WO2012133500A1 - Azeotropic composition or azeotrope-like composition - Google Patents

Azeotropic composition or azeotrope-like composition Download PDF

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WO2012133500A1
WO2012133500A1 PCT/JP2012/058082 JP2012058082W WO2012133500A1 WO 2012133500 A1 WO2012133500 A1 WO 2012133500A1 JP 2012058082 W JP2012058082 W JP 2012058082W WO 2012133500 A1 WO2012133500 A1 WO 2012133500A1
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composition
monofluoromethane
trifluoromethane
mol
azeotrope
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PCT/JP2012/058082
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French (fr)
Japanese (ja)
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高田　直門
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セントラル硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/504—Azeotropic mixtures containing halogenated solvents all solvents being halogenated hydrocarbons
    • C11D7/505—Mixtures of (hydro)fluorocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/32—The mixture being azeotropic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to an azeotrope composition and an azeotrope-like composition containing monofluoromethane and trifluoromethane, and more particularly, an intermediate for producing monofluoromethane, a refrigerant, and an etching agent or chamber used in a process for producing a semiconductor thin film.
  • the present invention relates to an azeotropic composition or an azeotrope-like composition useful as a cleaning agent or the like.
  • Monofluoromethane and trifluoromethane are stable gases having boiling points of ⁇ 78 ° C. and ⁇ 82 ° C., respectively, and are useful substances as refrigerants.
  • Monofluoromethane can be produced by fluorination of methyl chloride with hydrogen fluoride (Patent Document 1), and trifluoromethane can be produced by fluorination of chloroform in the same manner.
  • the present invention includes monofluoromethane and trifluoromethane, which can be an azeotropic composition that can be regarded as the same substance, or an azeotrope-like composition having substantially the same composition in the gas phase portion and the liquid phase portion. It is an object to provide a composition.
  • the present invention is as follows.
  • Invention 2 The composition of Invention 1, comprising 15 to 85 mol% of monofluoromethane.
  • Invention 3 The composition of Invention 1 or Invention 2, characterized by containing 50-80 mol% of monofluoromethane.
  • invention 5 A refrigerant, an etching agent, or a cleaning gas containing at least the composition according to any one of Inventions 1 to 4.
  • the azeotropic composition or azeotrope-like composition of monofluoromethane and trifluoromethane of the present invention is a composition that does not destroy the ozone layer and hardly undergoes a composition change. Useful as an etchant or chamber cleaning agent in the process.
  • FIG. 1 is a monofluoromethane / trifluoromethane vapor-liquid equilibrium diagram of the azeotropic composition of Example 1.
  • monofluoromethane and trifluoromethane those having a monofluoromethane content of 0.1 mol% to 99.9 mol% are useful as refrigerants and semiconductor gases.
  • the inventor has found that two types of fluoroalkanes, namely 62 mol% of monofluoromethane and 38 mol% of trifluoromethane form a composition having an azeotropic point, and the mixing ratio before and after that, that is, 15 to 85 mol% of monofluoromethane.
  • the present invention has been found to form an azeotrope-like composition in which the composition of the gas phase portion and the liquid phase portion is substantially the same in the region of 85 to 15 mol% of trifluoromethane, and is useful as a refrigerant or semiconductor gas. It came to.
  • monofluoromethane and trifluoromethane which are separately produced, can be mixed in the above ratio, and monofluoromethane and trifluoromethane of arbitrary composition can be mixed.
  • One component can be added to the composition in the above ratio, or it can be obtained by distillation of a composition containing both components.
  • a stabilizer in the composition and azeotrope-like composition according to the present invention, can be used in combination when used as a refrigerant.
  • Stabilizers include epoxides such as propylene oxide, 1,2-butylene oxide and glycidol; phosphites such as dimethyl phosphite, diisopropyl phosphite and diphenyl phosphite; thiophosphites such as trilauryl trithiophosphite; Phosphine sulfides such as triphenoxyphosphine sulfide and trimethylphosphine sulfide; boron compounds such as boric acid, triethylborate, triphenylborate, phenylboronic acid, diphenylboronic acid; phenols such as 2,6-di-tert-butylparacresol Nitroalkanes such as nitromethane and nitroethane; acrylic acid esters such as methyl acrylate and ethyl acrylate; other dioxanes, tert-butanol, Pentaerythri
  • ethers such as dimethyl ether and pentafluorodimethyl ether
  • amines such as perfluoroethylamine
  • fluoroalkanes such as fluoroethane and 1,3,3,3-tetrafluoropropane
  • alkanes such as methane and ethane.
  • compositions and azeotrope-like compositions according to the present invention are useful as semiconductor gases. That is, W, WSi x , Ti, TiN, Ta 2 O 5 , Mo, Re, Ge, Si 3 N deposited on a substrate such as a silicon wafer, metal, glass, single crystal, or polycrystal in the manufacturing process of a semiconductor thin film. 4, Si, SiO 2, WSi x deposited on the wall surface of etching or deposition chamber such as SiO 2 or the like, TiN, Ta 2 O 5, Si 3 N 4, oxides such as SiB, nitrides, carbides, boride and It can be used for cleaning these composites. When used as an etching gas or a cleaning gas, an etching technique using plasma is preferably employed.
  • the composition can include a reducing gas such as 3 H 6 , C 3 H 8 , HI, HBr, HCl, CO, NO, NH 3 , H 2 , and can be used as an etching gas or a cleaning gas.
  • the cleaning with the composition of the present invention and the azeotrope-like composition can be performed by any of the thermal decomposition method, the photodecomposition method, and the plasma method, but the plasma method is preferable.
  • the plasma method may be generated in the chamber using high frequency or microwave, but a remote plasma method in which the plasma method is generated outside the chamber and introduced into the chamber is preferably employed.
  • the cleaning agent of the present invention can be applied to a film forming apparatus for forming a thin film by a CVD method in a manufacturing process such as a semiconductor device such as a semiconductor device or a liquid crystal device, an optical device, a coating tool, a manufacturing apparatus for manufacturing a whisker, powder or the like.
  • application to a film forming apparatus is particularly preferable, and it is more preferable to use the film forming apparatus for a semiconductor device using a silicon compound such as a semiconductor device or a liquid crystal device.
  • the component analysis was performed by a gas chromatograph (detector: FID), and numerical values obtained by converting the area% of the chromatogram to mol% were shown.
  • Example 1 Measurement of each component in a gas phase and a liquid phase in a vapor-liquid equilibrium state at 0 ° C. (set temperature) of a composition composed of monofluoromethane and trifluoromethane was performed as follows. Monofluoromethane and trifluoromethane were each charged in a stainless steel container (50 cc) with the mass shown in Table 1, solidified with liquid nitrogen, exhausted with a vacuum pump, and returned to room temperature four times. It was immersed in a constant temperature bath (actual temperature: ⁇ 0.1 ° C.).
  • FIG. 1 shows a monofluoromethane / trifluoromethane vapor-liquid equilibrium diagram.
  • composition of 62 mol% monofluoromethane and 38 mol% trifluoromethane it was the highest azeotropic composition that was rare as a fluoroalkane-based composition. Both compositions are azeotropic over the entire composition range, indicating that they are suitable as refrigerant and semiconductor gas compositions.
  • a range of 15 to 85 mol% monofluoromethane and 85 to 15 mol% trifluoromethane, particularly 50 to 80 mol% monofluoromethane and 50 to 20 mol% trifluoromethane is preferred as the azeotrope-like composition.
  • the range of 50 to 80 mol% monofluoromethane and 50 to 20 mol% trifluoromethane is preferred.
  • the azeotropic composition and azeotrope-like composition of the present invention are useful as a refrigerant and a semiconductor gas.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
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Abstract

[Problem] To provide a composition containing monofluoromethane and trifluoromethane that can be an azeotropic composition that can be regarded as a homogeneous substance, or an azeotrope-like composition in which the composition in the gas phase part and liquid phase part is substantially the same. [Solution] An azeotropic composition or azeotrope-like composition comprising monofluoromethane and trifluoromethane, wherein monofluoromethane is contained in the amount of 15-85 mol%. Specifically, the composition is an azeotropic composition comprising monofluoromethane in the amount of 62 mol% and trifluoromethane in the amount of 38 mol%. This composition is useful as a coolant, as a semiconductor gas, etc.

Description

共沸組成物または共沸様組成物Azeotropic composition or azeotrope-like composition
　本発明は、モノフルオロメタンおよびトリフルオロメタンを含む共沸組成物および共沸様組成物に関し、より詳しくは、モノフルオロメタンの製造中間物、冷媒、半導体薄膜の製造工程で使用するエッチング剤またはチャンバーのクリーニング剤などとして有用な共沸組成物または共沸様組成物に関する。 The present invention relates to an azeotrope composition and an azeotrope-like composition containing monofluoromethane and trifluoromethane, and more particularly, an intermediate for producing monofluoromethane, a refrigerant, and an etching agent or chamber used in a process for producing a semiconductor thin film. The present invention relates to an azeotropic composition or an azeotrope-like composition useful as a cleaning agent or the like.
　モノフルオロメタンとトリフルオロメタンは、沸点がそれぞれ－７８℃と－８２℃の安定な気体であり冷媒等として有用な物質である。モノフルオロメタンは塩化メチルのフッ化水素を用いたフッ素化等により製造することができ（特許文献１）、トリフルオロメタンはクロロホルムを同様にフッ素化して製造することができる。 Monofluoromethane and trifluoromethane are stable gases having boiling points of −78 ° C. and −82 ° C., respectively, and are useful substances as refrigerants. Monofluoromethane can be produced by fluorination of methyl chloride with hydrogen fluoride (Patent Document 1), and trifluoromethane can be produced by fluorination of chloroform in the same manner.
特開２００６－１１１６１１号公報JP 2006-111161 A
　非共沸の混合ガスを冷媒、半導体ガス（エッチング剤、クリーニング剤）等に用いた場合、使用中に組成が変化して性能に大きく影響を及ぼすことがある。そこで、本発明では、ので、同一物質と見なせる共沸組成物もしくは、実質的に気相部と液相部の組成が同一の共沸様組成物となりうる、モノフルオロメタンとトリフルオロメタンとを含む組成物を提供することを課題とする。 When a non-azeotropic mixed gas is used as a refrigerant, a semiconductor gas (etching agent, cleaning agent), etc., the composition may change during use and the performance may be greatly affected. Therefore, the present invention includes monofluoromethane and trifluoromethane, which can be an azeotropic composition that can be regarded as the same substance, or an azeotrope-like composition having substantially the same composition in the gas phase portion and the liquid phase portion. It is an object to provide a composition.
　本発明者が鋭意検討した結果、モノフルオロメタンとトリフルオロメタンが特定の組成で共沸現象を示すことを見出し、本発明を完成するに至った。 As a result of intensive studies by the present inventors, it was found that monofluoromethane and trifluoromethane exhibit an azeotropic phenomenon with a specific composition, and the present invention has been completed.
　本発明は、次の通りである。 The present invention is as follows.
　［発明１］モノフルオロメタンとトリフルオロメタンからなる共沸組成物または共沸様組成物。 [Invention 1] An azeotropic or azeotrope-like composition comprising monofluoromethane and trifluoromethane.
　［発明２］モノフルオロメタンを15～85mol％含むことを特徴する、発明１の組成物。 [Invention 2] The composition of Invention 1, comprising 15 to 85 mol% of monofluoromethane.
　［発明３］モノフルオロメタンを50～80mol％含むことを特徴する、発明１または発明２の組成物。 [Invention 3] The composition of Invention 1 or Invention 2, characterized by containing 50-80 mol% of monofluoromethane.
　［発明４］モノフルオロメタン62mol％、トリフルオロメタン38mol％からなる共沸組成物。 [Invention 4] An azeotropic composition comprising 62 mol% monofluoromethane and 38 mol% trifluoromethane.
　［発明５］少なくとも発明１乃至発明から4の何れかに記載された組成物を含む、冷媒、エッチング剤、または、クリーニングガス。 [Invention 5] A refrigerant, an etching agent, or a cleaning gas containing at least the composition according to any one of Inventions 1 to 4.
　本発明のモノフルオロメタンとトリフルオロメタンとの共沸組成物または共沸様組成物は、オゾン層を破壊することがなく、組成変化をほとんど伴わない組成物であるので、冷媒、半導体薄膜の製造工程でエッチング剤またはチャンバーのクリーニング剤として有用である。 The azeotropic composition or azeotrope-like composition of monofluoromethane and trifluoromethane of the present invention is a composition that does not destroy the ozone layer and hardly undergoes a composition change. Useful as an etchant or chamber cleaning agent in the process.
実施例１の共沸組成物のモノフルオロメタン／トリフルオロメタン気液平衡線図。1 is a monofluoromethane / trifluoromethane vapor-liquid equilibrium diagram of the azeotropic composition of Example 1. FIG.
　モノフルオロメタンとトリフルオロメタンの組成物において、モノフルオロメタンの含量が0.1mol％から99.9mol％のものは冷媒、半導体ガスとして有用である。本発明者は、２種類のフルオロアルカン即ちモノフルオロメタン６２mol％とトリフルオロメタン３８mol％が共沸点を有する組成物を形成すること、およびその前後の混合割合、即ち、モノフルオロメタンが15～85mol％、トリフルオロメタンが85～15mol％の領域で、気相部と液相部の組成が実質的に同じである共沸様組成を形成し、冷媒や半導体ガスとして有用であることを見出し、本発明に至った。 In the composition of monofluoromethane and trifluoromethane, those having a monofluoromethane content of 0.1 mol% to 99.9 mol% are useful as refrigerants and semiconductor gases. The inventor has found that two types of fluoroalkanes, namely 62 mol% of monofluoromethane and 38 mol% of trifluoromethane form a composition having an azeotropic point, and the mixing ratio before and after that, that is, 15 to 85 mol% of monofluoromethane. The present invention has been found to form an azeotrope-like composition in which the composition of the gas phase portion and the liquid phase portion is substantially the same in the region of 85 to 15 mol% of trifluoromethane, and is useful as a refrigerant or semiconductor gas. It came to.
　前記共沸組成物または共沸様組成物を調製するには、モノフルオロメタンとトリフルオロメタンは各々別々に製造したものを前記比率に混合することができ、任意組成のモノフルオロメタンとトリフルオロメタンの組成物へ、前記比率になるように一方の成分を添加することができ、または、両成分を含む組成物の蒸留によって得ることもできる。 In order to prepare the azeotropic composition or the azeotrope-like composition, monofluoromethane and trifluoromethane, which are separately produced, can be mixed in the above ratio, and monofluoromethane and trifluoromethane of arbitrary composition can be mixed. One component can be added to the composition in the above ratio, or it can be obtained by distillation of a composition containing both components.
　本発明による組成物および共沸様組成物には、冷媒として使用する際には、安定剤を併用することができる。 In the composition and azeotrope-like composition according to the present invention, a stabilizer can be used in combination when used as a refrigerant.
安定剤としては、プロピレンオキシド、１，２－ブチレンオキシド、グリシドールなどのエポキシド類；ジメチルホスファイト、ジイソプロピルホスファイト、ジフェニルホスファイトなどのホスファイト類；トリラウリルトリチオホスファイトなどのチオホスファイト類；トリフェノキシホスフィンサルファイド、トリメチルホスフィンサルファイドなどのホスフィンサルファイド類；ホウ酸、トリエチルボレート、トリフェニルボレート、フェニルボロン酸、ジフェニルボロン酸などのホウ素化合物；２，６－ジ－ｔｅｒｔ－ブチルパラクレゾールなどのフェノール類；ニトロメタン、ニトロエタンなどのニトロアルカン類；アクリル酸メチル、アクリル酸エチルなどのアクリル酸エステル；その他ジオキサン、ｔｅｒｔ－ブタノール、ペンタエリスリトール、パライソプロペニルトルエン；などの安定剤を組成物質量の０．０１～５％程度添加することができる。 Stabilizers include epoxides such as propylene oxide, 1,2-butylene oxide and glycidol; phosphites such as dimethyl phosphite, diisopropyl phosphite and diphenyl phosphite; thiophosphites such as trilauryl trithiophosphite; Phosphine sulfides such as triphenoxyphosphine sulfide and trimethylphosphine sulfide; boron compounds such as boric acid, triethylborate, triphenylborate, phenylboronic acid, diphenylboronic acid; phenols such as 2,6-di-tert-butylparacresol Nitroalkanes such as nitromethane and nitroethane; acrylic acid esters such as methyl acrylate and ethyl acrylate; other dioxanes, tert-butanol, Pentaerythritol, Paraiso propenyl toluene; may be added about 0.01 to 5% stabilizer composition weight of such.
　また、本発明の目的および効果を損なわない範囲で、本発明の組成物に他の化合物を混合することができる。この様な化合物としては、ジメチルエーテル、ペンタフルオロジメチルエーテルなどのエーテル類；パーフルオロエチルアミンなどのアミン類；ペンタフルオロエタン、１，１，２，２－テトラフルオロエタン、１，１，１，２－テトラフルオロエタン、１，３，３，３-テトラフルオロプロパンなどのフルオロアルカン類；メタン、エタンなどのアルカン類などが例示される。 Further, other compounds can be mixed with the composition of the present invention within a range not impairing the object and effect of the present invention. Examples of such compounds include ethers such as dimethyl ether and pentafluorodimethyl ether; amines such as perfluoroethylamine; pentafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetra Examples include fluoroalkanes such as fluoroethane and 1,3,3,3-tetrafluoropropane; alkanes such as methane and ethane.
　本発明による組成物および共沸様組成物は、半導体ガスとして有用である。すなわち、半導体薄膜の製造工程におけるシリコンウエハ、金属、ガラス、単結晶、多結晶などの基板上に堆積したＷ、ＷＳｉx、Ｔｉ、ＴｉＮ、Ｔａ2Ｏ5、Ｍｏ、Ｒｅ、Ｇｅ、Ｓｉ3Ｎ4、Ｓｉ、ＳｉＯ2等のエッチングまたは堆積室の壁面等に堆積したＳｉＯ2、ＷＳｉx、ＴｉＮ、Ｔａ2Ｏ5、Ｓｉ3Ｎ4、ＳｉＢ等の酸化物、窒化物、炭化物、ホウ素化物及びこれらの複合物のクリーニングに用いることができる。エッチングガスまたはクリーニングガスとして使用する場合、プラズマを利用したエッチングの手法が好ましく採用される。 The compositions and azeotrope-like compositions according to the present invention are useful as semiconductor gases. That is, W, WSi x , Ti, TiN, Ta 2 O 5 , Mo, Re, Ge, Si 3 N deposited on a substrate such as a silicon wafer, metal, glass, single crystal, or polycrystal in the manufacturing process of a semiconductor thin film. 4, Si, SiO 2, WSi x deposited on the wall surface of etching or deposition chamber such as SiO 2 or the like, TiN, Ta 2 O 5, Si 3 N 4, oxides such as SiB, nitrides, carbides, boride and It can be used for cleaning these composites. When used as an etching gas or a cleaning gas, an etching technique using plasma is preferably employed.
　本発明による組成物および共沸様組成物は、Ｎ2、Ｈｅ、Ａｒ、Ｎｅ、Ｋｒ等の不活性ガス、Ｏ2、Ｏ3、ＣＯ2、Ｆ2、ＮＦ3、Ｃｌ2、Ｂｒ2、Ｉ2、ＸＦn（Ｘ＝Ｃｌ，Ｉ．Ｂｒ，１≦ｎ≦７）等の酸化性ガス、ＣＨ4、Ｃ2Ｈ2，Ｃ2Ｈ4，Ｃ2Ｈ6、Ｃ3Ｈ4、Ｃ3Ｈ6、Ｃ3Ｈ8、ＨＩ、ＨＢｒ、ＨＣｌ、ＣＯ、ＮＯ、ＮＨ3、Ｈ2等の還元性ガスを含む組成物とすることができ、エッチングガスまたはクリーニングガスとして使用できる。 The compositions and azeotrope-like compositions according to the present invention comprise inert gases such as N 2 , He, Ar, Ne, Kr, O 2 , O 3 , CO 2 , F 2 , NF 3 , Cl 2 , Br 2 , An oxidizing gas such as I 2 or XF n (X = Cl, I.Br, 1 ≦ n ≦ 7), CH 4 , C 2 H 2 , C 2 H 4 , C 2 H 6 , C 3 H 4 , C The composition can include a reducing gas such as 3 H 6 , C 3 H 8 , HI, HBr, HCl, CO, NO, NH 3 , H 2 , and can be used as an etching gas or a cleaning gas.
　この組成物は、各種のガスを含む組成においてもモノフルオロメタンとトリフルオロメタンは組成物または共沸様組成物として挙動するため、液相／気相の相変化を伴う使用状態においてもモノフルオロメタンとトリフルオロメタンの成分の間の組成の変動は少ない。 In this composition, since monofluoromethane and trifluoromethane behave as a composition or an azeotrope-like composition even in a composition containing various gases, the monofluoromethane is used even in a use state involving a liquid phase / gas phase change. There is little compositional variation between the trifluoromethane components.
　本発明の組成物および共沸様組成物によるクリーニングは、熱分解法、光分解法、プラズマ法のいずれでも使用できるが、プラズマ法が好ましい。プラズマ法は、高周波またはマイクロ波を用いてチャンバー内で発生させてもよいが、チャンバー外で発生させてチャンバー内へ導入するリモートプラズマ法が好ましく採用される。本発明のクリーニング剤は、半導体デバイス、液晶デバイスなどの半導体装置、光デバイス、コーティング工具など製造プロセスにおいて薄膜をＣＶＤ法により形成する製膜装置やウイスカー、粉末などを製造する製造装置に適用できる。これらのうち、製膜装置への適用が特に好ましく、半導体デバイス、液晶デバイスなどのシリコン化合物を用いた半導体装置の製膜装置に使用するのがさらに好ましい。 The cleaning with the composition of the present invention and the azeotrope-like composition can be performed by any of the thermal decomposition method, the photodecomposition method, and the plasma method, but the plasma method is preferable. The plasma method may be generated in the chamber using high frequency or microwave, but a remote plasma method in which the plasma method is generated outside the chamber and introduced into the chamber is preferably employed. The cleaning agent of the present invention can be applied to a film forming apparatus for forming a thin film by a CVD method in a manufacturing process such as a semiconductor device such as a semiconductor device or a liquid crystal device, an optical device, a coating tool, a manufacturing apparatus for manufacturing a whisker, powder or the like. Among these, application to a film forming apparatus is particularly preferable, and it is more preferable to use the film forming apparatus for a semiconductor device using a silicon compound such as a semiconductor device or a liquid crystal device.
　以下に実施例をもって本発明を説明するが、実施態様はこれらに限られない。成分の分析は、ガスクロマトグラフ（検出器：ＦＩＤ）で行い、クロマトグラムの面積％をmol％に換算した数値を示した。 Hereinafter, the present invention will be described with reference to examples, but the embodiment is not limited thereto. The component analysis was performed by a gas chromatograph (detector: FID), and numerical values obtained by converting the area% of the chromatogram to mol% were shown.
　［実施例１］
　モノフルオロメタンとトリフルオロメタンとからなる組成物の０℃（設定温度）における気液平衡状態にある気相および液相中の各成分の測定を以下のようにして行なった。モノフルオロメタンとトリフルオロメタンをステンレス製容器（50cc）に各々表１に示す質量で仕込み、液体窒素で凝固させ真空ポンプで排気してから室温に戻す操作を４回繰り返した後、設定温度０℃（実温度：±0.1℃）の恒温槽に浸漬した。２時間後に液相部分をサンプリングし、８時間後に気相部分をヘッドスペース法でサンプリングし、分析した結果を表１のＣＨ3Ｆ気液平衡組成（mol％）に示す。また、図１にモノフルオロメタン／トリフルオロメタン気液平衡線図を示す。
Figure JPOXMLDOC01-appb-T000001
 [Example 1]
Measurement of each component in a gas phase and a liquid phase in a vapor-liquid equilibrium state at 0 ° C. (set temperature) of a composition composed of monofluoromethane and trifluoromethane was performed as follows. Monofluoromethane and trifluoromethane were each charged in a stainless steel container (50 cc) with the mass shown in Table 1, solidified with liquid nitrogen, exhausted with a vacuum pump, and returned to room temperature four times. It was immersed in a constant temperature bath (actual temperature: ± 0.1 ° C.). The liquid phase part was sampled after 2 hours, the gas phase part was sampled by the headspace method after 8 hours, and the analysis results are shown in CH 3 F vapor-liquid equilibrium composition (mol%) in Table 1. FIG. 1 shows a monofluoromethane / trifluoromethane vapor-liquid equilibrium diagram.
Figure JPOXMLDOC01-appb-T000001
　モノフルオロメタンが６２mol％、トリフルオロメタンが３８mol％の組成において、フルオロアルカン系組成物としては稀な最高共沸の共沸組成物であった。両者の組成物は全組成範囲にわたり共沸様であるので、冷媒、半導体ガス組成物として好適であることが示された。モノフルオロメタンが15～85mol％、トリフルオロメタンが85％～15mol％の領域、特にモノフルオロメタンが50～80mol％、トリフルオロメタンが50％～20mol％の領域が共沸様組成として好適である。 In a composition of 62 mol% monofluoromethane and 38 mol% trifluoromethane, it was the highest azeotropic composition that was rare as a fluoroalkane-based composition. Both compositions are azeotropic over the entire composition range, indicating that they are suitable as refrigerant and semiconductor gas compositions. A range of 15 to 85 mol% monofluoromethane and 85 to 15 mol% trifluoromethane, particularly 50 to 80 mol% monofluoromethane and 50 to 20 mol% trifluoromethane is preferred as the azeotrope-like composition.
　特にモノフルオロメタンが50～80mol％、トリフルオロメタンが50％～20mol％の領域が好適である。 In particular, the range of 50 to 80 mol% monofluoromethane and 50 to 20 mol% trifluoromethane is preferred.
　本発明の共沸組成物および共沸様組成物は、冷媒、半導体ガスとして有用である。 The azeotropic composition and azeotrope-like composition of the present invention are useful as a refrigerant and a semiconductor gas.

Claims (5)

  1. モノフルオロメタンとトリフルオロメタンからなる共沸組成物または共沸様組成物。 An azeotrope or azeotrope-like composition comprising monofluoromethane and trifluoromethane.
  2. モノフルオロメタンを15～85mol％含むことを特徴する、請求項１に記載の組成物。 The composition according to claim 1, comprising 15 to 85 mol% of monofluoromethane.
  3. モノフルオロメタンを50～80mol％含むことを特徴する、請求項１または請求項２に記載の組成物。 The composition according to claim 1 or 2, wherein the composition contains 50 to 80 mol% of monofluoromethane.
  4. モノフルオロメタン６２mol％、トリフルオロメタン３８mol％からなる共沸組成物。 An azeotropic composition comprising 62 mol% monofluoromethane and 38 mol% trifluoromethane.
  5. 少なくとも請求項１乃至請求項４の何れかに記載の組成物を含む、冷媒、エッチング剤またはクリーニングガス。 A refrigerant, an etching agent or a cleaning gas comprising at least the composition according to any one of claims 1 to 4.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
JPH11243084A (en) * 1997-12-16 1999-09-07 Lg Semicon Co Ltd Oxide-film etching method
JP2009188257A (en) * 2008-02-07 2009-08-20 Tokyo Electron Ltd Plasma etching method, plasma etching apparatus, and storage medium

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11243084A (en) * 1997-12-16 1999-09-07 Lg Semicon Co Ltd Oxide-film etching method
JP2009188257A (en) * 2008-02-07 2009-08-20 Tokyo Electron Ltd Plasma etching method, plasma etching apparatus, and storage medium

Non-Patent Citations (1)

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Title
ARTEMENKO, SERGEY ET AL.: "Azeotropy in the natural and synthetic refrigerant mixtures", INTERNATIONAL JOURNAL OF REFRIGERATION, vol. 30, no. 5, 2007, pages 831 - 839, XP022113052, DOI: doi:10.1016/j.ijrefrig.2006.11.010 *

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