WO2011102268A1 - Method for producing semiconductor gas - Google Patents

Method for producing semiconductor gas Download PDF

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Publication number
WO2011102268A1
WO2011102268A1 PCT/JP2011/052702 JP2011052702W WO2011102268A1 WO 2011102268 A1 WO2011102268 A1 WO 2011102268A1 JP 2011052702 W JP2011052702 W JP 2011052702W WO 2011102268 A1 WO2011102268 A1 WO 2011102268A1
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monofluoromethane
method
fluoride
according
catalyst
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PCT/JP2011/052702
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French (fr)
Japanese (ja)
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高田 直門
井村 英明
正宗 岡本
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セントラル硝子株式会社
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Priority to JP2010032525 priority
Priority to JP2010-143716 priority
Priority to JP2010143716 priority
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Publication of WO2011102268A1 publication Critical patent/WO2011102268A1/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/361Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58Preparation of carboxylic acid halides
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/3105After-treatment
    • H01L21/311Etching the insulating layers by chemical or physical means
    • H01L21/31105Etching inorganic layers
    • H01L21/31111Etching inorganic layers by chemical means
    • H01L21/31116Etching inorganic layers by chemical means by dry-etching

Abstract

Disclosed is a method for producing monofluoro methane, which involves at least a pyrolysis step in which a 1-methoxy-1,1,2,2-tetrafluoro ethane is pyrolyzed by bringing same into contact with a catalyst, and a step for collecting monofluoro methane from the pyrolysis product. As a consequence, it is possible to efficiently and practically produce monofluoro methane that essentially does not contain halogens except fluorine.

Description

A method of manufacturing a semiconductor gas

The present invention relates to a process for the preparation of monofluoromethane (CH 3 F), and more particularly, useful difluoro acetate fluoride as pharmaceutical and agrochemical intermediates as well as producing useful monofluoromethane as semiconductor gas such etchant or cleaning agent or a method for producing a derivative thereof at the same time.

Background of the Invention

As a method for producing monofluoromethane, fluorinated methyl chloride with hydrogen fluoride in the catalyst (chlorine - fluorine exchange) method of the known (Patent Document 1). This method is high selectivity, it is hard to say that efficient production methods low conversion rate. Further, monofluoromethane (boiling point: -78 ° C.) the target product with hydrogen chloride (boiling point: -85 ° C.) by-product is not only the boiling point is close, exhibits azeotropic behavior, distillation separation not easy, complicated purification processes are used (Patent Document 2). Furthermore, a method of fluorinating with tetra -n- butylammonium salt of methyl iodide is known (Non-Patent Document 1), the starting material is difficult to obtain as compared to the method of Patent Document 1. Further, starting materials for these methods are not only highly toxic, since ozone layer depleting substances, require careful handling. Further, as described in Patent Document 2, the chlorine highly reactive with radicals, bromine and an iodine is mixed with the product, because it affects the etching rate or the like, the use of these halogen-containing substance as a raw material It is undesirable.

Patent Document 3, when the synthesis of difluoro acetic acid fluoride or difluoro acetic ester by contacting the 1-alkoxy-1,1,2,2-tetrafluoroethane in a metal oxide catalyst, alkyl fluoride and as a by-product Although olefin and hydrogen fluoride is a decomposition product of the fluorinated alkyl is described as generating the yield of monofluoromethane, purity, isolation and purification methods, is not seen described in terms such as utilization method.

WO 2005/026090 pamphlet JP 2006-111611 JP JP 8-92162 discloses

J. Am. Chem. Soc. , 127 (7), 2050-2051 (2005)

Halogen - to the fluorine-containing semiconductor gas produced by fluorine exchange reaction, due to the raw materials, the chlorine that is repellent in a semiconductor device manufacturing process, bromine, often containing a halogen other than fluorine and iodine as impurities, It is known to cause various problems in precision etching such as anisotropic etching. Accordingly, the present invention provides a practical and a method for efficiently producing monofluoromethane substantially free of halogens other than fluorine.

The present inventors have studied a method for manufacturing the monofluoromethane, 1-methoxy-1,1,2,2-tetrafluoroethane from the pyrolysis product produced by thermal decomposition in contact with the catalyst It found to be able to easily isolate high-purity monofluoromethane with a high yield.

That is, the present invention is as follows.

[Invention 1]
And thermally decomposing pyrolysis step of 1-methoxy-1,1,2,2-tetrafluoroethane by contacting with the catalyst, the production of monofluoromethane at least a step of recovering the monofluoromethane from thermal decomposition products Method.

[Invention 2]
Recovering the mono-fluoro methane, a process comprising the step of separating the monofluoromethane liquefy a portion of the pyrolysis products present invention 1.

[Invention 3]
Some of the liquefaction of pyrolysis products is carried out by cooling the second aspect.

[Invention 4]
Cooling temperature is -80 ~ -5 ° C. invention 3.

[Invention 5]
Recovering the monofluoromethane is a process including the step of absorbing the difluoroacetic acid fluoride in an inert solvent for difluoroacetate fluoride invention 1.

[Invention 6]
Inert to difluoroacetate fluoride is a hydrocarbon compound invention 5.

[Invention 7]
Recovering the monofluoromethane is a step comprising contacting with the active compound against difluoroacetate fluoride invention 1.

[Invention 8]
Compounds active on difluoroacetate fluoride are water, alcohols, primary amines, secondary amines or αβ unsaturated carboxylic acid ester Invention 7.

[Invention 9]
In the step of contacting the active compound against difluoroacetate fluoride, invention 7 or 8 the presence of a solvent.

[Invention 10]
In the step of contacting the active compound against difluoroacetate fluoride, invention 7-9 to present a basic substance.

[Invention 11]
Pyrolysis process, metal oxides, partially fluorinated metal oxide, metal fluoride, phosphoric acid or untreated also comb untreated even comb treated fluorination is a phosphate treated fluorination catalyst, thermal decomposition Inventions 1 to 10, the temperature 100 ℃ ~ 400 ℃.

[Invention 12]
Pyrolysis process, alumina, a partially fluorinated alumina or aluminum fluoride as a catalyst, the invention 1-10 pyrolysis temperature is 130 ℃ ~ 260 ℃.

[Invention 13]
Etchant or cleaning gas in semiconductor device manufacturing process, characterized in that it comprises a monofluoromethane produced by the method according to any one of claims 1 to 12.

[Invention 14]
Etching process or cleaning process in a semiconductor device manufacturing process, which comprises using a monofluoromethane produced by the method according to any one of claims 1 to 12

[Invention 15]
Inventions 1 to 6 having the steps of extracting and obtaining difluoro acetate fluoride with obtaining monofluoromethane.

It is a cross-sectional schematic view of an etching sample used in Use Example 1 and 2 of monofluoromethane. It is a schematic sectional view after etching of samples used in Use Example 1 and 2 of monofluoromethane. It is a schematic cross-sectional view of a remote plasma apparatus used in Use Example 1 and 2 of monofluoromethane. It is a schematic view of apparatus used in Examples 1-21. Examples 22-24, a schematic view of apparatus used in Reference Examples 5 and 6. It is a schematic view of the apparatus used in Example 26. It is a schematic view of apparatus used in Example 27 and 28.

Detailed description

Production method of the present invention, since the raw material containing no chlorine and the like, it is possible to produce high purity monofluoromethane containing no halogen other than fluorine as an impurity. In the method of the present invention, it is possible to produce high purity monofluoromethane which can be used as etchant or cleaning agent in the semiconductor industry without performing purification operation by complicated means. In the production method of the present invention, high raw material to the load on the global environment such as ozone layer destruction is small, from the use of less toxic 1-methoxy-1,1,2,2-tetrafluoroethane practical manufacturing it is a method. Furthermore, difluoro acetic acid fluoride and the like obtained as a by-product because of its use as a pharmaceutical and agrochemical intermediates, can be effectively utilized raw materials.

Production method of the present invention, 1-methoxy-1,1,2,2-tetrafluoroethane to give a thermal decomposition product containing a monofluoromethane thermally decomposed in the presence of a catalyst, the thermal decomposition products from a process for producing separating the monofluoromethane. The reaction by this method is involved is expressed by the following equation.
CHF 2 CF 2 OCH 3 → CH 3 F + CHF 2 COF

1-methoxy-1,1,2,2-tetrafluoroethane the starting material of the present invention can be obtained by known production methods. For example, the method of reacting methanol with tetrafluoroethylene in the presence of potassium hydroxide 1-methoxy-1,1,2,2-tetrafluoroethane can be synthesized (J.Am.Chem.Soc., 73,1329 (1951)).

Thermal decomposition of the catalyst according to the present invention is a metal oxide, partially fluorinated metal oxide, a metal fluoride, phosphoric acid or phosphate is used as a solid catalyst.

As the metal oxide, alumina, titania, etc. can be exemplified zirconia, easy alumina availability is particularly preferred. Alumina may be added ammonia to an aqueous solution of an aluminum salt of aluminum sulfate, etc. aluminum nitrate to precipitate aluminum hydroxide, molded and dried to any size, molded shape. The crystalline form large γ- alumina having a specific surface area is preferable. Drying agents, adsorbents, the α- alumina or γ- alumina commercially available as such a catalyst carrier can be used. Metal oxide, prior to use, hydrogen fluoride, a partially oxygen atom in an organic fluorine compound gas was substituted with a fluorine atom, performs fluorination treatment to partially fluorinated metal oxide, catalyst in the reaction preferably fluorinated activity is prevented from being lowered. If not the fluorination treatment, the monofluoromethane and materials produced by thermal decomposition into contact with a metal oxide at the reaction temperature, while the catalyst is fluorinated with catalytic activity becomes unstable, monofluoromethane and difluoroacetate fluoride is decomposed, there is a by-product of hydrocarbon such as methane increases. The fluorination treatment, hydrogen fluoride not only less expensive as a fluorinating agent, does not occur the precipitation of carbon in the process preferred.

Among the metal fluoride, in particular aluminum fluoride (AlF 3) or calcium fluoride (CaF 2) are preferred. It is preferred that these fluorides are anhydrous. When preparing the water-containing material is preferably subjected to dehydration treatment by heating. In these catalysts, the metal is fully fluorinated, but the catalyst does not occur the phenomenon as in the case of metal oxides that withdrawing the fluorine from the feed or product, in a metal fluoride, hydrogen fluoride fluorination treatment with etc. preferred to activate the catalyst surface.

The catalyst for thermal decomposition (herein, together phosphoric acid and phosphate may be referred to as "phosphate".) Phosphoric acid or phosphate is preferable. Phosphate, or may be supported on a carrier. Examples of the phosphoric acid, orthophosphoric acid, polyphosphoric acid, may be any of metaphosphoric acid. The polyphosphoric acid, pyrophosphoric acid. Phosphates are those metal salts of phosphoric acid. Since handling is easy is preferably orthophosphoric acid.

The phosphate is not particularly limited, consisting of hydrogen, aluminum, boron, alkaline earth metals, titanium, zirconium, lanthanum, cerium, yttrium, rare earth metals, vanadium, niobium, chromium, manganese, iron, cobalt, nickel selected from the group, and at least one metal phosphate. Preferably, the phosphate is a main component of aluminum phosphate, cerium phosphate, boron phosphate, titanium phosphate, zirconium phosphate, and the like chromium-phosphate. It also preferably includes other metals. Specifically, cerium, lanthanum, yttrium, chromium, iron, cobalt, and nickel are preferable, cerium, iron, yttrium is more preferred. Of these, more preferably aluminum phosphate, cerium phosphate and phosphoric acid salts consisting two.

There is no particular restriction on the method for preparing the phosphate catalyst may be used as it is a commercially available phosphate, may be prepared by the general precipitation method. Specific preparation methods of the precipitation method, for example, a metal nitrate (s metals preparing a solution of the respective salt.) And the mixed aqueous solution of phosphoric acid, the pH was dropped diluted aqueous ammonia adjusting precipitated, aging left as required. Thereafter, washing with water, to confirm that well washed with like conductivity of the wash water. In some cases, confirmed by measuring the cation containing an aliquot of the slurry. Then filtered and dried. There is no particular limitation on the drying temperature. Preferably from 80 ℃ ~ 150 ℃. More preferably 100 ℃ ~ 130 ℃. Resulting dried body or align milled particle size, further molded into crushed pellets or spheres. Then fired in air or a nitrogen atmosphere under a condition of 200 ℃ ~ 1500 ℃. Preferably 400 ~ 1300 ° C., more preferably performed baking at 500 ℃ ~ 900 ℃.

Although the baking time depends on the temperature at about 1 hour to 50 hours, preferably about 2 hours to 24 hours. Firing process, since the process required for regulation of phosphate, and when treated at a temperature lower than the temperature of the thermal decomposition reaction, when the processing time is short, it does not exhibit sufficient catalytic activity in the initial reaction is there. Also, by performing at or prolonged baking treatment above a temperature range of not only requires excessive heating energy, causing the crystallization of the catalyst, since it may impair the catalytic activity unfavorably.

Operation of addition of the metal components other than the main component is preferably carried out using a metal salt, said metal nitrates, chlorides, oxides, used as such phosphates. Among them, it preferred because nitrate is larger water soluble. There is no particular limitation on the addition amount, generally is more than 1 gram atom relative to phosphorus 1 g atom, preferably 0.5 gram atoms or less. More preferably at most 0.3 gram-atom. The addition of these metal components may be performed in a metal salt solution prior to precipitation during catalyst preparation, also phosphate catalyst after the catalyst calcination may be carried out by immersing the metal salt solution.

Metal oxides, partially fluorinated metal oxides, metal fluorides, phosphoric acid or phosphate catalyst, as it is, it is also possible to use a powder as a fluidized bed catalyst, and tableted into pellets It can also be used as a fixed bed catalyst Te. When tableting the powder, it may be added a binder. Saccharide binder that conventionally commonly used, a polymer compound, metal oxide, or the like can be used, orthophosphoric acid, polyphosphoric acid, the addition of a small amount of phosphoric acid such as metaphosphoric acid, efficiently without impairing the catalytic activity It can be tableted molded into.

As the catalyst, it can be used as it is an active ingredient as described above, it is preferably used in a state of being supported on a carrier. The carrier, alumina, titania, zirconia, metal oxides such as zirconia sulfate (ZrO (SO 4)), silicon carbide, silicon nitride, although the activated carbon and the like, activated carbon is particularly preferable.

Catalysts carrying phosphoric acid, the carrier was impregnated by immersion in a phosphoric acid solution, or can be prepared by drying the one obtained by coating or adsorbed by spraying. If supporting the phosphate impregnated with a single solution of one or more compounds to be supported, or after being coated or adsorbed by spraying, it can be prepared by drying. Further, it was dried by impregnating such a solution of the first compound, also be further solutions of different compounds is impregnated and the like. Further, it is also possible by performing the process according precipitation of phosphate as described above in the presence of a carrier such as activated carbon to prepare a phosphate supported catalyst.

Activated carbon, wood, charcoal, coconut shell charcoal, palm Kakusumi, plant as a raw material of carbon ash, etc., peat, lignite, brown coal, bituminous coal, coal as a raw material of anthracite and the like, petroleum residue, the raw material oil carbon etc. or it may be any of synthetic resin such as petroleum or hydrocarbon polyvinylidene chloride to. Select from these commercial activated carbons can be used, for example, activated carbon (TOYO CALGON manufactured BPL granular activated carbon) produced from bituminous coal, coconut shell charcoal (Japan EnviroChemicals Chemicals Ltd. granular Shirasagi GX, SX, CX, XRC, Toyo Calgon Ltd. PCB), and the like, but not limited thereto. Shape, size is also used in conventional granular, but spherical, fibrous, powdery, if adapted to the honeycomb shape or the like reactor can be used in ordinary knowledge scope.

Activated carbon used in the present invention are large activated carbon having a specific surface area of ​​preferably. The specific surface area of the activated carbon is sufficient in a range of commercially available standards, are each 400m 2 / g ~ 3000m 2 / g, preferably 800m 2 / g ~ 2000m 2 / g. Furthermore, when using the active carbon carrier, ammonium hydroxide, sodium hydroxide, or immersed 10 hours about or longer at about room temperature in a basic aqueous solution such as potassium hydroxide, usually when using activated carbon catalyst support nitric performed, hydrochloric, pre-treated with an acid such as hydrofluoric acid, may be activated and the removal of ash in advance the carrier surface.

Catalyst supporting phosphate catalyst or a phosphate of the present invention is also pre hydrogen fluoride prior to use, the fluorination treatment is brought into contact with the fluorine-containing compound such as a fluorinated hydrocarbon or fluorinated and chlorinated hydrocarbon What to do, because it prevents the change in composition of the catalyst in the reaction, the life of the catalyst, is effective in abnormal reaction prevented.

Carriers such as metal oxides of the present invention may contain other atoms than the metal component and oxygen, alumina (Al 2 O 3), zirconia (ZrO 2), titania (TiO 2) and zirconia sulfate and at least one metal oxide is preferably selected from the group consisting of partially fluorinated oxide, alumina and partially fluorinated alumina is particularly preferred in view of catalytic activity and catalyst life. Ratio of oxygen atoms and fluorine atoms in the catalyst is not particularly limited.

In the present specification and claims, unless otherwise limited, partially fluorinated as described above, alumina that is like chlorinated, an oxide such as zirconia "alumina", oxides such as "zirconia" there is possible to display the name.

Fluorination treatment with hydrogen fluoride, can significantly enhance the activity of the reaction. At a temperature higher than the temperature of at least the thermal decomposition is preferably carried out by contacting with hydrogen fluoride. Specifically, in the case of metal fluorides, such as a metal oxide or aluminum fluoride such as alumina, it is about 200 ~ 600 ° C., preferably about 250 ~ 500 ° C., more preferably 300 ~ 400 ° C.. For phosphate alone is about 200 ~ 700 ° C., preferably about 250 ~ 600 ° C., more preferably 300 ~ 550 ° C.. On the other hand, in the case of phosphate supported catalyst is about 200 ~ 600 ° C., preferably about 250 ~ 500 ° C., more preferably 300 ~ 400 ° C.. Both takes time for the treatment is less than 200 ° C., to perform the process beyond the maximum temperature range is not preferable since it takes excessive heating energy. The processing time, the processing amount can not be limited because both processing temperatures involved, about 1 hour to 10 days, preferably about 3 hours to 7 days.

In pyrolysis, among the above-described catalyst, aluminum fluoride, calcium fluoride, a catalyst treated with alumina or aluminum phosphate hydrogen fluoride particularly preferred.

Pyrolysis gas phase flow continuous system but is mentioned as the most preferred form, but is not limited thereto. Size and shape of the reactor can be changed appropriately depending on the amount of the reaction product.

In pyrolysis, can also be present inert gases in the reaction conditions, separation of monofluoromethane and the inert gas is complicated.

Pyrolysis temperature depends on the type of catalyst or contact time is usually 100 ~ 400 ° C., preferably 110 ~ 350 ° C., more preferably 130 ~ 320 ° C., more preferably 130 ~ 260 ℃, 140 ~ 200 ℃ is particularly preferred. The reaction temperature is lower than 100 ° C., for selectivity of monofluoromethane the high conversion ratio is low, productivity is undesirably low. Although the conversion of the reaction temperature exceeds 400 ° C. is almost 100% is required harsh heat resistance reactor, not only not economically preferable since it takes excessive heating energy, the secondary reaction takes place there is. For example, as shown in Reference Example 5 described later, it generated difluoro acetic acid fluoride is the contact with the catalyst at elevated temperature, which may be decomposed into trifluoromethane (CHF 3). The CHF 3 (boiling point = -82 ° C.) is monofluoromethane (boiling point: -78 ° C.) as the target compound and has a boiling point close, since loading the distillation separation, it is desirable to suppress as much as possible generation .

The reaction time (contact time) is dependent on the reaction temperature, is usually 0.1 to 1000 seconds, preferably 1 to 500 seconds, more preferably 10 to 300 seconds. If the reaction time is shorter than 0.1 second, there is a possibility that the conversion is low, whereas, since the reduced long and productivity than 1000 seconds, respectively undesirable. Conversely, very reactive even at slow region of the reaction temperature is less than 100 ° C., it is possible to improve the conversion rate by increasing the contact time.

The reaction pressure is not particularly limited, a normal pressure, reduced pressure, or may be any of pressure. 0.05 ~ 0.5 MPa is preferably (0.5-5 atm) degree, usually, the pressure of the operation is easy near atmospheric pressure is preferred.

Thermal decomposition reaction, the conversion of 1-methoxy-1,1,2,2-tetrafluoroethane may be substantially 100%. Since conversion is correlated with by-product ratio of trifluoromethane, if it is desired to simplify the purification process reduces the production of trifluoromethane, preferably 30 to 95%, more preferably 50 to 90%. Conversion of low productivity of monofluoromethane is less than 30%, the by-product of trifluoromethane increases exceeds 95%.

Catalytic pyrolysis reaction may over time coking occurs, the activity of the catalyst may decrease. Reduced catalytic activity, 200 ° C. ~ 1200 ° C., preferably at 400 ° C. ~ 800 ° C., can be regenerated readily active by contacting with oxygen (oxygen treatment). Oxygen treatment is convenient to circulating oxygen loaded left or outside the device was loaded into the reaction tube of the catalyst. Distribution of oxygen may coexist other gases, oxygen, air, but such as nitrogen diluted oxygen can be used, air or air diluted with nitrogen is economically preferable. Moreover, chlorine gas having an oxidizing power such as fluorine may be used. Further, it preferred since the catalyst surface is brought into contact with hydrogen fluoride after the above treatment is further activated.

The main component of the thermal decomposition product formed by the thermal decomposition is monofluoromethane and difluoroacetic acid fluoride, other unreacted 1-methoxy-1,1,2,2-tetrafluoroethane (HFE-254pc), trace include methane (CH 4), ethylene (C 2 H 4), trifluoromethane (CHF 3), propylene (C 3 H 6), methyl difluoroacetate (CHF 2 COOCH 3), difluoroacetate (CHF 2 COOH) and the like it is that there is. How to get from the pyrolysis product is separated monofluoromethane is not limited. Specifically, a distillation separation method utilizing a boiling point difference of monofluoromethane and other components, absorption separation method utilizing the difference in solubility in a solvent, or the compound having an active hydrogen atom being difluoroacetate fluoride and the like reactive separation method for separating after having reacted with.

[Distillation separation method]
Monofluoromethane the target compound (boiling point: -78 ° C.) is other is a major component difluoroacetate fluoride (boiling point: 0 ° C.) and the unreacted HFE-254pc (boiling point: 40 ° C.) the boiling point difference between the large, and cooled pyrolysis product flowing out of the pyrolyzer (gas) can be separated and recovered easily ingredients which mainly monofluoromethane by simple cooling liquefaction. Of course, the thermal decomposition products pressurized can be liquefied, it is preferable to cool even then. At this time, a part of the component is liquefied, and the composition consisting mainly of monofluoromethane as low-boiling components, easily separated difluoroacetate fluoride or a mixture of difluoro acetic fluoride and HFE-254pc as a high boiling component it can. Although the composition can be varied arbitrarily by the cooling temperature, usually, in the low-boiling components, it may contain CH 4, C 2 H 4, CHF 3, C 3 H 6 or the like as impurities, high-boiling components it may include the same manner CHF 2 COOCH 3, CHF 2 COOH and the like in.

Cooling temperature, operating pressure, flow rate of gas is depends on the cooling capacity. Cooling temperature at the pressure conditions can be easily inferred from the data of the following description and the vapor pressure. Under atmospheric pressure, -80 ~ -5 ° C. Tosureba well, preferably -78 ~ -20 ° C.. Monofluoromethane 32 can be used without substantial condensation at -78 ° C. (liquefied) and cooled in the carbon dioxide gas and solid carbon dioxide (dry ice) refrigerant. As the cooling method is applicable is any known means not specifically limited. For example, the method according to condenser with a typical multi-tube structure, and a method of distributing gas to the packed tower having a filler for superficial or distilled cooled by the refrigerant or the like external to the internal and the like.

The rectification column of the pyrolysis product can be distilled separated using in place of the simple cooling liquefaction. The rectification column, a packed column, and the like bubble cap. Distillation apparatus for distillation process, known devices may follow the method. Distillation conditions may be set according to the composition of the low boiling component or a high-boiling component of interest. To increase the composition of monofluoromethane as low-boiling component, the top and -78 ° C. vicinity, preferably distilled bottoms as about 0 ~ 50 ° C.. In that case, the low boiling point components may be included CH 4 traces, C 2 H 4, CHF 3 , C 3 H 6 and the like. When using a rectification column, the low boiling components consisting of substantially only monofluoromethane which distillate is sufficiently high purity, may be a semiconductor gas product. High-boiling components which is taken from the bottom comprises HFE-254pc of difluoro acetic acid fluorides and unreacted as the main component. High-boiling component further by distillation to separate the difluoro acetic fluoride and HFE-254pc, difluoro acetic acid fluoride as synthetic raw material for various reactions, also, HFE-254pc can be used as a recycle material to the pyrolysis process.

[Absorption separation method]
Inert solvent pyrolysis products produced by pyrolysis do not react with difluoroacetate fluoride (hereinafter, referred to as. "Inert solvent") is contacted with the absorption difluoroacetic acid fluoride contained in the pyrolysis product in a solvent is, it is possible to take out the monofluoromethane undissolved.

Here, the inert solvent is in the liquid state upon contact for absorbing a solvent having no active hydrogen atoms. The solvent having no halogen atom other than fluorine such as chlorine is preferred. As such solvents, specifically, aliphatic or aromatic hydrocarbon compounds, ketones, ethers, and esters. Examples of the aliphatic hydrocarbon compound, preferably a hydrocarbon compound having 5 to 20 carbon atoms, pentane, hexane, heptane, octane, nonane, decane, undecane, cyclopentane, cyclohexane, cycloheptane, methyl cyclohexane, aromatic hydrocarbons Examples of the compound, aromatic compounds having 6 to 20 carbon atoms are preferred, benzene, toluene, o-, m- or p- xylene, mesitylene, ethylbenzene, fluorobenzene, o-, m- or p- trifluoromethyl benzene, bis trifluoromethyl benzene. Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, as the ether, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, the ester, methyl formate, ethyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl butyrate, ethyl butyrate, and butyric acid butyl. Alkyl groups included in these compounds can be used as well a isomer.

Contact between the thermal decomposition product and the inert solvent is carried out at -70 ~ + 20 ° C., preferably -30 ~ 0 ° C.. + Exceeds 20 ° C. and unfavorably solubility of difluoro acetic acid fluoride to the inert solvent is lowered absorption efficiency decreases. Further, at temperatures below -70 ° C., the viscosity of the inert solvent is increased, or sometimes solidifies, it may also be absorbed yield decreases further monofluoromethane undesirable. The contacting can also be carried out under pressure, in which case, the contact temperature also varies, but usually preferable in terms of apparatus and operations carried out at pressure near atmospheric pressure.

Method of contacting the pyrolysis products and the inert solvent is not limited, known gas - can be employed liquid contact method. For example, a packed column, plate column, spray column, scrubber, wetted wall tower, bubble column, three-phase fluidized bed and a method of using bubbles stirred tank. Of these, packed column, spray column, bubble column, and bubble agitation tanks are preferred.

The packed tower to circulate and supply the inert solvent through the top of the liquid distributor plate to supply heat decomposition products from below. Thermal decomposition products with a filler surface is maintained as an absorbent has been solvent reservoir provided in the packed column bottom or outside is absorbed in the inert solvent. Monofluoromethane which has not been absorbed is discharged from the packed tower top.

The spray tower, the inert solvent from the top of the hollow tower is dispersed into the column as a number of fine droplets from the spray nozzle, increasing the pyrolysis products fed from the bottom, difluoro acetic acid in the column the fluoride is absorbed in an inert solvent, monofluoromethane which has not been absorbed is discharged from the packed tower top.

The bubble column or bubble agitation tank, a container charged with an inert solvent blowing pyrolysis products from Ekisoko unit, difluoro acetic acid fluoride contained in the pyrolysis products with the increase of the air bubbles are absorbed in an inert solvent, it is absorbed never been monofluoromethane is discharged from the packed tower top. The bubble column, using a sparger blown into the tower of the pyrolysis products, or known methods may be applied to make the residence time as bubbles in the column of the pyrolysis products. The bubble agitation tank, it is possible to enhance the contact efficiency finer bubbles pyrolysis products blown been to the bath with baffles and stirring blades of the stirring tank.

These contact methods can also be used in combination apparatus of the same type of apparatus or different in series. Bubble column or bubble agitation tank (collectively, simply. It is referred to as "tank") When bubbling method using a multi-tank type which connects a plurality of tanks in series are preferred. As an example, a description for the case of absorption vessel group consisting of 3 tank. First, the thermal decomposition products introduced through the second vessel to the first vessel to set a pipe so as to recover the components consisting mainly of monofluoromethane. When an inert solvent in the first vessel is saturated with difluoroacetate fluoride, switching the introduction destination of pyrolysis products in the second tank, piping As through a third tank for recovering the components consisting mainly of monofluoromethane change. When an inert solvent in the second bath is saturated with difluoro acetic acid fluoride, the third tank as an introduction destination of the pyrolysis products, the first vessel was prepared in a reaction vessel inert solvent freshly prepared extraction absorption been solvent changing the piping to the outlet of the component that monofluoromethane mainly. It can be carried out in the same manner below.

The low boiling point components obtained in the absorption separation method, typically because it contains solvent used as absorption liquid, it is desirable to remove the solvent by distillation, it is easily removed by precision distillation to simple distillation or below it can.

The absorbent solution used in the absorption separation method (absorption already solvents), in addition to HFE-254pc of difluoro acetic acid fluorides and unreacted as the major component containing an inert solvent. Absorbing been solvent is more by distillation to separate the difluoro acetic fluoride and HFE-254pc, difluoro acetic acid fluoride as synthetic raw material for various reactions, also, HFE-254pc can be used as a recycle material to the pyrolysis process.

[Reaction separation method]
The reaction separation method, separated from monofluoromethane difluoroacetic acid fluoride contained in the reaction products generated by the thermal decomposition has been translated to a stable compound at a high boiling point by reaction. Can also be performed at the same time converted separation in the same vessel, it can be performed in different vessels. The become active compound reaction partners (reactants), water, alcohols or a primary amine or secondary amine, but compounds having active hydrogen atoms, such as αβ-unsaturated carboxylic acid esters limited to Absent. Of these, water or an alcohol is preferred. The reaction of these compounds can be exemplified by the following equation.

CHF 2 COF + H 2 O → CHF 2 COOH + HF
CHF 2 COF + ROH → CHF 2 COOR + HF
CHF 2 COF + RNH 2 → CHF 2 CONRH + HF
CHF 2 COF + R 2 NH → CHF 2 CONR 2 + HF

In the reaction formulas, R represents an organic group. In these reactions, it is present a basic substance as acid acceptor to stabilize the hydrogen fluoride (HF) catalyzed or as produced are preferred. Examples of the basic substance include sodium hydroxide, potassium hydroxide, sodium carbonate, alkali metal hydroxide or carbonate such as potassium carbonate, tertiary amines are preferred. When using water as a reaction reagent, the alkali metal, potassium is particularly preferable. The presence of a basic substance, difluoro acetic acid is converted into difluoro acetate.

The alcohols (ROH), but are not limited to, R is also alkyl or fluorinated alkyl group having 1 to 8 carbon atoms having a branch, also cycloalkyl group having an alkyl group as a substituent, aryl group include an aralkyl group, among these fluorine-containing alkyl group of the alkyl group or 2 to 8 carbon atoms having 1 to 8 carbon atoms preferred. Further, more preferably an alkyl group or a fluorinated alkyl group having 2 to 4 carbon atoms having 1 to 4 carbon atoms. Alcohol may be a polyhydric alcohol. Examples of the alkyl group having 1 to 8 carbon atoms, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, s- butyl, t- butyl group, n- pentyl group, as an example isopentyl it can be mentioned. Examples of the fluorine-containing alkyl group having 2 to 8 carbon atoms, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 2,2,3,3,3-pentafluoro-propyl, n- hexafluoropropyl group , it may be mentioned by way of example and hexafluoroisopropyl group. The polyhydric alcohols, valence 2-5, preferably those having 1 to 8 carbon atoms, more preferably those having 1 to 4 carbon atoms. Specifically, glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and pentaerythritol.

Alcohols may also be used as the metal alkoxide of the alcohol. Examples of the metal include sodium, potassium, and lithium is. Alkoxides sodium or potassium alcohols having 1 to 4 carbon atoms are preferred. Specifically, sodium methoxide, sodium ethoxide, sodium propoxide, potassium butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium butoxide and these alkyl groups include those isomers.

Primary amines, the secondary amines of the general formula R 1 R 2 NH (R 1 , R 2 is hydrogen or a linear, a branched or cyclic alkyl group, the total number of carbon atoms is 3 to 15 .) amine represented by are preferred. The total number of carbon atoms is less than 3 and a boiling point must be carried out in contact with a low temperature low, unfavorably has contamination risk to the lower boiling component.

The amine of the total number of carbon atoms is 3 to 15 represented by the general formula, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octyl , nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, such as pentadecyl amine. Of these, easily available diethylamine, dipropylamine, diisopropylamine, more preferably such as dibutylamine, diethylamine being particularly preferred. These amines can also be used as mixtures.

The αβ-unsaturated carboxylic acid ester, preferably an acrylic acid ester or methacrylic acid ester, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and methacrylic acid 2-ethylhexyl can be mentioned.

Water, alcohol, primary amine, a compound having an active hydrogen atom, such as secondary amine may be mixed with one another, the amount is used in excess with respect difluoro acetic acid fluoride. These agents may be used with an inert solvent. Preferably used when the agent is to ensure the fluidity to a compound having a low solid or melting point. The amount of the solvent is not limited, to the reagents 100 parts by weight, a 30 to 10,000 parts by weight, preferably 100 to 1,000 parts by weight. The inert solvent can be exemplified inert solvent as described in "absorption separation method".

Temperature of contacting is particularly well while no restricted otherwise heating and cooling does not, it is usually about 0 ~ 50 ° C.. Pressure may be carried out in particular under pressure or under reduced pressure does not affect the reaction may be carried out in particular pressure-vacuum it was not in the vicinity of atmospheric pressure.

Tertiary amines as basic substance to be present during the contacting is not particularly limited, the general formula, R 1 R 2 R 3 N (R 1, R 2, R 3 a linear, branched or cyclic and an alkyl group is preferably a tertiary amine represented by the total number of carbon atoms is 6 to 15.). Even total number of carbon atoms is 5 or less of a tertiary amine can capture hydrogen fluoride as the tertiary amine / hydrogen fluoride salts, such tertiary amines are tertiary amine / hydrogen fluoride salt formed is large water soluble the tertiary amine is decomposed with water or an aqueous solution reduces the recovery rate when recovering separated from the aqueous layer, undesirable waste increases. All tertiary amine number of 16 or more carbon atoms is because less water soluble are suitable for decomposition and recovery of water, is not preferable for practical use less hydrogen fluoride trapping amount per weight.

As the tertiary amine of general formula the total number of carbon atoms is from 6 to 15 represented by the tri -n- propyl amine, tri - isopropylamine, tri -n- butylamine, tri - isobutyl amine, tri -sec- butylamine, tri -tert- butylamine, tri -n- amylamine, tri - isoamylamine, tri -sec- amylamine, tri -tert- amylamine, N- methyl di -n- butylamine, N- methyl diisobutylamine, N- methyl di -tert- butylamine , N, N-diisopropyl-butyl amine, N, N-dimethyl -n- octylamine, N, N-dimethyl-nonyl amine, N, N-dimethyl decyl amine, N, N-dimethyl-undecyl-amine, N, N-dimethyldodecylamine amines, such as N- methyl dihexylamine Of these, tri -n- propyl amine, tri - isopropylamine, tri -n- butylamine, tri - isobutyl amine, tri -n- amylamine, tri - such as isoamyl amine, more preferably, tri -n- butylamine is particularly preferred . These tertiary amines may also be used as mixtures.

Tertiary amine is added to 0.5 mol per 1 mol of difluoro acetic acid fluoride. When using an excess of a tertiary amine, for example, a layer consisting of tertiary amines layer and free consisting difluoro acetic ester and tertiary amine / hydrogen fluoride salt to the reaction product solution produced by the esterification reaction forms is, these layers can be easily separated, tertiary amine is recovered.

Method of contacting reactants with the pyrolysis products is not limited, the same known gas to the method described in "absorption separation method" - can be employed liquid contact method. These contact methods can also be used in combination apparatus of the same type of apparatus or different in series. Bubble column or bubble agitation tank (collectively sometimes referred to as "tank".) When bubbling method using a multi-tank type which connects a plurality of tanks in series are preferred. As an example, it may be a plurality of tanks may be used one tank, but multi-tank type which connects a plurality of tanks in series are preferred. As an example, a description for the case of absorption vessel group consisting of 3 tank. First, the thermal decomposition products introduced through the second vessel to the first vessel to set a pipe so as to recover the components consisting mainly of monofluoromethane. When the reaction reagent or acid acceptor in reaction absorption liquid in the first tank is consumed, switching the introduction destination of pyrolysis products in the second tank, to recover the components consisting mainly of monofluoromethane through the third vessel to change the piping as. When the reaction reagent or acid acceptor in reaction absorption liquid of the second tank has been consumed, the and the third tank as an introduction destination of the pyrolysis products, prepared were charged and the reaction absorbing solution of freshly prepared extraction liquid contents one tank to change the piping to the outlet of the component that mainly monofluoromethane. It can be carried out in the same manner below.

Monofluoromethane in contact with the reaction absorbing solution does not react, no decrease in the yield due to the reaction. The components of the monofluoromethane obtained are processed in the reaction separation method primarily (low boilers), usually it contains CH 4, C 2 H 4, CHF 3, C 3 H 6 , etc. it can be purified by precision distillation.

Difluoro acetic acid produced in the reaction separation processes, difluoromethyl acetate, difluoro acetic esters, difluoro acid amide is separated respectively by using a known method, it can be purified. For example, the reaction absorption liquid of the esterification reaction, when washed with water and / or basic aqueous distillation can recover difluoro acetic acid ester, if a basic substance using a tertiary amine, immediately distilling the reaction absorbing solution also it is possible to recover a difluoro acetate ester.

[Purification method]
Low boiling point components obtained in the various separation methods may include acidic components traces. For example, the low-boiling components after separation by cooling liquefaction is sometimes difluoroacetate fluoride or hydrogen fluoride is mixed with entrainment or the like. Acidic component contained in the low boiling components were washed by contact with water and / or basic aqueous solution, can be removed by drying treatment, it can be a high purity monofluoromethane. Cleaning method, bubbling method and the like bubble column, such as a scrubber system using a packed column, various gas shown in "absorption separation method" - can be arbitrarily applied to the liquid contact method. As the basic aqueous solution, KOH aqueous solution, NaOH aqueous solution, although Ca (OH) 2 aqueous solution, and the like, high saturation solubility of the fluoride salts to produce upon contact, hardly cause troubles clogging of the apparatus KOH aqueous solution is preferred. After washing, soda lime, a synthetic zeolite, by dehydrating agent such as silica gel, it is desirable to remove the moisture. Further, soda lime or synthetic zeolite, silica gel is not only dehydration may also have the effect of removing unwanted by-products. The synthetic zeolite, 3A type, 4A type, 5A type, 10X type, such as 13X-type can be used. Washed monofluoromethane obtained by thermal decomposition and, only drying with zeolite, soda lime, etc., without the precision distillation can be easily 99% purity, thermally decomposed at optimal conditions If you, the purity can be 99.9% or more. This is of sufficient purity to be used as an etching gas or a cleaning gas in the semiconductor industry.

Further, the low-boiling component, it may be included trace amounts of CH 4, C 2 H 4, CHF 3, C 3 H 6 or the like, it is possible to further high purification by precision distillation. Rectification can be carried out by known methods using rectification tower filled with various fillers. Monofluoromethane (boiling point: -78 ° C.) and for rectification may be at atmospheric pressure, but pressure distillation is convenient because the cryogenic distillation.

Components containing monofluoromethane which impurities are concentrated by distillation, burned in air or oxygen, or catalyst used in the pyrolysis of the process of the present invention, in particular the catalyst in 500 ° C. of about of phosphate as an active ingredient in in contact with oxygen or the like to burn, it is possible to discard harmless by the generated gas is washed with an aqueous basic solution.

Monofluoromethane as products, the monofluoromethane prepared by the method of the present invention is cooled and solidified in liquid nitrogen or the like, after removing the air component by reducing the pressure in the vessel by a vacuum pump, back into a gas or liquid state It is moved to the cylinder for storage Te be prepared. The resulting product, organic purity, excellent both inorganic purity, a monofluoromethane containing no air or the like.

[Applications]
Monofluoromethane to a thin film device fabrication process with a focus on the semiconductor industry, optical device production process, such as in ultra-steel material manufacturing process, CVD method, a sputtering method, a sol-gel method, a thin film that is created by using a vapor deposition method, the thickness the membrane is useful as a so-called etching gas for etching (etching agent). The device when creating a thin film or the like in these processes, it is also useful as a so-called cleaning gas for removing a thin film or powder which is deposited to the piping or the like.

Monofluoromethane obtained by the present invention, the chlorine to form a deep impurity level in the semiconductor, suitable for the semiconductor manufacturing apparatus and semiconductor thin film processing application contains no halogen other than fluorine such as bromine substantially. This is because the reaction raw materials and auxiliary materials do not contain chlorine, bromine, iodine, mixed halogen element other than these fluorine caused by not occur. Monofluoromethane according to the method of the present invention halogen element containing no halogen such as chlorine from the viewpoint of influence on the etching rate and the anisotropic etching has been pointed out in the etch such as chlorine are preferred.

Monofluoromethane or etching gas containing it of the present invention, a silicon wafer, a metal plate, glass, single crystal, W deposited on a substrate such as polycrystalline, WSi x, Ti, TiN, Ta 2 O 5, Mo, Re, Ge, Si 3 N 4 , Si, can be suitably applied to a SiO 2 or the like.

When using monofluoromethane as the etching gas, RIE (reactive ion etching), ECR (electron cyclotron resonance) plasma etching, microwave etching technique etching utilizing plasma, such as high-frequency plasma etching is preferably used. Treatment conditions are not particularly limited, the type of target film, physical properties, productivity, by fine accuracy such, it is also possible to add various additives. N 2, the He, Ar, Ne, among inert gases Kr, etc., in particular Ar is a synergistic effect with monofluoromethane, higher etch rate. To increase productivity, when you want to increase the etch rate can addition of oxidizing gas. Specifically, O 2, O 3, CO 2, F 2, NF 3, Cl 2, Br 2, I 2, XF n (X = Cl, I.Br, 1 ≦ n ≦ 7) can be exemplified . Amount added plasma power, the shape of the device, depending on the performance and target film properties, typically less than 10 times the flow rate of monofluoromethane are preferred. If added more, sometimes excellent anisotropic etching performance of monofluoromethane is impaired.

Further, when it is desired to reduce the F radicals amount to promote isotropic etch, the addition of the reducing gas is preferable. The reducing gas, 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, HI, HBr, HCl, CO, NO, NH 3 is illustrated in H 2. Amount is desirably 10 times or less, more for significantly reduced the F radicals acting etching the addition, the etching rate decreases. Further, CH 4, CHF 3, the gas having a carbon number of 1 such as CH 2 F 2 is also effective for fine-tuning of the fluorine / carbon ratio of the etching gas. These added amount is preferably 10 times or less. The addition more excellent etching rate of monofluoromethane is impaired. Furthermore, CO will trap-produced HF in the form of HCOF, itself is efficient because acts as an etching agent. Amount of CO is, CH 3 F: CO (molar ratio) = 10: 1 to 1: 5, preferably from 5: 1 to 1: 1 is preferred.

To perform anisotropic etching, it is preferable that the gas pressure is less 5 Torr, undesirable because the etching rate becomes slower at pressures 0.001 Torr. Gas flow rate to be used, the reactor capacity of the etching apparatus, although depending on the wafer size, it is preferable to etch at a rate of between 10 SCCM ~ 10000 sccm. The temperature for etching, 400 ° C. or less is preferred, at a high temperature exceeding 400 ° C. It machining accuracy tends to isotropically etching proceeds in need there is not obtained, since the resist is significantly etched undesirable. By using this way it is mixed with hydrogen or a hydrogen-containing compound gas, for example, or can improve the etch rate selectivity between silicon and silicon oxide film during processing of the contact hole.

If, when the polymer accumulation is large, after etching, it can be ashed by using an oxidizing gas such as F 2, O 2.

When using a monofluoromethane as a cleaning gas, a removable deposits, specifically, SiO 2, WSi x, TiN , Ta 2 O 5, Si 3 N 4, oxides such as SiB, nitrides, carbides include borides and composites thereof. Among these, in particular, silicon-containing deposits a deposit containing at least silicon or compounds thereof are preferred as the object of elimination.

The cleaning gas containing monofluoromethane or it of the present invention, in consideration of the type of material used in the apparatus for producing a type and thickness as well as thin films such as the deposit to be removed, as an additive, O 2, O 3, CO 2, F 2, NF 3, Cl 2, Br 2, I 2, in XF n (wherein, X represents Cl, I or Br, n represents an integer of 1 ≦ n ≦ 7 .), it may be added CH 4, CH 2 F 2, CHF 3, N 2, He, Ar, Ne, one of Kr. The addition of oxygen is effective in cleaning rates increase. Specifically, CH 3 F: O 2 (molar ratio) of 10: 1 to 1: 5 by weight, more preferably from 5: 1 to 1: 3.N 2, He, Ne, Ar , Kr, among inert gases such as Xe, particularly Ar cleaning speed is improved by the synergistic effect with the monofluoromethane. F 2, NF 3, Cl 2 , Br 2, I 2, XF n (X = Cl, I.Br, 1 ≦ n ≦ 7), CH 4, CH 2 F 2, the addition of CHF 3 is removed target deposits it is effective in the control of the clean training speed according to the type.

For the cleaning conditions, has no particular selected appropriately limited in consideration of the material of the treatment apparatus, temperature, 800 ° C. If the device material is quartz or less, ceramics, metals such as aluminum used as the material If it is preferably 500 ° C. or less. Corrosion occurs unfavorable at these temperatures above. Next, the pressure, preferably to below 100 Torr exceeds 500 ° C., the load on the device exceeds 100 Torr (corrosion) takes undesirable.

Cleaning by cleaning gas of the invention, pyrogenic, photolytic methods, can be used in either plasma method, a plasma method is preferred. Plasma method may be generated in the chamber using a high frequency or microwave but the remote plasma method to introduce into the chamber by generating in the chamber outside is preferably employed. The cleaning method of the present invention, a semiconductor device, a semiconductor device such as a liquid crystal device, an optical device can be applied to a thin film in the manufacturing process such as a coating tool film forming apparatus and whiskers formed by a CVD method, a manufacturing apparatus for manufacturing such powders. Of these, particularly preferred application to film forming apparatus, a semiconductor device, more preferably for use in film forming apparatus of a semiconductor device using a silicon compound such as a liquid crystal device.

Specifically described by way of embodiments for the present invention are shown below, but the present invention these are not limited. Unless otherwise stated, percentages in the organic composition and purity (%) represents the area% was analyzed with gas chromatograph FID detector. Further, unless otherwise using "EPA the METHOD 624" corresponding columns for the analysis of a composition comprising a highly polar difluoroacetate fluoride (CHF 2 COF), etc. (composition taken by a sampling port A), monofluoro methane (CH 3 F), trifluoromethane (CHF 3) compositions containing predominantly low-boiling components such as (composition taken by a sampling port B) were analyzed using a silicon-based plot column.

[Preparation of Catalyst Example 1]
85% phosphoric acid (H 3 PO 4) 30g to aqueous phosphoric acid solution diluted with water 300cc immersing the granular activated carbon G2X 100 g of Japan EnviroChemicals Chemicals Co., Ltd., and allowed to stand for 3 days after stirred well. Then dried in a rotary evaporator, then, a nitrogen gas stream in an electric furnace, and calcined 5 hours at 350 ° C., was prepared phosphate on activated carbon catalyst.

[Preparation of Catalyst Example 2]
Aluminum nitrate nonahydrate the (Al (NO 3) 3 · 9H 2 O) 1000g (2.666mol) and cerium nitrate hexahydrate (Ce (NO 3) 3 · 6H 2 O) 128.6g (0.296mol) dissolved in pure water 5300Cc, it was added and stirred for an additional 85% phosphoric acid 306g (3.12mol). In this state, it was a clear solution. To this was 10% aqueous ammonia by large dropping funnel and added dropwise over (approximately 3000cc) for about 10 hours basic 1L. Solid concentration is high, since the stirrer from the middle dropwise became unstirrable was hand stirred with a stainless steel scoop. The resulting white precipitate was allowed to stand overnight, filtered off with suction was carried out 5 times with water washing.
The white solid was transferred to a stainless steel pad, and dried overnight in a 180 ° C. oven. Ground in a mortar, sieved and molded into pellets of 5mmφ × 5mmL at tablet press, and calcined 5 hours in a nitrogen stream 700 ° C., was prepared aluminum phosphate cerium phosphate catalyst.

[Preparation of Catalyst 3]
Aldrich aluminum phosphate (Aluminum phosphate) tableted molded into pellets of 5mmφ × 5mmL, and calcined 5 hours in a nitrogen stream 700 ° C., was prepared aluminum phosphate catalyst.

[Preparation of Catalyst 4]
Mantle length with a heater 1.5 m × inside diameter 55mm stainless steel (SUS316) manufactured by the reaction tube γ- alumina beads (Sumitomo Chemical, KHS-46) was 2kg filled. The heating mantle temperature was controlled to 50 ° C., while circulating nitrogen (1000 cc / min), hydrogen fluoride was vaporized in vaporizer (HF) was passed through at 4g / min. This distribution is especially observed fever (adsorption heat and reaction heat) within the inlet portion, the heating region is moved gradually toward the outlet. At this time, if the highest heat spot temperature exceeds 300 ° C., by lowering the HF feed rate 1 g / minute or less, to suppress local heat generation, after confirming that the temperature reaches a set temperature, slowly HF the feed rate was back up to 4g / minute. After the heating region has reached near the exit, the jacket set temperature raised to 250 ° C. by 50 ° C., was repeated fluorination of said γ- alumina. Then, set the jacket set temperature to 300 ℃, was gradually increased to 20g / min HF flow rate. Temperature of the heat spot at this time if it exceeds 350 ℃, lower the HF flow rate to 1g / minute. Jacket temperature 300 ° C., with HF flow rate 20 g / min conditions, from the point of substantial heat spot is no longer observed, and further continued for 24 hours fluorination treatment in the same conditions, then, while passing only the nitrogen, heater Turn power and cooling, to obtain a fluorinated treated alumina catalyst.

[Preparation Example of Catalyst 5]
Aldrich anhydrous aluminum fluoride and (AlF 3) tableted molded into pellets of 5mmφ × 5mmL, and calcined 5 hours in a nitrogen stream 700 ° C., was prepared aluminum fluoride catalyst.

Sensitivity Measurement of Reference Example 1 FID detector]
With a preparation of monofluoromethane and difluoroacetic acid fluoride were sensitivity measurement of FID detector. Monofluoromethane (40 kPa, 300 torr) and difluoroacetic acid fluoride (40 kPa, 300 torr) were taken into a cylinder (300 cc) (molar ratio: 1: 1, total pressure: 80 kPa, 600 torr), warmed to cylinder 25 ° C. , now take the sample of 0.2cc in gas syringe, using "EPA the METHOD 624" corresponding column performs gas chromatographic analysis to determine the area ratio.
CH 3 F area: CHF 2 COF area = 2.41: 1.00.

[Example 1]
Figure 3 shows the apparatus used in the experiment. An inner diameter with an electric furnace 52 to the outside has a sampling port A53 to the exit side 37 mm, using a stainless steel reaction tube 51 of length 500 mm, stainless steel was packed with stainless steel Raschig rings at the outlet of the reaction tube 51 Liebig connect the cooling pipe 54 jacketed high boiling compounds collector 55 a (-50 ° C. coolant distribution) 2 inborn (both circulated -50 ° C. refrigerant), and further, gas washing bottles A56 (contents: water, ice-cold 59), a gas washing bottle B57 (content: filled with 1: 50% KOH aqueous solution, ice-cold 59), gas washing bottles C58 (empty traps, ice cold 59), soda lime and synthetic zeolite 4A 1 connected in series with a drying tube 60 in this order, we provided the sampling port B61 at the exit of the drying tube.

Catalyst prepared in Preparation Example 1 of catalyzing (230 cc) was charged to the reaction tube 51 was heated electric furnace 52 under a stream of nitrogen at 15 cc / min. When the temperature of the catalyst reaches 50 ° C., hydrogen fluoride (HF) was introduced through the vaporizer at 0.6 g / min. While allowed to flow HF, slowly raised to 210 ° C., held for 15 hours. Stopping the flow of HF, the nitrogen flow rate after 2 hour hold increased to 200 cc / min, 1-methoxy-1,1,2,2-tetrafluoroethane (HFE-254pc) with rate of 0.5g / min, immediately after introduced through the vaporizer was stopped the flow of nitrogen. When the reaction temperature reaches a steady state at 300 ° C., result of sample gas collected in a sampling port A53 of the reaction tube outlet was analyzed by gas chromatograph FID detector ( "EPA the METHOD 624" corresponding column), and cooling the results of the samples gas collected gas after washing dried at a sampling port B61 was analyzed by gas chromatograph FID detector (silicon-based plot column) are shown in Table 1 and Table 2.

Figure JPOXMLDOC01-appb-T000001

Figure JPOXMLDOC01-appb-T000002

[Examples 2 to 21]
Using the catalyst prepared in Preparation Example 2-5 of the catalyst, under the conditions shown in Table 1 were experimentally as in Example 1. The results obtained are shown in Table 1 and Table 2.

[Example 22]
Figure 4 shows the apparatus used in the experiment. After through the flexible tube 75 immersed in the thermal decomposition reaction was carried out under the same conditions as in Example 1, ethanol bath maintained pyrolysis gas flowing out of the reaction tube 71 to -15 ° C., dry ice top - acetone bath in cooling with the separation column 78 (-15 ° C.) with a reflux condenser 79 maintained at -78 ° C., it is condensed higher boiling point components, collected in a high boiling compound collector 76 jacketed (-15 ° C.) , low-boiling components of ice water trap 81 which is not condensed, aqueous potassium hydroxide solution trap 82, through the drying tube 83 filled with synthetic zeolite 4A. A sampling port A73 shown in FIG. 4, a sampling port B84, a sampling port C80, by sampling the sample from the sampling port D77, and a gas chromatographic analysis using "EPA the METHOD 624" corresponding column. A sampling port B84, for a sampling port C80, and also analyzed "silicon-based Plot Column", the analysis result, it was confirmed that substantially matches between these columns. The results are shown in Table 3.

Figure JPOXMLDOC01-appb-T000003

[Reference Example 2]
Outside charged with internal diameter 23mm provided with an electric furnace, a stainless steel reaction tube of length 500mm Japan EnviroChemicals Chemicals Co., Ltd. of granular activated carbon G2X (50 cc), and heated in an electric furnace while flowing nitrogen at 15 cc / min. When the temperature of the reaction tube portion reaches 200 ° C., the starting material 1-methoxy-1,1,2,2-tetrafluoroethane (HFE-254pc) with 0.4 g / min, introduced through the vaporizer did. When the temperature of the reaction tube part becomes a steady state at 250 ° C., Analysis of the product gas, a conversion of 0.9%, substantially raw material was recovered.

[Reference Example 3]
Except that the temperature of the reaction tube section and 300 ° C., result of reaction in the same manner as in Reference Example 2, the conversion: was 2.6%. The temperature was raised to 300 ° C., but was similar to raw material recovery.

[Reference Example 4]
Outside charged with internal diameter 23mm provided with an electric furnace, a stainless steel reaction tube of length 500mm Japan EnviroChemicals Chemicals Co., Ltd. of granular activated carbon G2X (50 cc), and heated in an electric furnace while flowing nitrogen at 15 cc / min. When the temperature of the reaction tube interior reached 50 ° C., HF and (0.6 g / min) was introduced through the vaporizer. While allowed to flow HF, slowly raised to 300 ° C., and held for 5 hours. Stopping the flow of HF, after 2 hour hold increase the nitrogen flow rate to 200 cc / min, and change the nitrogen flow rate 15 cc / min, 1-methoxy-1,1,2,2-tetrafluoroethane (HFE-254pc) at 0.4 g / min, it was introduced through the vaporizer. When it becomes a steady state at a temperature 300 ° C. in the reaction tube part, the result of the analysis of product gas, the conversion rate: 2.8%, a substantially raw material recovery, HF activated carbon not carrying phosphoric acid be subjected to a treatment, the effect was not observed.

[Example 23]
Using the apparatus shown in FIG. Internal diameter 37mm provided with an electric furnace 72 to the outside has a sampling port A73 to the exit side, a stainless steel reaction tube 71 of length 500 mm, air trap 74 made of polyethylene to the outlet of the reaction tube 71, to -15 ° C. a sampling port to the outlet side has a jacketed high-boiling compounds collector 76 in reflux condenser 79 and the bottom was maintained at -78 ° C. acetone bath - kept flexible tube 75 of the coolant bath, dry ice overhead separation column 78 with B84 (-15 ° C.), ice water trap 81, a basic aqueous solution trap 82 (50% KOH aqueous solution, ice-cold), a synthetic zeolite 4A 1: each fluororesin or polyethylene with a drying tube 83 filled with 1 connect the manufacturing of pipes, the outlet of the drying tube 83 is open to the removal device.

Before starting the experiment, in the apparatus shown in Figure 4, the connection of the reaction tube 71 and the air trap 74 was separated and reclassified pipe to allow the exhaust directly to the scrubber outlet of the reaction tube 71. After filling the resulting catalyst 230cc in Preparation 4 of the catalyst in the reaction tube 71, the electric furnace 72 was heated under a stream of nitrogen at 15 cc / min, when the temperature of the catalyst reaches 50 ° C., the vaporizer hydrogen fluoride (HF) was introduced at a 1.0g / min through. While allowed to flow through the HF, the temperature was raised slowly to 350 ℃. It should be noted that, when the local heat generation was observed in the middle of raising the temperature is lower the feed rate to 0.1g / min, slowly to gradually 1.0g / minute after the local heat generation and it was confirmed that the converged It raised the HF feed rate. Upon reaching 350 ° C., after 30 hours hold, stop the flow of HF, lowering the nitrogen flow rate after 2 hour hold increase the 200 cc / min, an electric furnace temperature to 180 ° C., 1-methoxy-1,1, 2,2 tetrafluoroethane (HFE-254pc) introduced through the vaporizer at 0.2 g / min, and stopped the flow of nitrogen immediately. The reaction temperature is to change the setting of the electric furnace 72 so that 0.99 ° C., after reaching a steady state, the reaction tube outlet and air trap 74 is connected, back to the apparatus configuration shown in FIG. The effluent gas, air trap 74, after passing through the coiled 75, and collected in the separation column 78 (-15 ° C.) in a high boiling component is condensed high-boiling compounds collector jacketed 76 (-15 ° C.), low boiling point components of ice water trap 81 which is not condensed, aqueous potassium hydroxide solution trap 82, through the drying tube 83. Where a sample taken by a sampling port A73 was analyzed by gas chromatograph FID detector ( "EPA the METHOD 624" corresponding column), CH 3 F: 54.291% , CHF 2 COF: 22.126%, CHF 2 CF 2 OMe ( "Me" represents a methyl group or less the same..): 23.101%, other: was 0.482%. Furthermore, analysis of the samples collected in a sampling port B84 by gas chromatograph FID detector (silicon-based plot column), CH4: less than 0.001%, C 2 H 4: 0.017%, CHF 3: 0 .009%, CH 3 F: 99.961 %, C 3 H 6: 0.008%, others: was 0.004%. The results are shown in Tables 1 and 2.

[Example 24]
Except that the reaction temperature at 175 ° C., was subjected to the same experiment as in Example 23. When a sample taken by a sampling port A73 was analyzed by gas chromatograph FID detector ( "EPA the METHOD 624" corresponding column), CH 3 F: 69.544% , CHF 2 COF: 28.240%, CHF 2 CF 2 OMe: 1.351%, Others: was 0.685%. Furthermore, analysis of the samples collected in a sampling port B84 by gas chromatograph FID detector (silicon-based plot column), CH 4: 0.024%, C 2 H 4: 0.121%, CHF 3: 0 .126%, CH 3 F: 99.455 %, C 3 H 6: 0.003%, others: was 0.271%. The results are shown in Tables 1 and 2.

[Example 25]
Junsei Chemical Co., Ltd. anhydrous calcium chloride granular stainless steel reaction tube having an inner diameter of 23mm length 400 mm (particle size of about 2.5 ~ 3.5mm) (63g, bulk: 120 cc) was filled with a nitrogen 50 cc / It was heated to 160 ° C. while passing minute. Example 24 organic matter recovered jacketed high boiling compounds collector 76 (CHF 2 COF: 94.181%, CHF 2 CF 2 OMe: 4.569%) and is flowed at 0.3 g / min At the same time, to stop the supply of nitrogen. Fever of 10 ℃ ~ 20 ℃ in the vicinity of the entrance is seen, over time the heat spot is moved towards the exit. When the exit gas when organic was 77.9g fed was analyzed by gas chromatograph FID detector ( "EPA the METHOD 624" corresponding column), CHF 2 COF: 1.105% , CH 3 Cl: 4.708%, CHF 2 CF 2 OMe: 0.001%, CHF 2 COCl: 93.769%, Others: was 0.417%.

After the above analysis, with changing the raw material to CHF 2 CF 2 OMe (99.9% ), the reaction temperature was changed to 330 ° C.. Results outlet gas of the steady state (after 30 hours) was analyzed by gas chromatograph FID detector ( "EPA the METHOD 624" corresponding column), the composition, C 2 H 4: 2.406% , CH 3 F: 68. 486%, CHF 2 COF: 20.460 , CHF 2 CF 2 OMe: 7.656%, Others: was 0.992%. The results are shown in Table 1.

Then, the stopped supply of the raw material, while circulating nitrogen (100 cc / min), and then gradually cooled to room temperature by stopping heating of the electric furnace. The contents of the reaction tube is slightly coloration was observed, most showed no powdering and adhesion was the same shape as before the reaction. As a result of powder XRD measurement triturated The contents of an agate pot showed diffraction pattern of CaF 2.

[Reference Example 5]
HFE-254pc instead of purity 98.2% was obtained by distillation was collected in a jacketed high-boiling compounds collector 76 in Example 23 organic CHF 2 COF (main impurities CHF 2 CF 2 OMe : 1.1%) than that supplied the, the same experiment was performed as in example 23. When a sample taken by a sampling port A73 was analyzed by gas chromatograph FID detector ( "EPA the METHOD 624" corresponding column), CHF 3: 83.988%, CH3F: not detected, CHF 2 COF: not detected, CHF 2 CF 2 OMe: not detected, other: was 16.012%. Furthermore, analysis of the samples collected in a sampling port B84 by gas chromatograph FID detector (silicon-based plot column), CH 4: 0.368%, C 2 H 4: 0.238%, CHF 3: 92 .653%, CH 3 F: 0.569 %, C 3 H 6: 0.176%, CHF 2 CF 2 OMe: not detected, other: was 5.996%.

[Reference Example 6]
Except that the reaction temperature at 330 ° C., the same experiment was performed as in Example 23. When a sample taken by a sampling port A73 was analyzed by gas chromatograph FID detector ( "EPA the METHOD 624" corresponding column), CH 3 F: 26.013% , CHF 2 COF: 9.215%, CHF 2 CF 2 OMe: not detected (below the detection limit (0.001%)), other: was 64.772%. Furthermore, analysis of the samples collected in a sampling port B84 by gas chromatograph FID detector (silicon-based plot column), CH 4: 9.876%, C 2 H 4: 19.854%, CHF 3: 28 .812%, CH 3 F: 26.187 %, C 3 H 6: 4.877%, CHF 2 CF 2 OMe: not detected, other: was 10.397%. The results are shown in Tables 1 and 2.

[Example 26]
The apparatus used in the experiment shown in FIG. An inner diameter with an electric furnace 92 to the outside has a sampling port A93 to the exit side 37 mm, length 500mm with stainless steel reaction tube 91, the refrigerant bath 94 kept at -30 ° C. at the outlet of the reaction tube 91 stainless steel absorbing compartment A95 soaked in absorption tank B96 and filled with fluororesin air trap 97 and 300ccc soda lime 300 cc, the stainless steel drying tube 98 having a sampling port B99 to the outlet side turn connected with a fluorine resin or polyethylene pipe were open the outlet of the drying tube 98 the removal device. Each of the absorption vessel A95 and absorption tank B96 was charged toluene 170 g.

The catalyst 230cc obtained in Preparation Example 4 of the catalyst after charged to the reaction tube 91, the electric furnace 92 was heated under a stream of nitrogen at 15 cc / min, when the temperature of the catalyst reaches 50 ° C., the vaporizer hydrogen fluoride (HF) was introduced at a 1.0g / min through. While allowed to flow through the HF, the temperature was raised slowly to 350 ℃. It should be noted that, when the local heat generation was observed in the middle of raising the temperature is lower the feed rate to 0.1g / min, slowly to gradually 1.0g / minute after the local heat generation, it was confirmed that it has ceased It raised the HF feed rate. Upon reaching 350 ° C., after 20 hours hold, stop the flow of HF, lowering the nitrogen flow rate after 2 hour hold increase the 200 cc / min, an electric furnace temperature to 190 ° C., 1-methoxy-1,1, 2,2 tetrafluoroethane (HFE-254pc) introduced through the vaporizer at 0.10 g / min was stopped the flow of nitrogen immediately.

Results of the reaction to continue, and analyzed by total 132g (1 mol) Gas chromatograph the collected gas sampling port A93 FID detector when a HFE-254pc was passed through the reaction tube 91 of the ( "EPA the METHOD 624" corresponding column) It is shown in Table 1.

Drying tube outlet gas through a stainless steel cylinder was cooled with liquid nitrogen to obtain a collection of 29 g. Vaporize the collected matter shown in Table 2 was analyzed by silicon-based plot column. Moreover, the gas was analyzed by gas chromatograph FID detector ( "EPA the METHOD 624" corresponding column), monofluoromethane 87.02 area%, toluene 12.70 area%, and other components 0.28 area% there were.

After combining the absorbing tank A95 the contents of the absorption vessel B96 (424 g, inner toluene 340 g), Dixon packing was distilled using a pressure distillation tower of the theoretical plate number 10 steps filling. As a result, 99.2% of the difluoroacetate fluoride (84 g) was obtained.

[Example 27]
The apparatus used in the experiment shown in Fig. Internal diameter 37mm provided with an electric furnace 102 to the outside has a sampling port A103 to the exit side, a stainless steel reaction tube 101 of length 500mm provided, in a cooling bath kept at -30 ° C. at the outlet of the reaction tube 101 immersed stainless steel absorbing compartment A105 and absorption tank B106,200cc cleaning tank charged with water was charged (water trap) 107 and 300ccc soda lime, stainless steel drying tube equipped with a sampling port B109 on the outlet side 108 was connected with a fluorine resin or polyethylene pipe in this order, and open the outlet of the drying tube 108 to the abatement unit. Each of the absorption vessel A105 and absorption tank B106 was charged ethanol 200 cc.

The catalyst 230cc obtained in Preparation Example 4 of the catalyst after charged to the reaction tube 101, an electric furnace 102 was heated while introducing nitrogen at 15 cc / min, when the temperature of the catalyst reaches 50 ° C., the vaporizer hydrogen fluoride (HF) was introduced at a 1.0g / min through. While allowed to flow through the HF, the temperature was raised slowly to 350 ℃. It should be noted that, when the local heat generation was observed in the middle of raising the temperature is lower the feed rate to 0.1g / min, slowly to gradually 1.0g / minute after the local heat generation, it was confirmed that it has ceased It raised the HF feed rate. Upon reaching 350 ° C., after 20 hours hold, stop the flow of HF, lowering the nitrogen flow rate after 2 hour hold increase the 200 cc / min, an electric furnace temperature to 190 ° C., 1-methoxy-1,1, 2,2 tetrafluoroethane (HFE-254pc) introduced through the vaporizer at 0.10 g / min was stopped the flow of nitrogen immediately.

The reaction was continued, with total 132g (1 mol) Gas chromatograph the collected gas sampling port A103 FID detector when a HFE-254pc was passed through the reaction tube 101 of the ( "EPA the METHOD 624" corresponding column), sampled simultaneously the results of the collected gas mouth B109 was analyzed by gas chromatograph FID detector (silicon-based plot column) are shown in Table 1 and Table 2. Moreover, when the gas collected at a sampling port B109 was analyzed by gas chromatograph FID detector ( "EPA the METHOD 624" corresponding column), in monofluoromethane 99.67 area%, met other ingredients 0.33 area% It was.

[Example 28]
Absorption vessel A105, was charged with 20% KOH aqueous solution instead of ethanol in the absorption vessel B 106 (each 200 cc), cooled temperature of -2 ° C., except that the cleaning tank 107 and the air trap, subjected to the same experiment as in Example 27 It was. The analytical results are shown in Table 1 and Table 2. Further, when the gas collected at a sampling port B109 was analyzed by gas chromatograph FID detector ( "EPA the METHOD 624" corresponding column), in monofluoromethane 99.84 area%, met other ingredients 0.16 area% It was.

[Example 1 of monofluoromethane]
The monofluoromethane after purification and drying obtained in Example 20 and Example 23 were collected and cooled with liquid nitrogen to a stainless steel cylinder. Solidification with liquid nitrogen for the collected matter, a vacuum produced by a vacuum pump, three times degassed operation consisting of melting (room temperature), to remove air components. Using this gas into contact hole processing, showing an example of etching the interlayer insulating film (SiO 2). The cross section view of the sample before etching to Figure 1A schematically shows a cross-sectional schematic view of a sample after etching shown schematically in Figure 1B. The SiO 2 interlayer insulation film 22 is formed on a single crystal silicon wafer 21, to form a resist mask 23 having an opening portion as an etching mask on the SiO 2 film. 1B, the reference numeral 24 represents an edge defect portion.

It marks the schematic cross-sectional view of a remote plasma apparatus used in the experiment in Figure 2. It said gas (monofluoromethane): 50 SCCM from first gas inlet 4, Ar: 20 SCCM respectively introduced from the second gas inlet 5, a high frequency power source 3 in the sapphire tube 7 attached to the upper portion of the reaction chamber 1 ( 13.56 MHz, and excited using 50 W), the generated active species supplied to the chamber by the gas stream, was etched the sample 12 that is fixed to the sample holder 11. Each etching gas was introduced through a mass flow controller (not shown.). Substrate (sample holder 11) Temperature 25 ° C., the pressure 2.67 Pa (0.02 Torr), and sets the RF power density 2.2 W / cm 2. The relative etch rate, the area of the reaction chamber 1 of the exhaust gas mass analyzer (MS) SiF 3 obtained was analyzed by (mass number 85), when using monofluoromethane commercial product (monofluoromethane each was determined as 1.000 and the area ratio of the area of SiF 3 use example 2), the relative etch rate of monofluoromethane prepared in example 20 and example 23, 1.002 and 1.001 Met. The results are shown in Table 4.

Figure JPOXMLDOC01-appb-T000004
Use of monofluoromethane Example 2]
Commercially available semiconductor grade (pure content value in the product of the test results vote: 99.99%) using monofluoromethane in the same conditions as Example Using monofluoromethane 1] was subjected to etching test. The results are shown in Table 4.

Monofluoromethane obtained by the process of the present invention is a semiconductor gas (dry etching agents, cleaning agents) are useful as, difluoroacetate fluoride and its derivatives by-product, the catalyst of various reactions, intermediates of medicines, agricultural chemicals, and functional it is a useful compound used for the intermediate member or the like sex material.

1: Chamber 2: Ground 3: high-frequency power source 4: first gas inlet 5: second gas inlet 6: a third gas introducing port 7: sapphire tube 8: induction coil 9: Electronic pressure gauge 10 exhaust gas line 11 : sample holder 12: sample 21: silicon wafer 22: SiO 2 interlayer insulating film 23: resist mask 24: the edge defect section 51: reaction tube 52: electric furnace 53: sampling port A 54: Liebig condenser 55: high-jacketed boiling compounds collector 56: water trap 57: basic aqueous trap 58: empty trap 59: ice bath 60: soda lime tube 61: a sampling port B
71: reaction tube 72: electric furnace 73: Sampling port A 74: Check Trap 75: coiled 76: jacketed high boiling compounds collector 77: a sampling port D 78: separation column 79: reflux condenser 80: a sampling port C 81 : ice trap 82: basic aqueous trap 83: drying tube 84: a sampling port B
91: reaction tube 92: electric furnace 93: Sampling port A 94: refrigerant bath 95: absorption tank A 96: absorption tank B 97: Check Trap 98: drying tube 99: a sampling port B
101: Reaction tube 102: electric furnace 103: Sampling port A 104: refrigerant bath 105: absorbing compartment A 106: absorption vessel B 107: Water Trap 108: drying tube 109: Sampling port B

Claims (15)

  1. And thermally decomposing pyrolysis step of 1-methoxy-1,1,2,2-tetrafluoroethane by contacting with the catalyst, the production of monofluoromethane at least a step of recovering the monofluoromethane from thermal decomposition products Method.
  2. Recovering the mono-fluoro methane, method for producing monofluoromethane of claim 1 liquefy a portion of the pyrolysis products is a process comprising the step of separating the monofluoromethane.
  3. Some of the liquefied pyrolysis products, the manufacturing method of monofluoromethane of claim 2 carried out by cooling.
  4. Cooling temperature, a manufacturing method of monofluoromethane according to claim 3 which is -80 ~ -5 ° C..
  5. Recovering the mono-fluoro methane, method for producing monofluoromethane according to claim 1 is a process comprising the step of absorbing the difluoroacetic acid fluoride in an inert solvent for difluoroacetate fluoride.
  6. Inert to difluoroacetate fluoride The production method of monofluoromethane according to claim 5 which is a hydrocarbon compound.
  7. Step method for producing a monofluoromethane according to claim 1 is a process comprising the step of contacting an active compound against difluoroacetate fluoride to recover monofluoromethane.
  8. Compounds active on difluoroacetate fluoride are water, alcohols, primary amines, a manufacturing method of monofluoromethane according to claim 7 is a secondary amine or αβ unsaturated carboxylic acid ester.
  9. In the step of contacting the active compound against difluoroacetate fluoride method of monofluoromethane according to claim 7 or claim 8 the presence of a solvent.
  10. In the step of contacting the active compound against difluoroacetate fluoride method of monofluoromethane according to any one of claims 7 to 9, the presence of a basic substance.
  11. Pyrolysis process, metal oxides, partially fluorinated metal oxide, metal fluoride, phosphoric acid or untreated also comb untreated even comb treated fluorination is a phosphate treated fluorination catalyst, thermal decomposition method for producing monofluoromethane according to any one of claims 1 to 10, the temperature 100 ℃ ~ 400 ℃.
  12. Pyrolysis process, alumina, a partially fluorinated alumina or aluminum fluoride as a catalyst, the production method of monofluoromethane according to any one of claims 1 to 10, the thermal decomposition temperature is 130 ℃ ~ 260 ℃.
  13. Etchant or cleaning gas in semiconductor device manufacturing process, characterized in that it comprises a monofluoromethane produced by the method according to any one of claims 1 to 12.
  14. Etching process or cleaning process in a semiconductor device manufacturing process, which comprises using a monofluoromethane produced by the method according to any one of claims 1 to 12
  15. Method for producing monofluoromethane according to any one of claims 1 to 6 comprising the step of extracting and obtaining difluoro acetate fluoride with obtaining monofluoromethane.
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