structure of another filter device in FIG.

FIG. 4 is a diagram showing a configuration different from that of FIG. 1 in that a separate liquidator 4 is provided on the lower side (lower side) of the filter device 2.

5 is a schematic view showing the configuration of a filter device and a liquid flow machine.

FIG. 6 is a view showing an example in which the liquid flow apparatus 4 is provided below the CVD apparatus 1 which is the lower side of the filter apparatus 2.

FIG. 7: is a schematic diagram which showed the example in which the liquid flow machine 4 was installed in the lower part of the CVD apparatus 1 which is the lower side of the filter apparatus 2. FIG.

FIG. 8 is a diagram showing an example in which two systems of recovery devices are connected from the CVD apparatus 1. FIG.

FIG. 9 is a diagram showing another example in which two systems of recovery devices are connected from the CVD apparatus 1. FIG.

FIG. 10 is a diagram showing another example in which two systems of recovery devices are connected from the CVD apparatus 1. FIG.

11 is a schematic diagram showing an example of a filter composed of a two-layer structure.

※ Explanation of code for main part of drawing

1: CVD apparatus 2: filter apparatus

3: exhaust pump 4: liquidator

5: vaporizer 6: reactor

7: filter 8: collection

9: valve

The present invention relates to an apparatus for recovering a CVD source material contained in exhaust gas from a chemical vapor deposition (hereinafter referred to as "CVD") apparatus and a method for recovering a CVD source material using the same.

One of the thin film forming methods used in semiconductor manufacturing processes and the like is the CVD method. In the CVD method, a gas of one or two or more compounds (source materials) consisting of elements constituting the thin film material to be formed is supplied onto a substrate, and a chemical reaction (e.g., pyrolysis and oxidation at a high temperature or a surface of the substrate) is performed. , Reduction, polymerization, vapor phase chemical reaction, etc.) is a method of depositing and forming a desired thin film on a substrate.

Since CVD is a chemical reaction, it is possible to form a thin film of a wide variety of materials, and to control free composition by combining various gas-reactive materials, and to synthesize thin films of a completely new structure and composition that have not been known until now. It is also a method of forming a thin film at a temperature sufficiently lower than the melting point of these materials.

However, the exhaust gas from the CVD apparatus contains an unreacted source material or a solvent, such as an unreacted source material or a solvent thereof, which does not contribute to thin film formation, a mist thereof, dust from the formed thin film, alcohols, aldehydes, etc. produced by the film formation process. Many of these components in the exhaust gas are harmful, and they are prohibited from being discharged as they are in the atmosphere because they may adversely affect the human body and the environment.

Therefore, in order to process CVD exhaust gas, providing a filter apparatus in the exhaust apparatus of CVD exhaust gas is implemented.

However, when the CVD exhaust gas contains dust or unreacted source material or a solvent thereof or a mist thereof, as described above, especially when the source material is a high viscosity material, it is simply to be collected by a filter. In addition, dust and source materials (gas-like source materials, etc. are liquefied in the filter) are combined to cause clogging, which increases the pressure loss in a short time and significantly reduces the exhaust efficiency.

Moreover, when trying to suppress clogging by increasing the porosity of a filter, it was not practical because some particulate dust in a dust and some harmful substances passed through a filter.

Accordingly, an object of the present invention is to provide an apparatus for recovering a CVD source material, and a CVD source material using the same, which can efficiently collect and recover unreacted CVD source material in CVD exhaust gas, even if the pressure loss is not increased or is very slight. It is to provide a recovery method.

MEANS TO SOLVE THE PROBLEM The present inventors reached | attained this invention as a result of earnestly researching in view of said situation. That is, the present invention relates to a CVD source material recovery device in which a filter device is provided between a CVD device and an exhaust pump, wherein the filter in the filter device contains 50% by weight or more of acrylonitrile units and contains ionic groups. The present invention provides a CVD source material recovery apparatus, comprising an aggregate of fibers formed of acrylonitrile-based polymer containing 0.1 to 6.0 mmol / g, and having a porosity of 70 to 99%.

Preferably, the apparatus is characterized in that the filter in the filter apparatus has a nonuniform filter pore size (for example, a plurality of layers having different filter pore sizes), and installs a fluidizer in the filter apparatus or under the filter apparatus. It is to provide an apparatus for recovering the CVD source material.

The present invention also provides a method for recovering a CVD source material, wherein the CVD source material is collected using a CVD source material recovery apparatus, and the CVD source material is collected in a filter or a liquid filter.

Embodiment of the invention

The filter used in the present invention is composed of an aggregate of islands formed of an acrylonitrile-based polymer containing 50% by weight or more of acrylonitrile units and containing 0.1 to 6.0 mmol / g of ionic groups.

The ionic group to be contained may be a cationic group alone or an anionic group alone or a combination thereof. Preferably, the ionic group is not a cationic group alone, and more preferably cationic groups 0 to 30 as a ratio in the ionic group. %, Anionic groups 100-70% are preferred.

The fiber containing the ionic group may be produced by any method as long as the content of the ionic group is 0.1 to 6.0 mmol / g, but the following method is preferably used.

As a fiber containing an anionic group, the method of Unexamined-Japanese-Patent No. 62-62181 is preferable. That is, the starting acrylic fiber may be a fiber formed from an AN polymer containing 50% by weight or more of acrylonitrile (hereinafter referred to as AN), and may be any of short fiber, tow, and nonwoven fabric. As a method of imparting an anionic group to this AN fiber, the nitrile group (hereinafter referred to as CN group) is modified by a carboxyl group by alkali hydrolysis.

Here, the alkali metal hydroxide aqueous solution concentration at the time of hydrolysis treatment is 6.0 mol / 1000g or more, The hydroxide of alkali metals, such as Na, K, Li, or a mixture thereof is mentioned as a metal hydroxide to be used. The amount of the alkali metal hydroxide aqueous solution is preferably used in an amount of 4 parts by weight or more based on 1 part by weight of the fiber. Moreover, as reaction conditions, such as temperature conditions or processing time when the above alkali metal hydroxide aqueous solution is made to act, since the preferable conditions range differs according to the microstructure of a polymer, such as a published form of this fiber, crystallinity, or an alkali metal hydroxide aqueous solution concentration, etc., Although it is impossible to define uniquely, in general, it is preferable to use a temperature condition of 80 ° C. or higher because the reaction rate is increased and the treatment effect can be advantageously achieved as it is operated under high temperature. In addition, the anionic group referred to here has the property of being ionized in an aqueous medium to become an anion. In addition to the carboxyl group, there are, for example, sulfonic acid groups and phosphoric acid groups.

Preferred fibers containing cationic groups are the methods described in Stela Dragan, G. Grigoriu, Die Angewandte Makromolekulare Chemie 200 (1992) 27-36. That is, an amino group is given in reaction with CN group by processing the chemical | medical agent containing an amino group to AN system fiber containing AN 50 weight% or more. Bath conditions of the amination treatment here are H ₂ O / CN group = 2/1, amine / CN group = 5/1, treatment temperature = 108 DEG C, treatment time = 2 to 15 hours in mol concentration ratio. .

Examples of the drug include N, N-dimethyl-1, 2-diaminoethane, N, N-dimethyl-1, 3-diaminopropane, N, N-diethyl-1, 3-diaminopropane, and the like. have. In addition, the cationic group referred to herein has the property of being ionized in an aqueous medium to become a cation. Examples thereof include an amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group.

The ionic group content of the fiber used for this filter is generally 0.1 to 6.0 mmol / g, preferably 1.0 to 5.5 mmol / g. Moreover, when an ionic group is less than 0.1 mmol / g, the effect of this invention is hard to express. When it exceeds 6.0 mmol / g, the tensile strength as a fiber becomes weak and workability of a filter etc. deteriorates.                     

In the present invention, the fibers containing the above ionic groups are aggregated by a conventional method, and the method of forming the fibers is not particularly limited, but the porosity of the filter is 70 to 99%, preferably 80 to 97 Need to be%.

If the porosity is less than the above, clogging occurs when the CVD source material or the like is attempted to be collected in the filter, and the pressure loss increases in a short time, and the exhaust efficiency is significantly deteriorated. On the other hand, if the porosity exceeds the above, the collection function is remarkably lowered, and even if the fiber has an ionic group as described above, the CVD source material or the like cannot be effectively collected.

In addition, in the present invention, the density of the filter is not important, and the porosity should be as described above. Therefore, various filters having a wide range of filter densities can be used while the porosity is in the above range by variously selecting the density of the fiber itself to be used. There are various choices depending on the purpose of use and the environment of use.

It is preferable that the filter used for this invention has a pore ratio of non-uniformity, in addition to having the porosity mentioned above. The reason why the non-uniformity is preferable is not accurate, but it is assumed that it is difficult to cause clogging because the trapping material is not concentrated in a certain layer in the filter.

Here, the filter density is a value obtained by dividing the filter weight by the apparent volume of the filter, the filter porosity is the ratio of the void space volume occupied by the apparent volume of the filter, and the filter pore is the short diameter of the voids in the filter.

The nonuniformity of the filter pore may be nonuniform at least in parallel with the CVD exhaust gas flow, and does not necessarily have to be nonuniform in the direction perpendicular to the CVD exhaust gas flow.

Non-uniform (isotropically nonuniform) structures in both the parallel and vertical directions with respect to the CVD exhaust gas flow can be obtained, for example, by using a filter material having a three-dimensional nonwoven structure produced by known techniques.

In addition, a filter which is not nonuniform in the vertical direction to the CVD exhaust gas flow and is nonuniform in the parallel direction can be obtained by stacking a plurality of filters having different filter pore sizes, for example. Of course, even if the individual filters to be laminated is isotropically nonuniform, it does not interfere, but if the nonuniformity of the individual filters is the same, there is no difference from the above-mentioned case that is isotropically uniform as a whole as a whole, and in this case, It is preferable to stack a plurality of filters that are isotropically nonuniform in a range where the dispersion of s is small and have different average filter pore sizes.

In addition, the degree of nonuniformity of the filter pore size is the average of the filter pore diameter in the direction parallel to the CVD exhaust gas flow in any of the above isotropically nonuniform or laminated filters, and the standard deviation is 150. 350 micrometers, Preferably the average of filter pore diameters is 150-500 micrometers, and it is preferable that the standard deviation exists in the range of 170-310 micrometers in the point which is hard to produce clogging more.

The CVD source material recovery apparatus of the present invention can effectively collect and recover the CVD source material by providing a filter device using the specific filter between the CVD device and the exhaust pump.

In the CVD source material recovery apparatus of the present invention, preferably, a heater is provided in a pipe between the CVD apparatus and the filter apparatus.

This is because since the CVD source material is usually heated and gasified, when the exhaust gas from the CVD apparatus is discharged to a relatively low temperature pipe such as a room temperature, it may be liquefied and cannot be effectively recovered before reaching the filter apparatus. .

In the CVD source material recovery apparatus of the present invention, it is preferable to install a liquid flowr in the filter apparatus or below the filter apparatus. In other words, if the collection of CVD source material is continued using the apparatus of the present invention using the filter, the liquid containing the CVD source material or the CVD source material dissolved in the solvent is dropped completely without being included on the filter. . Since the filter does not change the capturing ability even if it cannot completely contain these liquids, the liquid containing the CVD source material of the liquid or the CVD source material dissolved in the solvent is accumulated in the lower part of the filter as the collection continues. Therefore, by installing a liquid flowr in the lower part of the filter in the filter device, it is possible to recover the CVD source material more than the liquid content of the filter without filter replacement. As the liquid flow device in the lower filter position, the filter lower portion may simply be a space part.

It is also possible to provide a liquid flow device under the filter device and to introduce CVD source material or the like dropped from the filter into the liquid flow liquid. This will not only make filter replacement unnecessary for a long time, but also increase the capacity of the liquid flow device. Even if an excessive amount of CVD source material is collected, the collection of the CVD source material can be continued by performing only the exchange of the liquidizer without stopping the operation of the CVD apparatus, which is more preferable.

In the CVD source material recovery device of the present invention, the shape of the filter, the structure of the filter device, and the like are not particularly limited, and a known one can be employed, but a specific example as an example is the CVD source material recovery method of the present invention described later. It describes in description of. Moreover, the structure of the said liquid flow machine should just have the said function, It is not specifically limited, It can be set as arbitrary structures, The specific example as an example is described in description of the CVD source material collection method of this invention mentioned later.

Hereinafter, the CVD source material recovery method of the present invention will be described.

1 is a schematic diagram of a CVD source material recovery apparatus of the present invention. (1) is a CVD apparatus, (2) is a filter apparatus, and (3) is an exhaust pump. The filter in the filter device is composed of an aggregate of fibers formed by an acrylonitrile polymer containing 50% by weight or more of acrylonitrile units and containing 0.1 to 6.0 mmol / g of ionic groups, and the porosity of the filter is 70 to It becomes 99%.

The CVD exhaust gas discharged from the CVD exhaust gas discharge port of the CVD apparatus 1 is guided to the filter device 2 through the pipe. A filter is provided in the filter apparatus 2, and unreacted source material in CVD exhaust gas, its solvent, dust, etc. are collected by a filter, and are discharged out of the system from the exhaust pump 3 outside. In addition, a decontamination facility may be optionally provided after the exhaust pump 3, such as a gaseous substance such as a low boiling point solvent or a decomposition product of a source material (water, carbon dioxide, ligand component, etc.) (not shown here). .

It is a schematic diagram which shows the structure of the filter apparatus in FIG. The cylindrical filter 7 is provided in the filter apparatus 2, and the exhaust gas discharged | emitted from the CVD apparatus 1 flows toward the center part of the cylindrical filter 7, and consists of the structure guide | induced to the exhaust pump 3. .

Since the filter 7 collects unreacted source material in the CVD exhaust gas, its solvent, dust and the like, the CVD source material can be recovered by appropriately removing the filter 7 from the filter device 2 and treating it in a conventional manner. .

FIG. 3 is a schematic diagram showing the structure of another filter device in FIG. 1. FIG. FIG. 3 differs from FIG. 2 in that a space portion is formed in the lower part of the filter 7 in the filter device 2, and the excitation is a liquid flow.

If the amount of CVD source material or the like collected in the filter 7 exceeds the holding capacity of the filter 7, it is dropped in the lower part of the filter 7, and thus, the collector ( 8) This becomes a reservoir.

The CVD source material can be recovered by taking the collection 8 and the filter 7 out of the filter apparatus 2 and treating it in a conventional manner as appropriate.

FIG. 4 is a configuration different from that in FIG. 1 in that a liquid flower 4 is separately provided on the lower side (lower portion) of the filter device 2. The CVD source material and the like collected by the filter device 2 are stored in the fluidizer 4 below the filter device 2 (lower part).

5 is a schematic view showing the configuration of such a filter device and a liquid flow machine. The fluidizer 4 is connected to the lower side (lower part) of the filter apparatus 2 via the valve 9. When the CVD source material or the like is collected by the filter 7, the valve 9 is opened, and when the retention capacity of the filter 7 is exceeded, the valve 9 is dropped into the lower part of the filter 7, so that the valve 9 is collected through the valve 9. Water 8 is stored in liquidator 4.

When the collection 8 is filled to the capacity of the liquid dispenser 4, the valve 9 is closed and the liquid exchanger 4 is replaced or the liquid dispenser 4 is removed to recover the collection 8. By reloading the liquidator 4 and opening the valve 9 again, the collection 8 can be recovered without stopping the CVD apparatus, and the CVD source material can be efficiently recovered in a conventional manner. .

FIG. 6 shows an example in which the liquidator 4 is provided below the CVD apparatus 1 although it is the lower side of the filter apparatus 2. The schematic diagram which showed the structure of a filter apparatus and a liquid flow machine in this case is FIG.

The piping for guiding the exhaust gas from the CVD apparatus 1 to the filter apparatus 2 is an example in which part of the piping is shared with the piping for guiding the collection 8 from the filter apparatus 2 to the liquidator 4. .

8 to 10 show an example in which two systems of recovery devices are connected from the CVD apparatus 1. In the CVD apparatus 1, a vaporizer 5 and a reactor (chamber) 6 of the source material are included. The source material in the vaporizer 5 is gasified and sent to the reactor 6, which is used for the CVD reaction in the reactor 6. The exhaust gas from the CVD apparatus 1 is discharged from the reactor 6 and is regulated for stabilization of the CVD reaction in the reactor 6, which is classified from the vaporizer 5 to bypass the reactor 6. There may be a case where it discharges, and the structure of FIGS. 8-10 is used in such a case.

In addition, although description is abbreviate | omitted in these figures, it is as above-mentioned that in the apparatus shown in any figure, it is preferable that the heater is provided in the piping between the CVD exhaust gas discharge port of a CVD apparatus, and a filter apparatus.

The CVD source material recovery apparatus and the CVD source material recovery method of the present invention are particularly useful for the recovery of CVD source materials generally referred to as high boiling point types, for example, tris (2,4-octanedionate) ruthenium), tris (6 -Methylheptan-2, 4-dionat) ruthenium, tris (5-methylheptan-2, 4-dionat) ruthenium, tris (3-methyldecane-4, 6-dionate) ruthenium, tris (2, 2 , 6-trimethyloctane-3, 5-dionat) ruthenium, tris (2, 6-dimethylnonan-3, 5-dionat) ruthenium, tris (3-methylnonan-4, 6-dionate) ruthenium, tris (6-Methyloctane-3, 5-dionat) ruthenium, tris (3, 8-dimethylnonan-4, 6-dionat) ruthenium, bis (ethylcyclopentadienyl) ruthenium, tris (2, 2, 6 , 6-tetramethyl-3, 5-heptanedionate) ruthenium, bis (cyclopentadienyl) ruthenium, cyclopentadienyl (n-butylcyclopentadienyl) ruthenium, cyclopentadienyl (ethyloxy Lopentadienyl) ruthenium, bis (2,4-octanedionate) platinum, trimethyl (methylcyclopentadienyl) platinum, trimethyl (ethylcyclopentadienyl) platinum, dimethyl (1, 5-cyclooctadiene) platinum , Methylcyclopentadienyl (1,5-cyclooctadiene) iridium, ethylcyclopentadienyl (1,5-cyclooctadiene) iridium, bis (6-ethyl-2, 2-dimethyl-3, 5-decane Dionat) copper, bis (1- (2-methoxy-ethoxy) -2, 2, 6, 6-tetramethyl-3, 5-heptanedionate) barium, bis (2, 2, 6, 6- Tetramethyl-3, 5-heptanedionate) barium, bis (2, 2, 6, 6-tetramethyl-3, 5-heptanedionate) strontium, bis (1- (2-methoxy-ethoxy)- 2, 2, 6, 6-tetramethyl-3, 5-heptanedionate) strontium, tetrakis (1-methoxy-2-methyl-2-propoxy) hafnium, tetrakis (1-methoxy-2- Methyl-2-propoxy) zirconium, tetrakis (1- (2-methoxy-ethoxy) -2, 2, 6, 6-tetramethyl-3, 5-heptanedionate) Leconium, Tetrakis (2, 2, 6, 6-tetramethyl-3, 5-heptanedionate) Zirconium, Tris (1-methoxy-2-methyl-2-propoxy) Bismuth, Tris (2, 2 , 6, 6-tetramethyl-3, 5-heptanedionate) bismuth, bis (1- (2-methoxy-ethoxy) -2, 2, 6, 6-tetramethyl-3, 5-heptanedionate ) Lead, bis (2, 2, 6, 6-tetramethyl-3, 5-heptanedionate) lead, bis (2, 2, 6, 6-tetramethyl-3, 5-heptanedionate) (2- It is useful for the recovery of CVD source materials such as methyl-2, 4-pentanedioxy) titanium.

When the CVD source material is a high boiling point type material, the source material is often dissolved in an organic solvent and used. Although the organic solvent used here is not specifically limited, For example, alcohols, such as methanol, ethanol, 2-propanol, n-butanol, acetate esters, such as ethyl acetate, butyl acetate, and methoxyethyl acetate, methyl cellosolve Ether alcohols such as ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, ethers such as tetrahydrofuran, lime, diglyme, trilime and dibutyl ether, methyl butyl ketone and methyl Ketones such as isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone and methylcyclohexanone, and hydrocarbons such as hexane, cyclohexane, heptane, octane, toluene and xylene Although appropriately selected depending on the solubility of the solute, the relationship between the use temperature and the boiling point, the flash point, and the like, ethers such as tetrahydrofuran, lime, and digim are particularly complex. It is preferably used here also stabilizing effect.

Example

Hereinafter, although an Example further demonstrates this invention, it is not limited to these.                     

[Reference Example]

An aggregate of fibers formed by a polymer containing 85% by weight of acrylonitrile units and containing 0.5 mmol / g of anionic groups (carboxyl groups) and 4.5 mmol / g of cationic groups (amino groups) as ionic groups. A cylindrical filter (outer diameter of 180 mm, inner diameter of 50 mm, length of 130 mm, porosity of 91.5%, average pore diameter of 350 µm, standard deviation of 250 µm) was used to constitute a filter device and a liquid flow as shown in FIG. The devices were all connected to the same filter device and the liquid flowr, to constitute a CVD source material recovery device having the same configuration as in FIG. 10, and to the metal thin film on the silicon wafer substrate by the CVD method under the conditions of Table 1 below using the CVD device. Was formed and the CVD source material was recovered from the generated CVD exhaust gas.

In addition, the outer diameter and inner diameter of a filter are as showing in FIG.

CVD source material Tris (2, 4-octanedionate) Ruthenium Solvent of CVD source material Butyl acetate CVD source concentration 0.5 mol / liter CVD source material (source material + solvent) supply 0.17 g / min Carrier gas Ar Carrier gas flow rate 300sccm Reaction gas O ₂ Reaction Gas Flow 30sccm Substrate temperature 350 ℃ Vaporization temperature 200 ℃ Chamber pressure 600㎩ Exhaust Gas Temperature at Emission from CVD Equipment 100 ℃ Exhaust piping temperature 100 ℃ Total CVD Source Material Supply 197.8 g

As a result, 22.2 g of CVD source material was recovered in the filter and 164.2 g of the CVD source material as the sum of the two types of exhaust gas recovered products. However, the Ru metal amount contained in the process exhaust gas is included in the recovery amount in terms of the source material amount. Since the CVD source material consumed by thin film formation was estimated to be about 1%, the recovery rate of the CVD source material was 95.2%.

EXAMPLE

As a filter, the fiber used in the reference example was used and it was set as the cylindrical filter of the same outer diameter, inner diameter, and length, but the filter which consists of two layers from which the porosity and pore distribution shown in FIG. 11 differs (the outer layer has a porosity of 91.5%, Average pore 350㎛, standard deviation 250㎛, thickness 35mm, inner layer porosity 86.4%, average pore 200㎛, standard deviation 235㎛, thickness 30mm, porosity 89.9%, average pore 300㎛, It carried out similarly to the reference example using the standard deviation of 250 micrometers).

As a result, 23.1 g of the CVD source material was recovered in the filter and 164.5 g of the CVD source material as the sum of the two types of exhaust gas recovered products. However, the amount of Ru metal contained in the process exhaust gas is included in the recovery amount in terms of the weight of the source material. Since the CVD source material consumed by thin film formation was estimated to be about 1%, the recovery rate of the CVD source material was 95.8%.

Since the present invention is configured as described above, a CVD source material recovery apparatus capable of efficiently collecting and recovering unreacted CVD source materials in CVD exhaust gas, even if there is no increase or a slight increase in pressure loss, and a CVD source using the same A material recovery method can be provided.

Claims (6)

In the CVD source material recovery apparatus provided with a filter apparatus between a CVD apparatus and an exhaust pump, the filter in this filter apparatus contains 50 weight% or more of acrylonitrile units, and 0.1-6.0 mmol of an ionic group. CVD source material recovery apparatus, comprising a plurality of layers having a porosity of 70 to 99% and different filter porosities of the fibers formed by the acrylonitrile-based polymer containing / g. . The method of claim 1, CVD source material recovery apparatus, characterized in that the heater is installed in the pipe between the CVD exhaust gas outlet and the filter device of the CVD apparatus. delete delete The method according to claim 1 or 2, CVD source material recovery apparatus, characterized in that the liquidator is installed in the filter device or below the filter device. A method of recovering a CVD source material, wherein the CVD source material is collected in a filter or a filter and a liquid discharger using the CVD source material recovery device according to claim 1 or 2, and the CVD source material is recovered therefrom.

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