JP2016117934A - Chemical vapor deposition device, chemical vapor deposition method - Google Patents

Abstract

A chemical vapor deposition apparatus capable of forming a uniform film on a plurality of deposition objects. A reaction container in which a film-forming object is accommodated, a gas supply pipe provided in the reaction container, and a rotation driving device that rotates the gas supply pipe around a rotation axis in the reaction container. The interior of the gas supply pipe is partitioned into a first gas circulation part and a second gas circulation part that extend along the rotation axis, and a first gas that circulates in the first gas circulation part is formed on the tube wall of the gas supply pipe. The first gas outlet for ejecting the gas into the reaction container and the second gas outlet for ejecting the second gas flowing through the second gas circulation part into the reaction container are arranged adjacent to each other in the circumferential direction of the rotation shaft. The chemical vapor deposition apparatus, wherein the relative angle around the rotation axis between the first gas outlet and the second gas outlet is 150 ° to 180 °. [Selection] Figure 1

Description

  The present invention relates to a chemical vapor deposition apparatus and a chemical vapor deposition method.

  A cutting tool having a hard layer coated on the surface has been used conventionally. For example, 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. As 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.

JP-A-5-295548 Special table 2011-528753 gazette JP-A-9-310179

  In the chemical vapor deposition apparatus described in Patent Documents 1 and 2, 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. Was dispersed. Further, in the chemical vapor deposition apparatus described in Patent Document 3, two (or two) are provided on the base plate for the purpose of avoiding operational troubles due to blockage of the gas inlet and performing stable chemical vapor deposition. A reduced-pressure vertical chemical vapor deposition apparatus provided with a gas inlet has also been proposed. However, when gas species having high reaction activity are used, the raw material gas is likely to react in the supply path. As a result, the reaction product generated by the reaction of the raw material gas may be deposited in the gas supply pipe or in the gas outlet, causing a problem in gas supply. As a result, the 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.

  According to one aspect of the present invention, 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. 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, and a pipe wall of the gas supply pipe includes A first gas outlet for ejecting the first gas flowing through the first gas circulation section into the reaction container, and a second gas jet for ejecting the second gas flowing through the second gas circulation section into the reaction container. An outlet is disposed adjacent to the circumferential direction of the rotating shaft, and the relative angle around the rotating shaft between the first gas outlet and the second gas outlet is 150 ° to 180 °. A vapor deposition apparatus is provided.

A configuration may be adopted in which a plurality of jet pairs each including the first gas jet port and the second gas jet port adjacent in the circumferential direction of the rotation shaft are provided in the axial direction of the gas supply pipe.
In two pairs of jet outlets adjacent to each other in the axial direction of the rotary shaft, a relative angle around the rotary axis between the first gas jet outlets belonging to different jet outlet pairs and the first gas belonging to different jet outlet pairs. It is good also as a structure whose relative angle around the said rotating shaft of 2 gas jet nozzles is 130 degrees or more.
In two pairs of jet outlets adjacent in the axial direction of the rotary shaft, a relative angle around the rotary axis between the first gas jet outlet and the second gas jet outlet belonging to different jet outlet pairs is 60 ° or less. It is good also as composition which is.

  According to one embodiment of the present invention, a chemical vapor deposition method is provided in which a film is formed on the surface of an object to be deposited using the 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 using ammonia-containing gas as the first gas may be used.

  According to the aspects of the present invention, 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. Sectional drawing which shows a gas supply pipe and a rotation drive device. The cross-sectional view of a gas supply pipe. The partial perspective view of a gas supply pipe. Explanatory drawing regarding arrangement | positioning of a gas jet nozzle. Sectional drawing for demonstrating arrangement | positioning of a gas jet nozzle. The perspective view for demonstrating arrangement | positioning of a gas jet nozzle. Sectional drawing which shows the other example of a gas supply pipe | tube.

  Embodiments of the present invention will be described below with reference to the drawings.

(Chemical vapor deposition equipment)
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, a TiN layer, a TiCN layer, and the like.

  As shown in FIG. 1, the chemical vapor deposition apparatus 10 according to the present embodiment 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. In the chemical vapor deposition apparatus 10 of the present embodiment, 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 formation 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 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 inside of the reaction vessel 6 is evacuated by the vacuum pump 45 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 is connected to the rotary gas introduction part 12 via the coupling 2a, a cylindrical support part 3a extending outside the base plate 1, a rotary gas introduction part 12 accommodated in the support part 3a. And a sliding portion 3b that seals while sliding the coupling 2a.

  The inside of the support portion 3 a 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. Of the outer peripheral surface of the rotary gas introduction component 12, 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.

Hereinafter, the configuration of the gas supply pipe 5 will be described in detail.
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. FIG. 5 is an explanatory diagram regarding the arrangement of the gas outlets. FIG. 6 is a cross-sectional view for explaining the arrangement of the gas outlets. FIG. 7 is a perspective view for explaining 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.

  As shown in FIG. 2, 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.

  As shown in FIGS. 3 and 4, 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. An outlet (second gas outlet) 17 is 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 outlet 17 ejects the source gas group B from the source gas group B circulation portion 15 into the internal space of the reaction vessel 6. The source gas group A outlet 16 and the source gas group B outlet 17 are each provided at a plurality of locations along the length direction (height direction) of the gas supply pipe 5 (see FIGS. 4 and 7).

  In the gas supply pipe 5 of this embodiment, as shown in FIG. 3 and FIG. 4, one source gas group A outlet 16 and one source gas group B outlet 17 are provided at approximately the same height. The source gas group A outlet 16 and the source gas group B outlet 17 adjacent to each other in the circumferential direction form a pair, and form an outlet pair 24 as shown in FIG. The gas supply pipe 5 is provided with a plurality of jet outlet pairs 24 in the height direction.

  The height positional relationship between the source gas group A outlet 16 and the source gas group B outlet 17 constituting the outlet pair 24 is such that both the source gas group A outlet 16 and the source gas group B outlet 17 are the same. The positional relationship intersects with 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.

  As a specific example, as shown in FIG. 5 (a), when the source gas group A outlet 16 and the source gas group B outlet 17 constituting the outlet pair 24 have the same height, FIG. As shown in (b), when a part of the source gas group A outlet 16 and a part of the source gas group B outlet 17 constituting the outlet pair 24 have the same height, these outlets Corresponds to the positional relationship “adjacent in the circumferential direction”. On the other hand, as shown in FIG. 5C, when the entire source gas group A outlet 16 and the entire source gas group B outlet 17 are provided at different heights, the positions are “adjacent in the circumferential direction”. Not relevant.

  The source gas group A outlet 16 and the source gas group B outlet 17 shown in FIG. 3 are outlets belonging to the same outlet pair 24. In the configuration shown in FIG. 4, the relative angle α around the axis of the source gas group A outlet 16 and the source gas group B outlet 17 is 180 °. The relative angle α can be changed within a range of 150 ° to 180 °.

  In the case of this embodiment, the relative angle α is equal to the center 18 of the outer peripheral side opening end of the source gas group A outlet 16 and the source gas around an axis centering on the center 13 (rotary shaft 22) of the gas supply pipe 5. It is defined as an angle formed with the center 19 of the outer peripheral side opening end of the group B outlet 17. Since the relative angle α is an angle around the axis, when the positions in the height direction of the centers 18 and 19 are different, the angles are obtained when the centers 18 and 19 are projected onto a plane orthogonal to the rotation axis 22.

  As shown in FIG. 7, in the height direction (axial direction) of the gas supply pipe 5, the source gas group A outlet 16 and the source gas group B outlet 17 are alternately arranged in close proximity to each other. In the present embodiment, as shown in FIG. 6, the source gas group A outlet 16 communicating with the source gas group A circulation portion 14 is provided at two different angular positions in the circumferential direction of the gas supply pipe 5. Is preferred. In addition, the source gas group B outlets 17 communicating with the source gas group B circulation portion 15 are also preferably provided at two different angular positions in the circumferential direction of the gas supply pipe 5. However, the source gas group A outlet 16 communicating with the source gas group A circulation part 14 and the source gas group B outlet 17 communicating with the source gas group B circulation part 15 are provided at one location in the height direction (axial direction). The case where it is provided in an angular position and the case where it is provided in three or more different angular positions may be sufficient.

  The relative angle β1 around the axis between the two source gas group A outlets 16 shown in FIG. 6 is preferably 130 ° or more. In addition, the relative angle β2 around the axis between the two source gas group B outlets 17 is preferably 130 ° or more.

  With the above configuration, the gas supply pipe 5 includes the jet group 25 (FIG. 7A) provided on the D1 side and the jet group 26 (FIG. 7B) provided on the D2 side shown in FIG. Have. In both the jet group 25 and the jet group 26, the source gas group A outlet 16 and the source gas group B outlet 17 are alternately arranged in the height direction of the gas supply pipe 5.

  The relative angle γ1 around the axis of the source gas group A outlet 16 and the source gas group B outlet 17 adjacent in the axial direction in the outlet group 25 is preferably 60 ° or less. In addition, the relative angle γ2 around the axis between the source gas group A outlet 16 and the source gas group B outlet 17 adjacent in the axial direction in the outlet group 26 is preferably 60 ° or less.

(Chemical vapor deposition method)
In the chemical vapor deposition method using the chemical vapor deposition apparatus 10, 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. Thereby, a uniform film can be obtained in a predetermined large area in the reaction vessel 6. This is because when the source gas group is ejected from the rotating gas supply pipe 5, the source gas group A and the source gas group B are uniformly diffused while being stirred by the swirl component due to the rotational movement of the gas supply pipe 5. Because it is done. 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. When 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.

  As the source gas group A, one or more gases selected from an inorganic source gas and an organic source gas not containing a metal element and a carrier gas can be used. As 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.

For example, when forming a hard layer on the surface of the cutting tool base using the chemical vapor deposition apparatus 10, NH ₃ and a carrier gas (H ₂ ) are selected as the source gas group A, and TiCl ₄ is used as the source gas group B. By selecting a carrier gas (H ₂ ) and performing chemical vapor deposition, a surface-coated cutting tool having a hard layer of TiN layer can be produced.
Further, for example, CH ₃ CN, N ₂ and carrier gas (H ₂ ) are selected as the source gas group A, and TiCl ₄ , N ₂ and carrier gas (H ₂ ) are selected as the source gas group B, and chemical vapor deposition is performed. By doing so, a surface-coated cutting tool having a hard layer of a TiCN layer can be produced.
Further, for example, NH ₃ and carrier gas (H ₂ ) are selected as the source gas group A, and TiCl ₄ , AlCl ₃ , N ₂ and carrier gas (H ₂ ) are selected as the source gas group B and chemical vapor deposition is performed. Thus, a surface-coated cutting tool having a hard layer of an AlTiN 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. And is ejected from the source gas group B outlet 17 into the internal space of the reaction vessel 6. 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.

  In the chemical vapor deposition apparatus 10 of the present embodiment, 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. By adopting a configuration in which mixing is performed inside the container 6, it is possible to adjust the progress of gas mixing and the arrival time of the gas on the cutting tool base surface. Thereby, it can suppress that the inside of the gas supply pipe | tube 5 is obstruct | occluded with the reaction product, or a jet nozzle is obstruct | occluded with the deposited film | membrane component.

  However, 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. The 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.

  Therefore, in the chemical vapor deposition apparatus 10 of the present embodiment, the relative angle α around the axis between the source gas group A outlet 16 and the source gas group B outlet 17 adjacent in the circumferential direction of the gas supply pipe 5 is set to 150 ° or more. . With such a configuration, the raw material gas group A and the raw material gas group B are ejected in the radial direction of the gas supply pipe 5 in substantially opposite directions. As a result, the raw material gas group A and the raw material gas group B are not mixed immediately after jetting, but are mixed after being diffused uniformly from the gas supply pipe 5 in the radial direction. As a result, a homogeneous reaction occurs in the radial direction of the reaction vessel 6, and a hard layer can be formed with a uniform film quality on the plurality of cutting tool bases placed on the tray 8a.

  The uniformity of the film quality of the hard layer also depends on the reaction activity between the raw material gas group A and the raw material gas group B. In the case of this embodiment, 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.

  Further, in the chemical vapor deposition apparatus 10 of the present embodiment, as shown in FIG. 4, a plurality of jetting outlet pairs 24 adjacent in the circumferential direction are provided in the height direction (axial direction) of the gas supply pipe 5. Thereby, in each stage (tray 8a) of the work accommodating portion 8, the raw material gas group A and the raw material gas group B are uniformly diffused and mixed in the radial direction without staying, so a wide area on the tray 8a. A homogeneous hard layer can be formed.

Further, in the chemical vapor deposition apparatus 10 of the present embodiment, as shown in FIGS. 6 and 7, the source gas group A outlet 16 and the source gas group B outlet are formed on the side surfaces D1 and D2 of the gas supply pipe 5 in the height direction. 17 have a jet group 25 and a jet group 26 in which 17 are alternately arranged. With such a configuration, the raw material gas group A and the raw material gas group B are ejected relatively close to each other in the height direction in both the side surfaces D1 and D2. Thereby, the source gas group A and the source gas group B can be suppressed from staying in a state of being separated from each other, and the uniformity of the film quality can be improved, which is more preferable.
However, the source gas group A outlet 16 communicating with the source gas group A circulation part 14 and the source gas group B outlet 17 communicating with the source gas group B circulation part 15 are provided at one location in the height direction (axial direction). The case where it is provided in an angular position and the case where it is provided in three or more different angular positions may be sufficient.

  In the present embodiment, the case where the gas supply pipe 5 is a cylindrical pipe has been described. However, as shown in FIG. 8, a gas supply pipe 5 </ b> A composed of a rectangular pipe having a rectangular cross section may be used. Moreover, you may use the gas supply pipe | tube which consists of not only a rectangular cross-section but a hexagonal shape or an octagonal square tube.

  In this example, the chemical vapor deposition apparatus 10 of the embodiment described with reference to FIGS. 1 to 7 (hereinafter simply referred to as “this 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.

A WC-based cemented carbide substrate having a JIS standard CNMG120408 shape (thickness: 4.76 mm × inscribed circle diameter: 12.7 mm, 80 ° rhombus) as a film formation on a jig (tray 8a). Was placed.
In addition, the film-formation object which consists of a WC base cemented carbide base | substrate is mounted at intervals of 20 mm-30 mm along the radial direction of a jig | tool (tray 8a), and is substantially equal intervals along the circumferential direction of a jig | tool. It mounted so that it might become.

Using the apparatus of this example, 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. Was spouted into the reaction vessel 6. Thereby, the hard layer (hard film) of Examples 1 to 10 and Comparative Examples 1 to 8 was formed by chemical vapor deposition on the surface of the film-formed object composed of the WC-based cemented carbide substrate.
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 10 and Comparative Examples 1 to 8.

In Table 2, the relative angle α is a relative angle around the axis of the source gas group A outlet 16 and the source gas group B outlet 17 belonging to the same outlet pair 24.
The relative angle β1 is a relative angle between the source gas group A outlets 16 in the two outlet pairs 24 adjacent in the height direction. The relative angle β2 is a relative angle between the source gas group B outlets 17 in the two outlet pairs 24 adjacent in the height direction.
The relative angle γ1 is a relative angle around the axis of the source gas group A outlet 16 and the source gas group B outlet 17 adjacent in the height direction on one side surface (side surface D1) of the gas supply pipe 5. The relative angle γ2 is a relative angle around the axis of the source gas group A outlet 16 and the source gas group B outlet 17 adjacent in the height direction on one side surface (side surface D2) of the gas supply pipe 5.
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.

  About each sample of Examples 1-10 and Comparative Examples 1-8, the film quality uniformity of the formed hard film was investigated. For each of the conditions, the residual chlorine content of the hard coating formed on the surface of 10 WC-based cemented carbide substrates placed on the inner peripheral side near the center hole of the ring-shaped jig (tray 8a) And an electron beam microanalyzer (EPMA, Electron-Probe-Micro-Analyzer), and the average value of these values was determined as “the amount of residual chlorine in the film formed on the substrate on the inner periphery side of the jig”. Further, with respect to 10 WC-based cemented carbide substrates placed on the outer peripheral side of the ring-shaped jig (tray 8a), the residual chlorine amount was measured in the same manner, and the average value of these was determined as “base on the outer side of the jig”. The amount of residual chlorine in the film formed above was determined. Furthermore, the difference between the “residual chlorine amount of the film formed on the substrate on the inner periphery side of the jig” and the “residual chlorine amount of the film formed on the substrate on the outer periphery side of the jig” It was calculated as “difference in residual chlorine amount on the outer peripheral side”. Table 3 shows the values obtained above.

  The amount of residual chlorine measured in this example has a correlation with the film quality of the hard film, and the smaller the amount of residual chlorine, the better the film quality. It is considered that the smaller the difference in the amount of residual chlorine between the inner peripheral side and the outer peripheral side, the smaller the difference in film quality between the inner peripheral side and the outer peripheral side.

In this example, when the raw material gas group A containing NH ₃ gas is used, since the reactivity is high, a hard film can be formed at a low temperature, whereas the film quality is higher than when the raw material gas group A containing no NH ₃ gas is used. Since it is inferior, the amount of residual chlorine tends to increase. Accordingly, the amount of residual chlorine shown in Table 3 corresponds to the superiority or inferiority of the film quality of the hard coating, and the magnitude of the difference in residual chlorine content between the substrates corresponds to the magnitude of the relative film quality difference between the hard coatings. .

  Moreover, about the AlTiN film | membrane of Examples 5-10 and Comparative Examples 3, 4, 7, and 8, EPMA (electron beam microanalyzer) analysis is performed, The Al content rate (atomic ratio) with respect to the total amount of Al and Ti in a film | membrane ) Was derived. The results are shown in Table 4.

  From the results of Table 3, in Examples 1 to 10 in which the relative angle α around the axis between the source gas group A outlet 16 and the source gas group B outlet 17 in the outlet pair 24 is 150 ° or more, the source gas group As a result, even when gas species having high reaction activity were used, the “difference in residual chlorine content between the inner and outer peripheral sides” was as small as 0.04 atomic% or less. 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. Also in the results of Table 4, in Examples 5 to 10, the average content ratio of Al in the total amount of Al and Ti is almost the same between the inner peripheral side and the outer peripheral side, and an AlTiN film having a uniform film quality is formed. It had been.

In particular, Examples 1, _{3, 5} to 10 include ammonia gas (NH ₃ ) in the source gas group A, and the ammonia gas has a reactive activity with the metal chloride gas (TiCl ₄ , AlCl _3, etc.) in the source gas group B. Despite being high, it was possible to form a TiN film, a TiCN film, and an AlTiN film with a uniform film quality over a wide range on the jig.
Also, in the film formation using the gas species as shown in Examples 2 and 4 whose reaction activities are not so high as the source gas, by setting the respective film formation conditions, it is uniform over a wide range on the jig. A film with a film quality could be formed.

  On the other hand, in Comparative Examples 1 to 4 in which the relative angle α was narrowed to 60 ° or 120 °, from the results in Table 3, the “difference in residual chlorine amount between the inner peripheral side and the outer peripheral side” was larger than in the example. . Similarly, in the results of Table 4, the difference in the average content ratio of Al in the total amount of Al and Ti was larger than in the examples. From these, it was confirmed that Comparative Examples 1 to 4 were inferior in film quality homogeneity as compared with Examples 1 to 10.

  In Comparative Examples 5 to 8 in which the flow paths of the raw material gas group A and the raw material gas group B were not separated, there was a condition in which the film quality homogeneity was good. Occlusion occurred. Further, as shown in Table 4, it was confirmed that the difference in the average content ratio of Al in the total amount of Al and Ti was significantly larger than that in Examples, and the composition of the AlTiN film was varied.

  Further, from the results of Examples 1 to 6, 8, and 10 in Tables 3 and 4, the relative angle β1 between the source gas group A outlets 16 and the relative angle β2 between the source gas group B outlets 17 are set to 130 °. By setting it as the above, the film | membrane of the uniform and outstanding film quality could be formed over the wide range on a jig | tool. On the other hand, Example 7 in which the relative angles β1 and β2 are 120 ° has a relatively large difference in the amount of residual chlorine shown in Table 3, and Example 9 in which the relative angles β1 and β2 are 30 ° is shown in Table 4. The average content ratio of Al shown was lower than that of the other examples.

As described above, 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.

  DESCRIPTION OF SYMBOLS 5,5A ... Gas supply pipe | tube, 6 ... Reaction container, 10 ... Chemical vapor deposition apparatus, 22 ... Rotating shaft, 24 ... Outlet pair, 2 ... Motor (rotary drive device), 14 ... Raw material gas group A distribution part (1st Gas distribution part), 15 ... Raw material gas group B flow part (second gas flow part), 16 ... Raw material gas group A outlet (first gas outlet), 17 ... Raw material gas group B outlet (second gas jet) Exit)

Claims (8)

A reaction container in which the film-forming object is accommodated, a gas supply pipe provided in the reaction container, and a rotation driving device that rotates the gas supply pipe around the rotation axis in the reaction container,
The inside of the gas supply pipe is partitioned into a first gas circulation part and a second gas circulation part extending along the rotation axis,
On the wall of the gas supply pipe, a first gas outlet for ejecting the first gas flowing through the first gas circulation part into the reaction vessel, and a second gas flowing through the second gas circulation part are provided. A second gas jetting port to be jetted into the reaction vessel is disposed adjacent to the circumferential direction of the rotating shaft,
The chemical vapor deposition apparatus, wherein a relative angle between the first gas ejection port and the second gas ejection port around the rotation axis is 150 ° or more and 180 ° or less.   2. The plurality of jet nozzle pairs each including the first gas jet nozzle and the second gas jet nozzle adjacent to each other in the circumferential direction of the rotation shaft are provided in the axial direction of the gas supply pipe. Chemical vapor deposition equipment. In two pairs of jet outlets adjacent in the axial direction of the rotating shaft,
The relative angle around the rotation axis of the first gas outlets belonging to different jet outlet pairs and the relative angle around the rotation axis of the second gas jet outlets belonging to different jet outlet pairs are 130 ° or more. The chemical vapor deposition apparatus according to claim 2, wherein In two pairs of jet outlets adjacent in the axial direction of the rotating shaft,
4. The chemical vapor deposition apparatus according to claim 2, wherein a relative angle around the rotation axis between the first gas outlet and the second gas outlet belonging to the different outlet pairs is 60 ° or less. 5.   A chemical vapor deposition method for forming a film on the surface of an object to be deposited using the chemical vapor deposition apparatus according to any one of claims 1 to 4.   The chemical vapor deposition method according to claim 5, wherein the gas supply pipe is rotated at a rotation speed of 10 rotations / minute or more and 60 rotations / minute or less.   The chemical vapor deposition method according to claim 5 or 6, wherein a source gas containing no metal element is used as the first gas, and a source gas containing a metal element is used as the second gas.   The chemical vapor deposition method according to claim 7, wherein an ammonia-containing gas is used as the first gas.

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