WO2007148457A1 - Apparatus for catalytic chemical vapor deposition - Google Patents

Apparatus for catalytic chemical vapor deposition Download PDF

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Publication number
WO2007148457A1
WO2007148457A1 PCT/JP2007/055838 JP2007055838W WO2007148457A1 WO 2007148457 A1 WO2007148457 A1 WO 2007148457A1 JP 2007055838 W JP2007055838 W JP 2007055838W WO 2007148457 A1 WO2007148457 A1 WO 2007148457A1
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WO
WIPO (PCT)
Prior art keywords
catalyst body
temperature
wire
tungsten
mixture
Prior art date
Application number
PCT/JP2007/055838
Other languages
French (fr)
Japanese (ja)
Inventor
Hideki Matsumura
Keisuke Ohdaira
Kazuhiro Honda
Original Assignee
Japan Advanced Institute Of Science And Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Japan Advanced Institute Of Science And Technology filed Critical Japan Advanced Institute Of Science And Technology
Publication of WO2007148457A1 publication Critical patent/WO2007148457A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/24—Deposition of silicon only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides

Definitions

  • Catalytic Chemical Vapor D osition method Cat_CVD method
  • the invention relating to this thin film deposition technology includes the semiconductor industry such as semiconductor integrated circuits, liquid crystal displays and solar cells, the organic industry such as food packaging films and plastic containers, and the textile industry such as water-repellent finishing of fabrics. Field, machine parts by surface protection film formation etc., automotive industry field, etc., using a thin film in any of the products, it is related to a wide range of industrial fields.
  • the catalytic chemical vapor deposition method may be referred to as “Cat_CVD method”, the catalytic chemical vapor deposition device as “Cat-CVD apparatus”, and tungsten as “W”.
  • the source gas molecules are decomposed by physical collision with electrons in plasma generated by discharge.
  • the plasma enhanced chemical vapor deposition method (PECVD) is known and widely used industrially.
  • the raw material gas is decomposed by a catalytic decomposition reaction with a heated catalyst body, and the decomposition species generated thereby or the species newly generated by the decomposition species are transported to the substrate.
  • the Cat-CVD method for depositing a thin film on the substrate was invented.
  • Fig. 1 (a), (b), and (c) show tungsten (W) wire as catalyst and silane (SiH) gas as source gas.
  • the reaction behavior on the surface of the catalyst body W when a silicon thin film is formed is schematically shown for each temperature of the catalyst body W.
  • the quadruple is adsorbed after dissociating into SiH indicated by symbol 12 and H atom indicated by symbol 13.
  • FIG. 1 (b) schematically shows the case where the temperature of the surface of the tungsten catalyst body 14 has risen to around 600 ° C or higher.
  • SiH is further decomposed on the surface of the tungsten catalyst body 14, and is denoted by SiH as indicated by reference numeral 15.
  • thermal chemical vapor deposition thermal chemical vapor deposition
  • the deposition precursor was said to be SiH when depositing the film by thermal CVD.
  • FIG. 1 (c) schematically shows a case where the temperature of the surface of the tungsten catalyst body 14 further rises to 1000 ° C or higher.
  • SiH is represented by Si indicated by reference numeral 16 and by 4 indicated by reference numeral 4
  • the surface temperature of the tungsten catalyst body 14 is about 1000 ° C, the bond with the silicon (Si) atoms formed on the tungsten catalyst body 14 is not broken, and WSi, Ten 'silicide is formed.
  • the temperature of the catalyst body is further increased to promote thermal desorption of Si atoms from the surface of the tungsten catalyst body 14.
  • the catalyst body temperature is set to 1700 ° C or higher, which is a sufficiently high temperature for the thermal desorption of the S source element to prevent surface modification of the catalyst body such as silicide.
  • the catalyst body heated in the Cat_CVD method is used to suppress the surface modification of the catalyst body such as silicidation rather than thermal decomposition of source gas molecules.
  • the source gas is already decomposed in the process of dissociative adsorption, even at room temperature.
  • the catalyst body uses a metal wire that is easy to heat, and is generally heated by energizing it directly.
  • the heat is fixed from the catalyst body wire at the fixed electrode portion. Conduction to the support part will inevitably lower the catalyst body temperature.
  • the metal catalyst body wire fixing jig 23, which is an electrode fixing portion of the catalyst body wire 21, is covered with a metal cap 22, and the inside of the cap 22
  • Patent Document 1 The idea of filling the gas with another gas that does not react with the catalyst material was born.
  • Patent Document 1 WO2002Z025712 Disclosure of the invention
  • the catalyst body is tungsten and the source gas is a silicon-containing gas such as SiH
  • the temperature-decreasing portion of the catalyst body is likely to be silicided, and the portion that is easily deteriorated mechanically is likely to break.
  • the present invention decomposes a raw material gas by a catalytic cracking reaction with a heated catalyst body, and transports a cracked species generated thereby or a species newly generated by the cracked species to a substrate.
  • a catalytic chemical vapor deposition apparatus Cat-CVD apparatus
  • the catalyst body such as silicidation, caused by the temperature drop in the part of the catalyst body where the temperature falls below the temperature of other parts
  • the purpose is to suppress the occurrence of surface modification.
  • An object of the present invention is to eliminate such a phenomenon.
  • the present invention provides a catalytic body in a Cat_CVD apparatus.
  • a catalytic body in a Cat_CVD apparatus.
  • only the temperature-decreasing part where the temperature is lower than the temperature of the other part in the catalyst body is different from the other part in the catalyst body due to the temperature reduction of the temperature-decreasing part. It is proposed to form a compound or mixture that prevents the formation of the catalyst body at least on the surface of the temperature-decreasing portion.
  • the fixed portion at the end of the catalyst body is an electrode portion for energizing and heating the catalyst body, and the fixed portion that holds the catalyst body in the middle also comes into contact with other members, so that the temperature is lowered by heat conduction. It is possible to cause denaturation of the fixed part due to the influence of the raw material gas caused by this temperature drop.
  • a compound or a mixture is formed on the surface of the catalyst body of the fixed portion so that the catalyst body is hardly modified.
  • the entire catalyst body is made of a compound or a mixture that is difficult to modify, there is a concern that the action of the catalyst body itself may change due to the compounding or mixture. Therefore, only the portion of the catalyst body where the temperature decreases, but only a portion that is so local that it does not affect the properties of the thin film deposited on the substrate, can be compounded or mixed to suppress denaturation. This is the gist of the present invention.
  • any one of tungsten, molybdenum, tantalum, nichrome, inconel, stainless steel, iridium, and rhenium, which is a material suitable for high-temperature heating, is a linear catalyst body wire that can be easily heated, for example. Can be used as
  • the compound or mixture may be a compound or mixture containing an element other than silicon.
  • the compound or mixture may be a metal carbide such as tungsten carbide.
  • the compound or mixture may be a metal compound such as tantalum 'tungsten or a metal mixture.
  • the compound or mixture may be a mixture or metal oxide in which a metal oxide is mixed in the catalyst body.
  • a portion for fixing the catalyst body for example, a fixing portion at the end of the catalyst body and a fixing portion for holding the catalyst body in the middle are covered with a cap of a cylindrical member, and the cap is placed in the cap.
  • the present invention can be applied to a structure in which a gas that does not react with the catalytic medium (for example, an inert gas) is filled to prevent a raw material gas that modifies the catalyst body from entering the fixed portion.
  • the end of the catalyst body is covered with a cap of a cylindrical member, an inert gas is introduced into the cap, the end of the catalyst body extends, and the cap opening on the side that enters the cap Therefore, the present invention can be applied to a structure in which the inert gas is ejected from the gas and a gas that denatures the catalyst body, for example, a raw material gas cannot enter the cap.
  • a compound or mixture that suppresses denaturation is also formed on the surface of the catalyst body located near the outside of the cap, such as the force at the end of the catalyst body in the cap, the force at the opening end of the cap.
  • the temperature of the catalyst body in the vicinity of the outside of the cap opening end is feared to be lowered by the gas blown out from the cap (for example, inert gas), and this portion may also be modified.
  • the range of the catalyst body located in the vicinity of the opening end depends on the temperature of the catalyst body.
  • silane gas is decomposed using a tungsten (W) wire at about 1700 ° C at the center of the catalyst body, an area of 4 cm from the open end of the cap to the outside can be considered.
  • the Cat-CVD apparatus of the present invention in the catalyst body used, silicidation caused by the temperature decrease of the catalyst body portion where the temperature is lower than the temperature in other portions. Thus, the occurrence of catalyst surface modification can be suppressed.
  • the Cat_CVD apparatus of the present invention described above proposes a method for preventing the modification of the catalyst body in the catalytic chemical vapor deposition method. The invention's effect
  • a compound or mixture that suppresses the occurrence of surface modification of the catalyst body, such as silicide, caused by the temperature decrease is formed on at least the surface of the portion of the catalyst body that is lower in temperature than the other parts.
  • Cat—CVD apparatus catalytic chemical vapor deposition apparatus
  • FIG. 3 is a schematic diagram showing a state in which a linear catalyst body is attached to a catalyst body fixing jig
  • Fig. 4 is a schematic diagram of an end fixing portion of the linear catalyst body
  • Fig. 5 is a linear diagram.
  • FIG. 3 is a schematic diagram of a portion that holds and fixes the middle of a catalyst body.
  • the catalyst body illustrated in FIG. 3 is attached to a rectangular frame made up of two opposing rod-shaped catalyst body fixing jigs 32 and two opposing bar-shaped catalyst body fixing jigs 33. Draw a V-shaped catalyst body wire 31 alternately between the two catalyst body fixing jigs 32 multiple times. It was made to go like this.
  • Both ends of the catalyst body wire 31 are hooked and fixed to the catalyst body end fixing portion 34 at the end by a hooking member, and are energized from the power supply line 36. Further, the catalyst body wire 31 is hooked and fixed to the hooking member at the catalyst body fixing portion 35 which is the position of the top of the V shape in the middle.
  • the surface of the catalyst body wire 31 is covered with a compound or mixture that is difficult to modify.
  • the catalyst body wire 31 is in contact with other members, and the temperature is lowered by heat conduction.
  • the portion of the catalyst body wire 31 whose surface is covered with a compound or mixture that is difficult to modify may be collectively referred to as “near catalyst body fixing portion 37”.
  • the catalyst body fixing portion 37 which is a range in which a compound or mixture is formed on the surface of the catalyst body wire 31 in order to prevent modification of the catalyst body wire 31, It is about 4 cm from the fixed part of the catalyst wire.
  • silane (SiH 3) gas is used as the source gas.
  • tungsten carbide is used as the catalyst body wire 31 as a compound or mixture formed on the surface of the tungsten wire, in order to prevent modification of the tungsten wire.
  • Tungsten carbide formed on the surface of the catalyst body wire 31 that is a tungsten wire can be formed by carbonizing the surface of the tungsten wire.
  • the end of the catalyst body wire 41 which is a tungsten (W) wire, is connected to the inside of the metal catalyst body wire fixing jig 44 having a role as an electrode member from the outside. Fastened with fasteners such as screws and nuts.
  • the catalyst body wire fixing jig 44 is inserted into the supporting metal substrate 46 through an insulating member 45.
  • a catalyst body wire 41 is inserted into one end side of the catalyst body wire fixing jig 44, and the other end side is connected as an electrode to a power supply unit (not shown).
  • a metal cap 43 which is a cylindrical hollow body, is detachably attached to the catalyst body wire fixing jig 44 so that the catalyst body wire 41 is disposed therein. The metal cap 43 is exposed through the opening.
  • the metal cap 43 has a large diameter at one end side (lower side in FIG. 4) attached to the catalyst body wire fixing jig 44 and the other end side (upper side in FIG. 4). ) Has a small diameter.
  • the introduced inert gas for example, nitrogen gas
  • the introduced inert gas flows into the metal cap 43 through the flow path penetrating the inside of the catalyst body wire fixing jig 44, and the gold From the small-diameter opening of the genus cap 43, it spouts outward in FIG.
  • tungsten carbide which is a compound or mixture for preventing denaturation formed on the end of catalyst body wire 41 in a portion that may be denatured due to a decrease in temperature, is fastened to jig 44 for fixing catalyst body wire. It is formed about 4cm outside the opening of the metal cap from the end of the metal cap (the range of the thick line indicated by reference numeral 42 in Fig. 4).
  • FIG. 5 is a schematic diagram of a holding and fixing portion that holds the catalyst body wire 41 in the middle of the wiring, and the same reference numerals as those in FIG. 4 denote the same parts.
  • the catalyst body fixing wire is arranged so as to draw a V shape, and the fixed catalyst body line is the top of the V shape as shown in FIG. It is fixed to the catalyst body fixing jig 54.
  • an insulating holding tool 55 is provided, which passes through the two catalyst body wires 41, 41, which are the hypotenuses of the V-shape, in parallel with a predetermined gap therebetween. Pass the catalyst body wire through the metal cap 43, and inside the catalyst body wire fixing jig 54 to which the metal cap 43 is attached, the ends of the two parallel catalyst body wires 41 and 41 are external It is fastened with screws and nuts.
  • the metal cap 43 is the same as that described with reference to FIG. 4, and is a cylindrical hollow body, one end of which is detachably attached to the catalyst body wire fixing jig 54, and the other end is an opening. ing. As in FIG. 4, the metal cap 43 has a large-diameter cylinder on one end and a small-diameter cylinder on the other end.
  • the catalyst wire fixing jig 54 is attached to the supporting metal substrate 46 via the insulating member 51a, and the gas flow member 56 is interposed via the insulating member 5 lb at the opposite position via the supporting metal substrate 46. And attached to the supporting metal substrate 46.
  • the catalyst body wire fixing metal jig 54 and the gas flow member 56 are opposed to each other with a sealed chamber serving as a predetermined gap interposed in the plate thickness portion of the support metal substrate 46.
  • the gas that has flowed through the gas flow member 56 flows into the catalyst body wire fixing jig 54 and the metal cap 43 through the sealed chamber, and flows out from the opening of the metal cap. .
  • the position held by the insulating holder 55 from the portion fastened to the catalyst body wire fixing jig 54, that is, the outside from the opening of the metal cap 43 Tungsten carbide as a compound for preventing modification or as a mixture is formed on the surface of the catalyst body wire 41 up to a position of about 4 cm toward the surface (thick line indicated by reference numeral 42 in FIG. 5).
  • FIG. 6A is an enlarged view of the catalyst body wire fixing jig 44 shown in FIG. 4 and its surroundings
  • FIG. 6B is an enlarged view of the metal cap 43 shown in FIG. 4 and its surroundings.
  • the end of the portion 42 where the tungsten carbide is formed on the surface of the catalyst body wire 41 has a large diameter cylinder at the bottom and a small diameter cylinder at the top.
  • Shaped metal catalyst body wire fixing jig 44 is taken into the inside from the end of the small diameter cylinder. And it is fastened with fasteners such as screws and nuts from the outside.
  • the catalyst body wire fixing jig 44 is attached to the supporting metal substrate 46 via a cylindrical insulating member 45.
  • FIG. 6 (b) a hollow body metal cap having a shape in which a lower diameter cylinder is mounted on the upper part and a small diameter cylinder is placed on the upper part so as to cover the catalyst body wire fixing jig 44. 43 is detachably attached, and the catalyst body wire 42 with tungsten carbide (WC) formed on the surface thereof is exposed through the opening of the metal cap 43 while maintaining a predetermined gap.
  • FIG. 7 is a schematic diagram for explaining an example of a method for forming tungsten carbide (WC) on the surface of a catalyst body wire 41 made of tungsten (W).
  • tungsten carbide (WC) By forming tungsten carbide (WC) on the surface of the catalyst body wire 71 made of tungsten (W), silicidation of the surface of the catalyst body wire 71 is remarkable even if the temperature of the fixed portion of the catalyst body wire 71 decreases. It is suppressed.
  • This carbonized layer is formed by heating the catalyst body wire 71 in methane gas. In order to limit the carbonization region, electricity is supplied only between the catalyst body fixed electrode portion and the portion to be carbonized. Carbonized by heating. This is because the original function of the catalyst is impaired if it is carbonized more than necessary.
  • a clip 75 is attached to the end of the region to be carbonized of the catalyst body wire 71, and the attachment portion and the end of the catalyst body wire 71 are attached.
  • the AC power supply 74 is heated only locally between the two and heated locally, and only the heated portion is carbonized. Therefore, an electric current is passed between the clip 75 and the metal catalyst wire fixing jig 77 serving as an electrode. As a result, tungsten carbide is formed on the surface portion (the portion indicated by reference numeral 72 in FIG. 7) of the catalyst body wire 71 that is energized and heated.
  • the thickness of the carbide layer made of tungsten carbide is only 10 / m as shown in the scanning electron microscope cross-sectional photograph of Fig. 8 in order to maintain the strength of the tungsten (W) medium. Yes.
  • a tungsten catalyst wire having a thickness of 0.5 mm is used.
  • silane (SiH 3) gas is used as the source gas, the fixed portion of the catalyst body wire 41 and the vicinity thereof
  • the metal cap 43 is easily connected to the catalyst body wire end fixing portion and the vicinity thereof, and the catalyst body wire fixing portion and the vicinity thereof.
  • Inactive, inactive Nitrogen gas which is a natural gas, is allowed to flow to suppress intrusion of the raw material gas, silane (SiH) gas.
  • tungsten 'silicide (WSi) formed on the tungsten wire surface is about 5 times larger than that of tungsten itself at room temperature.
  • the resistance of the tungsten wire as a whole seems to increase. In fact, it slightly decreases.
  • the surface layer of the tungsten wire is slightly carbonized by 10 / im as shown in FIG.
  • this 10 ⁇ thick carbide layer alone does not produce a large overall resistance change.
  • the temperature is likely to decrease.
  • the catalyst body wire 41 located inside the metal cap 43 and the outside of the opening of the metal cap 41 have a length of about 4 cm.
  • the surface of the catalyst body wire 41 is preliminarily formed on tungsten carbide, so that denaturation and silicidation due to temperature decrease can be suppressed.
  • FIG. 10 shows the change over time of the resistance of the entire tungsten wire when the tungsten wire is exposed to silane gas at 1650 ° C.
  • the temperature of the tungsten catalyst wire is around 1750 ° C, sometimes about 1800 ° C to avoid silicidation. Therefore, the resistance does not change greatly when observed on the time scale shown in FIG. 10, but here, the phenomenon is accelerated and observed by lowering the catalyst body temperature.
  • reference numeral 101 is a change with time of the resistance of the entire tungsten wire when the tungsten wire is exposed to silane gas at 1650 ° C.
  • reference numeral 102 is the change over time of the resistance of the entire tungsten wire when a tungsten wire having a surface formed of tungsten carbide having a thickness of 10 ⁇ m is exposed to silane gas at 1650 ° C.
  • reference numeral 103 is tanda. This is the change over time in the resistance of the entire tungsten wire when the stainless wire is exposed to silane gas at 1800 ° C.
  • FIG. 10 shows that the resistance of the tungsten catalyst wire decreases after the silane gas is supplied.
  • the result of this study is that the surface of the temperature-decreasing portion of the tungsten catalyst body wire is compounded with carbonization or the like, thereby extending the life of the tungsten catalyst wire by about 5 times or more. Show me.
  • a conventional Cat-CVD device which enabled continuous operation during film deposition for about 3 weeks, was replaced with a compound or mixture that suppresses denaturation on the surface of the catalyst body wire as shown in Figs. 4 and 5 to which the present invention was applied.
  • a compound such as tungsten carbide, it is possible to create a device that can operate continuously for about three months.
  • a silicon film is formed using SiH gas or the like as a raw material.
  • the temperature drop at the end of the catalyst body begins to denature after 3 weeks of continuous use.
  • the lifetime is extended five times or more.
  • the adoption of the present invention realizes a Cat-CVD apparatus that can withstand continuous operation for three months.
  • tungsten carbide is applied to the surface of the tungsten catalyst wire.
  • WC tungsten carbide
  • the catalyst body may be molybdenum, tantalum, nichrome, inconel, stainless steel, iridium, or rhenium in addition to tungsten.
  • the compound or mixture formed on the surface of the catalyst body is a compound or mixture containing an element other than silicon, such as a metal carbide such as tungsten carbide, or a metal compound such as tantalum tungsten.
  • the mixture may be a mixture or a metal oxide in which a metal oxide is mixed in the catalyst body.
  • a part for fixing the catalyst body for example, a fixed part at the end of the catalyst body and a fixed part for holding the contact medium in the middle are covered with a metal cap of a cylindrical member, and the gold
  • the present invention was applied to a structure in which a gas (for example, an inert gas) that does not react with the catalyst body is filled in the metal cap to prevent the raw material gas for modifying the catalyst body from entering the fixed portion.
  • a gas for example, an inert gas
  • the portion to be fixed and the surface of the catalyst body in the vicinity thereof may be formed of a compound or mixture for preventing modification.
  • Fig. 1 is a schematic diagram illustrating the reaction of SiH on the surface of a tungsten catalyst wire.
  • (a) is room temperature
  • (b) is 600 ° C
  • (c) is a schematic diagram illustrating the case of 1000 ° C or higher.
  • FIG. 2 is a diagram illustrating a cap structure used for holding a conventional catalyst body.
  • FIG. 3 is a schematic diagram illustrating a state in which a linear catalyst body is attached to a catalyst body fixing jig.
  • FIG. 4 is a diagram illustrating the present invention, and is a schematic diagram illustrating an end fixing portion of a linear catalyst body
  • FIG. 5 is a diagram for explaining the present invention, and is a schematic diagram for explaining a holding / fixing portion for holding and fixing the middle of a linear catalyst body.
  • FIG. 6 (a) Enlarged view of the catalyst body wire fixing jig shown in FIG. 4 and its surroundings, (b) Enlarged view of the metal cap shown in FIG. 4 and its surroundings.
  • FIG. 7 is a schematic diagram for explaining a method of forming tungsten carbide on the surface of a tungsten catalyst body wire.
  • FIG.8 Cross section SEM of tungsten catalyst wire with tungsten carbide layer formed on the surface image.
  • FIG. 9 An X-ray diffraction pattern of a tungsten catalyst wire with a tungsten carbide layer formed on the [9] surface.

Abstract

[PROBLEMS] An apparatus for catalytic chemical vapor deposition (Cat-CVD apparatus) in which a feed gas is decomposed by contact with a heated catalyst structure and a decomposition species generated by the decomposition or a species newly generated from the decomposition species is transported to a substrate to deposit a thin film on the substrate. That part of the catalyst structure which has a lower temperature than the other parts is inhibited from suffering a catalyst structure surface alteration attributable to the low temperature, such as silicidation. [MEANS FOR SOLVING PROBLEMS] In the Cat-CVD apparatus, only that part of the catalyst structure which has a lower temperature than the other parts has, disposed in at least the surface of the catalyst structure, a compound or mixture preventing that low-temperature part from undergoing an alteration which is different from that occurring in the other parts of the catalyst structure and is caused by the temperature decrease in that low-temperature part.

Description

明 細 書  Specification
触媒化学気相堆積装置  Catalytic chemical vapor deposition equipment
技術分野  Technical field
[0001] この発明は、薄膜堆積技術に関し、特に、低温薄膜堆積技術として公知である触 媒化学気相堆積法（Catalytic Chemical Vapor D印 osition法 = Cat_CVD法）を実 現する装置の機構に関する。この薄膜堆積技術に係る発明は、半導体集積回路、液 晶ディスプレイ、太陽電池等の半導体産業分野、あるいは食品包装フィルム、プラス ティック 'コンテナ一等の有機産業分野、布地の撥水加工等の繊維産業分野、機械 部品の表面保護膜形成等による機械、 自動車産業分野等、およそ製品のいずれか に薄膜を使用してレ、る広レ、範囲の産業分野に関連してレ、る。  TECHNICAL FIELD [0001] The present invention relates to a thin film deposition technique, and more particularly, to a mechanism of an apparatus for realizing a catalytic chemical vapor deposition method (Catalytic Chemical Vapor D osition method = Cat_CVD method), which is known as a low temperature thin film deposition technology. The invention relating to this thin film deposition technology includes the semiconductor industry such as semiconductor integrated circuits, liquid crystal displays and solar cells, the organic industry such as food packaging films and plastic containers, and the textile industry such as water-repellent finishing of fabrics. Field, machine parts by surface protection film formation etc., automotive industry field, etc., using a thin film in any of the products, it is related to a wide range of industrial fields.
[0002] なお、以下、本明細書において、触媒化学気相堆積法を「Cat_CVD法」、触媒化 学気相堆積装置を「Cat - CVD装置」、タングステンを「W」と表すことがある。 Hereinafter, in the present specification, the catalytic chemical vapor deposition method may be referred to as “Cat_CVD method”, the catalytic chemical vapor deposition device as “Cat-CVD apparatus”, and tungsten as “W”.
背景技術  Background art
[0003] 薄膜を 300°C以下、基板が有機フィルムの場合には 80°C以下の低温で形成する 方法としては、放電により発生するプラズマ中電子との物理的衝突により原料ガス分 子を分解する、プラズマ化学気相堆積法（PECVD = Plasma Enhanced Chemical Va por D印 osition法）が知られ、工業的にも広く使われている。  [0003] As a method of forming a thin film at a low temperature of 300 ° C or lower and 80 ° C or lower when the substrate is an organic film, the source gas molecules are decomposed by physical collision with electrons in plasma generated by discharge. The plasma enhanced chemical vapor deposition method (PECVD) is known and widely used industrially.
[0004] しかし、この方法では、基板にプラズマ中の荷電粒子が衝突することによる損傷が 生じる。また、原料ガス分子と加速電子との 3次元空間での点と点の衝突現象を用い てガス分子を分解しているため、その分解効率は低ぐガスの利用効率が低いと言う 欠点もあった。  [0004] However, in this method, damage is caused by collision of charged particles in plasma with the substrate. In addition, since the gas molecules are decomposed by using the point-to-point collision phenomenon in the three-dimensional space between the source gas molecules and the accelerated electrons, the decomposition efficiency is low and the utilization efficiency of the gas is low. It was.
[0005] これらを解決する手段として、加熱した触媒体との接触分解反応により原料ガスを 分解し、これによつて生成された分解種または当該分解種が新たに生成する種を基 板に輸送して当該基板に薄膜を堆積する Cat— CVD法が発明された。  [0005] As means for solving these problems, the raw material gas is decomposed by a catalytic decomposition reaction with a heated catalyst body, and the decomposition species generated thereby or the species newly generated by the decomposition species are transported to the substrate. Thus, the Cat-CVD method for depositing a thin film on the substrate was invented.
[0006] この方法では、原料ガス分子と触媒体表面との反応、すなわち点と面の接触反応 を用いているのでガス分解の効率が高ぐガスの利用効率が PECVD法の 5倍から 1 0倍にも高められるという長所がある。 [0007] さらに、ガス分子の分解にプラズマを用いていないので、下地基板を傷めないで膜 堆積ができるとの長所がある。このため、この方法は表面が脆弱な化合物半導体デ バイスの表面コート膜の形成法として注目されてレ、て、すでに小型の量産機が販売さ れている。 [0006] In this method, since the reaction between the raw material gas molecules and the surface of the catalyst body, that is, the point-to-surface contact reaction, is used, the gas utilization efficiency is high. There is an advantage that it can be doubled. Furthermore, since plasma is not used for decomposition of gas molecules, there is an advantage that film deposition can be performed without damaging the base substrate. For this reason, this method is attracting attention as a method for forming a surface coat film of a compound semiconductor device having a fragile surface, and small-scale mass-production machines have already been sold.
[0008] この Cat_CVD法では、その原理から容易に想像できるように、触媒体表面は絶え ず原料ガス等の堆積室内に存在するガスに曝されていて、そのガス分子との表面反 応の進行による触媒体表面の変性のおそれがある。  [0008] In this Cat_CVD method, as can be easily imagined from the principle, the surface of the catalyst body is constantly exposed to the gas existing in the deposition chamber such as the source gas, and the surface reaction with the gas molecules proceeds. There is a risk of modification of the surface of the catalyst body due to.
[0009] 図 1 (a)、 (b)、 (c)はタングステン (W)線を触媒体、シラン（SiH )ガスを原料ガスと  [0009] Fig. 1 (a), (b), and (c) show tungsten (W) wire as catalyst and silane (SiH) gas as source gas.
4  Four
してシリコン薄膜を形成する場合の、触媒体 W表面での反応の様子を、触媒体 Wの 温度ごとに模式的に示したものである。  The reaction behavior on the surface of the catalyst body W when a silicon thin film is formed is schematically shown for each temperature of the catalyst body W.
[0010] まず、図 1 (a)に示すタングステン触媒体 14が室温の場合、符号 11で示す SiH分  [0010] First, when the tungsten catalyst body 14 shown in FIG.
4 子は、符号 12で示す SiHと符号 13で示す H原子に解離してから吸着される。  The quadruple is adsorbed after dissociating into SiH indicated by symbol 12 and H atom indicated by symbol 13.
3  Three
[0011] SiH分子は元々安定な分子であるから、これがタングステン触媒体 14の表面とィ匕  [0011] Since the SiH molecule is originally a stable molecule, this is the same as the surface of the tungsten catalyst body 14.
4  Four
学結合を作って吸着するためには、一度分解される必要があるからである。  This is because in order to create a chemical bond and adsorb it, it must be decomposed once.
[0012] 図 1 (b)はタングステン触媒体 14の表面の温度が上昇し、 600°C前後以上になった ときを模式的に示している。 [0012] FIG. 1 (b) schematically shows the case where the temperature of the surface of the tungsten catalyst body 14 has risen to around 600 ° C or higher.
[0013] タングステン触媒体 14の表面で SiHはさらに分解され、符号 15で示す SiHと符 [0013] SiH is further decomposed on the surface of the tungsten catalyst body 14, and is denoted by SiH as indicated by reference numeral 15.
3 2 号 13で示す 2つの H原子に解離してから吸着されるようになる。これがいわゆる熱化 学気相堆積 (熱 CVD)を起こす温度領域であり、旧来から SiHガスを用いてシリコン  It becomes adsorbed after dissociating into two H atoms as shown in 3 2 No.13. This is the temperature range where so-called thermal chemical vapor deposition (thermal CVD) occurs, and silicon has traditionally been used with SiH gas.
4  Four
膜を熱 CVD法により堆積する時の堆積前駆体が SiHであるといわれていたことに相  It is said that the deposition precursor was said to be SiH when depositing the film by thermal CVD.
2  2
当する温度領域である。  This is the temperature range.
[0014] 図 1 (c)はタングステン触媒体 14の表面の温度が更に上昇し、 1000°C以上になつ たときを模式的に示している。 [0014] FIG. 1 (c) schematically shows a case where the temperature of the surface of the tungsten catalyst body 14 further rises to 1000 ° C or higher.
[0015] タングステン触媒体 14の表面温度が 1000°C以上となると、もはや SiHの形でも W [0015] When the surface temperature of the tungsten catalyst body 14 exceeds 1000 ° C, it is no longer in the form of SiH.
2 表面に留まることが出来なくなり、結局 SiHは符号 16で示す Siと、符号 13で示す 4  2 It is impossible to stay on the surface, and eventually SiH is represented by Si indicated by reference numeral 16 and by 4 indicated by reference numeral 4
4  Four
つの H原子に解離して吸着するようになる。  Dissociates into two H atoms and becomes adsorbed.
[0016] ただし、タングステン触媒体 14の表面温度が 1000°C程度では、タングステン触媒 体 14上に形成されたシリコン（Si)原子との結合は切れず、 WSi、すなわちタンダス テン 'シリサイドが形成される。 [0016] However, when the surface temperature of the tungsten catalyst body 14 is about 1000 ° C, the bond with the silicon (Si) atoms formed on the tungsten catalyst body 14 is not broken, and WSi, Ten 'silicide is formed.
[0017] このタングステン'シリサイドが形成される触媒体表面変性を防ぐために、 Cat-CV[0017] In order to prevent the surface modification of the catalyst body in which this tungsten 'silicide is formed, Cat-CV
D法においては、触媒体温度をさらに上げて、 Si原子のタングステン触媒体 14表面 からの熱脱離を促進する。 In the method D, the temperature of the catalyst body is further increased to promote thermal desorption of Si atoms from the surface of the tungsten catalyst body 14.
[0018] そのため、 Cat_CVD法により SiHガスを原料としてシリコン膜を形成する場合に [0018] Therefore, when forming a silicon film using SiH gas as a raw material by the Cat_CVD method.
4  Four
は、触媒体温度を、 S源子の熱脱離がシリサイドィ匕などの触媒体表面変性を防止す るのに十分に高い温度である、 1700°C以上に設定する。  The catalyst body temperature is set to 1700 ° C or higher, which is a sufficiently high temperature for the thermal desorption of the S source element to prevent surface modification of the catalyst body such as silicide.
[0019] すなわち、 Cat_CVD法において加熱した触媒体を用いるのは、原料ガス分子を 熱分解するためではなぐこのシリサイド化等、触媒体表面変性を抑えるためである。 原料ガスは解離吸着の過程で、たとえ室温であっても、すでに分解されているのであ る。 [0019] That is, the catalyst body heated in the Cat_CVD method is used to suppress the surface modification of the catalyst body such as silicidation rather than thermal decomposition of source gas molecules. The source gas is already decomposed in the process of dissociative adsorption, even at room temperature.
[0020] ところ力 触媒体が高温に加熱されていたとしても、それはどこかで室温に近い温 度の物体で保持しなければならなレ、。  [0020] Where force Even if the catalyst body is heated to a high temperature, it must be held somewhere near the room temperature.
[0021] 触媒体としては、多くの場合、加熱の簡単な金属線を用い、それに直に通電加熱し て昇温するのが一般的である力 その固定電極部では熱が触媒体線から固定支持 部に伝導してしまい、どうしても触媒体温度が下がってしまう。  [0021] In many cases, the catalyst body uses a metal wire that is easy to heat, and is generally heated by energizing it directly. The heat is fixed from the catalyst body wire at the fixed electrode portion. Conduction to the support part will inevitably lower the catalyst body temperature.
[0022] そのように触媒体温度が低下した部分では、触媒体表面から S源子を十分に熱脱 離させられなくなり、その部分がシリサイド化してしまう。  [0022] In such a portion where the temperature of the catalyst body is lowered, the S source element cannot be sufficiently thermally detached from the surface of the catalyst body, and the portion is silicided.
[0023] そこで、図 2にその構造を示すように、触媒体線 21の電極固定部である金属製の 触媒体線固定治具 23を金属製のキャップ 22で覆レ、、そのキャップ 22内を触媒体材 料と反応しない他のガスで充満させておくとのアイデアが生まれた（特許文献 1)。  Therefore, as shown in FIG. 2, the metal catalyst body wire fixing jig 23, which is an electrode fixing portion of the catalyst body wire 21, is covered with a metal cap 22, and the inside of the cap 22 The idea of filling the gas with another gas that does not react with the catalyst material was born (Patent Document 1).
[0024] これは、触媒体材料と反応しなレ、他のガス、例えば、不活性ガスを矢印 26で示すよ うに金属キャップ 22内に導入し、これによつて、キャップ 22内を前記の不活性ガスで 充満させ、触媒体を変性させるようなガス、例えば、原料ガスが矢印 28で示すように キャップ 22内に侵入できないようにするものである。なお、触媒体の端部を固定する 触媒体線端部が固定される触媒体線固定治具 23と、支持金属基板 25との間に絶縁 部材 24が設けられており、その絶縁性が確保されている。  [0024] This is because a gas that does not react with the catalyst body material, another gas, for example, an inert gas, is introduced into the metal cap 22 as indicated by an arrow 26, whereby the inside of the cap 22 is in the above-described state. A gas that is filled with an inert gas and denatures the catalyst body, for example, a raw material gas is prevented from entering the cap 22 as indicated by an arrow 28. An insulating member 24 is provided between the catalyst body wire fixing jig 23 for fixing the end portion of the catalyst body and the supporting metal substrate 25 to secure the end of the catalyst body. Has been.
特許文献 1： WO2002Z025712 発明の開示 Patent Document 1: WO2002Z025712 Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0025] 上記の手法は、市販の Cat— CVD装置に使用されて、触媒体の使用寿命の延長 に効果を出している。しかし、それでも、金属キャップ 22の開口部からの触媒体と反 応する原料ガスの侵入を完全に抑えることは難しい。また、この金属キャップ 22の開 口部付近 29は、金属キャップ 22内から吹き出る不活性ガスのために冷やされて、条 件によっては、金属キャップ 22の開口部付近 29でシリサイド化等、触媒体表面変性 が生じる問題も生じている。条件によっては、触媒体固定部ではなぐ金属キャップ 2 2の開口部付近 29でシリサイド化等、触媒体表面変性が生じるのである。  [0025] The above-described method is used in a commercially available Cat-CVD apparatus, and is effective in extending the service life of the catalyst body. However, it is still difficult to completely suppress the intrusion of the raw material gas that reacts with the catalyst body from the opening of the metal cap 22. In addition, the vicinity 29 of the opening of the metal cap 22 is cooled by the inert gas blown out from the inside of the metal cap 22, and depending on conditions, the catalyst body such as silicidation is formed near the opening 29 of the metal cap 22. There is also the problem of surface modification. Depending on the conditions, surface modification of the catalyst body such as silicidation occurs in the vicinity 29 of the opening of the metal cap 22 that is not in the catalyst body fixing portion.
[0026] 例えば、触媒体がタングステンで、原料ガスが SiH等のシリコン含有ガスである場  [0026] For example, when the catalyst body is tungsten and the source gas is a silicon-containing gas such as SiH
4  Four
合、触媒体の温度低下部分は上述のようにシリサイド化し易ぐその部分が機械的に 劣化して断線し易くなる等の問題も生じる。  In this case, as described above, the temperature-decreasing portion of the catalyst body is likely to be silicided, and the portion that is easily deteriorated mechanically is likely to break.
[0027] すなわち、公知の触媒体固定部を金属キャップ 22で覆うとの手法は、一定の効果 を得たものの、 Cat— CVD装置を何ヶ月も連続運転することが求められる本格量産 時には、この触媒体使用寿命の延長は、まだなお解決しなければならない課題とし て残っていた。 [0027] That is, the known method of covering the catalyst body fixing portion with the metal cap 22 has obtained a certain effect, but in the case of full-scale mass production that requires continuous operation of the Cat-CVD apparatus for many months. Extending the service life of the catalyst body remained an issue that had yet to be resolved.
[0028] 本発明は、加熱した触媒体との接触分解反応により原料ガスを分解し、これによつ て生成された分解種または当該分解種が新たに生成する種を基板に輸送して当該 基板に薄膜を堆積する触媒化学気相堆積装置 (Cat— CVD装置）において、当該 触媒体のうち他の部分の温度より温度低下する部分における、その温度低下に起因 する、シリサイド化等、触媒体表面変性の発生を抑えることを目的とする。  [0028] The present invention decomposes a raw material gas by a catalytic cracking reaction with a heated catalyst body, and transports a cracked species generated thereby or a species newly generated by the cracked species to a substrate. In a catalytic chemical vapor deposition apparatus (Cat-CVD apparatus) that deposits a thin film on a substrate, the catalyst body, such as silicidation, caused by the temperature drop in the part of the catalyst body where the temperature falls below the temperature of other parts The purpose is to suppress the occurrence of surface modification.
[0029] すなわち、通電加熱された金属線を触媒体として一般的に用いる Cat— CVD装置 では、固定電極部で熱が固定支持部に伝導し、触媒体温度が下がる。このため、シリ コン系原料ガスを用いた場合、その部分がシリサイド化し、触媒体強度が低下してや がて断線するおそれがある。本発明は、このような現象の解消を図ることを目的にし ている。  That is, in a Cat-CVD apparatus that generally uses a current-heated metal wire as a catalyst body, heat is conducted to the fixed support portion at the fixed electrode portion, and the temperature of the catalyst body decreases. For this reason, when the silicon-based source gas is used, the portion may be silicided, and the strength of the catalyst body may be reduced, and there is a possibility that the wire will be broken. An object of the present invention is to eliminate such a phenomenon.
課題を解決するための手段  Means for solving the problem
[0030] 前記の課題を解決するため、この発明は、 Cat_CVD装置において、前記触媒体 において温度が当該触媒体における他の部分の温度より低下する部分である温度 低下部分のみ、当該温度低下部分の温度低下に起因して触媒体における他の部分 とは異なる変性が当該温度低下部分で生じることを防止する化合物または混合物を 、当該温度低下部分における前記触媒体の少なくとも表面に形成することを提案す るものである。 [0030] In order to solve the above-mentioned problems, the present invention provides a catalytic body in a Cat_CVD apparatus. In this case, only the temperature-decreasing part where the temperature is lower than the temperature of the other part in the catalyst body is different from the other part in the catalyst body due to the temperature reduction of the temperature-decreasing part. It is proposed to form a compound or mixture that prevents the formation of the catalyst body at least on the surface of the temperature-decreasing portion.
[0031] 触媒体において温度が当該触媒体における他の部分の温度より低下する部分で ある温度低下部分のみ、当該温度低下部分の温度低下に起因して触媒体における 他の部分とは異なる変性が当該温度低下部分で生じることを防止する化合物または 混合物を、当該温度低下部分における前記触媒体の少なくとも表面に形成して、触 媒体の表面変性の時間を遅らせ、触媒体の使用寿命の延長を図るものである。  [0031] Only the temperature-decreasing part in the catalyst body where the temperature is lower than the temperature of the other part of the catalyst body is modified differently from the other parts of the catalyst body due to the temperature reduction of the temperature-decreasing part. A compound or mixture that prevents the temperature lowering portion from being formed is formed on at least the surface of the catalyst body in the temperature lowering portion, thereby delaying the surface modification time of the catalytic medium and extending the service life of the catalyst body. Is.
[0032] 触媒体の端の固定部分や、触媒体を途中で保持する固定部分等、例えば他の部 材との接触による熱伝導によって触媒体の温度が他所より低下する温度低下部分に 限定して、局所的に触媒体が変性しにくくなるような化合物または混合物を当該温度 低下部分の触媒体の表面に形成することで、温度低下に起因する、シリサイドィ匕等、 触媒体表面変性の発生を抑制し、触媒体の使用寿命を延長するものである。  [0032] It is limited to a temperature-decreasing portion where the temperature of the catalyst body is lowered from other places due to heat conduction due to contact with other parts, such as a fixed part at the end of the catalyst body or a fixed part that holds the catalyst body halfway. Thus, by forming a compound or mixture that makes it difficult for the catalyst body to be locally modified on the surface of the catalyst body at the temperature-decreasing portion, the catalyst body surface modification such as silicidation caused by the temperature decrease can be prevented. It suppresses and extends the service life of the catalyst body.
[0033] 触媒体の端の固定部分は触媒体を通電加熱するための電極部であり、触媒体を 途中で保持する固定部分ともども、他の部材と接触することから熱伝導により温度低 下が生じ、この温度低下を原因とする原料ガスの影響で当該固定部分に変性が発 生すること力 Sある。本発明は、この変性を抑えるために当該固定部分の触媒体の表 面に触媒体が変性しにくくなるような化合物または混合物を形成するものである。  [0033] The fixed portion at the end of the catalyst body is an electrode portion for energizing and heating the catalyst body, and the fixed portion that holds the catalyst body in the middle also comes into contact with other members, so that the temperature is lowered by heat conduction. It is possible to cause denaturation of the fixed part due to the influence of the raw material gas caused by this temperature drop. In the present invention, in order to suppress this modification, a compound or a mixture is formed on the surface of the catalyst body of the fixed portion so that the catalyst body is hardly modified.
[0034] なお触媒体全体を変性しにくい化合物または混合物とすることも考えられるが、そ れでは、触媒体そのものの作用がその化合物化あるいは混合物化により変化するこ とが危惧される。そこで、触媒体の中で温度が低下する部分で、基板に堆積される薄 膜の性質に影響を与えないほど局所的な部分のみを、変性を抑制する化合物化あ るいは混合物化することが、本発明の骨子である。  [0034] Although it is conceivable that the entire catalyst body is made of a compound or a mixture that is difficult to modify, there is a concern that the action of the catalyst body itself may change due to the compounding or mixture. Therefore, only the portion of the catalyst body where the temperature decreases, but only a portion that is so local that it does not affect the properties of the thin film deposited on the substrate, can be compounded or mixed to suppress denaturation. This is the gist of the present invention.
[0035] なお、触媒体の表面のみに変性を抑える化合物あるいは混合物を形成するのは、 加熱時の触媒体の引っ張り強度等、触媒体が本来持っている物理的性質は変えな レ、ようにと考えたからである。 [0036] ただし、触媒体の化合物化あるいは混合物化が触媒体の強度を落とす等の弊害を 生まなければ、触媒体を化合物化あるいは混合物化する領域を触媒体表面に限定 する必要はない。 [0035] It should be noted that the formation of a compound or mixture that suppresses denaturation only on the surface of the catalyst body does not change the physical properties inherent to the catalyst body, such as the tensile strength of the catalyst body during heating. Because I thought. [0036] However, it is not necessary to limit the region where the catalyst body is compounded or mixed to the surface of the catalyst body unless the compounding or mixture of the catalyst body causes adverse effects such as reducing the strength of the catalyst body.
[0037] 前記触媒体としては、高温加熱に適した素材である、タングステン、モリブデン、タ ンタル、ニクロム、インコネル、ステンレス、イリジウム、レニウムのいずれかを、例えば 加熱が容易な線状の触媒体線として使用することができる。  [0037] As the catalyst body, any one of tungsten, molybdenum, tantalum, nichrome, inconel, stainless steel, iridium, and rhenium, which is a material suitable for high-temperature heating, is a linear catalyst body wire that can be easily heated, for example. Can be used as
[0038] 前記化合物または混合物は、シリコン以外の他の元素を含む化合物または混合物 とすることができる。 [0038] The compound or mixture may be a compound or mixture containing an element other than silicon.
[0039] また、前記化合物または混合物は、炭化タングステン等の金属炭化物とすることが できる。  [0039] The compound or mixture may be a metal carbide such as tungsten carbide.
[0040] あるいは、前記化合物または混合物は、タンタル 'タングステン等の金属化合物や 金属混合物とすることができる。  [0040] Alternatively, the compound or mixture may be a metal compound such as tantalum 'tungsten or a metal mixture.
[0041] 更に、前記化合物または混合物は、触媒体内に金属酸化物を混合する混合物ある いは金属酸化物とすることができる。  [0041] Further, the compound or mixture may be a mixture or metal oxide in which a metal oxide is mixed in the catalyst body.
[0042] また、触媒体を固定する部分、例えば、触媒体の端の固定部分および触媒体を途 中で保持するための固定部分を、筒状部材のキャップで覆レ、、そのキャップ内に触 媒体と反応しないガス (例えば不活性ガス）を充満させて、触媒体を変性させる原料 ガスが当該固定部分に侵入するのを防止する構造に本発明を適用することができる  [0042] Further, a portion for fixing the catalyst body, for example, a fixing portion at the end of the catalyst body and a fixing portion for holding the catalyst body in the middle are covered with a cap of a cylindrical member, and the cap is placed in the cap. The present invention can be applied to a structure in which a gas that does not react with the catalytic medium (for example, an inert gas) is filled to prevent a raw material gas that modifies the catalyst body from entering the fixed portion.
[0043] 例えば、触媒体の端部を筒状部材のキャップで覆い、当該キャップ内に不活性ガス を導入し、触媒体の端部が延びて、当該キャップ内に入ってくる側のキャップ開口か ら当該不活性ガスを噴き出させ、当該キャップ内に、触媒体を変性させるようなガス、 例えば、原料ガスが侵入できないようにする構造に本発明を適用することができる。 [0043] For example, the end of the catalyst body is covered with a cap of a cylindrical member, an inert gas is introduced into the cap, the end of the catalyst body extends, and the cap opening on the side that enters the cap Therefore, the present invention can be applied to a structure in which the inert gas is ejected from the gas and a gas that denatures the catalyst body, for example, a raw material gas cannot enter the cap.
[0044] この場合、キャップ内の触媒体端部のほ力、、キャップの開口端部力、らキャップ外の 近傍に位置する触媒体の表面にも、変性を抑える化合物または混合物を形成する。 キャップ開口端部の外部近傍の触媒体は、キャップ内から吹き出るガス（例えば不活 性ガス）により温度低下が危惧され、この部分も変性のおそれがあるからである。  [0044] In this case, a compound or mixture that suppresses denaturation is also formed on the surface of the catalyst body located near the outside of the cap, such as the force at the end of the catalyst body in the cap, the force at the opening end of the cap. This is because the temperature of the catalyst body in the vicinity of the outside of the cap opening end is feared to be lowered by the gas blown out from the cap (for example, inert gas), and this portion may also be modified.
[0045] ここで開口端部近傍に位置する触媒体の範囲とは、触媒体の温度にもよるが、例え ば触媒体中央部で約 1700°Cのタングステン (W)線を用いてシランガスを分解する 場合、キャップの開口端部から外部に向けて 4cmまでの領域が考えられる。 [0045] Here, the range of the catalyst body located in the vicinity of the opening end depends on the temperature of the catalyst body. For example, when silane gas is decomposed using a tungsten (W) wire at about 1700 ° C at the center of the catalyst body, an area of 4 cm from the open end of the cap to the outside can be considered.
[0046] 以上説明した本発明の Cat— CVD装置によれば、使用されている触媒体において 、他の部分における温度よりも温度が低下する触媒体部分の、その温度低下に起因 する、シリサイド化等、触媒体表面変性の発生を抑えることができる。すなわち、本発 明による Cat— CVD装置を用いて触媒化学気相堆積法を実施すると、触媒体の変 性を防止することができる。そこで、以上説明した本発明の Cat_CVD装置は、触媒 化学気相堆積法における触媒体の変性を防止法をも提案してレ、るものである。 発明の効果 [0046] According to the Cat-CVD apparatus of the present invention described above, in the catalyst body used, silicidation caused by the temperature decrease of the catalyst body portion where the temperature is lower than the temperature in other portions. Thus, the occurrence of catalyst surface modification can be suppressed. In other words, when the catalytic chemical vapor deposition method is performed using the Cat-CVD apparatus according to the present invention, it is possible to prevent the catalyst body from changing. Therefore, the Cat_CVD apparatus of the present invention described above proposes a method for preventing the modification of the catalyst body in the catalytic chemical vapor deposition method. The invention's effect
[0047] 本発明によれば、触媒体のうち他の部分より温度低下する部分の少なくとも表面に 、温度低下に起因する、シリサイドィヒ等、触媒体表面変性の発生を抑える化合物また は混合物を形成したので、 Cat— CVD装置内での触媒体の使用寿命が飛躍的に延 長される。  [0047] According to the present invention, a compound or mixture that suppresses the occurrence of surface modification of the catalyst body, such as silicide, caused by the temperature decrease is formed on at least the surface of the portion of the catalyst body that is lower in temperature than the other parts. As a result, the service life of the catalyst body in the Cat-CVD equipment is dramatically extended.
[0048] そこで、例えば、 3週間程度の連続使用しか可能でなかった従来の触媒体の使用 寿命を本発明の採用によって 3ヶ月間の連続使用に耐えられるものとし、本格量産に 要求される長期の連続運転を可能にする Cat— CVD装置を提供することができる。 発明を実施するための最良の形態  [0048] Therefore, for example, the service life of a conventional catalyst body that could only be used continuously for about 3 weeks is assumed to be able to withstand continuous use for 3 months by adopting the present invention, and long-term required for full-scale mass production. Cat-CVD equipment that enables continuous operation of the system can be provided. BEST MODE FOR CARRYING OUT THE INVENTION
[0049] 以下、本発明の最良の形態としての実施例を説明する。 [0049] Examples according to the best mode of the present invention will be described below.
実施例 1  Example 1
[0050] 以下添付図面を参照して、本発明に係る触媒化学気相堆積装置 (Cat— CVD装 置）の実施例を説明する。  Hereinafter, with reference to the accompanying drawings, an embodiment of a catalytic chemical vapor deposition apparatus (Cat—CVD apparatus) according to the present invention will be described.
[0051] 図 3は線状の触媒体を触媒体固定用冶具に取り付けた状態を表した模式図、図 4 は線状の触媒体の端部固定部の模式図、図 5は線状の触媒体の途中を保持固定す る部分の模式図である。 [0051] Fig. 3 is a schematic diagram showing a state in which a linear catalyst body is attached to a catalyst body fixing jig, Fig. 4 is a schematic diagram of an end fixing portion of the linear catalyst body, and Fig. 5 is a linear diagram. FIG. 3 is a schematic diagram of a portion that holds and fixes the middle of a catalyst body.
[0052] まず触媒体の取付け方法、取り付け位置を概念的に説明する。 First, a method for attaching the catalyst body and an attachment position will be conceptually described.
[0053] 図 3に例示する触媒体の取り付けは、対向する 2本の棒状の触媒体固定用冶具 32 と、同じく対向する 2本の棒状の触媒体固定用冶具 33とで方形状の枠体を形成し、 線状の触媒体線 31を 2本の触媒体固定用冶具 32の間を交互に複数回、 V字を描く ように行きかわせたものである。 [0053] The catalyst body illustrated in FIG. 3 is attached to a rectangular frame made up of two opposing rod-shaped catalyst body fixing jigs 32 and two opposing bar-shaped catalyst body fixing jigs 33. Draw a V-shaped catalyst body wire 31 alternately between the two catalyst body fixing jigs 32 multiple times. It was made to go like this.
[0054] 触媒体線 31の両端は端部の触媒体端固定部 34に掛止部材によって掛止、固定さ れ、電力供給線 36から通電されるようになつている。また触媒体線 31はその途中で ある V字の頂部の位置である触媒体固定部 35において掛止部材に掛止、固定され ている。  [0054] Both ends of the catalyst body wire 31 are hooked and fixed to the catalyst body end fixing portion 34 at the end by a hooking member, and are energized from the power supply line 36. Further, the catalyst body wire 31 is hooked and fixed to the hooking member at the catalyst body fixing portion 35 which is the position of the top of the V shape in the middle.
[0055] このように配置されている触媒体線 31のうち、変性しにくい化合物または混合物で その表面が覆われるのは、触媒体線 31が他の部材に接し、熱伝導によって温度低 下のおそれがある部分、すなわち触媒体端固定部 34とその近傍、および触媒体固 定部 35とその近傍である。本明細書、図面において、この触媒体線 31のうち、変性 しにくい化合物または混合物でその表面が覆われる部分を総称して、「触媒体固定 部近傍 37」ということがある。  [0055] Of the catalyst body wires 31 arranged in this manner, the surface of the catalyst body wire 31 is covered with a compound or mixture that is difficult to modify. The catalyst body wire 31 is in contact with other members, and the temperature is lowered by heat conduction. There is a feared portion, that is, the catalyst body end fixing portion 34 and its vicinity, and the catalyst body fixing portion 35 and its vicinity. In the present specification and drawings, the portion of the catalyst body wire 31 whose surface is covered with a compound or mixture that is difficult to modify may be collectively referred to as “near catalyst body fixing portion 37”.
[0056] 本発明では、使用する触媒体の温度にもよるが、例えば、触媒体中央部で約 1700 。( のタングステン (W)線を用いてシランガスを分解する場合は、触媒体線 31の変性 を防ぐために触媒体線 31の表面に化合物または混合物を形成する範囲である触媒 体固定部近傍 37は、触媒体線の固定部から約 4cmである。  [0056] In the present invention, depending on the temperature of the catalyst body to be used, for example, about 1700 at the center of the catalyst body. (When the silane gas is decomposed using the tungsten (W) wire, the vicinity of the catalyst body fixing portion 37, which is a range in which a compound or mixture is formed on the surface of the catalyst body wire 31 in order to prevent modification of the catalyst body wire 31, It is about 4 cm from the fixed part of the catalyst wire.
[0057] 次に図 4を参照して、触媒体線 31の触媒体端固定部 34における変性防止の化合 物または混合物の形成範囲について説明する。  Next, with reference to FIG. 4, the range of formation of the modification-preventing compound or mixture in the catalyst body end fixing portion 34 of the catalyst body wire 31 will be described.
[0058] 本実施例では原料ガスとしてシラン（SiH )ガスを使用している。  In this embodiment, silane (SiH 3) gas is used as the source gas.
4  Four
[0059] また触媒体線 31をタングステン線、タングステン線の変性を防止するためにその表 面に形成する化合物または混合物として炭化タングステンを採用している。タンダス テン線である触媒体線 31の表面に形成する炭化タングステンは、タングステン線の 表面を炭化することによって形成できる。  [0059] Further, tungsten carbide is used as the catalyst body wire 31 as a compound or mixture formed on the surface of the tungsten wire, in order to prevent modification of the tungsten wire. Tungsten carbide formed on the surface of the catalyst body wire 31 that is a tungsten wire can be formed by carbonizing the surface of the tungsten wire.
[0060] 図 4に示すように、タングステン (W)線である触媒体線 41の端部は、電極部材とし ての役割を有する金属製の触媒体線固定用冶具 44の内部に、外部からビスとナット 等の締着具により締着されている。  [0060] As shown in FIG. 4, the end of the catalyst body wire 41, which is a tungsten (W) wire, is connected to the inside of the metal catalyst body wire fixing jig 44 having a role as an electrode member from the outside. Fastened with fasteners such as screws and nuts.
[0061] 触媒体線固定用冶具 44は、絶縁部材 45を介して支持金属基板 46に貫装されて いる。触媒体線固定用冶具 44の一端側には触媒体線 41が揷入され、他端側が電 極として不図示の電源部に接続される。 [0062] 触媒体線固定用冶具 44には、さらに筒状の中空体である金属キャップ 43が触媒 体線 41をその内部に配置するように着脱可能に取り付けられていて、触媒体線 41は 金属キャップ 43の開口部から露出するようになってレ、る。 The catalyst body wire fixing jig 44 is inserted into the supporting metal substrate 46 through an insulating member 45. A catalyst body wire 41 is inserted into one end side of the catalyst body wire fixing jig 44, and the other end side is connected as an electrode to a power supply unit (not shown). [0062] Further, a metal cap 43, which is a cylindrical hollow body, is detachably attached to the catalyst body wire fixing jig 44 so that the catalyst body wire 41 is disposed therein. The metal cap 43 is exposed through the opening.
[0063] また、図示のように、金属キャップ 43は触媒体線固定用冶具 44に取り付けられてい る一端側（図 4中、下側）が大口径で、他端側（図 4中、上側）の開口部が小口径にな つている。 Further, as shown in the figure, the metal cap 43 has a large diameter at one end side (lower side in FIG. 4) attached to the catalyst body wire fixing jig 44 and the other end side (upper side in FIG. 4). ) Has a small diameter.
[0064] 支持金属基板 46に貫装されている触媒体線固定用冶具 44の内部には気体通流 用の流路が貫通されている。  [0064] Inside the catalyst body wire fixing jig 44 inserted through the supporting metal substrate 46, a gas flow passage is penetrated.
[0065] そして、矢示 47で示すように導入された不活性ガス（例えば、窒素ガス）が触媒体 線固定用冶具 44の内部を貫通する流路を介して金属キャップ 43内に流れ込み、金 属キャップ 43の小口径の開口部から図 4中、上側に向かって外に噴き出るようになつ ている。 [0065] Then, as shown by an arrow 47, the introduced inert gas (for example, nitrogen gas) flows into the metal cap 43 through the flow path penetrating the inside of the catalyst body wire fixing jig 44, and the gold From the small-diameter opening of the genus cap 43, it spouts outward in FIG.
[0066] このため触媒体線 41の端部側で、温度低下による変性のおそれがある部分に形 成する変性防止の化合物または混合物である炭化タングステンは、触媒体線固定用 冶具 44に締着されている端部から金属キャップの開口部の外側約 4cmのところまで 形成されている（図 4中符号 42で示す太線の範囲）。  [0066] For this reason, tungsten carbide, which is a compound or mixture for preventing denaturation formed on the end of catalyst body wire 41 in a portion that may be denatured due to a decrease in temperature, is fastened to jig 44 for fixing catalyst body wire. It is formed about 4cm outside the opening of the metal cap from the end of the metal cap (the range of the thick line indicated by reference numeral 42 in Fig. 4).
[0067] 図 5は、触媒体線 41を配線途中で保持する保持固定部の模式図で、図 4と同一名 称のものは同一符号を付してある。  FIG. 5 is a schematic diagram of a holding and fixing portion that holds the catalyst body wire 41 in the middle of the wiring, and the same reference numerals as those in FIG. 4 denote the same parts.
[0068] 図 3に示すように V字形状を描くように触媒体固定用冶具の間を行きかって配置、 固定されている触媒体線は、図 5図示のように、その V字形状の頂部で触媒体固定 用冶具 54に固定されている。  [0068] As shown in FIG. 3, the catalyst body fixing wire is arranged so as to draw a V shape, and the fixed catalyst body line is the top of the V shape as shown in FIG. It is fixed to the catalyst body fixing jig 54.
[0069] その固定部分では、 V字の斜辺である 2本の触媒体線 41、 41を所定の間隙を設け て平行に貫通させる絶縁保持具 55が配置され、さらにこの 2本の平行となった触媒 体線を金属キャップ 43内を通し、さらに金属キャップ 43が取り付けられている触媒体 線固定用冶具 54の内部に、 2本平行となっている触媒体線 41、 41の端部が外部か らビスとナット等の締着具により締着される。  [0069] In the fixed portion, an insulating holding tool 55 is provided, which passes through the two catalyst body wires 41, 41, which are the hypotenuses of the V-shape, in parallel with a predetermined gap therebetween. Pass the catalyst body wire through the metal cap 43, and inside the catalyst body wire fixing jig 54 to which the metal cap 43 is attached, the ends of the two parallel catalyst body wires 41 and 41 are external It is fastened with screws and nuts.
[0070] 金属キャップ 43は、図 4で説明したものと同様で、筒状の中空体で一端が着脱可 能に触媒体線固定用冶具 54に取り付けられており、他端側が開口部となっている。 図 4同様、金属キャップ 43は一端側が大口径の円筒で、他端側が小口径の円筒に なっている。 [0070] The metal cap 43 is the same as that described with reference to FIG. 4, and is a cylindrical hollow body, one end of which is detachably attached to the catalyst body wire fixing jig 54, and the other end is an opening. ing. As in FIG. 4, the metal cap 43 has a large-diameter cylinder on one end and a small-diameter cylinder on the other end.
[0071] 触媒体線固定用冶具 54は絶縁部材 51aを介して支持金属基板 46に取り付けらて おり、支持金属基板 46を介した反対位置にはガス通流部材 56が絶縁部材 5 lbを介 して支持金属基板 46に取り付けられている。触媒体線固定用金属冶具 54とガス通 流部材 56とは、所定の間隙となる密閉室を支持金属基板 46の板厚部に介在して対 向するようになっている。  [0071] The catalyst wire fixing jig 54 is attached to the supporting metal substrate 46 via the insulating member 51a, and the gas flow member 56 is interposed via the insulating member 5 lb at the opposite position via the supporting metal substrate 46. And attached to the supporting metal substrate 46. The catalyst body wire fixing metal jig 54 and the gas flow member 56 are opposed to each other with a sealed chamber serving as a predetermined gap interposed in the plate thickness portion of the support metal substrate 46.
[0072] したがってガス通流部材 56に矢示 57に示すように窒素ガス（N )を通流させると、  Accordingly, when nitrogen gas (N 2) is caused to flow through the gas flow member 56 as indicated by an arrow 57,
2  2
ガス通流部材 56を貫流したガスが、上記密閉室を経て触媒体線固定用冶具 54内、 さらに金属キャップ 43内を貫流して、金属キャップの開口部から外に流出するように なっている。  The gas that has flowed through the gas flow member 56 flows into the catalyst body wire fixing jig 54 and the metal cap 43 through the sealed chamber, and flows out from the opening of the metal cap. .
[0073] タングステン (W)製の触媒体線 41のうち、触媒体線固定用冶具 54に締着された部 分から絶縁保持具 55に保持された位置すなわち、金属キャップ 43の開口部から外 側に向けた約 4cmの位置まで、触媒体線 41の表面には変性防止の化合物または混 合物としての炭化タングステンが形成されている（図 5中の符号 42で示す太線)。  [0073] Of the catalyst body wire 41 made of tungsten (W), the position held by the insulating holder 55 from the portion fastened to the catalyst body wire fixing jig 54, that is, the outside from the opening of the metal cap 43 Tungsten carbide as a compound for preventing modification or as a mixture is formed on the surface of the catalyst body wire 41 up to a position of about 4 cm toward the surface (thick line indicated by reference numeral 42 in FIG. 5).
[0074] 図 6 (a)は、図 4に示す触媒体線固定用冶具 44とその周囲の拡大図、図 6 (b)は図 4に示す金属キャップ 43とその周囲の拡大図である。  FIG. 6A is an enlarged view of the catalyst body wire fixing jig 44 shown in FIG. 4 and its surroundings, and FIG. 6B is an enlarged view of the metal cap 43 shown in FIG. 4 and its surroundings.
[0075] 図 6 (a)に示すように触媒体線 41の表面に炭化タングステンが形成された部分 42 の端部は、下部を大口径の円筒でその上部に小口径の円筒を載置した形状の金属 製触媒体線固定用冶具 44の小口径円筒の端部からその内部に取り入れられる。そ して、その外部からビスとナット等の締着具により締着されている。触媒体線固定用 冶具 44は、また円筒状の絶縁部材 45を介して支持金属基板 46に取り付けられてい る。  [0075] As shown in Fig. 6 (a), the end of the portion 42 where the tungsten carbide is formed on the surface of the catalyst body wire 41 has a large diameter cylinder at the bottom and a small diameter cylinder at the top. Shaped metal catalyst body wire fixing jig 44 is taken into the inside from the end of the small diameter cylinder. And it is fastened with fasteners such as screws and nuts from the outside. The catalyst body wire fixing jig 44 is attached to the supporting metal substrate 46 via a cylindrical insulating member 45.
[0076] さらに図 6 (b)に示すように、触媒体線固定用冶具 44を覆うように下部を大口径の 円筒でその上部に小口径の円筒を載置した形状の中空体の金属キャップ 43が、着 脱可能に取り付けられてレ、て、表面を炭化タングステン (WC)が形成された触媒体 線 42が所定の間隙を維持して金属キャップ 43内を通りその開口部から露出している [0077] 図 7はタングステン (W)製の触媒体線 41の表面に炭化タングステン (WC)を形成 する方法の一例を説明する模式図である。タングステン (W)製の触媒体線 71の表面 に炭化タングステン (WC)を形成することで、触媒体線 71の固定部分で温度低下が 生じても、触媒体線 71の表面のシリサイド化は著しく抑制される。 Further, as shown in FIG. 6 (b), a hollow body metal cap having a shape in which a lower diameter cylinder is mounted on the upper part and a small diameter cylinder is placed on the upper part so as to cover the catalyst body wire fixing jig 44. 43 is detachably attached, and the catalyst body wire 42 with tungsten carbide (WC) formed on the surface thereof is exposed through the opening of the metal cap 43 while maintaining a predetermined gap. Have FIG. 7 is a schematic diagram for explaining an example of a method for forming tungsten carbide (WC) on the surface of a catalyst body wire 41 made of tungsten (W). By forming tungsten carbide (WC) on the surface of the catalyst body wire 71 made of tungsten (W), silicidation of the surface of the catalyst body wire 71 is remarkable even if the temperature of the fixed portion of the catalyst body wire 71 decreases. It is suppressed.
[0078] この炭化層は、メタンガス中において触媒体線 71を加熱することで作られるが、そ の炭化領域を限定するため、触媒体固定電極部と炭化をさせたい部分との間のみを 通電加熱して炭化している。必要以上に炭化すると触媒本来の機能を損なうからで ある。  [0078] This carbonized layer is formed by heating the catalyst body wire 71 in methane gas. In order to limit the carbonization region, electricity is supplied only between the catalyst body fixed electrode portion and the portion to be carbonized. Carbonized by heating. This is because the original function of the catalyst is impaired if it is carbonized more than necessary.
[0079] よって限られた範囲のみを炭化させるため、図 7に示すように、触媒体線 71の炭化 させたい領域の端に、クリップ 75を取り付け、当該取り付け部分と触媒体線 71の端 部との間にのみ交流電源 74から電流を流して局所的に加熱し、その加熱された部分 のみを炭化させるものである。したがってクリップ 75と電極となる金属製の触媒体線 固定用冶具 77の間を通電させるものである。これにより通電加熱された触媒体線 71 の表面部分（図 7中符号 72で示す部分）に炭化タングステンが形成される。  Therefore, in order to carbonize only a limited range, as shown in FIG. 7, a clip 75 is attached to the end of the region to be carbonized of the catalyst body wire 71, and the attachment portion and the end of the catalyst body wire 71 are attached. The AC power supply 74 is heated only locally between the two and heated locally, and only the heated portion is carbonized. Therefore, an electric current is passed between the clip 75 and the metal catalyst wire fixing jig 77 serving as an electrode. As a result, tungsten carbide is formed on the surface portion (the portion indicated by reference numeral 72 in FIG. 7) of the catalyst body wire 71 that is energized and heated.
[0080] この炭化タングステンによる炭化層の厚さは、タングステン (W)製の媒体の強度を 維持するため、図 8の走査型電子顕微鏡断面写真に示すように、わずか 10 / mの厚 さとしている。ちなみに、本実施例では、太さ 0. 5mmのタングステン製触媒体線を用 いている。  [0080] The thickness of the carbide layer made of tungsten carbide is only 10 / m as shown in the scanning electron microscope cross-sectional photograph of Fig. 8 in order to maintain the strength of the tungsten (W) medium. Yes. Incidentally, in this embodiment, a tungsten catalyst wire having a thickness of 0.5 mm is used.
[0081] 図 7中符号 72で示す部分の表面を X線回折で観測したところ、図 9に示すように、 炭化タングステン、およびタングステンそのものに特徴的な回折ピークから、その表面 が炭化してレ、ることが確認された。  [0081] When the surface of the portion indicated by reference numeral 72 in FIG. 7 was observed by X-ray diffraction, as shown in FIG. 9, the surface was carbonized from the diffraction peaks characteristic of tungsten carbide and tungsten itself. That was confirmed.
[0082] 再び図 4および図 5に戻り、触媒体線 41の温度低下部分である触媒体線端固定部 とその近傍、及び触媒体線固定部とその触媒体固定部近傍での動作を説明する。  [0082] Returning again to Figs. 4 and 5, the operation of the catalyst body wire end fixing portion and its vicinity, which are the temperature-decreasing portion of the catalyst body wire 41, and the operation of the catalyst body wire fixing portion and its vicinity of the catalyst body fixing portion are described. To do.
[0083] 原料ガスとしてシラン（SiH )ガスを使用すると、触媒体線 41の固定部とその近傍  [0083] When silane (SiH 3) gas is used as the source gas, the fixed portion of the catalyst body wire 41 and the vicinity thereof
4  Four
では、温度低下によってシリサイド化し使用中にシリサイド層が太って、遂には強度 不足ために断線のおそれがある。  In this case, silicidation occurs due to a decrease in temperature, the silicide layer becomes thick during use, and eventually there is a risk of disconnection due to insufficient strength.
[0084] 図 4及び図 5に示すように他の部分より低温となり易レ、、触媒体線端固定部とその 近傍、及び触媒体線固定部とその触媒体固定部近傍を金属キヤプ 43で覆レ、、不活 性ガスである窒素ガスを通流させて、原料ガスのシラン（SiH )ガスの浸入を抑える。 [0084] As shown in Figs. 4 and 5, the metal cap 43 is easily connected to the catalyst body wire end fixing portion and the vicinity thereof, and the catalyst body wire fixing portion and the vicinity thereof. Inactive, inactive Nitrogen gas, which is a natural gas, is allowed to flow to suppress intrusion of the raw material gas, silane (SiH) gas.
4  Four
しかし、これでも、キャップ開口部付近から徐々にシリサイド化が進行して、約 500時 間の連続使用後には断線する可能性が高い。  However, even in this case, silicidation gradually proceeds from the vicinity of the cap opening, and there is a high possibility of disconnection after about 500 hours of continuous use.
[0085] また、シリサイド化が生じ、これが進行すると、タングステン線の長さ方向に測った全 体の電気抵抗は低下する。タングステン線表面に形成されるタングステン'シリサイド (WSi )の電気抵抗率はタングステン自身の抵抗率より室温で比較すると約 5倍大き[0085] Further, when silicidation occurs and progresses, the overall electrical resistance measured in the length direction of the tungsten wire decreases. The electrical resistivity of tungsten 'silicide (WSi) formed on the tungsten wire surface is about 5 times larger than that of tungsten itself at room temperature.
2 2
いので、タングステン線全体の抵抗は増大しそうに思われる力 実際は、わずかに低 下していく。  Therefore, the resistance of the tungsten wire as a whole seems to increase. In fact, it slightly decreases.
[0086] これは、シリサイド化の進行とともに全体の断面積が拡大し、シリサイド化した部分 の抵抗率の増大の効果を打ち消すからである。また、シリサイド層とタングステン線の 抵抗率の差は、 1700°C以上の高温ィ匕では、それほど大きくもないこともその傾向を 強めている。  This is because as the silicidation progresses, the entire cross-sectional area increases, negating the effect of increasing the resistivity of the silicidized portion. In addition, the difference in resistivity between the silicide layer and the tungsten wire is not so large at high temperatures of 1700 ° C or higher, which intensifies this tendency.
[0087] そこで、タングステン線の表層を図 8に示すように 10 /i mだけわずかに炭化する。 0 . 5mmの太さのタングステン線にとってこの 10 μ ΐηの厚さの炭化層は、それだけで は、大きな全体の抵抗変化を生まなレ、ものである。  [0087] Therefore, the surface layer of the tungsten wire is slightly carbonized by 10 / im as shown in FIG. For a tungsten wire with a thickness of 0.5 mm, this 10 μΐη thick carbide layer alone does not produce a large overall resistance change.
[0088] タングステン製の触媒体線 41のシリサイド化を抑えるために、温度低下が生じ易い 、金属キャップ 43の内部に位置する触媒体線 41と金属キャップ 41の開口部の外側 4cm程度の長さまで、触媒体線 41の表面をあら力じめ炭化タングステンに形成して おくことで、温度低下に起因する変性、シリサイドィ匕を抑えることができる。  [0088] In order to suppress silicidation of the catalyst body wire 41 made of tungsten, the temperature is likely to decrease. The catalyst body wire 41 located inside the metal cap 43 and the outside of the opening of the metal cap 41 have a length of about 4 cm. In addition, the surface of the catalyst body wire 41 is preliminarily formed on tungsten carbide, so that denaturation and silicidation due to temperature decrease can be suppressed.
[0089] 図 10は、タングステン線を 1650°Cでシランガス中に曝した際の、タングステン線全 体の抵抗の経時変化を表したものである。実際の Cat— CVD装置では、シリサイド化 を避けるため、タングステン製触媒体線の温度は 1750°C前後、時として 1800°C程 度を用いる。そこで、図 10図示の時間スケールで観察した場合に抵抗が大きく変化 することはないが、ここでは、触媒体温度を下げて、現象を加速して観察している。  [0089] FIG. 10 shows the change over time of the resistance of the entire tungsten wire when the tungsten wire is exposed to silane gas at 1650 ° C. In an actual Cat-CVD system, the temperature of the tungsten catalyst wire is around 1750 ° C, sometimes about 1800 ° C to avoid silicidation. Therefore, the resistance does not change greatly when observed on the time scale shown in FIG. 10, but here, the phenomenon is accelerated and observed by lowering the catalyst body temperature.
[0090] 図 10中、符号 101で示すものはタングステン線を 1650°Cでシランガス中に曝した 際のタングステン線全体の抵抗の経時変化である。符号 102で示すものは、表面に 1 0 μ m厚の炭化タングステンを形成したタングステン線を 1650°Cでシランガス中に曝 した際のタングステン線全体の抵抗の経時変化である。符号 103で示すものはタンダ ステン線を 1800°Cでシランガス中に曝した際のタングステン線全体の抵抗の経時変 化である。 In FIG. 10, what is denoted by reference numeral 101 is a change with time of the resistance of the entire tungsten wire when the tungsten wire is exposed to silane gas at 1650 ° C. What is indicated by reference numeral 102 is the change over time of the resistance of the entire tungsten wire when a tungsten wire having a surface formed of tungsten carbide having a thickness of 10 μm is exposed to silane gas at 1650 ° C. What is indicated by reference numeral 103 is tanda. This is the change over time in the resistance of the entire tungsten wire when the stainless wire is exposed to silane gas at 1800 ° C.
[0091] 図 10は、シランガス投入後、タングステン製の触媒体線の抵抗が低下することを示 している。  FIG. 10 shows that the resistance of the tungsten catalyst wire decreases after the silane gas is supplied.
[0092] 符号 101、 102で示すように、 10 x m厚程度の薄い炭化層の場合、全体の抵抗値 は、表面を炭化してレヽなレ、タングステン線のそれと同じである。  [0092] As indicated by reference numerals 101 and 102, in the case of a thin carbonized layer having a thickness of about 10 x m, the entire resistance value is the same as that of a tungsten wire formed by carbonizing the surface.
[0093] 1650°Cでシランガス中に曝すことにより、シリサイド化した場合には次のようになつ た。 [0093] In the case of silicidation by exposure in silane gas at 1650 ° C, the following occurred.
[0094] 表面に 10 μ m厚程度の薄い炭化層を形成してもシリサイド化による触媒体線の電 気抵抗の低下を防げた訳ではないが、その進行速度、すなわち電気抵抗の時間変 化率が、大幅に減少した。すなわち、表面を炭化しない場合に比べ、シリサイド化に より同じ抵抗になる時間は、図中の曲線を外揷して、約 5— 10倍も延びていることが 確認された。  [0094] The formation of a thin carbon layer of about 10 μm thickness on the surface did not prevent the decrease in the electrical resistance of the catalyst body wire due to silicidation, but the progress speed, that is, the time variation of the electrical resistance. The rate has decreased significantly. In other words, compared to the case where the surface was not carbonized, it was confirmed that the time required to achieve the same resistance by silicidation was extended about 5-10 times outside the curve in the figure.
[0095] すなわち、この検討結果は、タングステン製の触媒体線の温度低下部分の表面を 炭化等の化合物化することで、タングステン製触媒体線の寿命を約 5倍以上は延ば せることを示してレ、る。  [0095] That is, the result of this study is that the surface of the temperature-decreasing portion of the tungsten catalyst body wire is compounded with carbonization or the like, thereby extending the life of the tungsten catalyst wire by about 5 times or more. Show me.
[0096] そこで、図 2に示す触媒体固定電極部の構造において、 SiHガスを用いたシリコン  Therefore, in the structure of the catalyst body fixed electrode portion shown in FIG. 2, silicon using SiH gas is used.
4  Four
膜堆積時の連続運転が約 3週間可能となっていた従来の Cat— CVD装置を、本発 明を適用した図 4、図 5に示すように触媒体線の表面に変性を抑える化合物または混 合物、たとえば炭化タングステンを形成することで、約 3ヶ月の連続運転ができる装置 とすることが、可能となるのである。  A conventional Cat-CVD device, which enabled continuous operation during film deposition for about 3 weeks, was replaced with a compound or mixture that suppresses denaturation on the surface of the catalyst body wire as shown in Figs. 4 and 5 to which the present invention was applied. By forming a compound, such as tungsten carbide, it is possible to create a device that can operate continuously for about three months.
[0097] 例えば、タングステン製の触媒体線を用いて、 SiHガス等を原料としてシリコン膜を [0097] For example, using a catalyst body wire made of tungsten, a silicon film is formed using SiH gas or the like as a raw material.
4  Four
形成する場合、図 2に示すキャップ構造を用いただけでは、触媒体の端の温度低下 部分は連続使用 3週間後には変性を始める。しかし、本発明のように、触媒体の端の 温度低下部分の表面にシリコン以外の元素からなる化合物または混合物を形成する と、その寿命は 5倍以上に延びる。すなわち、本発明の採用により 3ヶ月間の連続運 転に耐えられる Cat— CVD装置が実現するのである。  When forming the cap structure shown in Fig. 2, the temperature drop at the end of the catalyst body begins to denature after 3 weeks of continuous use. However, when a compound or mixture composed of an element other than silicon is formed on the surface of the temperature-decreasing portion at the end of the catalyst body as in the present invention, the lifetime is extended five times or more. In other words, the adoption of the present invention realizes a Cat-CVD apparatus that can withstand continuous operation for three months.
[0098] なお本実施例では、タングステン製の触媒体線の表面に炭化タングステン (WC)を 形成することで、タングステン製触媒体線の使用寿命を延長したが、これに限定する ものでない。 [0098] In this example, tungsten carbide (WC) is applied to the surface of the tungsten catalyst wire. By forming it, the service life of the tungsten catalyst wire was extended, but this is not a limitation.
[0099] すなわち触媒体としては、タングステンの他、モリブデン、タンタル、ニクロム、インコ ネル、ステンレス、イリジウム、レニウムのいずれでもよレ、。  That is, the catalyst body may be molybdenum, tantalum, nichrome, inconel, stainless steel, iridium, or rhenium in addition to tungsten.
[0100] また触媒体の表面に形成する化合物または混合物としては、シリコン以外の他の元 素を含む化合物または混合物で、例えば、炭化タングステン等の金属炭化物、さらに はタンタル ·タングステン等の金属化合物や混合物、さらにまた触媒体内に金属酸化 物を混合する混合物あるいは金属酸化物とすることができる。  [0100] The compound or mixture formed on the surface of the catalyst body is a compound or mixture containing an element other than silicon, such as a metal carbide such as tungsten carbide, or a metal compound such as tantalum tungsten. The mixture may be a mixture or a metal oxide in which a metal oxide is mixed in the catalyst body.
[0101] 本実施例では、触媒体を固定する部分、たとえば触媒体の端の固定部分および触 媒体を途中で保持するための固定部分を、筒状部材の金属キャップで覆レ、、その金 属キャップ内に触媒体と反応しなレ、ガス (例えば不活性ガス）を充満させて、触媒体 を変性させる原料ガスが当該固定部分に侵入するのを防止する構造にして本発明を 適用した。しかし、金属キャップおよび不活性ガスを使用せずに、固定される部分と その近傍の触媒体の表面を変性防止の化合物または混合物で形成してもよい。 図面の簡単な説明 [0101] In this example, a part for fixing the catalyst body, for example, a fixed part at the end of the catalyst body and a fixed part for holding the contact medium in the middle are covered with a metal cap of a cylindrical member, and the gold The present invention was applied to a structure in which a gas (for example, an inert gas) that does not react with the catalyst body is filled in the metal cap to prevent the raw material gas for modifying the catalyst body from entering the fixed portion. . However, without using a metal cap and an inert gas, the portion to be fixed and the surface of the catalyst body in the vicinity thereof may be formed of a compound or mixture for preventing modification. Brief Description of Drawings
[0102] [図 1]タングステン製の触媒体線の表面における SiHの反応を説明する模式図であ  [0102] Fig. 1 is a schematic diagram illustrating the reaction of SiH on the surface of a tungsten catalyst wire.
4  Four
つて、 （a)は室温、（b)は 600°C、（c)は 1000°C以上の場合を説明する模式図。  Therefore, (a) is room temperature, (b) is 600 ° C, and (c) is a schematic diagram illustrating the case of 1000 ° C or higher.
[図 2]従来の触媒体保持に用いられているキャップ構造を説明する図。  FIG. 2 is a diagram illustrating a cap structure used for holding a conventional catalyst body.
[図 3]線状の触媒体を触媒体固定用冶具に取り付ける状態を説明する模式図。  FIG. 3 is a schematic diagram illustrating a state in which a linear catalyst body is attached to a catalyst body fixing jig.
[図 4]本発明を説明する図であって、線状の触媒体の端部固定部を説明する模式図  FIG. 4 is a diagram illustrating the present invention, and is a schematic diagram illustrating an end fixing portion of a linear catalyst body
[図 5]本発明を説明する図であって、線状の触媒体の途中を保持固定する保持固定 部を説明する模式図。 FIG. 5 is a diagram for explaining the present invention, and is a schematic diagram for explaining a holding / fixing portion for holding and fixing the middle of a linear catalyst body.
[図 6] (a)図 4に示す触媒体線固定用冶具とその周囲の拡大図、（b)図 4に示す金属 キャップとその周囲の拡大図。  [FIG. 6] (a) Enlarged view of the catalyst body wire fixing jig shown in FIG. 4 and its surroundings, (b) Enlarged view of the metal cap shown in FIG. 4 and its surroundings.
[図 7]タングステン製の触媒体線の表面に炭化タングステンを形成する方法を説明す る模式図。  FIG. 7 is a schematic diagram for explaining a method of forming tungsten carbide on the surface of a tungsten catalyst body wire.
[図 8]表面に炭化タングステン層が形成されたタングステン製触媒体線の断面 SEM 像。 [Fig.8] Cross section SEM of tungsten catalyst wire with tungsten carbide layer formed on the surface image.
園 9]面に炭化タングステン層が形成されたタングステン製触媒体線の X線回折バタ ーンを表す図。 [Fig. 9] An X-ray diffraction pattern of a tungsten catalyst wire with a tungsten carbide layer formed on the [9] surface.
園 10]タングステン製の触媒体線の抵抗の経時変化を表す図。 [Sen 10] A graph showing the change over time of the resistance of a tungsten catalyst wire.
符号の説明 Explanation of symbols
11 SiH分子 11 SiH molecule
4  Four
12 SiH分子  12 SiH molecule
3  Three
13 H原子  13 H atom
14 タングステン原子  14 Tungsten atom
15 SiH分子  15 SiH molecule
2  2
16 Si原子  16 Si atoms
21 触媒体線 21 Catalyst wire
22 金属キャップ 22 Metal cap
23 触媒体線固定治具  23 Catalyst wire fixing jig
24 絶縁部材  24 Insulating material
25 支持金属基板  25 Support metal substrate
26 触媒体材料と反応しないガス  26 Gas that does not react with catalyst material
27 触媒体固定部支持棒  27 Cathode fixing part support rod
28 触媒体材料と反応するガス  28 Gas reacting with catalyst material
29 金属キャップの入り口部分  29 Entrance part of metal cap
31 触媒体線  31 catalyst wire
32、 33 触媒体固定用治具  32, 33 Catalyst body fixing jig
34 触媒体端固定部  34 Catalyst end fixing part
35 触媒体固定部  35 Catalyst body fixing part
36 電力供給線  36 Power supply line
37 触媒体固定部近傍 37 Near catalyst fixing part
1 触媒体線 1 Catalyst body wire
2 触媒体線の表面に化合物または混合物が形成された部分 金属キャップ 2 Parts where a compound or mixture is formed on the surface of the catalyst wire Metal cap
触媒体線固定用治具 Catalytic wire fixing jig
絶縁部材 Insulation material
支持金属基板 Support metal substrate
触媒体固定部支持棒Catalytic body fixing part support rod
, 51b 絶縁部材 , 51b Insulating material
触媒体線固定用治具 Catalytic wire fixing jig
絶縁保持具 Insulating retainer
ガス通流部材 Gas flow member
触媒体線 Catalyst wire
触媒体線の表面に化合物または混合物が形成された部分 交流電源 The part where the compound or mixture is formed on the surface of the catalyst wire AC power supply
クリップ The clip
金属キャップ Metal cap
触媒体線固定用治具 Catalytic wire fixing jig
絶縁部材 Insulation material
支持金属基板 Support metal substrate

Claims

請求の範囲 The scope of the claims
[1] 加熱した触媒体との接触分解反応により原料ガスを分解し、これによつて生成され た分解種または当該分解種が新たに生成する種を基板に輸送して当該基板に薄膜 を堆積する触媒化学気相堆積装置であって、  [1] The source gas is decomposed by catalytic cracking reaction with the heated catalyst body, and the decomposed species generated thereby or the newly generated species are transported to the substrate and a thin film is deposited on the substrate. A catalytic chemical vapor deposition apparatus,
前記触媒体において温度が当該触媒体における他の部分の温度より低下する部 分である温度低下部分のみ、当該温度低下部分の温度低下に起因して触媒体にお ける他の部分とは異なる変性が当該温度低下部分で生じることを防止する化合物ま たは混合物を、当該温度低下部分における前記触媒体の少なくとも表面に形成した 、ことを特徴とする触媒化学気相堆積装置。  In the catalyst body, only the temperature-decreasing part, which is a part where the temperature is lower than the temperature of the other part in the catalyst body, is different from the other parts in the catalyst body due to the temperature reduction of the temperature-decreasing part. A catalytic chemical vapor deposition apparatus characterized in that a compound or a mixture that prevents generation of water in the temperature lowering portion is formed on at least the surface of the catalyst body in the temperature lowering portion.
[2] 前記触媒体がタングステン、モリブデン、タンタル、ニクロム、インコネル、ステンレス 、イリジウム、レニウムのいずれかであることを特徴とする請求項 1記載の触媒化学気 相堆積装置。  2. The catalytic chemical vapor deposition apparatus according to claim 1, wherein the catalyst body is any one of tungsten, molybdenum, tantalum, nichrome, inconel, stainless steel, iridium, and rhenium.
[3] 前記化合物または混合物がシリコン以外の他の元素を含む化合物または混合物で あることを特徴とする請求項 1又は 2記載の触媒化学気相堆積装置。  3. The catalytic chemical vapor deposition apparatus according to claim 1 or 2, wherein the compound or mixture is a compound or mixture containing an element other than silicon.
[4] 前記化合物または混合物が金属炭化物であることを特徴とする請求項 1乃至 3のい ずれか一項記載の触媒化学気相堆積装置。 4. The catalytic chemical vapor deposition apparatus according to any one of claims 1 to 3, wherein the compound or mixture is a metal carbide.
[5] 前記化合物または混合物が、金属化合物または金属混合物であることを特徴とす る請求項 1乃至 3のいずれか一項記載の触媒化学気相堆積装置。 5. The catalytic chemical vapor deposition apparatus according to any one of claims 1 to 3, wherein the compound or mixture is a metal compound or a metal mixture.
[6] 前記化合物または混合物が、触媒体内に金属酸化物を混合する混合物あるいは 金属酸化物であることを特徴とする請求項 1乃至 3のいずれか一項に記載の触媒化 学気相堆積装置。 6. The catalytic chemical vapor deposition apparatus according to any one of claims 1 to 3, wherein the compound or mixture is a mixture or metal oxide in which a metal oxide is mixed in a catalyst body. .
PCT/JP2007/055838 2006-06-22 2007-03-22 Apparatus for catalytic chemical vapor deposition WO2007148457A1 (en)

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