WO2017010426A1 - Dispositif de dépôt chimique en phase vapeur et procédé de dépôt chimique en phase vapeur - Google Patents

Dispositif de dépôt chimique en phase vapeur et procédé de dépôt chimique en phase vapeur Download PDF

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Publication number
WO2017010426A1
WO2017010426A1 PCT/JP2016/070292 JP2016070292W WO2017010426A1 WO 2017010426 A1 WO2017010426 A1 WO 2017010426A1 JP 2016070292 W JP2016070292 W JP 2016070292W WO 2017010426 A1 WO2017010426 A1 WO 2017010426A1
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Prior art keywords
gas
vapor deposition
chemical vapor
supply pipe
source gas
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PCT/JP2016/070292
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English (en)
Japanese (ja)
Inventor
翔 龍岡
健志 山口
Original Assignee
三菱マテリアル株式会社
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Priority claimed from JP2016135275A external-priority patent/JP2017020111A/ja
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Priority to US15/740,951 priority Critical patent/US20180195172A1/en
Priority to EP16824406.9A priority patent/EP3321391A4/fr
Priority to CN201680037152.6A priority patent/CN107709607A/zh
Priority to KR1020177037602A priority patent/KR20180027436A/ko
Publication of WO2017010426A1 publication Critical patent/WO2017010426A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber

Definitions

  • the present invention relates to a chemical vapor deposition apparatus and a chemical vapor deposition method.
  • This application claims priority based on Japanese Patent Application No. 2015-138721 filed in Japan on July 10, 2015 and Japanese Patent Application No. 2016-135275 filed in Japan on July 07, 2016. , The contents of which are incorporated herein.
  • a cutting tool with a hard layer coated on the surface has been used conventionally.
  • a surface-coated cutting tool in which a WC base cemented carbide or the like is used as a base and a hard layer such as TiC or TiN is coated on the surface by a chemical vapor deposition method is known.
  • an apparatus for coating a hard layer on the surface of a cutting tool base for example, chemical vapor deposition apparatuses described in Patent Documents 1 to 3 are known.
  • a raw material gas is obtained by stacking a tray in which a cutting tool base is placed in a reaction vessel in a vertical direction and rotating a gas supply pipe extending in the vertical direction in the vicinity of the tray.
  • a gas supply pipe extending in the vertical direction in the vicinity of the tray.
  • two (or two) locations are provided on the base plate for the purpose of avoiding operational troubles due to gas inlet clogging and performing stable chemical vapor deposition.
  • a reduced-pressure vertical chemical vapor deposition apparatus provided with a gas inlet has also been proposed.
  • gas species having high reaction activity are used as the source gas, the source gas easily reacts in the supply path.
  • reaction product generated by the reaction of the raw material gas may be deposited in the gas supply pipe or in the gas outlet, resulting in a problem in gas supply.
  • reaction state of the gas varies, and the uniformity of the film quality for each cutting tool in the reaction vessel may be reduced.
  • An object of the present invention is to provide a chemical vapor deposition apparatus and a chemical vapor deposition method capable of forming a uniform film on a plurality of deposition objects.
  • a reaction container in which an object to be deposited is accommodated, a gas supply pipe provided in the reaction container, and a rotation for rotating the gas supply pipe around a rotation axis in the reaction container. And an interior of the gas supply pipe is partitioned into a first gas circulation part and a second gas circulation part extending along the rotation axis.
  • a set of gas jets composed of at least three gas jets arranged adjacent to each other in the direction is installed, and the set of gas jets reacts the first gas flowing through the first gas flow part with the reaction. It includes at least one or more first gas outlets for jetting into the container and at least one second gas outlet for jetting the second gas flowing through the second gas circulation part into the reaction vessel.
  • a chemical vapor deposition apparatus is provided.
  • the relative angle around the rotation axis of the two gas ejection ports installed in the same gas circulation part may be 60 ° or more. It is good also as a structure by which the group of the said gas jet nozzle is provided with two or more by the axial direction of the said gas supply pipe
  • a chemical vapor deposition method in which a film is formed on the surface of an object to be deposited using the above chemical vapor deposition apparatus.
  • the gas supply pipe may be rotated at a rotation speed of 10 rotations / minute or more and 60 rotations / minute or less.
  • a method of using a source gas containing no metal element as the first gas and using a source gas containing a metal element as the second gas may be used.
  • a method of using a source gas containing no metal element as the second gas and using a source gas containing a metal element as the first gas may be used. It is good also as a method of using ammonia containing gas as said 1st gas or 2nd gas using the source gas which does not contain the said metal element.
  • a chemical vapor deposition apparatus and a chemical vapor deposition method capable of forming a uniform film on a plurality of deposition objects are provided.
  • Sectional drawing of the chemical vapor deposition apparatus which concerns on embodiment.
  • FIG. 1 is a cross-sectional view of a chemical vapor deposition apparatus according to an embodiment.
  • FIG. 2 is a cross-sectional view showing the gas supply pipe and the rotary drive device.
  • FIG. 3 is a cross-sectional view of the gas supply pipe.
  • the chemical vapor deposition apparatus 10 of this embodiment is a CVD (Chemical Vapor Deposition) apparatus that forms a film on the surface of an object to be deposited by reacting a plurality of source gases in a heated atmosphere.
  • the chemical vapor deposition apparatus 10 of the present embodiment can be suitably used for manufacturing a surface-coated cutting tool that coats a hard layer on the surface of a cutting tool base made of cemented carbide or the like.
  • Examples of the cutting tool base include WC-based cemented carbide, TiCN-based cermet, Si 3 N 4- based ceramics, Al 2 O 3- based ceramics, and cBN-based ultra-high pressure sintered body.
  • Examples of the hard layer include an AlTiN layer and a TiSiN layer.
  • the chemical vapor deposition apparatus 10 includes a base plate 1, a work storage unit 8 installed on the base plate 1, and a bell-type reaction that covers the work storage unit 8 and covers the base plate 1.
  • a container 6 and a box-shaped external heating heater 7 that covers a side surface and an upper surface of the reaction container 6 are provided.
  • the connection portion between the base plate 1 and the reaction vessel 6 is sealed, and the internal space of the reaction vessel 6 can be maintained in a reduced pressure atmosphere.
  • the external heating heater 7 raises the temperature in the reaction vessel 6 to a predetermined film forming temperature (for example, 700 ° C. to 1050 ° C.) and holds it.
  • the work accommodating portion 8 is configured by stacking a plurality of trays 8a on which a cutting tool base body, which is an object to be deposited, is placed in the vertical direction. Adjacent trays 8a are arranged with a sufficient gap for the source gas to circulate. All the trays 8a of the work accommodating portion 8 have a through hole through which the gas supply pipe 5 is inserted.
  • the upper surface of the tray 8a is a mounting surface on which the cutting tool base is mounted. Since each tray 8a is arranged horizontally and the gas supply pipe 5 extends in the vertical direction, the mounting surface (upper surface) of the tray 8a is arranged facing the axial direction of the gas supply pipe 5.
  • the base plate 1 is provided with a gas introduction part 3, a gas discharge part 4, and a gas supply pipe 5.
  • the gas introduction unit 3 is provided through the base plate 1 and supplies two kinds of source gas group A (first gas) and source gas group B (second gas) to the internal space of the reaction vessel 6.
  • the gas introduction part 3 is connected to the gas supply pipe 5 on the inner side (reaction vessel 6 side) of the base plate 1.
  • the gas introduction unit 3 includes a source gas group A introduction pipe 29 connected to the source gas group A source 41 and a source gas group B introduction pipe 30 connected to the source gas group B source 42.
  • the source gas group A introduction pipe 29 and the source gas group B introduction pipe 30 are connected to the gas supply pipe 5.
  • the gas introduction unit 3 is provided with a motor (rotary drive device) 2 that rotates the gas supply pipe 5.
  • the gas discharge unit 4 is provided through the base plate 1 and connects the vacuum pump 45 and the internal space of the reaction vessel 6.
  • the vacuum pump 45 evacuates the reaction vessel 6 through the gas discharge unit 4.
  • the gas supply pipe 5 is a tubular member extending vertically upward from the base plate 1.
  • the gas supply pipe 5 is installed so as to penetrate the center portion of the work accommodating portion 8 in the vertical direction. In the case of this embodiment, the upper end of the gas supply pipe 5 is sealed, and the raw material gas group is injected from the side surface of the gas supply pipe 5 to the outside.
  • FIG. 2 is a cross-sectional view showing the base plate 1, the gas introduction part 3, and the gas discharge part 4.
  • the gas exhaust unit 4 includes a gas exhaust pipe 11 connected to a gas exhaust port 9 that penetrates the base plate 1.
  • the gas exhaust pipe 11 is connected to the vacuum pump 45 shown in FIG.
  • the gas introduction part 3 includes a cylindrical support part 3a extending outward from the lower surface of the base plate 1, a rotary gas introduction part 12 accommodated in the support part 3a, and a rotary gas introduction part 12 via the coupling 2a. And a sliding portion 3b that seals the coupling 2a while sliding the coupling 2a.
  • the inside of the support part 3a communicates with the inside of the reaction vessel 6.
  • the support part 3a is provided with a source gas group A introduction pipe 29 and a source gas group B introduction pipe 30 that penetrate the side wall of the support part 3a.
  • the source gas group A introduction pipe 29 is provided closer to the reaction vessel 6 than the source gas group B introduction pipe 30 in the vertical direction.
  • the source gas group A introduction pipe 29 has a source gas group A inlet 27 that opens to the inner peripheral surface of the support portion 3a.
  • the source gas group B introduction pipe 30 has a source gas group B inlet 28 that opens to the inner peripheral surface of the support portion 3a.
  • the rotary gas introduction component 12 has a cylindrical shape coaxial with the support portion 3a.
  • the rotary gas introduction component 12 is inserted into the support portion 3 a and is driven to rotate around the rotation shaft 22 by the motor 2 connected to the end portion (lower end portion) opposite to the reaction vessel 6.
  • the rotary gas introduction component 12 is provided with a through hole 12a that penetrates the side wall of the rotary gas introduction component 12, and a through hole 12b.
  • the through hole 12a is provided at the same height as the source gas group A introduction port 27 of the support portion 3a.
  • the through hole 12 b is provided at the same height as the source gas group B inlet 28.
  • a sealing portion 12c having a larger diameter than that of other portions is provided between the through hole 12a and the through hole 12b. The sealing portion 12c abuts on the inner peripheral surface of the support portion 3a and isolates the source gas group A flowing from the source gas group A inlet 27 and the source gas group B flowing from the source gas group B inlet 28. .
  • a partition member 35 is provided inside the rotary gas introduction component 12.
  • the partition member 35 partitions the interior of the rotary gas introduction component 12 into a source gas group A introduction path 31 and a source gas group B introduction path 32 that extend along the height direction (axial direction).
  • the source gas group A introduction path 31 is connected to the source gas group A introduction port 27 through the through hole 12a.
  • the source gas group B introduction path 32 is connected to the source gas group B introduction port 28 through the through hole 12b.
  • a gas supply pipe 5 is connected to the upper end of the rotary gas introduction component 12.
  • FIG. 3 is a cross-sectional view of the gas supply pipe 5.
  • FIG. 4 is a partial perspective view of the gas supply pipe 5.
  • 5A to 5C are explanatory diagrams regarding the arrangement of the gas outlets.
  • the gas supply pipe 5 is a cylindrical pipe. Inside the gas supply pipe 5, a plate-shaped partition member 5a extending along the height direction (axial direction) is provided. The partition member 5a vertically divides the gas supply pipe 5 in the diametrical direction so as to include the central axis (rotary shaft 22) of the gas supply pipe 5, and bisects the inside of the gas supply pipe 5.
  • the interior of the gas supply pipe 5 is partitioned into a source gas group A circulation part (first gas circulation part) 14 and a source gas group B circulation part (second gas circulation part) 15 by the partition member 5a.
  • the source gas group A circulation part 14 and the source gas group B circulation part 15 respectively extend over the entire height of the gas supply pipe 5.
  • the lower end of the partition member 5 a is connected to the upper end of the partition member 35.
  • the source gas group A circulation section 14 is connected to the source gas group A introduction path 31, and the source gas group B circulation section 15 is connected to the source gas group B introduction path 32. Therefore, the distribution path of the source gas group A supplied from the source gas group A source 41 and the distribution path of the source gas group B supplied from the source gas group B source 42 are partitioned by the partition member 35 and the partition member 5a.
  • the flow paths are independent from each other.
  • the gas supply pipe 5 includes a plurality of source gas group A outlets (first gas outlets) 16 penetrating the gas supply pipe 5 and a plurality of source gas group B jets. Outlets (second gas ejection ports) 17a and 17b are provided.
  • the source gas group A outlet 16 jets the source gas group A from the source gas group A circulation section 14 into the internal space of the reaction vessel 6.
  • the source gas group B outlets 17 a and 17 b eject the source gas group B from the source gas group B circulation portion 15 into the internal space of the reaction vessel 6.
  • a plurality of source gas group A outlets 16 and source gas group B outlets 17a and 17b are provided along the length direction (height direction) of the gas supply pipe 5 (see FIG. 4).
  • the source gas group A outlet 16 and the source gas group B outlets 17a and 17b are provided at substantially the same height.
  • a set 24 of jets is configured with three gas jets (raw gas group A jet 16 and source gas group B jets 17 a and 17 b) adjacent in the circumferential direction as one set.
  • the gas supply pipe 5 is provided with a plurality of jet outlet sets 24 in the height direction.
  • the height positional relationship between the source gas group A outlet 16 and the source gas group B outlets 17a and 17b constituting the jet outlet set 24 is the same as the source gas group A outlet 16 and the source gas group B outlet 17a. All of 17b are in a positional relationship that intersects one plane 23 having the rotation axis 22 shown in FIG. 4 as a normal line. Such a positional relationship is defined as a positional relationship “adjacent in the circumferential direction” in the present embodiment.
  • FIG. 5A when the raw material gas group A outlet 16 and the raw material gas group B outlets 17a and 17b constituting the jet outlet set 24 are the same height, FIG. As shown in FIG. 4, when a part of the raw material gas group A outlet 16 and a part of the raw material gas group B outlets 17a and 17b constituting the outlet set 24 are the same height, these outlets Corresponds to the positional relationship “adjacent in the circumferential direction”. On the other hand, as shown in FIG.
  • the source gas group A outlet 16 and the source gas group B outlets 17a and 17b shown in FIG. 3 are outlets belonging to the same outlet group 24.
  • the relative angle ⁇ between the two source gas group B outlets 17a and 17b communicating with the source gas group B circulation portion 15 is 120 °.
  • the relative angle ⁇ can be changed within a range of 60 ° or more and less than 180 °. When the relative angle ⁇ is less than 60 °, the film quality of the film formed on the workpiece surface varies greatly.
  • the relative angle ⁇ is preferably in the range of 120 ° to less than 180 °.
  • the relative angle ⁇ is around the axis around the center 13 (rotary shaft 22) of the gas supply pipe 5, and the center 18a of the outer peripheral side opening end of one source gas group B outlet 17a, It is defined as an angle formed with the center 18b of the outer peripheral opening end of the other source gas group B outlet 17b. Since the relative angle ⁇ is an angle around the axis, when the positions in the height direction of the centers 18 a and 18 b are different, the angles are obtained when the centers 18 a and 18 b are projected onto a plane orthogonal to the rotation axis 22.
  • jet outlet set 24 is not particularly limited as long as it is three or more.
  • the source gas group A source 41 and the source gas group B source 42 to the source gas group A and the source gas group B source 42 are rotated while the gas supply pipe 5 is rotated around the rotation axis 22 by the motor 2.
  • the source gas group B is supplied to the gas introduction unit 3.
  • the rotation speed of the gas supply pipe 5 is preferably in the range of 10 rotations / minute to 60 rotations / minute. More preferably, it is the range of 20 rotations / minute or more and 60 rotations / minute or less, More preferably, it is the range of 30 rotations / minute or more and 60 rotations / minute or less.
  • the rotation speed of the gas supply pipe 5 is adjusted according to the gas types of the source gas group A and source gas group B and the height of reaction activity.
  • the rotational speed is set to a speed exceeding 60 revolutions / minute, since the source gas is mixed in the vicinity of the gas supply pipe 5, problems such as blockage of the ejection port are likely to occur.
  • the source gas group A one or more kinds of gases selected from inorganic source gases not containing metal elements and organic source gases and a carrier gas can be used.
  • the source gas group B one or more gases selected from an inorganic source gas and an organic source gas and a carrier gas can be used.
  • the source gas group B is a gas containing at least one metal.
  • NH 3 and carrier gas (H 2 ) are selected as source gas group A
  • AlCl 3 , TiCl 4 , N 2 and carrier gas (H 2 ) are selected as source gas group B and chemical vapor deposition is performed.
  • a surface-coated cutting tool having a hard layer of an AlTiN layer can be produced.
  • NH 3 and carrier gas (H 2 ) are selected as the source gas group A
  • AlCl 3 , ZrCl 4 , N 2 and carrier gas (H 2 ) are selected as the source gas group B and chemical vapor deposition is performed.
  • a surface-coated cutting tool having a hard layer of an AlZrN layer can be produced.
  • NH 3 and carrier gas (H 2 ) are selected as the source gas group A, and TiCl 4 , SiCl 4 , N 2 and carrier gas (H 2 ) are selected as the source gas group B and chemical vapor deposition is performed.
  • a surface-coated cutting tool having a hard layer of TiSiN layer can be produced.
  • NH 3 and carrier gas (H 2 ) are selected as source gas group A, and AlCl 3 , TiCl 4 , ZrCl 4 , N 2 and carrier gas (H 2 ) are selected as source gas group B.
  • chemical vapor deposition a surface-coated cutting tool having a hard layer of an AlTiZrN layer can be produced.
  • the source gas group A supplied from the source gas group A source 41 passes through the source gas group A introduction pipe 29, the source gas group A inlet 27, the source gas group A introduction path 31, and the source gas group A distribution section 14. Then, the gas is ejected from the raw material gas group A outlet 16 into the internal space of the reaction vessel 6.
  • the source gas group B supplied from the source gas group B source 42 includes a source gas group B introduction pipe 30, a source gas group B inlet 28, a source gas group B introduction path 32, and a source gas group B distribution section 15.
  • the two source gas group B jet outlets 17a and 17b are jetted into the internal space of the reaction vessel 6 via.
  • the raw material gas group A and the raw material gas group B ejected from the gas supply pipe 5 are mixed in the reaction vessel 6 outside the gas supply pipe 5, and a hard layer is formed on the surface of the cutting tool base on the tray 8a by chemical vapor deposition. Is deposited.
  • the raw material gas group A and the raw material gas group B are separated without being mixed in the gas supply pipe 5, ejected from the rotating gas supply pipe 5, and then reacted. Mix inside the container 6.
  • the source gas groups A and B By separately supplying the source gas groups A and B in this way, it is possible to suppress the inside of the gas supply pipe 5 from being blocked by the reaction product or from being blocked by the deposited film component. Can do.
  • the raw material gas group A and the raw material gas group B ejected from the gas supply pipe 5 have a relatively high concentration in the vicinity of the gas supply pipe 5 and are diffused to a uniform concentration as the distance from the gas supply pipe 5 increases in the radial direction. Therefore, when the raw material gas group A and the raw material gas group B are mixed in the vicinity of the gas supply pipe 5 and mixed with a film quality of a hard layer (film) formed at a position away from the gas supply pipe 5. Therefore, the film quality of the hard layer formed in the film will be different. If it does so, it becomes impossible to obtain the hard layer of uniform film quality over a desired large area area.
  • a difference in film quality may occur due to a difference in reactivity between the two kinds of source gas species and the gas type of the source gas group B.
  • the gas species A1 and A2 are included in the source gas group A, if the gas species A2 is more reactive with the gas species B1 of the source gas group B than the gas species A1, the vicinity of the gas supply pipe 5 Then, the reaction between the gas species A2 and the gas species B1 is likely to proceed. As a result, the film quality varies depending on the distance from the gas supply pipe 5.
  • the chemical vapor deposition apparatus 10 of the present embodiment three jet outlets (source gas group A outlet 16, source gas group B outlets 17a and 17b) adjacent to each other in the circumferential direction of the gas supply pipe 5 are installed.
  • source gas group A outlet 16 source gas group B outlets 17a and 17b
  • the concentrations of the source gas groups A and B in the vicinity of the gas supply pipe 5 can be easily adjusted.
  • the mixing timing of the raw material gas group A and the raw material gas group B can be freely adjusted by adjusting the space
  • the mixing condition of the source gas group A and the source gas group B can be changed around the axis, and the mixing condition of the gas group considering the reactivity between the gas species can be obtained.
  • the chemical vapor deposition apparatus 10 of the present embodiment a homogeneous reaction occurs in the reaction vessel 6, and a hard layer is formed with a uniform film quality on the plurality of cutting tool bases placed on the tray 8a. be able to.
  • the uniformity of the film quality of the hard layer also depends on the mutual reaction activity of the source gas group A and the source gas group B.
  • the contact distance between the source gas group A and the source gas group B can be controlled by adjusting the rotation speed of the gas supply pipe 5. Therefore, the uniformity of the film quality can be further improved by adjusting the rotational speed according to the type of the raw material gas group.
  • a plurality of sets 24 of jet nozzles adjacent in the circumferential direction are provided in the height direction (axial direction) of the gas supply pipe 5.
  • the group 24 of jet nozzles was comprised by three jet nozzles, as shown in FIG. 6, you may provide four jet nozzles.
  • the gas supply pipe 5 shown in FIG. 6 has two source gas group A outlets 16a and 16b and two source gas group B outlets 17a and 17b. Even in such a configuration, by adjusting the positions of the four jet outlets, the concentrations of the source gas group A and the source gas group B in the vicinity of the gas supply pipe 5 and the mixing timing of the gas species are adjusted. It is possible to form a hard layer having a uniform film quality.
  • the relative angle ⁇ around the axes of the two source gas group A outlets 16a and 16b shown in FIG. 6 can be changed within a range of 60 ° or more and less than 180 °.
  • the relative angle ⁇ is preferably in the range of 120 ° to less than 180 °.
  • the relative angle ⁇ is around an axis centering on the center 13 (rotating shaft 22) of the gas supply pipe 5 and the center 19a of the outer peripheral opening end of one source gas group A outlet 16a and the other source gas group A. It is defined as the angle formed with the center 19b of the outer peripheral side opening end of the jet outlet 16b. Since the relative angle ⁇ is an angle around the axis, when the positions of the centers 19 a and 19 b in the height direction are different, the angles are obtained when the centers 19 a and 19 b are projected onto a plane orthogonal to the rotation axis 22.
  • the gas supply pipe 5 is a cylindrical pipe.
  • a gas supply pipe 5A made of a square pipe having a rectangular cross section may be used.
  • the gas supply pipe 5A shown in FIG. 7 is configured to have four jets (source gas group A jets 16a and 16b, source gas group B jets 17a and 17b), but the three jets shown in FIG. It is good also as a structure which has.
  • tube which consists of not only a rectangular cross-section but a hexagonal shape or an octagonal square tube.
  • the chemical vapor deposition apparatus 10 of the embodiment described with reference to FIGS. 1 to 5C (hereinafter simply referred to as “the present example apparatus”) was used.
  • the bell-shaped reaction vessel 6 had a diameter of 250 mm and a height of 750 mm.
  • a heater that can heat the inside of the reaction vessel 6 to 700 ° C. to 1050 ° C. was used as the external heating heater 7.
  • As the tray 8a a ring-shaped jig having an outer diameter of 220 mm in which a central hole having a diameter of 65 mm was formed at the center was used.
  • the film-formed objects made of the WC-based cemented carbide substrate are placed at intervals of 20 mm to 30 mm along the radial direction of the jig (tray 8a), and are almost equally spaced along the circumferential direction of the jig. It mounted so that it might become.
  • various source gas groups A and source gas groups B are respectively supplied to the gas supply pipe 5 at a predetermined flow rate, and the source gas group A and the source gas group B are rotated while the gas supply pipe 5 is rotated.
  • the hard layers (hard coatings) of Examples 1 to 12 and Comparative Examples 1 to 4 were formed on the surface of the film-formed object made of the WC-based cemented carbide substrate by chemical vapor deposition.
  • Table 1 shows the components and compositions of the source gas group A and source gas group B used for chemical vapor deposition.
  • Table 2 shows various conditions of chemical vapor deposition in Examples 1 to 12 and Comparative Examples 1 to 4.
  • the unit “SLM” shown in Table 2 is a standard flow rate L / min (Standard).
  • the standard flow rate is a volume flow rate per minute converted to 20 ° C. and 1 atm (1 atm).
  • the unit “rpm” shown in Table 2 is the number of rotations per minute, and here means the rotation speed of the gas supply pipe 5.
  • the average content ratio (atomic ratio) Al / Al + Zr (atomic%) in the total amount of Al and Zr in Al was determined.
  • the average content ratio (atomic ratio) Ti / Ti + Si (atomic%) in the total amount of Ti and Si in Ti was determined.
  • the average content ratio (atomic ratio) Al / Al + Ti + Zr (atomic%) in the total amount of Al, Ti, and Zr in Al was determined.
  • the average content ratio (atomic ratio) of Al or Ti was also obtained for the 10 WC-base cemented carbide substrates placed on the outer peripheral side of the ring-shaped jig (tray 8a) in the same manner as described above.
  • the average content ratio (atomic ratio) of Al or Ti of the film formed on the base on the inner side of the jig and “Al or Ti of the film formed on the base on the outer side of the jig”
  • the difference from the “average content ratio (atomic ratio)” was determined as “the difference between the average content ratio (atomic ratio) of Al or Ti on the inner peripheral side and the outer peripheral side”. Tables 3 and 4 show the values obtained above.
  • the source gas group A outlet 16 and the source gas group B outlets 17a and 17b in the outlet set 24 are combined in the circumferential direction of the rotating shaft at least three in total.
  • “average content ratio (atomic ratio of Al or Ti on the inner peripheral side and outer peripheral side)” ) Difference ” was 0.04 or less (atomic ratio). Therefore, it was confirmed that a hard film having a uniform film quality was formed even if the substrate was placed on any part of the jig (tray 8a) disposed in the reaction vessel 6.
  • the source gas group A contains ammonia gas (NH 3 ), and the ammonia gas is highly reactive with the metal chloride gas (AlCl 3 , TiCl 4 , ZrCl 4, etc.) of the source gas group B, but the AlTiN film, An AlZrN film, a TiSiN film, and an AlTiZrN film could be formed in a wide and uniform film quality on the jig.
  • the relative angle of the jet outlet is 60 ° or more, the “difference in the average content ratio (atomic ratio) of Al or Ti on the inner peripheral side and the outer peripheral side” is 0.03 or less (atomic ratio) And even better film quality uniformity was obtained.
  • Comparative Examples 1 to 4 in which the total number of the raw material gas group A outlet 16 and the raw material gas group B outlet 17 installed adjacent to each other in the circumferential direction of the rotating shaft is two, those in Tables 3 and 4 are used. From the results, the “difference in the average content ratio (atomic ratio) of Al or Ti on the inner peripheral side and the outer peripheral side” was larger than that in the example. From these results, it was confirmed that Comparative Examples 1 to 4 were inferior in film quality homogeneity as compared to Examples 1 to 12.
  • the chemical vapor deposition apparatus and the chemical vapor deposition method of the present invention can form a uniform film over a large area even in the case of forming a film using gas species having high reaction activity with each other in a raw material gas group that has been difficult in the past. Since it can be formed, it can sufficiently satisfy industrial use in terms of energy saving and cost reduction.
  • the chemical vapor deposition apparatus and chemical vapor deposition method of the present invention are not only very effective in the production of surface-coated cutting tools coated with a hard layer, but also press dies that require wear resistance, and sliding properties. Needless to say, it can be used for various types of film-forming objects depending on the type of film to be formed by vapor deposition, such as film formation on a machine part that requires the above.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne un dispositif de dépôt chimique en phase vapeur comprenant : une cuve de réaction contenant un matériau devant être déposé ; un tube d'alimentation en gaz agencé à l'intérieur de la cuve de réaction ; et un dispositif d'entraînement en rotation destiné à faire tourner le tube d'alimentation en gaz autour d'un axe de rotation à l'intérieur de la cuve de réaction ; ce dispositif étant caractérisé en ce que l'intérieur du tube d'alimentation en gaz est divisé en une première partie d'écoulement de gaz et en une seconde partie d'écoulement de gaz s'étendant le long de l'axe de rotation, en ce que des ensembles d'orifices d'éjection comprenant au moins trois orifices d'éjection de gaz, qui sont agencés adjacents les uns aux autres dans le sens circonférentiel, sont installés dans les parois tubulaires du tube d'alimentation en gaz, et en ce que les ensembles d'orifices d'éjection comprennent chacun un premier orifice d'éjection de gaz pour l'éjection, dans la cuve de réaction, d'un premier gaz s'écoulant dans la première partie d''écoulement de gaz, et/ou un second orifice d'éjection de gaz pour l'éjection, dans la cuve de réaction, d'un second gaz s'écoulant dans la seconde partie d'écoulement de gaz.
PCT/JP2016/070292 2015-07-10 2016-07-08 Dispositif de dépôt chimique en phase vapeur et procédé de dépôt chimique en phase vapeur WO2017010426A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US15/740,951 US20180195172A1 (en) 2015-07-10 2016-07-08 Chemical vapor deposition apparatus and chemical vapor deposition method
EP16824406.9A EP3321391A4 (fr) 2015-07-10 2016-07-08 Dispositif de dépôt chimique en phase vapeur et procédé de dépôt chimique en phase vapeur
CN201680037152.6A CN107709607A (zh) 2015-07-10 2016-07-08 化学蒸镀装置及化学蒸镀方法
KR1020177037602A KR20180027436A (ko) 2015-07-10 2016-07-08 화학 증착 장치, 화학 증착 방법

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015-138721 2015-07-10
JP2015138721 2015-07-10
JP2016-135275 2016-07-07
JP2016135275A JP2017020111A (ja) 2015-07-10 2016-07-07 化学蒸着装置、化学蒸着方法

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08250429A (ja) * 1995-03-14 1996-09-27 Hitachi Ltd 半導体の気相成長方法及び装置
JP2012533876A (ja) * 2009-07-16 2012-12-27 ウォニク アイピーエス カンパニ リミテッド 半導体製造装置
JP2014129562A (ja) * 2012-12-28 2014-07-10 Sumitomo Electric Hardmetal Corp 表面被覆部材およびその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08250429A (ja) * 1995-03-14 1996-09-27 Hitachi Ltd 半導体の気相成長方法及び装置
JP2012533876A (ja) * 2009-07-16 2012-12-27 ウォニク アイピーエス カンパニ リミテッド 半導体製造装置
JP2014129562A (ja) * 2012-12-28 2014-07-10 Sumitomo Electric Hardmetal Corp 表面被覆部材およびその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3321391A4 *

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