KR20220139095A - Method for manufacturing fluorinated cyclopropane gas and gas composition for etching comprising the same - Google Patents

Abstract

The present invention relates to a method for manufacturing fluorinated cyclopropane gas, and a gas composition for etching comprising the same. According to the present invention, in the presence of a halogen catalyst, the yield is improved as a supply ratio of fluorinated olefin to hexafluoropropylene oxide (HFPO) is increased, and in a synthesis process, the present invention has low pressure, short reaction time, and has an effect of having a higher yield than conventional manufacturing methods. In addition, according to the present invention, it is possible to provide the gas composition for etching containing the fluorinated cyclopropane gas as an etching gas.

Description

Method for manufacturing fluorinated cyclopropane gas and gas composition for etching comprising the same

The present invention relates to a method for producing a fluorinated cyclopropane gas, and more particularly, to a method for producing a fluorinated cyclopropane gas used as an etching gas.

In semiconductor manufacturing, extremely fine processing technology is required, and a dry etching method is widely used instead of a wet method. The dry etching method is a method of generating a plasma in a vacuum space to form a fine pattern on the surface of a material in molecular units. As an etching gas, CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F CF-based gases such as ₈ are used.

Among them, some methods using a fluorinated cyclopropane compound as an etching gas are known. Patent Document 1 discloses a dry etching agent containing C _a F _b H _c . Here, a, b, and c of this C _a F _b H _c each represent a positive integer, and the relationship between 2≤a≤5, c<b≥1, 2a+2>b+c, and b≤a+c is satisfied with However, the cases of a=3, b=4, and c=2 are excluded.

On the other hand, Patent Document 2 discloses a dry etching process of a mixed gas containing a C ₃ H ₂ F ₄ gas, but in particular, a method for producing a fluorinated cyclopropane gas is not disclosed.

In general, cyclic hydrocarbons such as fluorinated cyclopropane often exist as intermediate compounds, and their synthesis method is difficult, so there is a problem in that they cannot be produced in a sufficiently high yield for commercial use.

Japanese Patent Laid-Open No. 2013-030531 Korean Patent Publication No. 2016-0112928

The technical problem to be achieved by the present invention is to provide a method for producing a fluorinated cyclopropane gas having an improved yield.

Another technical object of the present invention is to provide a gas composition for etching comprising a fluorinated cyclopropane gas.

The technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

In order to solve the above-described technical problem, the present invention may provide a method for producing a fluorinated cyclopropane gas.

The method for producing the fluorinated cyclopropane gas is prepared by chemical reaction by mixing hexafluoropropylene oxide (HFPO) and fluorinated olefin in the presence of a catalyst, and the fluorination compared to the hexafluoropropylene oxide (HFPO) As the mixing ratio of the olefin is increased, the yield of the product can be improved.

The structure of the fluorinated cyclopropane may be represented by Formula 1 below.

[Formula 1]

In Formula 1, R1 and R2 may be H, F, Cl, Br, methoxy group, ethoxy group, C1-C4 straight-chain alkyl or C1-C4 branched-chain alkyl regardless of each other.

The fluorinated olefin is F ₂ C=CH ₂ , F ₂ C=CF ₂ , F ₂ C=CFCl, F2C=CHF, F ₂ C=CFBr, F ₂ C=CCl ₂ , F ₂ C=CBr ₂ , F It may be at least one selected from ₂ C=CFOCH ₃ and F ₂ C=CFOC ₂ H ₅ .

The fluorinated olefin may be mixed in the same amount or in an excess of the hexafluoropropylene oxide (HFPO).

The catalyst may be a halogen or a halogen compound, and for example, may include at least one selected from Br ₂ , CBr ₄ , FeBr ₃ , FeCl ₃ , AlCl ₃ and I ₂ , and specifically, I ₂ may be, but is not limited thereto.

The catalyst may be included in an amount of 0.1 to 10 mol% based on the total amount of the hexafluoropropylene oxide (HFPO) and the fluorinated olefin mixed.

The manufacturing method of the fluorinated cyclopropane gas is a supply step of supplying hexafluoropropylene oxide (HFPO) to the first cylinder, supplying fluorinated olefin to the second cylinder, and supplying a catalyst to the third cylinder (S01) ); After the supply step, in the presence of the catalyst, the hexafluoropropylene oxide (HFPO) and the fluorinated olefin in a chemical reactor to chemically react to synthesize a product (S02); After the synthesis step, a cleaning step of removing acidic impurities from the cleaning column (S03); After the washing step, an adsorption step (S04) of adsorbing residual impurities using an adsorbent in an adsorption device; After the adsorption step, a distillation step (S05) of distilling in a distillation column to remove by-products and unreacted materials for purification, and recovering the remaining unreacted materials to the chemical reactor; and a receiving step (S06) of receiving the purified product after the distillation step.

In the supply step (S01), the hexafluoropropylene oxide (HFPO) and the fluorinated olefin may be mixed and supplied in a molar ratio of 1:1 to 1:10.

In the synthesis step (S02), the reaction pressure may be 5 to 40 bar, the reaction temperature may be 150 to 200 °C, and the reaction time may be 5 to 45 hours.

In the washing step (S03), the acidic impurities may include a C ₂ F ₄ O compound.

In the adsorption step (S04), the moisture content may be controlled to 10 ppm or less and the acidity to 1 ppm or less.

The adsorbent may include at least one of silica gel, zeolite, molecular sieve (MS-4A, MS-10X, MS-13X), and activated carbon.

In the distillation step (S05), the purity may be controlled to 99.99% or more.

The by-product removed in the distillation step (S05) may include cC ₃ F ₆ , the unreacted product may include hexafluoropropylene oxide (HFPO), and the remaining unreacted product may include a fluorinated olefin.

The present invention for achieving the above-described other technical problem, the etching gas containing the fluorinated cyclopropane of Formula 1; and an additive gas mixed with the etching gas; and may provide an etching gas composition for etching at least one or more amorphous carbon film, silicon oxide film, silicon nitride film, or multilayer stacked film thereof formed on a substrate.

The etching gas may be prepared by chemically reacting hexafluoropropylene oxide (HFPO) and fluorinated olefin in the presence of a catalyst.

The fluorinated olefin is F ₂ C=CH ₂ , F ₂ C=CF ₂ , F ₂ C=CFCl, F2C=CHF, F ₂ C=CFBr, F ₂ C=CCl ₂ , F ₂ C=CBr ₂ , F It may be at least one selected from ₂ C=CFOCH ₃ and F ₂ C=CFOC ₂ H ₅ .

The etching gas may have a purity of 99.99% or more, a moisture content of 10 ppm or less, and an acidity of 1 ppm or less.

The additive gas is H ₂ , O ₂ , O ₃ , CO, CO ₂ , COCl ₂ , COF ₂ , CF ₃ OF, NO ₂ , F ₂ , NF ₃ , Cl ₂ , Br ₂ , I ₂ , CH ₄ , C ₂ H ₂ , C ₂ H ₄ , C ₂ H ₆ , C ₃ H ₄ , C ₃ H ₆ , C ₃ H ₈ , HF, HI, HBr, HCl, NO, NH ₃ , YF _n (where Y is Cl, Br or I, and n is an integer of 1 to 7), He, Ar, Ne, Kr, and Xe may include at least one selected from the group consisting of.

The substrate may be a silicon wafer.

According to the present invention described above, the method for producing a fluorinated cyclopropane gas of the present invention has the effect of having a low pressure and a short reaction time during the synthesis process, and having a higher yield than the conventional production method.

1 is a block flow diagram illustrating a manufacturing process of fluorinated cyclopropane for semiconductors from an embodiment of the present invention.
Table 1 is a table indicating the process conditions of the manufacturing process of fluorinated cyclopropane according to an embodiment of the present invention.
Table 2 shows the results of gas chromatography analysis received from the chemical reactor according to the manufacturing process of fluorinated cyclopropane according to an embodiment of the present invention.
Table 3 is a table indicating the process conditions of the manufacturing process of fluorinated cyclopropane including the presence or absence of a catalyst according to an embodiment of the present invention.
Table 4 shows the gas chromatography analysis results obtained from the chemical reactor according to the manufacturing process of fluorinated cyclopropane including the presence or absence of a catalyst according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the accompanying drawings. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention. Rather, the embodiments introduced herein are provided so that the disclosed subject matter may be thorough and complete, and the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as commonly used dictionary definitions should be interpreted as having meanings consistent with the meanings in the context of the related art, and unless explicitly defined in the present application, they are not to be interpreted in an ideal or excessively formal meaning. .

In the specification, the singular expression includes the plural expression unless the context clearly dictates otherwise. In addition, terms such as “comprise” or “have” are intended to designate that the features, numbers, steps, components, or combinations thereof described in the specification exist, and one or more other features, numbers, steps, configurations It should not be construed as excluding the possibility of the presence or addition of elements or combinations thereof.

In addition, in the following description of the present invention, if it is determined that a detailed description of a related well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

Method for producing fluorinated cyclopropane gas

The present invention is prepared by chemical reaction by mixing hexafluoropropylene oxide (HFPO) and fluorinated olefin in the presence of a catalyst, and increasing the mixing ratio of the fluorinated olefin compared to the hexafluoropropylene oxide (HFPO) It is possible to provide a method for producing a fluorinated cyclopropane gas represented by the following Chemical Formula 1, in which the yield of the product is improved.

[Formula 1]

In Formula 1, R1 and R2 may be H, F, Cl, Br, methoxy group, ethoxy group, C1-C4 straight-chain alkyl or C1-C4 branched-chain alkyl regardless of each other. For example, R1 and R2 are independently H, that is, the compound of Formula 1 may be 1,1,2,2-tetrafluorocyclopropane, but is not limited thereto.

The fluorinated olefin is F ₂ C=CH ₂ , F ₂ C=CF ₂ , F ₂ C=CFCl, F2C=CHF, F ₂ C=CFBr, F ₂ C=CCl ₂ , F ₂ C=CBr ₂ , F It may be at least one selected from ₂ C=CFOCH ₃ and F ₂ C=CFOC ₂ H ₅ . For example, the fluorinated olefin may be F ₂ C=CH ₂ (1,1-difluoroethylene), but is not limited thereto.

The catalyst may be a halogen or a halogen compound, for example, the catalyst may include at least one selected from Br ₂ , CBr ₄ , FeBr ₃ , FeCl ₃ , AlCl ₃ and I ₂ , specifically, I ₂ may be, but is not limited thereto.

The mixing amount of the fluorinated olefin relative to the hexafluoropropylene oxide (HFPO) may be the same or in excess. If the mixing amount of the fluorinated olefin compared to the hexafluoropropylene oxide (HFPO) is small, there is a problem in that the yield and the amount of the product decrease.

The catalyst may be included in 0.1 to 10 mol% of the total of the hexafluoropropylene oxide (HFPO) and the fluorinated olefin mixture, for example, may be included in 1 to 5 mol%, but is not limited thereto . When the catalyst is included in a small amount of 1 mol% or less, the effect of catalyst addition is not expressed, whereas when it is included in an excess of 5 mol% or more, it participates in the reaction and causes an increase in by-products, and a decrease in yield and production may cause problems with More specifically, it may be included in 3 mol%, but is not limited thereto.

1 is a block flow diagram illustrating a manufacturing process of fluorinated cyclopropane for semiconductors from an embodiment of the present invention.

Referring to FIG. 1 , hexafluoropropylene oxide (HFPO) (1) is supplied to a first cylinder (10), a fluorinated olefin (2) is supplied to a second cylinder (11), and a third cylinder (12) ) may be provided with a supply step (S01) in which the catalyst 3 is supplied.

After the feeding step (S01), the hexafluoropropylene oxide (HFPO) (1) and the fluorinated olefin (2) are mixed in a chemical reactor (13), and the catalyst (3) is mixed together to synthesize a product A synthesis step S02 may be provided.

The size of the chemical reactor may be 1L to 1000L, and is not limited thereto, and may be appropriately adjusted by those skilled in the art in consideration of the production amount.

In the supplying step (S01), the hexafluoropropylene oxide (HFPO) and the fluorinated olefin may exist in a gaseous phase, and the catalyst may exist in a solid, liquid or gaseous phase.

In the supply step (S01), the hexafluoropropylene oxide (HFPO) and the fluorinated olefin may be mixed in a molar ratio of 1:1 to 1:10, and may be in a molar ratio of 1:1 to 1:6, However, the present invention is not limited thereto. When the hexafluoropropylene oxide (HFPO) and the fluorinated olefin are mixed in a molar ratio of 1:6 or less, it is possible to prevent a problem that the chemical reaction proceeds at a high pressure, resulting in a decrease in production. More specifically, it may be a molar ratio of 1:3, but is not limited thereto.

The chemical reactor pressure in the synthesis step (S02) may be 5 to 40 bar, for example, 9 to 33 bar. When the reactor pressure is 9 to 33 bar, the synthesis of reactants provided in the gas phase may be easy. On the other hand, when the reactor pressure is 34 bar or more, since the chemical reaction proceeds at a high pressure, it may cause a problem in that the yield and production amount of the product existing in the gas phase decreases. More specifically, it may be 10 to 19 bar, but is not limited thereto.

In the synthesis step (S02), the reaction temperature may be 150 to 200 °C, for example, 160 to 190 °C. If the reaction temperature is 160 ℃ or less, the synthesis reaction of the reactants may not be expressed and unreacted substances may increase, whereas if the reaction temperature is 190 ℃ or more, a side reaction of the thermal decomposition reaction of the final product is caused, resulting in yield and production This can lead to reduced problems. In one embodiment, the reaction temperature may be 180 ℃, but is not limited thereto.

The reaction time in the synthesis step (S02) may be 5 to 45 hours, for example, 12 to 30 hours. When the reaction time is 12 hours or less, the synthesis reaction of the reactants may not be sufficient, and thus the yield and production may be reduced. On the other hand, if the reaction time is 30 hours or more, the reaction may cause an increase in by-products, which may cause a decrease in yield and production. More specifically, it may be 16 to 20 hours, but is not limited thereto.

In the synthesis step (S02), the chemical reactor 13 may be performed batchwise or continuously. For example, the manufacturing process may be performed in a batch type, but is not limited thereto.

The chemical reactor 13 may be selected from a batch reactor, a plug flow reactor (PFR), a packed bed reactor (PBR), and a fluidized-bed reactor (FBR). have. The type is not limited thereto, and a chemical reactor capable of gas phase reaction may be used.

The chemical reactor 13 may further include a temperature control unit (TCU) of a type selected from a jacket type, a coil type, a plate type, and a tubular type to control the temperature. The chemical reactor 13 may further include a pressure regulator selected from a pressure regulator or a back pressure regulator to control the pressure.

After the synthesis step (S02), a washing step (S03) of washing the product using water and an aqueous alkali solution may be provided. In the washing step ( S03 ), a washing column and a circulation pump installed under the washing column may be included. The circulation pump may circulate water and an aqueous alkali solution in the cleaning column, thereby removing acidic impurities contained in the product gas. For example, the aqueous alkali solution may be an aqueous KOH solution or an aqueous NaOH solution. In the washing step (S03), an acidic impurity C ₂ F ₄ O compound may be removed, and thus the acidity may be controlled to a condition of 1 ppm or less. For example, the C ₂ F ₄ O compound may be a compound including trifluoroacetyl fluoride or tetrafluorooxirane, but is not limited thereto.

After the washing step (S03), an adsorption step (S04) in which impurities not removed in the washing step are adsorbed using an adsorbent in the adsorption device 15 may be provided. In the adsorption step (S04), the moisture content may be controlled to a condition of 10 ppm or less. The adsorption device 15 may further include a condenser for removing moisture from the generated gas.

The adsorbent may include at least one of silica gel, zeolite, molecular sieve (MS-4A, MS-10X, MS-13X), and activated carbon.

After the adsorption step (S04), a distillation step (S05) of purification by distilling in the distillation column 16 to remove by-products and unreacted materials may be provided. In the distillation step (S05), the purity may be controlled to 99.99% or more. The by-product removed in the distillation step (S05) may include cC ₃ F ₆ , and the unreacted product may include hexafluoropropylene oxide (HFPO).

The residual unreacted material (4) in the distillation step (S05) may be recovered to the chemical reactor (13). The residual unreacted material 4 may include fluorinated olefins.

After the distillation step (S05), it may include a receiving step (S06) of receiving the purified product (5).

The purified final product 5 may exist in a gaseous phase.

Etching gas composition

In the present invention, the etching gas containing the fluorinated cyclopropane represented by the formula (1); and an additive gas mixed with the etching gas.

The etching gas composition may etch at least one amorphous carbon film, a silicon oxide film, a silicon nitride film, or a multilayer stacked film thereof formed on the substrate.

The etching gas may be 1,1,2,2-tetrafluorocyclopropane, but is not limited thereto.

The etching gas may be prepared by the manufacturing method disclosed in the present invention, manufactured by a known manufacturing method, or commercially available as it is or purified according to needs.

The etching gas may be prepared by chemically reacting hexafluoropropylene oxide (HFPO) and fluorinated olefin in the presence of a catalyst.

The fluorinated olefin is F ₂ C=CH ₂ , F ₂ C=CF ₂ , F ₂ C=CFCl, F2C=CHF, F ₂ C=CFBr, F ₂ C=CCl ₂ , F ₂ C=CBr ₂ , F ₂ C=CFOCH ₃ and F ₂ C=CFOC ₂ H ₅ may be at least one selected from, and specifically, F ₂ C=CH ₂ may be, but is not limited thereto.

The etching gas may have a moisture content of 10 ppm or less, an acidity of 1 ppm or less, and a purity of 99.99% or more.

The etching gas may be of high purity, and by using the high purity, when used in a semiconductor etching process, it may be used to simultaneously etch a silicon oxide film, a silicon nitride film, or a silicon oxide film and a silicon nitride film.

The etching gas may further include an additive gas when used as the etching composition.

The additive gas is H ₂ , O ₂ , O ₃ , CO, CO ₂ , COCl ₂ , COF ₂ , CF ₃ OF, NO ₂ , F ₂ , NF ₃ , Cl ₂ , Br ₂ , I ₂ , CH ₄ , C ₂ H ₂ , C ₂ H ₄ , C ₂ H ₆ , C ₃ H ₄ , C ₃ H ₆ , C ₃ H ₈ , HF, HI, HBr, HCl, NO, NH ₃ , YF _n (where Y is Cl, Br or I, and n is an integer of 1 to 7), He, Ar, Ne, Kr, and Xe may include at least one selected from the group consisting of. Among them, in terms of further accelerating the etching rate of the metal, the additive gas may include O ₂ , COF ₂ , F ₂ , NF ₃ , Cl ₂ , for example, O ₂ may be used, but this It is not limited. In addition, the additive gas may increase the plasma density to increase the etching rate, and in consideration of ease of availability, He or Ar may be further included.

About the said addition gas, 1 type, or 2 or more types can also be mixed and added, and a person skilled in the art can adjust suitably.

Although it does not specifically limit as a board|substrate to be used, A silicon wafer can be used as an example.

<Example>

HFPO (mol) VDF (mol) HFPO:VDF
(molar ratio) Reaction temperature (℃) Chemical reactor pressure (°C) Reaction time (hr) Example 1 9.50 9.50 1:1 180 18 17 Example 2 6.27 12.54 1:2 180 19 16 Example 3 2.35 7.05 1:3 180 10 17 Example 4 0.04 0.28 1:7 180 34 17

Table 1 is a table indicating the process conditions of the manufacturing process of fluorinated cyclopropane according to an embodiment of the present invention. Referring to Table 1, the feed amounts and process conditions of the first reactant and the second reactant are presented. . Both HFPO as the first reactant and VDF as the second reactant were supplied in a gas phase. In the process conditions of Examples 1 to 4, I ₂ was added as a catalyst, and the amount of catalyst was added in the same proportion of 3 mol% of the mixed amount of HFPO and VDF feed for all examples. The process pressure and time may be adjusted according to the mixing ratio of HFPO and VDF. Example 1 was carried out at 18 bar, Example 2 at 19 bar, and Example 3 at 10 bar. In particular, in Example 4, when the reaction was performed for the same process time, the reactor pressure was 34 bar, it can be seen that the process was performed at a considerable high pressure. Therefore, in Example 4 in which the supply amount of VDF compared to HFPO was supplied at a ratio of 1:7, the feed amount of HFPO was supplied at a significantly lower level than in the other examples, and it can be seen that the reaction pressure was also significantly high.

Example Analysis Conversion rate (%) Selectivity (%) transference number (%) VDF C ₂ F ₄ O compound cC ₃ F ₆ HFPO cC ₃ H ₂ F ₄ unknown compound Etc 3.86 min 4.19 min 4.70 min 5.08min 8.74 min 25.17 min 26.43 min One 31.43 20.33 21.69 0.55 23.03 0.55 0.00 2.42 98.90 46.59 46.08 2 56.34 8.92 9.27 3.39 21.29 0.40 0.05 0.31 89.81 71.16 63.91 3 66.00 6.37 6.74 0.56 18.57 0.46 0.07 1.22 97.77 75.95 74.26 4 86.15 0.39 1.15 0.07 11.80 0.24 0 0.06 99.42 99.10 98.52

Table 2 is a gas chromatography (GC) analysis result of the gas received from the chemical reactor according to the manufacturing process of fluorinated cyclopropane according to an embodiment of the present invention.

The numerical value of the result shown in Table 2 may be a component ratio (mol%) obtained by multiplying the area ratio of each peak obtained by gas chromatography of the gas received from the chemical reactor by a coefficient correcting the sensitivity of each gas. In addition, the 'unknown compound' indicated in Table 2 can be inferred as high boiling point substances.

Referring to Table 2, the conversion rate and the selectivity may be calculated according to Equations 1 and 2 below. The conversion rate may be calculated as a rate at which a reactant is converted into a product based on the reactant (HFPO). In addition, the selectivity may be calculated as a ratio of the amount of the reference material used (consumed) to the amount of the reference material (HFPO) changed (consumed) by the reaction. In the following formula, the HFPO content and the cC ₃ H ₂ F ₄ content are the contents in the purity measured by the gas chromatography method.

[Equation 1]

% conversion based on HFPO=[{ HFPO feed mole - (HFPO feed mole x HFPO content of product)} / HFPO feed mole] x 100

[Equation 2]

Selectivity based on HFPO (%)=[{(moles of HFPO feed + moles of VDF feed) x cC ₃ H ₂ F ₄ content of product} / {moles of HFPO feed - (moles of HFPO feed x HFPO content)}] x 100

In addition, the yield can be derived from Equation 3 below.

[Equation 3]

Yield (%) = (conversion x selectivity) / 100

Therefore, referring to Table 2, as the ratio of VDF increases, the production of by-products, C ₂ F ₄ O compound and cC ₃ F ₆ , is suppressed, and the effect of increasing the yield can be confirmed. On the other hand, in Example 4, it can be seen that the feed amount of HFPO is reduced by proceeding in the high-pressure process of the reactor pressure of 34 bar. As a result, the amount of fluorinated cyclopropane (cC ₃ H ₂ F ₄ ), which is the target, is small, and thus a problem in that the production amount per batch is reduced may occur.

HFPO (mol) VDF (mol) HFPO:VDF
(molar ratio) Reaction temperature (℃) Chemical Reactor Pressure (℃) Reaction time (hr) With or without catalyst Example 3 2.35 7.05 1:3 180 10 17 O Comparative Example 1 17 X Comparative Example 2 24 X

Table 3 is a table indicating the process conditions of the manufacturing process of fluorinated cyclopropane including the presence or absence of a catalyst according to an embodiment of the present invention.

Referring to Table 3, the catalyst addition amount of Example 3 was added in a ratio of 3 mol% with respect to the mixed amount of HFPO and VDF feed, but, unlike in Comparative Examples 1 and 2, it can be seen that the halogen catalyst was not added. The feed amount, temperature, and pressure of the reactants were controlled in the same way, but in Comparative Example 2, the reaction time was increased and carried out for 24 hours.

Analysis Conversion rate (%) Selectivity (%) transference number (%) VDF C ₂ F ₄ O compounds cC ₃ F ₆ HFPO cC ₃ H ₂ F ₄ unknown compound Etc 3.86 min 4.19min 4.70 min 5.08 min 8.74min 25.17 min 26.43 min Example 3 66.00 6.37 6.74 0.56 18.57 0.46 0.07 1.22 97.77 75.95 74.26 Comparative Example 1 73.00 4.29 4.55 2.45 14.30 0.32 0.07 1.02 90.20 63.41 57.20 Comparative Example 2 66.70 6.56 6.30 0.61 18.10 0.32 0.07 1.34 97.56 74.21 72.40

Table 4 shows the results of gas chromatography analysis received from the chemical reactor according to the manufacturing process of fluorinated cyclopropane including the presence or absence of a catalyst according to an embodiment of the present invention. Referring to Table 4, under the same process conditions, It can be seen that Example 3 achieved a higher yield than Comparative Example 1 that did not include a catalyst. However, when the catalyst is not included as in the process conditions of Comparative Example 2, in order to obtain a yield similar to that in the case where the catalyst is included, a reaction time increased by 7 hours or more is required compared to the conventional one. Therefore, it can be said that the presence of a halogen catalyst for producing the product, fluorinated cyclopropane (cC ₃ H ₂ F ₄ ) in high yield, is effective.

According to the present invention described above, in the method for producing a fluorinated cyclopropane gas of the present invention, in the presence of a halogen catalyst, as the supply ratio of fluorinated olefin to hexafluoropropylene oxide (HFPO) increases, the yield is improved, and the synthesis During the process, it has a low pressure, a short reaction time, and has the effect of having a higher yield than the conventional manufacturing method.

1: hexafluoropropylene oxide (HFPO), 2: fluorinated olefin, 3: catalyst, 4: residual unreacted material, 5: product, 10: first cylinder, 11: second cylinder, 12: third cylinder, 13 : reactor, 14: washing device, 15: adsorption device, 16: distillation column

Claims (19)

hexafluoropropylene oxide (HFPO) and fluorinated olefin are mixed and chemically reacted in the presence of a catalyst,
A method for producing a fluorinated cyclopropane gas represented by the following Chemical Formula 1, in which the yield of the product is improved as the mixing ratio of the fluorinated olefin to the hexafluoropropylene oxide (HFPO) is increased:
[Formula 1]

In Formula 1, R1 and R2 independently represent H, F, Cl, Br, a methoxy group, an ethoxy group, a C1-C4 straight-chain alkyl or a C1-C4 branched-chain alkyl. According to claim 1,
The fluorinated olefin is F ₂ C=CH ₂ , F ₂ C=CF ₂ , F ₂ C=CFCl, F2C=CHF, F ₂ C=CFBr, F ₂ C=CCl ₂ , F ₂ C=CBr ₂ , F ₂ C=CFOCH ₃ and F ₂ C=CFOC ₂ H ₅ At least one selected from the group consisting of, a method for producing a fluorinated cyclopropane gas. According to claim 1,
A method for producing a fluorinated cyclopropane gas, wherein the hexafluoropropylene oxide (HFPO) is mixed in the same amount or in excess of the fluorinated olefin. According to claim 1,
The catalyst is a halogen or a halogen compound, a method for producing a fluorinated cyclopropane gas. 4. The method of claim 3,
The catalyst is Br ₂ , CBr ₄ , FeBr ₃ , FeCl ₃ , AlCl ₃ and I ₂ A method for producing a fluorinated cyclopropane gas comprising at least one selected from the group consisting of. 4. The method of claim 3,
The catalyst is included in 0.1 to 10 mol% of the total amount of the hexafluoropropylene oxide (HFPO) and the fluorinated olefin mixture, the method for producing a fluorinated cyclopropane gas. According to claim 1,
A supply step of supplying hexafluoropropylene oxide (HFPO) to the first cylinder, supplying a fluorinated olefin to the second cylinder, and supplying a catalyst to the third cylinder (S01);
After the supply step, in the presence of the catalyst, the hexafluoropropylene oxide (HFPO) and the fluorinated olefin in a chemical reactor to chemically react to synthesize a product (S02);
After the synthesis step, a cleaning step of removing acidic impurities from the cleaning column (S03);
After the washing step, an adsorption step (S04) of adsorbing residual impurities using an adsorbent in an adsorption device;
After the adsorption step, a distillation step (S05) of distilling in a distillation column to remove by-products and unreacted materials for purification, and recovering the remaining unreacted materials to the chemical reactor; and
After the distillation step, receiving step (S06) of receiving the purified product; Method for producing a fluorinated cyclopropane gas comprising a. 8. The method of claim 7,
In the supply step, hexafluoropropylene oxide (HFPO) and the fluorinated olefin are mixed and supplied in a molar ratio of 1:1 to 1:10, a method for producing fluorinated cyclopropane. 8. The method of claim 7,
In the synthesis step, the reaction pressure is 5 to 40 bar, the reaction temperature is 150 to 200 ℃, the reaction time is 5 to 45 hours, a method for producing a fluorinated cyclopropane gas. 8. The method of claim 7,
In the washing step, the acidic impurities include a C ₂ F ₄ O compound, a method for producing a fluorinated cyclopropane gas. 8. The method of claim 7,
In the adsorption step, the moisture content is 10 ppm or less, the acidity is controlled to 1 ppm or less, a method for producing a fluorinated cyclopropane gas. 8. The method of claim 7,
The adsorbent comprises at least one of silica gel, zeolite, Molecular sieve (MS-4A, MS-10X, MS-13X) and activated carbon. 8. The method of claim 7,
In the distillation step, the purity is controlled to 99.99% or more, a method for producing a fluorinated cyclopropane gas. 8. The method of claim 7,
The by-product removed in the distillation step includes cC ₃ F ₆ , the unreacted product includes hexafluoropropylene oxide (HFPO), and the remaining unreacted product includes fluorinated olefin, fluorinated cyclopropane gas manufacturing method. Etching gas containing fluorinated cyclopropane represented by Formula 1; and
Including; an additive gas mixed with the etching gas;
An etching gas composition for etching at least one or more amorphous carbon film, silicon oxide film, silicon nitride film, or multilayer laminated film thereof formed on a substrate:
[Formula 1]

In Formula 1, R1 and R2 independently represent H, F, Cl, Br, methoxy group, ethoxy group, C1-C4 straight-chain alkyl or C1-C4 branched-chain alkyl. 16. The method of claim 15,
The etching gas is prepared by chemical reaction of hexafluoropropylene oxide (HFPO) and fluorinated olefin in the presence of a catalyst, an etching gas composition. 16. The method of claim 15,
The fluorinated olefin is F ₂ C=CH ₂ , F ₂ C=CF ₂ , F ₂ C=CFCl, F2C=CHF, F ₂ C=CFBr, F ₂ C=CCl ₂ , F ₂ C=CBr ₂ , F ₂ C=CFOCH ₃ and F ₂ C=CFOC ₂ H ₅ At least one selected from among, the etching gas composition. 16. The method of claim 15,
The etching gas has a moisture content of 10 ppm or less, an acidity of 1 ppm or less, and a purity of 99.99% or more, an etching gas composition. 16. The method of claim 15,
The additive gas is H ₂ , O ₂ , O ₃ , CO, CO ₂ , COCl ₂ , COF ₂ , CF ₃ OF, NO ₂ , F ₂ , NF ₃ , Cl ₂ , Br ₂ , I ₂ , CH ₄ , C ₂ H ₂ , C ₂ H ₄ , C ₂ H ₆ , C ₃ H ₄ , C ₃ H ₆ , C ₃ H ₈ , HF, HI, HBr, HCl, NO, NH ₃ , YF _n (where Y is Cl, Br or I, and n is an integer of 1 to 7), He, Ar, Ne, Kr, and at least one selected from Xe, the etching gas composition comprising.

Images