JP2016117950A - Production method of cylindrical target material, and cylindrical target material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a cylindrical target member, capable of producing a target material in which ceramic is uniformly sintered in high density without making crack by using a capsule HIP method.SOLUTION: The method incudes: a filling process for filling a material to be sintered 2A in a capsule container 10; and a sintering process for sintering the material to be sintered 2A while pressure is applied on the capsule container 10. The capsule container 10 includes; a container body 11 with a cylindrical outer wall section, and a middle core 12 provided in the container body 11. In the filling process, the material to be sintered 2A is filled in a space surrounded by the container body 11 and the middle core 12, and a mold lubricant 31 is always included between the capsule container 10 and the material to be sintered 2A. In the mold lubricant 31, reactivity with the material to be sintered 2A in a sinter temperature region in the sintering process is lower than that between the material to be sintered 2A and the capsule container 10, and an amount of the mold lubricant 31 is controlled so that thickness of the mold lubricant 31 is 1 mm or more after sintering process.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a method for manufacturing a cylindrical target material and a cylindrical target material.

  Conventionally, a sputtering method is known as a method for forming a film of ceramics such as IGZO (registered trademark) or ITO. Sputtering apparatuses that perform the sputtering method include a sputtering target that uses a flat type (flat type target) and a cylindrical type (cylindrical target).

  Among these, a sputtering apparatus using a cylindrical target is configured to perform sputtering while rotating the cylindrical target while cooling the target material from the inside of the cylindrical target. Therefore, in the sputtering apparatus using a cylindrical target, the usage efficiency of the target material is 70% or more. This usage efficiency is very high compared to the usage efficiency of the target material of 20% to 30% in a sputtering apparatus using a flat target, and is useful from the viewpoint of resource saving and reduction of the economic burden. .

  The target material described above can be obtained by sintering ceramics under pressure and heating conditions. One method for solidifying ceramics by pressurization and heating is hot isostatic pressing (hereinafter sometimes referred to as “HIP”). In particular, when the ceramic is powder, the capsule HIP method is used. In the capsule HIP method, an isotropic pressure is applied in a high-temperature, high-pressure gas to a metal capsule container hermetically sealed with ceramics to obtain a sintered body of ceramics to be sintered. This is a method (see, for example, Patent Document 1).

JP 2003-267790 A

However, the above method has the following problems.
When the sintered body is formed by the capsule HIP method, cracks are likely to occur in the sintered body during the capsule HIP process due to the difference in thermal expansion coefficient between the material to be sintered, which is ceramic, and the metal capsule container. Therefore, when manufacturing a target material using a capsule HIP method, the method which can suppress a crack and a crack was calculated | required.

  This invention is made | formed in view of the said situation, Comprising: The subject of this invention is using the capsule HIP method, without generating a crack in the cylindrical target material by which ceramics were sintered uniformly and with high density. An object of the present invention is to provide a method of manufacturing a cylindrical target material that can be manufactured. Moreover, it is providing the dense cylindrical target material manufactured by such a manufacturing method.

  In order to solve the above-described problems, one embodiment of the present invention is a method for manufacturing a cylindrical target material that is cylindrical and is formed of a ceramic sintered body, and that is a material for forming the ceramic sintered body in a capsule container. A filling step of filling a sintered material, and a sintering step of sintering the material to be sintered while pressurizing the capsule container. The capsule container is a cylindrical metal container having a bottom. Yes, in the filling step, a cylindrical core is disposed coaxially with the capsule container in the capsule container and filled with the material to be sintered, and further between the capsule container and the material to be sintered, And a release agent is always interposed between the core and the material to be sintered, and the release agent has a reactivity with the material to be sintered in a sintering temperature region of the sintering step. The material to be sintered and the capsule The reactivity between the container and the reactivity between the material to be sintered and the core, and the amount of the release agent is the thickness of the release agent after the sintering treatment The manufacturing method of the cylindrical target material currently controlled so that it may become 1 mm or more.

  In one aspect of the present invention, in the filling step, the powder of the material to be sintered and the release agent are provided in a state where a partition for separating the material to be sintered and the release agent is provided in the capsule container. The capsule container is filled with powder, and the partition is opposed to the space formed between the inner wall surface of the capsule container and the surface of the partition facing the inner wall surface, and the surface of the core and the surface. It is good also as a manufacturing method provided in the space formed between the said partition surfaces so that the said amount of mold release agent can be filled.

  In one aspect of the present invention, in the filling step, a coating film containing the release agent and a solvent is applied to the inside of the capsule container and the surface of the core, and the solvent is removed by drying to form a coating film Then, the manufacturing method of filling the material to be sintered may be used.

  Another aspect of the present invention is a method for producing a cylindrical target material having a cylindrical shape and made of a ceramic sintered body, wherein a capsule container is filled with a material to be sintered which is a forming material of the ceramic sintered body. A filling step and a sintering step of sintering the material to be sintered while pressurizing the capsule container, and the capsule container is provided coaxially with a cylindrical outer wall portion and the outer wall portion. A cylindrical inner wall portion and an annular bottom portion connecting the outer wall portion and the inner wall portion, and in the filling step, the capsule material is filled with the material to be sintered. In addition, a release agent is always interposed between the capsule container and the material to be sintered, and the release agent reacts with the material to be sintered in the sintering temperature region of the sintering step. The material to be sintered and the capsule container And the amount of the mold release agent is controlled so that the thickness of the mold release agent after the sintering process is 1 mm or more. Provide a method.

  In one aspect of the present invention, in the filling step, the powder of the material to be sintered and the release agent are provided in a state where a partition for separating the material to be sintered and the release agent is provided in the capsule container. The capsule is filled with powder, and the partition can be filled with the amount of the release agent in a space formed between the inner wall surface of the capsule container and the surface of the partition facing the inner wall surface. It is good also as a manufacturing method provided by controlling in this way.

  In one aspect of the present invention, in the filling step, a coating material containing the release agent and a solvent is applied to the inside of the capsule container, and the solvent is dried and removed to form a coating film. It is good also as a manufacturing method filled with a binding material.

  One embodiment of the present invention may be a manufacturing method using, in the filling step, a material obtained by molding the release agent into a sheet shape as the release agent.

  One embodiment of the present invention may be a manufacturing method in which a metal having a melting point higher than a temperature at which the sintering process is performed is used as the mold release agent.

  In one embodiment of the present invention, the mold release agent may have a relative density of 85% or less after the sintering process.

  One embodiment of the present invention may be a manufacturing method using a metal oxide as a forming material and a relative density of 85% or less after the sintering treatment as the release agent.

  In one embodiment of the present invention, the release agent may be a manufacturing method including alumina powder.

  Another embodiment of the present invention provides a cylindrical target material having a relative density of 100%.

  According to the present invention, there is provided a method for producing a cylindrical target material, which is capable of producing a cylindrical target material in which ceramics are uniformly and densely sintered using a capsule HIP method without causing cracks. can do. In addition, a dense cylindrical target material can be provided.

It is explanatory drawing of the cylindrical target material manufactured with the manufacturing method of 1st Embodiment. It is a schematic diagram explaining the capsule container used with the manufacturing method of the cylindrical target material of 1st Embodiment. It is explanatory drawing about the manufacturing method of the cylindrical target material which concerns on 1st Embodiment. It is a schematic diagram explaining the capsule container used with the manufacturing method of the cylindrical target material of 2nd Embodiment. It is explanatory drawing about the manufacturing method of the cylindrical target material which concerns on 2nd Embodiment. It is explanatory drawing about the manufacturing method of the cylindrical target material which concerns on 3rd Embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments. In all the drawings below, the dimensions and ratios of the constituent elements are appropriately changed in order to make the drawings easy to see.

[First embodiment]
1-3 is explanatory drawing about the manufacturing method of the cylindrical target material which concerns on this embodiment.

[Cylindrical target material]
First, the cylindrical target material manufactured in the manufacturing method of the cylindrical target material of this embodiment is demonstrated using FIG. FIG. 1 is an explanatory diagram of a sputtering target 1 having a cylindrical target material manufactured by the manufacturing method of the present embodiment. FIG. 1A is a schematic perspective view of the sputtering target 1, and FIG. 1B is a cross-sectional view taken along line Ib-Ib in FIG. In the figure, the end face is indicated by a solid line, and the configuration behind the end face in the visual field direction is indicated by a broken line. The same applies to the drawings used in this specification.

  As shown in the figure, the sputtering target 1 includes a target material 2 having a cylindrical shape, a backing tube 3 that holds the target material 2, and a bonding layer 4 that joins the target material 2 and the backing tube 3. ing. The target material 2 corresponds to a “cylindrical target material” manufactured in the method for manufacturing a cylindrical target material according to the present embodiment.

Here, in this specification, the “cylindrical” refers to a hollow solid body having a through hole in the axial direction of the column. A solid solid body without a through hole is referred to as a “column”. In addition, the “axis” of the cylinder refers to a straight line that passes through the center of the bottom surface of the cylinder and is parallel to the side surface of the cylinder.
Hereinafter, it demonstrates in order.

(Target material)
The target material 2 has a through hole 2a provided in the axial direction. Such a target material 2 may be constituted by connecting a plurality of target materials in the axial direction, but is preferably an integral sintered body.

  In addition, the length L1 of the target material 2 is preferably formed so as to extend 0.5 m or more in the axial direction. In detail, it is preferable that the target material 2 is formed long according to the width of an object on which a thin film is formed by sputtering. For example, when forming a film on a mother glass, it is preferable to use a long target material 2 according to the generation of the mother glass that is the film formation target, and an 8.5 generation mother glass (2200 mm × 2500 mm) is formed. In the case of an object, the length L1 is preferably about 3 m.

  The target material 2 uses a ceramic powder sintered body (ceramic sintered body) as a forming material. Various ceramics can be used as the ceramic material for forming the ceramic sintered body, depending on the type of thin film deposited by the sputtering apparatus. Some) and those that are semiconductor forming materials.

  Examples of the ceramic that is a material for forming the conductor include zinc oxide, indium oxide, and tin oxide. Moreover, it is good also as including 2 or more types of ceramics which are the formation material of these conductors. Moreover, other metal atoms may be doped in the ceramics which are the materials for forming these conductors. In addition, as a ceramic that is a material for forming a conductor, those having a generally known configuration can be applied.

  For example, in the case where the target material 2 includes tin oxide and indium oxide as the forming materials, when the target material 2 is used to form a film by sputtering, indium tin oxide (a composite oxide of tin oxide and indium oxide) A thin film of tin-doped indium oxide (ITO) is obtained.

  Further, when the target material 2 includes zinc oxide and indium oxide as forming materials, when the target material 2 is used to form a film by sputtering, IZO (registered trademark), which is a composite oxide of zinc oxide and indium oxide. ) Is obtained.

  In addition, as ceramics as a conductor forming material, zinc oxide is the main component, and gallium oxide, aluminum oxide or titanium oxide is a composite oxide of TZO (titanium-doped zinc oxide), AZO (aluminum-doped zinc oxide). ), GZO (gallium-doped zinc oxide), TAZO (titanium, aluminum-doped zinc oxide), and the like.

  For example, when the target material 2 is a mixture of gallium oxide and zinc oxide, a film of GZO, which is a composite oxide of gallium oxide and zinc oxide, can be obtained by using the target material 2 to form a film by sputtering.

  When the target material 2 is a mixture of aluminum oxide and zinc oxide, when the target material 2 is used to form a film by sputtering, an AZO thin film that is a composite oxide of aluminum oxide and zinc oxide is obtained.

  Further, when the target material 2 is a mixture of titanium oxide and zinc oxide, a thin film of TZO, which is a composite oxide of titanium oxide and zinc oxide, is obtained when the target material 2 is used to form a film by sputtering.

  Examples of ceramics that are semiconductor forming materials include IGZO (registered trademark), which is a composite oxide of indium oxide, gallium oxide, and zinc oxide. When the target material 2 is a mixture of indium oxide, gallium oxide, and zinc oxide, a thin film of IGZO that is a composite oxide of indium oxide, gallium oxide, and zinc oxide is formed by sputtering using the target material 2 Is obtained. In addition, as a ceramic which is a semiconductor, those having a generally known configuration can be applied.

  The target material 2 preferably has a relative density of the ceramic sintered body constituting the target material 2 of 99% or more and 100% or less. When the target material 2 included in the sputtering target 1 has such a relative density, when used for film formation with a sputtering apparatus, abnormal discharge hardly occurs and film formation can be performed stably.

Here, the “relative density” of the ceramic sintered body refers to the ratio of the density of the ceramic sintered body actually obtained to the theoretical density of the ceramic sintered body, and can be determined by the following equation. In the following formula, the ceramic sintered body is simply referred to as a sintered body.
Relative density (%) = 100 × [(density of sintered body) / (theoretical density of sintered body)]

The density of the ceramic sintered body can be measured by a length measurement method.
In this specification, the “length measurement method” means that the ceramic sintered body is processed to prepare a test piece having a predetermined shape, and then the dimension of the test piece is measured and measured separately. It refers to the method of calculating the density from the mass of the test piece. As the shape of the test piece, various shapes can be adopted as long as the shape can be accurately measured and the volume can be calculated. For example, shapes such as a cylinder, a cube, and a rectangular parallelepiped can be exemplified.

As the theoretical density of the ceramic sintered body, literature values can be adopted when the ceramic sintered body is composed of a single ceramic. For example, simple substance density of the indium oxide is 7.18 g / cm ^3, single density of tin oxide 6.95 g / cm ^3, single density gallium oxide is 5.88 g / cm ^3, single density of zinc oxide 5.61g / Cm ³ .

  When the ceramic sintered body is composed of a mixture of multiple ceramics, the density of each ceramic, which is the raw material of the sintered body, is multiplied by the mixing mass ratio of each ceramic, and the sum of those values (mass average) Value).

  However, if information on single-phase crystals with the same proportion of metal atoms contained in the ceramic sintered body is described in the JCPDS (Joint Committee of Powder Diffraction Standards) card, it is described in the JCPDS card. The theoretical density of the corresponding crystal can be used as the theoretical density in the above formula.

As a specific example, a case where a ceramic sintered body is used for the purpose of forming an IGZO film is assumed. In this case, the ceramic sintered body uses a mixture of indium oxide powder, gallium oxide powder, and zinc oxide powder as a forming material. For example, when a ceramic sintered body is mixed so that the atomic ratio of indium, gallium, and zinc is In: Ga: Zn = 1: 1: 1, the JCPDS card has InGaZnO ₄ (In: Ga: Zn = 1: 1: 1) Information on single phase crystals is described. Therefore, the theoretical density (6.379 g / cm ³ ) of the single phase crystal of InGaZnO ₄ described in the JCPDS card (No. 381104) can be set as the theoretical density in the above formula.

In addition, in a ceramic sintered body, when mixed so that the atomic ratio of indium, gallium, and zinc is In: Ga: Zn = 2: 2: 1, In ₂ described in the JCPDS card (No. 381097). The theoretical density (6.495 g / cm ³ ) of the single-phase crystal of Ga ₂ ZnO ₇ (In: Ga: Zn = 2: 2: 1) can be set as the theoretical density in the above formula.

The ceramic sintered body used for the purpose of forming the IGZO film as described above has a composition that satisfies the following conditions.
Condition: Metal atomic ratio In: Ga: Zn = x: y: z, 0.2 ≦ x / (x + y) ≦ 0.8 and 0.1 ≦ z / (x + y + z) are satisfied.

When such a ceramic sintered body is used, the sputtering target 1 becomes a target capable of forming an IGZO film having a composition represented by the following formula (1) in the sputtering method.
In _x Ga _y Zn _z O _a (1)
(However, x, y, z, and a in the formula satisfy 0.2 ≦ x / (x + y) ≦ 0.8, 0.1 ≦ z / (x + y + z), and a = 1.5x + 1.5y + z. )

  When the ceramic sintered body is adjusted to have such a ratio, the obtained IGZO film has good transistor characteristics.

  If the percentage of metal atoms in the ceramic sintered body does not match the percentage of metal atoms in the single-phase crystal described in the JCPDS card, the deviation is within 5%. The theoretical density of the single phase crystal can be the theoretical density in the above formula.

(Backing tube)
The backing tube 3 is inserted into the through hole 2 a of the target material 2. In the sputtering target 1 of the present embodiment, the backing tube 3 has a cylindrical shape and has a through hole 3a provided in the axial direction.

  The length L2 of the backing tube 3 is longer than the length L1 of the target material 2. Therefore, both ends of the backing tube 3 are exposed from the through hole 2 a in a state where the backing tube 3 is inserted into the through hole 2 a of the target material 2.

  A flange portion 301 is provided at one end of the backing tube 3. The flange portion 301 and the other end 302 of the backing tube 3 function as a jig for the target material 2 when attached to a sputtering apparatus in which the sputtering target 1 is used. Therefore, the size of the flange portion 301 is determined according to the sputtering apparatus in which the sputtering target 1 is used.

  As the material for forming the backing tube 3, various materials are used as long as no alteration or deformation occurs in the sputtering conditions (film formation conditions) in the sputtering apparatus in which the sputtering target 1 is used and the formation conditions of the bonding layer 4 described later. can do.

  For example, as a material for forming the backing tube 3, a metal material having a high melting point such as Ti, Nb, Ta, Cr, V, Hf, Zr, Mo, and W can be employed in addition to copper and stainless steel.

  In addition, the backing tube 3 may be integrally formed with one component, and may be formed by connecting a plurality of components.

  The bonding layer 4 is disposed between the inner wall 2x of the through hole 2a of the target material 2 and the outer wall 3x of the backing tube, and bonds the target material 2 and the backing tube 3 together. Examples of the material for forming the bonding layer 4 include low melting point solder such as indium solder (In solder).

  The target material 2 and the sputtering target 1 using the target material 2 are configured as described above.

[Method of manufacturing cylindrical target material]
Next, a method for manufacturing a cylindrical target material will be described with reference to FIGS.
In the manufacturing method of the cylindrical target material of the present embodiment, a ceramic capsule as a raw material of the cylindrical target material is filled in a metal capsule container, and hot isostatic pressing (HIP) processing is performed. A ceramic sintered body is obtained. Hereinafter, the HIP process using such a capsule container may be referred to as “capsule HIP”.

  In the following description, first, a capsule container, a material to be sintered, and a release agent used in the method for manufacturing a cylindrical target material of the present embodiment will be described, and then a method for manufacturing the cylindrical target material will be described.

[Capsule container]
FIG. 2 is a schematic diagram illustrating a capsule container used in the method for manufacturing a cylindrical target material according to this embodiment. 2A is a schematic perspective view of the capsule container 10, and FIG. 2B is a cross-sectional view taken along line IIb-IIb in FIG. 2A.

  As shown in FIGS. 2A and 2B, the capsule container 10 is a cylindrical metal container having a bottom. The capsule container 10 of the present embodiment includes a container main body 11 having an internal space and a lid 15 having a degassing exhaust pipe (not shown).

  Furthermore, a core 12 is disposed coaxially with the container body 11 inside the container body 11. The core 12 is a separate member from the container body 11 and stands on the bottom 11 c of the container body 11.

  In such a capsule container 10, a space 19 filled with a material to be sintered is formed in a space surrounded by the outer wall portion 11 a, the inner wall portion 11 b (core 12), and the bottom portion 11 c of the container body 11. .

  In the following description, the capsule container having the form shown in FIG. 2 may be referred to as “capsule with center core”.

  Of the capsule container 10, the material for forming the container body 11 and the lid 15 may be a material that can sufficiently seal the material to be sintered and that is sufficiently deformed at the sintering temperature in the capsule HIP process but does not have a risk of bursting. That's fine. For example, a metal material such as iron, aluminum, stainless steel, niobium, tantalum, nickel, platinum, or copper is used as a material for forming the container body 11 and the lid 15. Specifically, the iron is preferably carbon steel, and is preferably mild steel having a carbon content of about 0.3% or less. As the copper, oxygen-free copper is preferably used. For example, SUS304 is used as the stainless steel.

  As a material for forming the container body 11 and the lid 15, tantalum, niobium, and platinum can be suitably used when the sintering temperature of the capsule HIP process is 1300 ° C. or higher. Moreover, when the sintering temperature of the capsule HIP treatment is 900 ° C. or higher and 1300 ° C. or lower, iron or stainless steel can be suitably used. Moreover, when the sintering temperature of the capsule HIP process is 900 ° C. or lower, nickel, copper, or the like can be suitably used.

  In the capsule container 10, the material for forming the core 12 can be used as long as it does not deform at the sintering temperature of the capsule HIP treatment, and is preferably a metal material.

Examples of the material for forming the core 12 include heat resistant steel, superalloy (Fe base, Co base, Ni base), stainless steel, high melting point metal (niobium, tantalum, molybdenum, hafnium, tungsten, etc.), Inconel, Hastelloy, etc. metal;
Metal carbides such as silicon carbide, tantalum carbide, tungsten carbide, titanium carbide;
Metal borides such as titanium boride and zirconium boride;
Can be mentioned.

  In the capsule container 10, different materials can be used for the forming material of the container body 11 and the forming material of the core 12.

  The thickness of the container body 11 of the capsule container 10, that is, the thickness of the outer wall portion 11a and the bottom portion 11c is not particularly limited, and is preferably 1 mm or more and 4 mm or less. Within this range, the capsule container 10 can be easily softened and deformed, and can shrink following the sintered body as the sintering reaction proceeds.

[Sintered material]
As a material to be sintered, a corresponding ceramic powder is used according to the target material 2 to be manufactured. When the target material 2 is a single ceramic sintered body, a single powder is also used as the material to be sintered. Moreover, when the target material 2 is a sintered body of a plurality of ceramics, for example, when the target material 2 is a raw material of ITO, a mixture of ceramic powders corresponding to the material to be sintered is used.

  When the material to be sintered is a mixture, the capsule container 10 may be filled after being mixed in advance. As a mixing method, a conventionally known method can be adopted, and it may be dry or wet.

  The average particle diameter of the material to be sintered is generally 0.6 μm or more, preferably 1 μm or more and 5 μm or less, which is easy to handle. Here, the “average particle size” refers to a 50% cumulative volume fraction particle size distribution in a particle size distribution measured by a laser diffraction / scattering method.

In addition, when manufacturing the sputtering target used for the purpose of forming the IGZO film as described above, the material to be sintered is mixed with a composition that satisfies the following conditions.
Mixing conditions: In the metal atomic ratio In: Ga: Zn = x: y: z, 0.2 ≦ x / (x + y) ≦ 0.8 and 0.1 ≦ z / (x + y + z) are satisfied. .

  In the ceramic sintered body, the relationship of 0.2 ≦ x / (x + y) ≦ 0.5 and 0.1 ≦ z / (x + y + z) ≦ 0.8 is particularly preferable.

In particular, the mass ratio (indium oxide powder: gallium oxide powder: zinc oxide powder) is approximately 44.2: 29.9: 25.9 (in molar ratio: In: Ga: Zn = 1: 1: 1). It is preferable to perform uniform mixing. Thus, it is possible to IGZO sintered body to obtain a characteristic favorable InGaZnO ₄ as described above.

Further, the mass ratio (indium oxide powder: gallium oxide powder: zinc oxide powder) is approximately 50.8: 34.3: 14.9 (in molar ratio: In: Ga: Zn = 2: 2: 1). It is preferable to perform uniform mixing. Thus, it is possible to IGZO sintered body to obtain a characteristic favorable _In 2 _Ga 2 ZnO ₇ described above.

In the case of mixing indium oxide powder: gallium oxide powder: zinc oxide powder at a mass ratio of approximately 50.8: 34.3: 14.9 (Molar ratio of In: Ga: Zn = 2: 2: 1), The tap density of the ceramic powder is 3.25 g / cm ³ or more. It can filled with a lot of ceramic powder in a capsule container, and since the capsule container after the capsule HIP treatment is easily processed to shrink symmetrically, preferably at 3.8 g / cm ³ or more 6.4 g / cm ³ or less .

When mixing indium oxide powder: gallium oxide powder: zinc oxide powder at a mass ratio of approximately 44.2: 29.9: 25.9 (molar ratio In: Ga: Zn = 1: 1: 1) The tap density of the ceramic powder is 3.18 g / cm ³ or more. Preferably is 3.8 g / cm ³ or more 6.3 g / cm ³ or less.

The mixing method is not particularly limited as long as it can be uniformly mixed, and dry mixing or wet mixing (ball mill or the like) is performed using a super mixer, an intensive mixer, a Henschel mixer, an automatic mortar, or the like. The wet mixing may be performed by, for example, a wet ball mill using a hard ZrO ₂ ball, a vibration mill, or a planetary ball mill. A mixing time when using a wet ball mill, a vibration mill, or a bead mill is about 12 hours to 78 hours. preferable. For liquid separation and drying, known methods may be employed.

  When mixing is sufficiently performed and the composition becomes uniform, each component does not segregate in the manufactured target, and the obtained target has a uniform resistance distribution. That is, it is preferable because the target portion does not have a high resistance region and a low resistance region, and causes abnormal discharge such as arcing due to charging in the high resistance region during sputtering film formation.

〔Release agent〕
The release agent is a material having low reactivity with the material of the capsule container 10 and the material to be sintered in the sintering temperature region of the capsule HIP process described later. Here, that a certain material has low reactivity with the material of the capsule container 10 means that the reactivity between the material and the material of the capsule container 10 is higher than the reactivity between the material of the capsule container 10 and the material to be sintered. Means relatively low. In addition, a certain material has a low reactivity with the material to be sintered, the reactivity between the material and the material to be sintered is relatively less than the reactivity between the material of the capsule container 10 and the material to be sintered. Means low.

  The release agent is, for example, one or both of a metal and a metal compound. However, boron nitride, metal carbide and metal boride are excluded.

  Examples of the metal compound include metal nitride (silicon nitride, titanium nitride, gallium nitride, zirconium nitride, tantalum nitride, niobium nitride, hafnium nitride, vanadium nitride, chromium nitride, etc.), metal oxide (aluminum oxide (alumina), silicon dioxide) , Chromium (III) oxide, magnesium oxide, zirconium oxide (zirconia) and the like, and composite oxides composed of two or more metal oxides thereof.

  Examples of the metal include refractory metals having a melting point of 2000 ° C. or higher (tantalum, niobium, tungsten, molybdenum, hafnium, rhenium, iridium, etc., or an alloy made of two or more of these metals).

  In particular, the mold release agent is preferably made of a metal having a melting point higher than the sintering temperature of the material to be sintered as described above. For example, a refractory metal having a melting point of 2000 ° C. or higher is more preferable. Such a release agent is more preferably one having a relative density of 85% or less after the sintering treatment.

  Since such a mold release agent does not advance sintering at the sintering temperature of the material to be sintered, the shape at the time of preparation is maintained. In this state, the compressive stress during the capsule HIP treatment is relieved by the malleability and ductility of the metal forming the release agent, so that it is difficult to apply the compressive stress to the obtained sintered body, and breakage is easily suppressed.

  Further, if the relative density after the sintering treatment is 85% or less, the space between the release agents buffers the compressive stress at the time of the capsule HIP treatment, so that a compressive stress is applied to the obtained sintered body. Difficult to control damage.

  Alternatively, the release agent is preferably a metal oxide as a forming material and a relative density after the sintering treatment of 85% or less. In the case of a metal oxide, alumina or a composite oxide containing alumina and silicon dioxide is more preferable. The composition of the composite oxide containing alumina and silicon dioxide may be such that silicon dioxide is 54% by mass or less.

  Even with such a release agent, if the relative density after the sintering treatment is 85% or less, the space between the release agents buffers the compressive stress during the capsule HIP treatment, and thus the obtained firing It is easy to suppress damage to the body.

  The sintering temperature of the material to be sintered described above is included in the range of approximately 900 ° C. or more and 1400 ° C. or less. Therefore, when alumina, magnesium oxide, a composite oxide containing alumina and silicon dioxide, or a refractory metal with a melting point of 2000 ° C. or higher is used as a release agent, the release agent itself is densified by sintering during the sintering process. It keeps a constant volume without doing.

  In the sintering process, a release agent is always interposed between the capsule container 10 and the material to be sintered. Therefore, if no release agent is interposed, heat generated between the capsule container 10 and the material to be sintered is assumed. The release agent can relieve the stress.

  The metal carbide exerts a reducing action on the material to be sintered at the time of sintering, and may cause problems such as reacting with the material to be sintered or gasification of the reduced metal to prevent the capsule HIP process from proceeding. Metal borides may react with the material to be sintered. Further, when boron nitride is used as a mold release agent, it may react with the obtained sintered body to cause cracks or diffusion of boron (contamination).

  As a form of the mold release agent of this embodiment, it is a powder or a ball, for example. When the release agent is a powder or a ball, it is easy to form a space between the release agents, buffer the compressive stress during the capsule HIP process, and easily suppress breakage.

  When the release agent is in the form of powder, hollow particles and porous particles can be preferably used.

  Moreover, the mold release agent may contain a binder component. In the deaeration process at the time of the capsule HIP process to be described later, it can also serve as a process for removing the binder component.

  The average particle diameter of the release agent before the capsule HIP treatment is not particularly limited, but particles having a small specific surface area are preferable in order to make the release agent more difficult to sinter.

  For example, the release agent preferably has a larger average particle size. The average particle size of the release agent is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more and 100 μm or less.

  When the average particle diameter of the release agent is less than 10 μm, granulation treatment may be performed to form aggregated particles, and the average particle diameter may be increased (specific surface area is decreased).

  When the release agent has such a specific surface area, it is easy to maintain a low density state in the capsule HIP process. Therefore, the mold release agent can be plastically deformed even if it is partially sintered during the capsule HIP process, and the thermal stress during or after the capsule HIP process can be absorbed by the plastic deformation. For this reason, it becomes difficult to produce a crack in the target material 2 obtained.

  The relative density after the capsule HIP process varies depending on the conditions of the capsule HIP process described later, but a material in which the relative density after the capsule HIP process is 85% or less is more preferable, and the relative density after the capsule HIP process is 80% or less. More preferred is a material.

  After the capsule HIP treatment, the material to be sintered becomes a sintered body, for example, the relative density becomes high density of 98% or more, but when the release agent maintains the low density relative density as described above, It is possible to absorb and relax thermal stress by exhibiting a buffering effect.

〔Filling rate〕
The sintered material described above preferably has a powder characteristic such that when the capsule container 10 is filled, the filling rate of the entire capsule container is 50% or more.

  As will be described in detail later, in the capsule HIP process, the capsule container filled with the material to be sintered is pressurized while being sintered. The capsule container pressurizes the material to be sintered filled therein while being entirely contracted by the applied pressure.

  At that time, it is empirically known that when the shrinkage rate of the capsule container is 50% or more, the capsule container is easily damaged by the strain at the time of shrinkage. Here, the “shrinkage ratio” (%) can be considered as the ratio of the volume during capsule HIP processing to the volume of the capsule container at normal pressure with respect to the capsule container filled with the material to be sintered. .

  Therefore, in order to suppress breakage in the capsule HIP process, it is preferable to control the capsule container filled with the material to be sintered so that the volume at the capsule HIP process is 50% or more of the volume at normal pressure. I understand.

  Such control is performed when the “substance occupying the space in the capsule container” is “the filling ratio of the entire capsule container” (%), and “the filling ratio of the entire capsule container”. Can be realized when the ratio is 50% or more. By controlling in this way, there is no possibility that the capsule container 10 is damaged by the external pressure applied to the capsule container 10 during the capsule HIP process.

When the capsule HIP process is performed with a capsule having a core, examples of the “substance present in the capsule container” include a material to be sintered, a core, and a release agent. That is, the “filling ratio of the entire capsule container” can be obtained by the following formula (I). In the following formula (I), “filling rate of the entire capsule container” is described as “overall filling rate”.
Total filling rate (%) = filling rate A (%) + filling rate B (%) + filling rate C (%) (I)

（ただし、α＝被焼結材料の体積、β＝中芯体積）

(Where α = volume of the material to be sintered, β = core volume)

  Since the core has a solid structure, there is no volume change even when pressurized. Therefore, it can be considered that the filling rate of the core is 100%, and the filling rate B can be considered as a ratio of the volume of the core that occupies the internal space of the capsule container.

  The “filling rate of the material to be sintered” (%) can be defined as follows depending on the properties of the material to be sintered.

First, when the material to be sintered is powder or ball, the filling ratio A of the material to be sintered is the theoretical density of the sintered body when it is assumed that the sintered body after the capsule HIP treatment has reached the theoretical density. Refers to the ratio of the tap density of the material to be sintered filled in the capsule container. The filling rate of the material to be sintered can be obtained by the following formula. The theoretical density described above can be adopted.
Filling rate of sintered material (%) = 100 × (tap density of sintered material / theoretical density of sintered body)

  The “tap density” refers to an apparent density measured based on JIS K5101-12-2 “Pigment test method—Part 12: Apparent density or apparent specific volume—Section 2: Tamping method”.

  The material to be sintered is mechanically crushed after calcining at about 1000 ° C., granulated by a spray drying method, or pressed by uniaxial pressing or cold isostatic pressing (CIP). You may pre-process so that it may become the tap density which can implement | achieve a filling rate. A known organic binder may be used in combination during granulation or pressure molding by spray drying.

Thus, when the material to be sintered is a molded body having a certain shape, the filling rate A of the material to be sintered can be obtained by the following equation.
Filling ratio of sintered material (%) = 100 × (density of sintered material molded body / theoretical density of sintered body)

  The “filling rate of release agent” (%) can be defined as follows depending on the properties of the release agent.

  The filling rate C of the release agent refers to the ratio of the density of the release agent before the capsule HIP treatment (before sintering) to the density of the release agent after the capsule HIP treatment (after sintering). The filling rate C of the release agent can be determined from the relative density of the release agent before sintering and the relative density of the release agent after sintering.

  When the release agent is a powder or a ball, the “density of the release agent before sintering” is the above-described tap density. When the release agent is a molded body having a certain shape, the “density of the release agent before sintering” is the density of the molded body of the release agent.

[Method of manufacturing cylindrical target material]
The manufacturing method of the cylindrical target material of this embodiment includes a filling process for filling a capsule container with a material to be sintered, which is a material for forming a ceramic sintered body, and a sintering process for the material to be sintered while pressurizing the capsule container. (Capsule HIP treatment) and a sintering step.

  FIG. 3 is an explanatory view for explaining the method of manufacturing the cylindrical target material of the present embodiment, and is a view having the same field of view as FIG. In FIG. 3, the capsule container 10 (capsule with a core) shown in FIG. 2 is used as the capsule container.

(Filling process)
First, as shown to Fig.3 (a), what inserted the core 12 in the container main body 11 is prepared. Thereafter, the container body 11 is filled with the release agent 31 by pressing it down. At this time, the mold release agent 31 is pressed down from the bottom 11c until the thickness d is reached.

  Next, as shown in FIG. 3B, the cylindrical first partition (partition) 7 and second partition (partition) 8 are inserted into the space 19 of the container body 11 so as to be coaxial with the core 12.

  The first partition 7 and the second partition 8 are for separating the filling space so that the material to be sintered and the release agent 31 are not mixed when the container body 11 is filled, and the release agent 31. This is for controlling the volume of the space filled. The first partition 7 and the second partition 8 have a sheet shape, and are removed from the container body 11 after the filling of the material to be sintered and the release agent 31 is completed. Therefore, various materials such as paper, resin, and metal can be used as the material for forming the first partition 7 and the second partition 8.

  The diameter of the cylindrical first partition 7 having a large diameter is set so that the distance from the container body 11 is d. That is, when the inner diameter of the container main body 11 is R1, the diameter of the first partition 7 is R1-2d.

  The diameter of the cylindrical second partition 8 with a small diameter is set so that the distance from the center core 12 is d. That is, when the diameter of the center core 12 is R2, the diameter of the second partition 8 is R2 + 2d).

  By inserting the first partition 7 and the second partition 8 as described above, the distance between the first partition 7 and the container body 11 and the distance between the second partition 8 and the core 12 are different from the wall surfaces. A space controlled by d is formed.

  Next, a space formed between the inner wall surface 11x of the container main body 11 and the surface of the first partition 7 facing the inner wall surface 11x, and the surface 12x of the core 12 and the surface of the second partition 8 facing the surface 12x. The release agent 31 is filled in the space formed between the two. At this time, the filling amount is controlled so that the height from the upper end of the filled release agent 31 to the upper end of the container body 11 is d.

  Further, the material to be sintered 2A is filled between the first partition 7 and the second partition 8. At this time, the material to be sintered 2A is filled while applying vibration until there is no volume change. At this time, the filling amount is controlled so that the height from the upper end of the filled sintered material 2A to the upper end of the container body 11 is d.

  Next, as shown in FIG. 3C, the mold release agent 31 is pressed and filled on the filled material to be sintered 2 </ b> A and the mold release agent 31. As a result, the material to be sintered 2A is filled into the container main body 11 in a state surrounded by the release agent 31. After the release agent 31 is filled, the first partition 7 and the second partition 8 are removed.

  After filling with the release agent 31, the lid 15 is welded to the container body 11 to seal the capsule container 10.

  When the release agent 31 and the material to be sintered 2A are filled in this way, the amount of the release agent 31 is from the bottom of the container body 11 to the material to be sintered 2A, and from the container body 11 to the material to be sintered 2A. The thickness, the thickness from the core 12 to the material to be sintered 2A, and the thickness from the lid 15 to the material to be sintered 2A are all controlled to be the thickness d.

  The thickness d is set so that the thickness of the release agent 31 after the capsule HIP processing described later is 1 mm or more, and the filling amount of the release agent 31 is controlled. Preferably, the thickness of the release agent 31 after the capsule HIP process is controlled to be 2 mm or more and 8 mm or less, more preferably 3 mm or more and 7 mm or less.

  It is important that the release agent 31 is filled in such an amount that the “thickness after the capsule HIP process” is 1 mm or more. When filling the release agent 31 before the capsule HIP treatment, it is assumed that the release agent 31 is somewhat sintered and contracted by the capsule HIP treatment, and is filled to be thicker than 1 mm. Is preferred. For example, it is confirmed by preliminary experiments how much the release agent 31 is shrunk by the capsule HIP process, and the “thickness after the capsule HIP process” is 1 mm after considering the shrinkage rate of the obtained release agent 31. The above amount may be filled. Further, based on information obtained from literature values and the like, it is also possible to fill an amount that ensures that the “thickness after the capsule HIP process” is 1 mm or more after assuming the shrinkage rate of the release agent 31.

  When such an amount of the release agent 31 is filled, the release agent 31 sufficiently buffers the volume change during the capsule HIP process and the volume change after the capsule HIP process, and cracks the target material 2. Hard to generate. Furthermore, the residual stress inherent in the target material 2 can be reduced. By reducing the residual stress, it is possible to reduce problems such as the occurrence of cracks that are triggered by sputtering impact when used in a sputtering apparatus.

(Sintering process)
Next, while the capsule container 10 is heated, the inside of the capsule container 10 is decompressed via an exhaust pipe (not shown) of the lid 15. As a result, volatile components such as gas adhering to the material to be sintered 2A and adsorbed moisture can be removed.

  The heating temperature of the capsule container 10 at the time of deaeration is preferably 100 ° C. or higher and 600 ° C. or lower. When the material to be sintered 2A contains an organic binder and the organic binder is removed simultaneously with the degassing treatment, the heating temperature of the capsule container 10 at the time of degassing is 450 ° C. or higher and 700 ° C. as described above. It is preferable that it is below ℃.

Depressurization is performed until the pressure in the capsule container 10 becomes 1.33 × 10 ⁻² Pa or less. When the pressure in the capsule container 10 is 1.33 × 10 ⁻² Pa or less, it is preferable because the gas adhering to the material to be sintered 2A and the adsorbed moisture are sufficiently removed. Thereafter, the exhaust pipe connected to the capsule container is closed, and the capsule container is sealed.

  Next, as shown in FIG. 3 (d), the capsule container 10 is placed in an unillustrated HIP device, and HIP processing is performed (capsule HIP processing). In the capsule HIP process, pressure is applied to the sintered material 2A inside the capsule container 10 by applying pressure from the outside of the capsule container 10 using a gas under high temperature and high pressure as a pressure medium.

The conditions for the capsule HIP treatment are preferably such that the relative density of the sintered body is 98% or more and 100% or less. If the sintered body has a relative density of 98% or more, for example, when forming a film by sputtering using the sintered body, abnormal discharge hardly occurs and the film can be stably formed.
For example, it may be set as follows.

  The gas as the pressure medium is preferably an inert gas such as nitrogen or argon.

  The pressure applied to the capsule container 10 is preferably 50 MPa or more.

  The sintering time in the capsule HIP treatment is preferably 1 hour or longer.

  Although the sintering temperature in the capsule HIP process varies depending on the forming material of the capsule container 10 and the kind of the material to be sintered 2A, for example, 900 ° C. or higher and 1400 ° C. or lower is preferable. If the sintering temperature is within the above range, the material of the capsule container 10 is softened and deformed. Therefore, during the capsule HIP process, a suitable pressure is applied to the sintered material 2A inside the capsule container 10 via the capsule container 10. be able to.

  The cooling conditions after the capsule HIP treatment are preferably cooled at a rate of 200 ° C./hour or less, more preferably 150 ° C./hour, and further 100 ° C./hour until the temperature in the HIP apparatus reaches 200 ° C. preferable. When the temperature in the HIP apparatus becomes 200 ° C. or lower, the gas as the pressure medium is discharged from the HIP apparatus and returned to atmospheric pressure.

  The capsule HIP process is performed as described above. After the capsule HIP treatment, an integrally molded body in which the target material 2 that is a ceramic sintered body and the core 12 are integrated is taken out from the capsule container 10 as a product. At that time, due to the effect of filling the mold release agent 31, the bonding between the product and the container body 11 is suppressed, and the product can be easily taken out.

  The taken out product can be made the target material 2 by removing the inner core 12 by BTA (Boring & Trepanning Association) processing and providing a through hole. At that time, the front surface (curved surface exposed to the outside) of the target material 2 may be appropriately ground and polished.

Thus, the manufacturing method of the cylindrical target material of this embodiment at the time of using "a capsule with a center core" as a capsule container can be implemented.
The obtained target material 2 can be made into a cylindrical sputtering target shown in FIG. 1 by appropriately inserting a backing tube into the through hole and fixing with a low melting point solder or the like.

  According to the manufacturing method as described above, the following effects can be obtained.

  (1) First, since the periphery of the material to be sintered is surrounded by a release agent during sintering, the capsule container and the material to be sintered are prevented from being joined, and the resulting sintered body (target material 2) is cracked. Is less likely to occur.

  The capsule container, mold release agent, and obtained sintered body used in the manufacturing method of the present embodiment are different in material and have different thermal expansion coefficients. Therefore, in the cooling stage after the capsule HIP process, thermal stress is generated with cooling. As described above, the “capsule container” of the present embodiment includes the container body 11 and the lid 15.

  Specifically, in the sintering process in the capsule HIP process, the capsule container is in a state of being heated and pressurized from the outside and compressed, but after the sintering process in the capsule HIP process is finished, The temperature and pressure applied to the capsule container begins to drop.

As the pressure and temperature decrease, the capsule container begins to deform in the direction of expansion from the state of being elastically deformed and compressed.
On the other hand, as the temperature decreases, the sintered body starts to shrink in accordance with the thermal expansion coefficient specific to the material.
When the capsule HIP process enters the cooling process in this manner, the capsule container is displaced in the direction in which it expands, and the sintered body is displaced in the direction in which it is contracted.

  Therefore, when the capsule container and the sintered body are joined in the capsule HIP process, thermal stress (tensile stress) is generated at the interface between the expanding capsule container and the shrinking sintered body, and the sintered body is cracked. Cheap.

  On the other hand, in the manufacturing method of the present embodiment, the capsule HIP process is performed with a release agent always interposed between the capsule container and the material to be sintered. Since the mold release agent does not react (adhere) to the capsule container or the sintered body, even if the above-mentioned displacement in the reverse direction occurs, the interface between the capsule container and the mold release agent, the mold release agent, and the coating Peeling at the interface with the sintered material (sintered body) can prevent the generation of thermal stress.

  Further, it is considered that the sintered body is separated from the mold release agent and contracts according to the coefficient of thermal expansion as it is naturally cooled independently, and does not accumulate residual stress.

  Also, in the sintering process of the capsule HIP process, if the capsule container and the material to be sintered are in contact with each other, the interface portion where the capsule container and the material to be sintered are joined and the materials to be sintered are sintered. The behavior against shrinkage due to pressurization and volume change (shrinkage) due to sintering is different between the inside of the sintered body. Then, tensile stress is generated between the interface portion and the inside, and the sintered body is likely to crack.

  On the other hand, in the manufacturing method of the present embodiment, by using a release agent, it is possible to prevent the capsule container and the material to be sintered from being joined and to suppress the occurrence of cracks in the sintered body.

  As described above, the use of a release agent can suppress the generation of cracks in the sintered body (target material 2) during production.

  (2) Moreover, since the release agent used has a relative density of 85% or less after the capsule HIP treatment, it is possible to exhibit a buffering effect and absorb and relax thermal stress. Moreover, since the stress generated during the capsule HIP process can be relaxed, the stress inherent in the sintered body (target material 2) can be reduced.

  When no release agent is used, a large residual stress is generated in the target material 2. If the target material 2 has residual stress, cracks that are triggered by sputtering impact are likely to occur during use in the sputtering apparatus. When the target material 2 is increased in size, the residual stress also increases, so that such a problem is likely to become remarkable.

  On the other hand, according to the manufacturing method of the present embodiment, since residual stress can be reduced, the occurrence of cracks in the sintered body (target material 2) during use can be suppressed. When manufacturing a large cylindrical target material having a length L1 shown in FIG. 1 of 300 mm or more, and further 700 mm or more, the generation of cracks is suppressed particularly advantageously compared to the case where no release agent is used. Can do.

  (3) Moreover, in the manufacturing method of this embodiment, since the cylindrical target material 2 is manufactured using the capsule container 10 which is a capsule with a central core, the cylindrical target material 2 penetrates at the position of the central core 12. Hole 2a is formed. In the capsule container 10, since the core 12 is a separate member from the container body 11, the diameter of the core 12 can be changed as appropriate.

  When changing the diameter of the through-hole 2a according to various sputter apparatuses, if it tries to cope with it by grinding the inside of the through-hole 2a, many grinding | debris derived from a sintered compact will arise and a waste of material will increase. On the other hand, when the capsule container 10 is used in the manufacturing method of the cylindrical target material, the size of the through-hole 2a of the cylindrical target material 2 can be controlled only by replacing the core 12 to be used with a different diameter. Is possible.

  Therefore, it becomes possible to suppress the generation amount of grinding scraps derived from the sintered body. Since the sintered body may contain various rare earth elements and rare metals (rare metals), resource generation is reduced and cost competitiveness is enhanced by suppressing the generation amount of grinding scraps derived from the sintered body.

  That is, according to the manufacturing method of the present embodiment, it is possible to manufacture a cylindrical target material in which ceramics are uniformly and densely sintered using a capsule HIP method without causing cracks.

[Second Embodiment]
The manufacturing method according to the second embodiment of the present invention can be performed in the same manner as the manufacturing method according to the first embodiment of the present invention described above, except that the capsule container to be used is changed.

  FIG. 4A is a schematic perspective view of the capsule container 20 used in the manufacturing method of the present embodiment, and FIG. 4B is a cross-sectional view taken along line IVb-IVb in FIG.

  As shown in FIGS. 4A and 4B, the capsule container 20 is a container made of a metal material, and includes a container body 21 having an internal space and a degassing exhaust pipe (not shown). And a lid 25 having

  The container main body 21 includes a cylindrical outer wall portion 21a, a cylindrical inner wall portion 21b provided coaxially with the outer wall portion 21a, and an annular bottom portion 21c that connects the outer wall portion 21a and the inner wall portion 21b. Yes. The container body 21 has a through hole 21d in which the inner wall portion 21b and the bottom portion 21c communicate with each other.

Such a container main body 21 can be manufactured as follows, for example.
First, a through-hole is provided in the bottom of the container body 11 used in the first embodiment, and the container body 21 is formed. Next, a cylinder having an outer diameter inscribed in the through hole is inserted into the formed through hole. Next, with the cylinder inserted, the cylinder and the container body 21 are welded. Next, an excess portion of the cylinder is cut to form a cylindrical inner wall portion 21b.

  As the container main body 21, not only the above-mentioned method but what was manufactured by various methods can be used.

  The lid 25 is formed in an annular shape in plan view, and a through hole 23 communicating with the through hole 21d is provided at the center.

  In such a capsule container 20, a space 29 filled with a material to be sintered is formed in a space surrounded by the outer wall portion 21 a, the inner wall portion 21 b, and the bottom portion 21 c of the container body 21.

  In the following description, the capsule container having the form shown in FIG. 4 may be referred to as a “hollow capsule”.

  As a forming material of the capsule container 20, the same forming material as the capsule container 10 of the first embodiment described above can be used. Moreover, in the capsule container 20, the formation material of the outer wall part 21a and the formation material of the inner wall part 21b can also be varied.

  The thicknesses of the outer wall 21a, the inner wall 21b and the bottom 21c of the capsule container 20 and the thickness of the lid 25 are not particularly limited and are preferably 1 mm or more and 4 mm or less. Within this range, the capsule container 20 can be easily softened and deformed, and can shrink following the sintered body as the sintering reaction proceeds.

[Method of manufacturing cylindrical target material]
The manufacturing method of the cylindrical target material of this embodiment includes a filling process for filling a capsule container with a material to be sintered, which is a material for forming a ceramic sintered body, and a sintering process for the material to be sintered while pressurizing the capsule container. (Capsule HIP treatment) and a sintering step.

  FIG. 5 is an explanatory view for explaining the method of manufacturing the cylindrical target material of the present embodiment, and is the same view as FIG. In FIG. 5, the capsule container 20 (hollow capsule) shown in FIG. 4 is used as the capsule container.

(Filling process)
First, as shown in FIG. 5A, the container main body 21 is filled with a release agent 31 by pressing it down. At this time, the release agent 31 is pressed down from the bottom 21c until the thickness d is reached.

  Next, as shown in FIG. 5B, the cylindrical first partition 7 and second partition 8 are inserted into the space 29 of the container body 21 so as to be coaxial with the inner wall portion 21b.

  The diameter of the cylindrical first partition 7 having a large diameter is set so that the distance from the outer wall portion 21a is d. That is, when the inner diameter of the container main body 21 is R1, the diameter of the first partition 7 is R1-2d.

  The diameter of the cylindrical second partition 8 having a small diameter is set so that the distance from the inner wall portion 21b is d. That is, when the diameter of the inner wall portion 21b is R2, the diameter of the second partition 8 is R2 + 2d).

  By inserting the first partition 7 and the second partition 8 as described above, the distance between the first partition 7 and the outer wall portion 21a and the distance between the second partition 8 and the inner wall portion 21b are different from the wall surfaces. A space controlled by d is formed.

  Next, the inner wall surface 21x of the container body 21 (the wall surface of the outer wall portion 21a facing the space 29, the wall surface of the inner wall portion 21b facing the space 29) and the partition surface facing the inner wall surface 21x are formed. The release agent 31 is filled in the space. That is, the mold release agent 31 is filled between the first partition 7 and the outer wall portion 21a and between the second partition 8 and the inner wall portion 21b.

  Further, the material to be sintered 2A is filled between the first partition 7 and the second partition 8. At this time, the material to be sintered 2A is filled while applying vibration until there is no volume change. At this time, the filling amount is controlled so that the height from the upper end of the filled sintered material 2A to the upper end of the container body 21 is d.

  At this time, in the capsule container 20, the filling amount of the material to be sintered 2A is controlled so that the entire filling rate becomes 50% or more. In the capsule container 20 which is a hollow capsule, since the substances present in the capsule container are the material to be sintered and the release agent, the overall filling rate (%) is equal to the filling rate of the material to be sintered and the mold release. Equal to the sum of the filling factor The values shown in the first embodiment can be adopted for the filling rate of the material to be sintered and the filling rate of the release agent.

  Next, as shown in FIG. 5 (c), the release agent 31 is pressed and filled on the filled material to be sintered 2A. As a result, the material to be sintered 2A is filled into the container main body 21 in a state surrounded by the release agent 31. After the release agent 31 is filled, the first partition 7 and the second partition 8 are removed.

  After filling with the release agent 31, the lid 25 is welded to the container body 21 to seal the capsule container 20.

(Sintering process)
Next, while the capsule container 20 is heated, the inside of the capsule container 20 is decompressed via an exhaust pipe (not shown) of the lid 25. As a result, volatile components such as gas adhering to the material to be sintered 2A and adsorbed moisture can be removed.

  Next, as shown in FIG. 5 (d), the capsule container 20 is placed in a not-shown HIP device, and HIP processing is performed (capsule HIP processing). After the sintering process, the capsule container is cooled, and when the temperature in the HIP apparatus becomes 200 ° C. or lower, the gas as the pressure medium is discharged from the HIP apparatus and returned to atmospheric pressure.

  The capsule HIP process is performed as described above. After the capsule HIP treatment, the sintered body is taken out from the capsule container 20. At that time, due to the effect of filling the mold release agent 31, the bonding between the sintered body and the container main body 21 is suppressed and can be easily taken out. A through-hole is formed in the taken-out sintered body at a position corresponding to the inner wall portion 21b. This through hole corresponds to the through hole 2a of the target material 2 shown in FIG.

  The sintered body taken out can be used as the target material 2 by removing the mold release agent 31 adhering to the surface (the front surface and the inside of the through hole). At that time, the surface of the target material 2 may be appropriately ground and polished.

Thus, the manufacturing method of the cylindrical target material of this embodiment at the time of using a "hollow capsule" as a capsule container can be implemented.
The obtained target material 2 can be made into a cylindrical sputtering target shown in FIG. 1 by appropriately inserting a backing tube into the through hole and fixing with a low melting point solder or the like.

  According to the manufacturing method as described above, the following effects can be obtained in addition to the effects (1) and (2) in the first embodiment described above.

  In the manufacturing method of this embodiment, since the cylindrical target material 2 is manufactured using the capsule container 20 that is a hollow capsule, the through hole 2a of the cylindrical target material 2 is formed at the position of the inner wall portion 21b. In the container main body 21, the inner wall part 21b is joined and integrated with the bottom part 21c.

  When the container main body 11 and the core 12 are separate members as in the capsule container 10 of the first embodiment, when inserting the core 12 into the container body 11, the container body 11 and the core 12 are It tends to be difficult to be accurately coaxial. On the other hand, when the container main body 11 and the core 12 are not coaxial, the through-hole 2a formed in the target material 2 to be obtained is eccentric, so that grinding for shaft alignment is necessary. End up.

  On the other hand, when the inner wall 21b is joined and integrated as a part of the container main body 21 as in the capsule container 20 of the present embodiment, the outer wall 21a The inner wall portion 21b can be accurately coaxial.

  In addition, when the capsule HIP process is performed using the capsule container 10 of the first embodiment and the sintered body contracts during cooling after the capsule HIP process, pressure is applied from the sintered body to the core 12. At that time, since the core 12 has a solid structure, there is no escape from the shrinking sintered body, and even if a mold release agent is interposed between the sintered body and the core 12, The core 12 tends to be in a state of being shrink-fitted into the sintered body. Therefore, in order to obtain the target material 2, processing (BTA processing) for removing the core 12 is required in many cases.

  On the other hand, as in the capsule container 20 of the present embodiment, if the inner wall portion 21b is cylindrical, the sintered body contracts, so that the inner wall portion 21b is shrink-fitted into the sintered body. Since the inner wall portion 21b can be deformed inward, the stress is relieved. Furthermore, since a release agent is always present between the sintered body and the inner wall portion 21b, it is easy to take out only the sintered body from the capsule container 20 after the capsule HIP process. Therefore, in the manufacturing method of the present embodiment using the capsule container 20, it is possible to save the trouble of subsequent processing.

  That is, according to the manufacturing method of the present embodiment, it is possible to manufacture a cylindrical target material in which ceramics are uniformly and densely sintered using a capsule HIP method without causing cracks.

[Third embodiment]
The production method according to the third embodiment of the present invention can be carried out in the same manner as the production methods according to the first and second embodiments described above, except that the form of the release agent is different.

  In the first and second embodiments described above, a powder or ball-shaped release agent is used. In addition, when filling the capsule container with the release agent, a partition that prevents mixing with the material to be sintered is set up in advance, and the space formed by the partition is filled with, for example, a powder release agent. It was.

  On the other hand, in the manufacturing method of the present embodiment, the following can be adopted as the form of the release agent and the filling method.

  First, as a form of a mold release agent, foil shape, metal plating, a sheet shape, a coating film (coating film), a molded object, a fireproof heat insulation brick, etc. are mentioned. In these, since it is easy to handle, a sheet form and a coating film are preferable.

  As the foil-like release agent, for example, a metal foil can be used. The metal foil is included in the “sheet material” in the present invention.

  Examples of the material of the metal foil include the following metals. For example, tantalum, niobium, tungsten, molybdenum, hafnium, rhenium, iridium, or the like, a metal having a melting point of 2000 ° C. or higher, or an alloy of these two or more metals can be given.

  A metal foil having a thickness of 0.1 mm or more and less than 0.5 mm may be used. In that case, it is good to adjust so that the thickness of a mold release agent may hold | maintain 1 mm after completion | finish of a sintering process by using multiple metal foils. Alternatively, the metal foil and another release agent may be combined and adjusted so that the release agent has a thickness of 1 mm after the sintering process is completed.

  In the case where the release agent is metal plating, the inner wall surface of the capsule container that has been previously plated with the metal shown as the release agent of the first embodiment can be used. At that time, the plating layer of the metal plating may be adjusted so as to maintain a thickness of 1 mm even after the sintering process. Further, the metal plating may be combined with another release agent, and the thickness of the release agent may be adjusted to be 1 mm after the sintering process is completed.

  Metal foil and metal plating are already 100% relative density, and there is almost no change in relative density during the sintering process, so we expect a stress relaxation effect due to plastic deformability due to the low relative density. I can't do it. However, the spreadability of the metal foil or the metal plating itself can absorb and relieve stress due to plastic deformation, so that the occurrence of cracks and the like in the sintered material can be suppressed.

  As the sheet-like mold release agent, one made of either or both of the metal and the metal compound shown as the mold release agent of the first embodiment can be used. Here, the “sheet shape” refers to a thin molded body in which a material shown as a release agent extends in a planar shape. Examples of the sheet-like release agent include various types having different thicknesses such as a sheet and a blanket made of the above forming material. The sheet-like release agent is included in the “sheet material” in the present invention.

  The thickness of the sheet-like release agent is not particularly limited as long as the thickness after the capsule HIP treatment is 1 mm or more. Since handling is easy, it is preferable that the thickness of a sheet-like mold release agent is 5 mm or more and 20 mm or less.

  In addition, the sheet-like release agent of the present embodiment may be a woven fabric or a nonwoven fabric containing one or both of the metal and the metal compound shown as the release agent of the first embodiment. In this case, the relative density of the sheet-like release agent is 3% or more and 30% or less, preferably 4% or more and 20% or less.

  Commercially available products can be used as the sheet-like release agent (sheet and blanket) of the present embodiment. Specifically, as a sheet, Isowool (registered trademark) 1260 ace paper (manufactured by Isolite Industry Co., Ltd.), Isowool 1500 ace paper (manufactured by Isolite Industry Co., Ltd.), SC paper 1260I (manufactured by Shin Nippon Thermal Ceramics Co., Ltd.) ), SC paper 1260 (manufactured by Shin Nippon Thermal Ceramics Co., Ltd.) and the like.

  As a blanket, SC blanket 1260 (manufactured by Nippon Steel Thermal Ceramics Co., Ltd.), SC blanket 1400 (manufactured by Nippon Steel Thermal Ceramics Co., Ltd.), SC blanket 1600MLS (manufactured by Nippon Steel Thermal Ceramics Co., Ltd.), Isowool 1260 blanket (Isolite) Industrial Co., Ltd.), Isowool 1260 Ace Blanket (produced by Isolite Industry Co., Ltd.), Isowool 1400 Blanket (produced by Isolite Industry Co., Ltd.), Isowool 1500 Ace Blanket (produced by Isolite Industry Co., Ltd.), Isowool 1600 Blanket (Isolite) Kogyo Co., Ltd.).

  Such a woven fabric or non-woven sheet-like mold release agent has many gaps in itself, so that the material to be sintered passes through the mold release agent during the capsule HIP treatment, and contact and reaction with the capsule container. As a result, cracks may occur in the sintered body. Therefore, a metal foil is further interposed between the material to be sintered and the capsule container, so that the material to be sintered and the capsule container are completely separated, and the contact and reaction between the material to be sintered and the capsule container are interrupted and cracks are generated. It is preferable that the sintered body does not have any.

  As the metal foil used in combination with the sheet-like release agent, any metal foil that does not melt at the HIP sintering temperature can be used. Examples of the metal foil forming material include stainless steel, iron, nickel, titanium, cobalt, platinum, chromium, vanadium, rhodium, zirconium, tantalum, niobium, tungsten, molybdenum, hafnium, rhenium, iridium, and the like.

  The release agent coating film is obtained by applying and drying a solution or dispersion containing one or both of the metal and the metal compound shown as the release agent of the first embodiment. More specifically, the coating film has a metal hydroxide, a metal oxide or metal nitride powder dispersed in a solvent, or a metal oxide precursor (metal salt, metal alkoxide, metal complex, etc.) as a solvent. It can be formed by applying the inorganic paint dissolved in the inside of the capsule container 10 and drying and removing the solvent.

  As the molded product of the release agent, a powdered release agent can be formed into a desired shape by uniaxial pressing or CIP, and fired at a low temperature so that the relative density is 85% or less.

  When a mold release agent is a fireproof heat insulation brick, what grind-processed the block-shaped fireproof heat insulation brick to the desired shape can be used. As the refractory heat insulating brick, one fired at a low temperature so that the relative density is 85% or less is used.

  The above-mentioned various types of release agents may be used alone or in combination. Moreover, even if it is a case where it uses independently, you may use multiple. For example, when a metal foil is used, a plurality of sheets may be laminated and used in order to obtain a desired thickness.

  FIG. 6 is a process diagram showing a method of manufacturing a cylindrical target material according to the present embodiment, and is a diagram specifically illustrating a filling process. 6A to 6C have the same field of view as FIGS. Moreover, in the figure, it has shown as using the capsule container 10 which is a capsule with a center core as a capsule container. In addition, a coating film is used as a release agent.

  First, as shown in FIG. 6A, a release agent coating film 32 is formed on the inner surface of the container body 11 and the outer peripheral surface of the core 12. The thickness of the coating film 32 is set such that the thickness of the release agent after the capsule HIP treatment is 1 mm or more. Thereafter, the core 12 is inserted into the container body 11.

  Next, as shown in FIG. 6B, the space 19 is filled with a material to be sintered. At this time, the material to be sintered 2A is filled while applying vibration until there is no volume change. At this time, the filling amount is controlled so that the height from the upper end of the filled sintered material 2A to the upper end of the container body 11 is d.

  Next, as shown in FIG. 6C, the mold release agent 31 is pressed and filled on the filled material to be sintered 2A. As a result, the material to be sintered 2A is filled into the container body 11 in a state surrounded by the release agent 31 and the coating film 32.

  After filling with the release agent 31, the lid 15 is welded to the container main body 11 to seal the capsule container 10 as in FIG. Thereafter, the target material 2 can be obtained in the same manner as in the first embodiment.

  Even with the manufacturing method as described above, it is possible to manufacture a cylindrical target material in which ceramics are uniformly and densely sintered using the capsule HIP method without causing cracks.

  In this embodiment, the coating film is used as the release agent. However, when a sheet-like release agent or a foil-like release agent is used as the release agent, an operation for pre-processing the capsule container is performed. It becomes unnecessary and operation becomes simple.

  When a sheet-like release agent or a foil-like release agent is used, it may be difficult to place the release agent at the bottom of the capsule container, but in that case, the outer and inner walls of the capsule container A plurality of shapes of release agents may be used in combination as appropriate, such that the surface with the part is covered with a sheet-like release agent or foil-like release agent, and the bottom is covered with a powder release agent.

  The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but it goes without saying that the present invention is not limited to such examples. Various shapes, combinations, and the like of the constituent members shown in the above-described examples are examples, and various modifications can be made based on design requirements and the like without departing from the gist of the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples.

[1. (When using a capsule with a core)
[Example 1-1]
(Raw material adjustment)
Indium oxide powder (In ₂ O ₃ , rare metal production, average particle size: 0.56 μm), gallium oxide powder (Ga ₂ O ₃ , Yamanaka Futec Co., Ltd., average particle size: about 1.5 μm) ), Zinc oxide powder (ZnO, manufactured by Hakusuitec Co., Ltd., average particle diameter: about 1.5 μm) was weighed so that the atomic ratio of indium element, gallium element and zinc element was 1: 1: 1. Dry mixing was performed for 1 hour with a super mixer (rotation speed: 3000 rpm) to obtain a mixed powder. The obtained mixed powder corresponds to “sintered material 2A” in the present specification.
The tap density of the mixed powder (ceramic powder) was 1.55 g / cm ³ .

(Raw material filling)
A stainless steel (SUS304) core (diameter: 128 mm, height 900 mm) was inserted into a stainless steel (SUS304) container main body (diameter: 184 mm, height 900 mm, thickness: 2.5 mm cylindrical container). A thing was prepared, and the release agent was stuffed into the bottom of the capsule container until the height was 4 mm.
As the release agent, aluminum oxide powder (Al ₂ O ₃ : manufactured by Sumitomo Chemical Co., Ltd., purity 99.9%, average particle diameter 45 μm) was used.
The “container main body” and “center core” correspond to the description in the description of the “capsule with center core”.

Next, a paper cylinder (diameter: 176 mm, height: 892 mm) is set up as a first partition in the capsule container, and is separated between the inner wall of the capsule container and the first partition (space width: 4 mm). The mold was packed and filled.
Similarly, a paper cylinder (diameter: 136 mm, height: 892 mm) is set up as a second partition in the capsule container, and is separated between the second partition and the center core (space width: 4 mm). The mold was packed and filled.

  Next, the space between the first partition and the second partition was filled while applying vibration until there was no volume change of the obtained mixed powder.

Note that the theoretical density of the sintered body is described in the JCPDS card as single crystal information of InGaZnO ₄ (JCPDS card number: 381104) having a composition ratio In: Ga: Zn = 1: 1: 1. The single crystal theoretical density (6.379 g / cm ³ ) described in the JCPDS card was employed.

  On the filled ceramic powder, a release agent was squeezed into a height of 4 mm, and the paper cylinder was removed.

For the mixed powder filled in the capsule container, the relative density (relative density before sintering) obtained from the tap density of the mixed powder and the theoretical density of mixed powder 6.379 g / cm ³ is 24.2%. there were.
The filling rate of the mixed powder with respect to the volume of the container body determined from the volume of the mixed powder and the relative density before sintering of the mixed powder was 8.8%.
Since the core portion does not shrink (does not deform) during HIP sintering, the filling factor of the core with respect to the volume of the container body was 48.4%.
As for the release agent, the relative density after sintering was 77% and the relative density before sintering was 28%, and the true relative density of the release agent was 36.4%. Using this true relative density, the filling rate of the release agent with respect to the volume of the container body determined from the volume of the release agent and the true relative density of the release agent was 5.5%.
The total filling factor of the mixed powder, the release agent and the core was 62.7%.

Next, an exhaust pipe was welded to the upper lid of the capsule container, and then the upper lid and the capsule container were welded. In order to confirm the soundness of the welded part of the capsule container, a He leak test was performed. The amount of leakage at this time was set to 1 × 10 ⁻⁶ Torr · L / second or less (where 1 Torr = 133.32 Pa).

Next, the inside of the capsule container is depressurized over 7 hours while being heated to 550 ° C., the inside of the capsule container is confirmed to be 1.33 × 10 ⁻² Pa or less, the exhaust pipe is closed, and the capsule container is sealed did.

  Next, the sealed capsule container was placed in a HIP device (manufactured by Kobe Steel, Ltd.), and capsule HIP treatment was performed. The sintering process in the capsule HIP process was performed at 1200 ° C. for 4 hours under a pressure medium of argon (Ar) gas (purity: 99.9%) having a pressure of 118 MPa. In the cooling process in the capsule HIP process, the cooling is performed at a cooling rate of 100 ° C./hour until the temperature in the HIP apparatus reaches 200 ° C., and then the natural cooling is performed to manufacture the cylindrical target material of Example 1-1. The method was carried out.

About Example 1-2 to 1-19 and Comparative Examples 1-1 to 1-9, the point which changed mainly about the mold release agent is shown below.
In Examples 1-2 to 1-19 and Comparative Examples 1-1 to 1-9, the size and dimensions of the capsule container are slightly different from those in Example 1-1. Moreover, the diameter of a 1st partition and a 2nd partition differs also with the magnitude | size change of a capsule container.
In Examples 1-20 to 1-25, the mixed powder (sintered material) is different from Example 1-1.

(Example 1-2)
The method for producing a cylindrical target material of Example 1-2 was carried out in the same manner as Example 1-1 except that the release agent was changed to alumina balls (Nikkato HD-2, diameter 2 mm).

(Example 1-3)
The same procedure as in Example 1-1 was conducted except that the release agent was changed to porous alumina balls (alumina support S-81-1, 95% or more of the total diameter was 4 mm to 5 mm, Fujimi Incorporated). The manufacturing method of 1-3 cylindrical target material was implemented.

(Example 1-4)
A stainless steel (SUS316L) core (diameter: 129 mm, height 900 mm) was inserted into a container body (diameter: 181 mm, height 900 mm, thickness: 2.5 mm cylindrical container) made of stainless steel (SUS304). A capsule container was prepared. A release agent was coated on the entire inner surface and upper lid of the capsule container until a thickness of 3 mm was formed to form a coating film. The material of the coating film is inorganic paint thermopreg H (composition of inorganic paint = Al ₂ O ₃ : 81 mass%, SiO ₂ : 13.9 mass%, ZrO ₂ : 5.1 mass%. Shin Nippon Thermal Ceramics Co., Ltd.) Made).

  The thickness of the coating film was determined by measuring the combined thickness of the capsule container wall and the coating film using calipers after the formation of the coating film, and subtracting the thickness of the capsule container wall.

  Next, the capsule container was filled with the obtained mixed powder until it reached a height of 894 mm while applying vibration until there was no volume change.

  Thereafter, the cylindrical target material manufacturing method of Example 1-4 was carried out in the same manner as in Example 1-1.

(Example 1-5)
Production of cylindrical target material of Example 1-5 in the same manner as in Example 1-1 except that the release agent was changed to ceramic cocoon (ceramic hollow body, all diameters were 3 mm to 6 mm, Marukoshi Kogyo). The method was carried out.

(Example 1-6)
The release agent was changed to a laminate of ceramic paper (SC paper 1260I, thickness 0.1 mm, made by Nippon Thermal Ceramics) and SUS foil, and the SUS foil was placed on the mixed powder side, and the partition (first The manufacturing method of the cylindrical target material of Example 1-6 was implemented like Example 1-1 except not using 1 partition and a 2nd partition.

(Example 1-7)
The release agent was changed to a ceramic blanket (SC blanket 1400, thickness 6 mm, New Japan Thermal Ceramics) and SUS foil, and the SUS foil was placed on the mixed powder side, and the partition (first The manufacturing method of the cylindrical target material of Example 1-7 was implemented like Example 1-1 except not using a partition and a 2nd partition.

(Example 1-8)
As a release agent, an alumina molded body having the following shape and size was used. As the alumina molded body, an alumina powder formed by CIP and fired at normal pressure and 1200 ° C. was used. The relative density of the alumina molded body was about 70%.
Alumina molded body 31A: cylindrical shape (annular) with a diameter of 185 mm, an inner diameter of 125 mm, and a thickness of 5 mm
Alumina molded body 31B: cylindrical shape with an outer diameter of 185 mm, an inner diameter of 175 mm, and a height of 890 mm Alumina molded body 31C: cylindrical shape with an outer diameter of 135 mm, an inner diameter of 125 mm, and a height of 890 mm Alumina molded body 31D: a diameter of 185 mm, an inner diameter of 125 mm, a thickness of 5 mm Cylindrical shape (annular)

The alumina molded body 31A was used as a mold release agent that fills the bottom of the container body 11 in the step shown in FIG.
The alumina molded body 31B was used as a release agent disposed on the container body 11 side in the step shown in FIG.
The alumina molded body 31C was used as a release agent disposed on the core 12 side in the step shown in FIG.
In the step shown in FIG. 3C, the alumina molded body 31D was used as a mold release agent that is further filled on the filled sintered material 2A.

  Cylindrical target of Example 1-8 in the same manner as in Example 1-1, except that the release agent was changed to the above-mentioned alumina molded body and no partition (first partition, second partition) was used. The manufacturing method of material was implemented.

(Example 1-9)
Example 1-1, except that the release agent was changed to a laminate of two molybdenum sheets (thickness 1 mm, High Purity Science Laboratory) and no partition (first partition, second partition) was used. The manufacturing method of the cylindrical target material of Example 1-9 was implemented in the same manner.

(Example 1-10)
Example 1-1, except that the release agent was changed to one in which two tungsten sheets (thickness 1 mm, High Purity Science Laboratory) were stacked, and no partition (first partition, second partition) was used. In the same manner as described above, the manufacturing method of the cylindrical target material of Example 1-10 was performed.

(Example 1-11)
Example 1-1, except that the release agent was changed to a stack of two tantalum sheets (thickness 1 mm, High Purity Science Laboratory) and that no partitions (first partition, second partition) were used. The manufacturing method of the cylindrical target material of Example 1-11 was implemented in the same manner.

(Example 1-12)
The cylindrical target material of Example 1-12 was changed in the same manner as Example 1-1 except that the release agent was changed to titanium nitride powder (all powder diameters were 53 μm or less, High Purity Science Laboratory). The manufacturing method was implemented.

(Example 1-13)
The cylindrical target material of Example 1-13 was changed in the same manner as in Example 1-1 except that the release agent was changed to chromium oxide powder (powder diameter is all 20 μm or less, High Purity Science Laboratory). The manufacturing method was implemented.

(Example 1-14)
The cylindrical target material of Example 1-14 was changed in the same manner as in Example 1-1 except that the release agent was changed to zirconium oxide powder (powder diameter was 75 μm or less, High Purity Science Laboratory). The manufacturing method was implemented.

(Example 1-15)
Except that the release agent was changed to zirconia balls (Nikkato YTZ-2, the diameter of all zirconia balls is 2 mm), the method for producing the cylindrical target material of Example 1-15 is the same as Example 1-1 Carried out.

(Example 1-16)
Production of cylindrical target material of Example 1-16 in the same manner as Example 1-1, except that the release agent was changed to tantalum powder (all powder diameters were 45 μm or less, High Purity Science Laboratory). The method was carried out.

(Example 1-17)
Production of cylindrical target material of Example 1-17 in the same manner as in Example 1-1 except that the release agent was changed to niobium powder (all powder diameters were 45 μm or less, High Purity Science Laboratory). The method was carried out.

(Example 1-18)
Production of cylindrical target material of Example 1-18 in the same manner as in Example 1-1 except that the release agent was changed to molybdenum powder (all powder diameters were 45 μm or less, High Purity Chemical Laboratory). The method was carried out.

(Example 1-19)
Except that the release agent was changed to tungsten powder (powder diameter is all 53 μm or less high-purity chemical research laboratory), the method for producing the cylindrical target material of Example 1-19 was the same as Example 1-1. Carried out.

[Example 1-20]
(Raw material adjustment)
Indium oxide powder (In ₂ O ₃ , manufactured by Male Mountain Metal (lower part), average particle size: 0.56 μm) and tin oxide powder (SnO ₂ , manufactured by Wako Pure Chemical Industries, Ltd., particle size: 3.5-5) 0.0 μm).
Weighing was performed so that the atomic ratio of indium element to tin element was 9: 1, and dry mixing was performed in the same manner as in Example 1-1 to obtain a mixed powder. The obtained mixed powder corresponds to “sintered material 2A” in the present specification.
The tap density of the obtained mixed powder (ceramic powder) was 2.02 g / cm ³ .

A method for producing a cylindrical target material of Example 1-20 was carried out in the same manner as Example 1-1 except that the mixed powder thus obtained was used.
In addition, about the mixed powder with which the capsule container was filled, the relative density (relative density before sintering) calculated | required from the tap density of mixed powder and the theoretical density 7.16g / cm < ³ > of mixed powder is 28.2. %Met.
Moreover, the filling rate of the mixed powder with respect to the volume of the container main body determined from the volume of the mixed powder and the relative density before sintering of the mixed powder was 10.3%.
In addition, the total filling factor of the mixed powder, the release agent, and the core was 64.2%.

[Example 1-21]
(Raw material adjustment)
Zinc oxide powder (ZnO: Hakusuitec Co., Ltd., purity 99.9%, primary particle size 1.5 μm), titanium monoxide powder (TiO (II): Furuuchi Chemical Co., Ltd., purity 99.9%), Primary particle size 1 μm or less) and aluminum oxide powder (Al ₂ O ₃ : manufactured by Sumitomo Chemical Co., Ltd., purity 99.9%, primary particle size 0.5 μm) were used.
Weigh so that the atomic ratio of zinc, titanium, and aluminum is Zn: Ti: Al = 98.2: 1.0: 0.8, and perform dry mixing in the same manner as in Example 1-1 to mix. A powder was obtained. The obtained mixed powder corresponds to “sintered material 2A” in the present specification.
The tap density of the obtained mixed powder (ceramic powder) was 1.51 g / cm ³ .

A method for producing a cylindrical target material of Example 1-21 was carried out in the same manner as in Example 1-1, except that the mixed powder thus obtained was used.
In addition, about the mixed powder with which the capsule container was filled, the relative density (relative density before sintering) calculated | required from the tap density of mixed powder and the theoretical density 5.6g / cm < ³ > of mixed powder is 27.0. %Met.
Moreover, the filling rate of the mixed powder with respect to the volume of the container main body obtained from the volume of the mixed powder and the relative density before sintering of the mixed powder was 9.86%.
Further, the total filling rate of the mixed powder, the release agent and the core was 63.8%.

[Example 1-22]
(Raw material adjustment)
Zinc oxide powder (ZnO: manufactured by Hakusuitec Co., Ltd., purity 99.9%, primary particle size 1.5 μm) and titanium monoxide powder (TiO (II): manufactured by Furuuchi Chemical Co., Ltd., purity 99.9%) Primary particle size of 1 μm or less).
Weighing was performed so that the atomic ratio of zinc to titanium was Zn: Ti = 98.2: 1.8, and dry mixing was performed in the same manner as in Example 1-1 to obtain a mixed powder. The obtained mixed powder corresponds to “sintered material 2A” in the present specification.
The tap density of the obtained mixed powder (ceramic powder) was 1.56 g / cm ³ .

A method for producing a cylindrical target material of Example 1-22 was carried out in the same manner as in Example 1-1 except that the mixed powder thus obtained was used.
In addition, about the mixed powder with which the capsule container was filled, the relative density (relative density before sintering) calculated | required from the tap density of mixed powder and the theoretical density 5.6g / cm < ³ > of mixed powder is 27.9. %Met.
Moreover, the filling rate of the mixed powder with respect to the volume of the container main body determined from the volume of the mixed powder and the relative density before sintering of the mixed powder was 10.2%.
Moreover, the total filling factor of the mixed powder, the release agent, and the core was 64.1%.

[Example 1-23]
(Raw material adjustment)
Indium oxide powder (In ₂ O ₃ , rare metal production, average particle size: 0.56 μm) and zinc oxide powder (ZnO, Hakusuitec, average particle size: 1.5 μm) are used. did.
Weighing was performed so that the atomic ratio of indium element to zinc element was 9: 1, and dry mixing was performed in the same manner as in Example 1-1 to obtain a mixed powder. The obtained mixed powder corresponds to “sintered material 2A” in the present specification.
The tap density of the obtained mixed powder (ceramic powder) was 1.81 g / cm ³ .

A method for producing a cylindrical target material of Example 1-23 was carried out in the same manner as Example 1-1 except that the mixed powder thus obtained was used.
In addition, about the mixed powder with which the capsule container was filled, the relative density (relative density before sintering) calculated | required from the tap density of mixed powder and the theoretical density 7.02g / cm < ³ > of mixed powder is 25.8. %Met.
Moreover, the filling rate of the mixed powder with respect to the volume of the container main body determined from the volume of the mixed powder and the relative density before sintering of the mixed powder was 9.43%.
Further, the total filling factor of the mixed powder, the release agent and the core was 63.3%.

[Example 1-24]
(Raw material adjustment)
Zinc oxide powder (ZnO: Hakusuitec Co., Ltd., purity 99.9%, primary particle size 1.5 μm) and aluminum oxide powder (Al ₂ O ₃ : Sumitomo Chemical Co., Ltd., purity 99.99%, Primary particle size 0.5 μm).
Weighing was performed such that the atomic ratio of zinc to aluminum was Zn: Al = 96.8: 3.2, and dry mixing was performed in the same manner as in Example 1-1 to obtain a mixed powder. The obtained mixed powder corresponds to “sintered material 2A” in the present specification.
The tap density of the obtained mixed powder (ceramic powder) was 1.56 g / cm ³ .

A method for producing a cylindrical target material of Example 1-24 was carried out in the same manner as in Example 1-1 except that the mixed powder thus obtained was used.
In addition, about the mixed powder with which the capsule container was filled, the relative density (relative density before sintering) calculated | required from the tap density of mixed powder and the theoretical density 5.6g / cm < ³ > of mixed powder is 27.8. %Met.
Moreover, the filling rate of the mixed powder with respect to the volume of the container main body determined from the volume of the mixed powder and the relative density before sintering of the mixed powder was 10.16%.
Moreover, the total filling factor of the mixed powder, the release agent, and the core was 64.1%.

[Example 1-25]
(Raw material adjustment)
Zinc oxide powder (ZnO: manufactured by Hakusuitec Co., Ltd., purity 99.9%, primary particle size 1.5 μm) and gallium oxide powder (Ga ₂ O ₃ : manufactured by Yamanaka Futec Co., Ltd., purity 99.99%, Primary particle size 1.5 μm).
Weighing was performed so that the atomic ratio of zinc and gallium was Zn: Ga = 95.8: 4.2, and dry mixing was performed in the same manner as in Example 1-1 to obtain a mixed powder. The obtained mixed powder corresponds to “sintered material 2A” in the present specification.
The tap density of the obtained mixed powder (ceramic powder) was 1.61 g / cm ³ .

A method for producing a cylindrical target material of Example 1-24 was carried out in the same manner as in Example 1-1 except that the mixed powder thus obtained was used.
In addition, about the mixed powder with which the capsule container was filled, the relative density (relative density before sintering) calculated | required from the tap density of mixed powder and the theoretical density 5.6g / cm < ³ > of mixed powder is 28.8. %Met.
Moreover, the filling rate of the mixed powder with respect to the volume of the container main body determined from the volume of the mixed powder and the relative density before sintering of the mixed powder was 10.52%.
In addition, the total filling factor of the mixed powder, the release agent, and the core was 64.4%.

(Comparative Example 1-1)
The method for producing the cylindrical target material of Comparative Example 1-1 was carried out in the same manner as Example 1-1, except that no release agent was used and no partition (first partition, second partition) was used. did.
(Comparative Example 1-2)
The release agent was changed to an alumina ball (Nikkato HD-2, diameter 2 mm), and it was not filled between the mixed powder and the container body, but was filled only between the mixed powder and the core. Except not using a partition, it carried out similarly to Example 1-1, and implemented the manufacturing method of the cylindrical target material of Comparative Example 1-2.

(Comparative Example 1-3)
Example 1-1, except that the release agent was changed to a ceramic blanket (SC blanket 1400, thickness 6 mm, manufactured by New Japan Thermal Ceramics) and no partition (first partition, second partition) was used. Then, the manufacturing method of the cylindrical target material of Comparative Example 1-3 was carried out.

(Comparative Example 1-4)
Except that the release agent was changed to titanium oxide powder (rutile, average diameter 2 μm, manufactured by High Purity Science Laboratory), in the same manner as Example 1-1, the method for producing the cylindrical target material of Comparative Example 1-4 Carried out.

(Comparative Example 1-5)
Comparative Example 1-5 was carried out in the same manner as Example 1-1 except that the release agent was changed to molybdenum foil (thickness 0.2 mm) and no partition (first partition, second partition) was used. The manufacturing method of the cylindrical target material was implemented.

(Comparative Example 1-6)
Comparative Example 1-6 in the same manner as in Example 1-1 except that the release agent was changed to SUS foil (thickness 0.1 mm) and the partition (first partition, second partition) was not used. The manufacturing method of the cylindrical target material was implemented.

(Comparative Example 1-7)
Production of cylindrical target material of Comparative Example 1-7 in the same manner as in Example 1-1 except that the release agent was changed to nickel powder (all powder diameters were 150 μm or less, High Purity Science Laboratory). The method was carried out.

(Comparative Example 1-8)
Except having changed the mold release agent into nickel foil (thickness 0.2mm, high purity science research institute), and not using a partition (1st partition, 2nd partition), it carried out similarly to Example 1-1. The manufacturing method of the cylindrical target material of Comparative Example 1-8 was implemented.

(Comparative Example 1-9)
The method for producing the cylindrical target material of Comparative Example 1-9 was carried out in the same manner as Example 1-1, except that the release agent was changed to titanium carbide (average diameter 2 μm to 5 μm, High Purity Science Laboratory). did.

The results of Examples 1-1 to 1-25 are shown in Tables 1 to 3, and the results of Comparative Examples 1-1 to 1-9 are shown in Tables 4 to 6.
Tables 1 and 4 show the size and material of the capsule container used and the size of the paper cylinder used as the first partition and the second partition. In Tables 1 and 4, “outer diameter” refers to the diameter of the inner space of the container body. In Tables 1 and 4, “inner diameter” refers to the diameter of the core.
“R1”, “R2”, “R1-2d”, and “R2 + 2d” shown in Tables 1 and 4 correspond to the dimensions shown in FIG.
Tables 2 and 5 collectively show information on the release agents used.
Tables 3 and 6 collectively show information on the sintered material used and the obtained sintered body (cylindrical target material).

  About Example 1-1 to 1-25, the metal capsule container was removed after capsule HIP processing, and the mode of the release agent was observed.

  First of all, the capsule body of the obtained sintered body (IGZO sintered body, ITO sintered body, AZO sintered body, GZO sintered body, TAZO sintered body, TZO sintered body, IZO sintered body) The release agent filled on the outer peripheral side (between the sintered body and the container body of the capsule container) was in a powder form before the capsule HIP treatment, but was in a solid form after the treatment. This solid mold release agent was not confirmed to be discolored on the contact surface between the metal capsule container and the sintered body, and could be easily peeled off from both.

  In addition, the release agent filled on the inner peripheral side of the capsule container (between the sintered body and the core) with respect to the sintered body was also solid after the capsule HIP treatment. The obtained sintered body was integrated with the core through a solid release agent. Discoloration could not be confirmed between the release agent and the sintered body and between the core.

The density of the peeled solid release agent was obtained by a length measurement method, and the relative density of the release agent after the capsule HIP treatment was obtained from the measurement result and the theoretical density. In Examples 1-1 to 1-25, the mold release agent did not sufficiently sinter and remained at a low density. In addition, the relative density was calculated | required with the following formula.
Relative density = (density of sintered body / theoretical density of sintered body) × 100

  On the other hand, the relative density of the obtained IGZO sintered body, ITO sintered body, AZO sintered body, GZO sintered body, TAZO sintered body, TZO sintered body, and IZO sintered body was 100.0%. . When various sintered bodies were observed with an electron microscope, the sintered bodies were uniform and dense with almost no voids.

  About the obtained various sintered compacts, the core and the mold release agent on the core side were cut out by BTA (Boring & Trepanning Association) processing to form through holes. Furthermore, various sintered bodies (IGZO sintered body, ITO sintered body, AZO sintered body, by surface grinding, outer periphery grinding and surface polishing so that the outer surface and inner surface of the sintered body are cylindrical. A cylindrical target material using a GZO sintered body, a TAZO sintered body, a TZO sintered body, and an IZO sintered body) as a forming material could be obtained. The obtained cylindrical target material was processed into an outer diameter of 153 mm, an inner diameter of 135 mm, and a length of 530 mm.

  Thereby, according to the manufacturing method of the cylindrical target material of the present invention, it is confirmed that a cylindrical target material having a length of 500 mm or more and a relative density of 100% can be obtained without cracking or chipping. did it.

  The obtained cylindrical target material is a set of five, and a Ti backing tube having an outer diameter of 133 mm, an inner diameter of 125 mm, and a length of 2940 mm is inserted into the through hole, and the cylindrical target material is backed by In solder. The tube was joined. The interval between the target materials (the length of the divided portion) was 0.2 mm.

Thus, it was confirmed that various targets having a relative density of 100% can be produced without causing cracks and chips using the target material produced by the method for producing a cylindrical target material of the present invention.
A cylindrical sputtering target material and a target formed therefrom were obtained.

On the other hand, for Comparative Examples 1-1 to 1-8, after the capsule HIP treatment, the obtained sintered body had many cracks, and thus could not be processed into a sputtering target as a cylindrical target material. It was.
Moreover, about Comparative Examples 1-1 to 1-3, the trace which the container material and the sintered compact reacted at the contact location of a capsule container and a sintered compact has been confirmed.
For Comparative Examples 1-1 and 1-2, EDX (energy dispersive X-ray fluorescence apparatus) analysis and EPMA (Electron Probe Microanalyzer) analysis were performed at the contact points between the capsule container and the sintered body. As a result of analysis, iron, chromium, and nickel, which are components of the capsule container (SUS304), were detected within a depth range of 2 to 3 mm from the surface of the sintered body. Moreover, the discoloration which became dark on the contact location surface of a sintered compact was confirmed.

About Comparative Example 1-3, it thinks as follows.
A ceramic blanket that is a non-woven fabric has many gaps. Therefore, in the filling process, the mixed powder passes through the gap of the ceramic blanket and comes into contact with the capsule container, and in part, the part where “the release agent is not interposed between the capsule container and the mixed powder”, that is, the capsule container It is considered that a part where the mixed powder and the mixed powder are in direct contact has occurred. In such a portion, it is considered that the mold release agent cannot perform a desired function, and stress is applied to the sintered body to cause a crack.

Moreover, about Comparative Examples 1-4 and 1-7, the trace which reacted between a mold release agent and a capsule container, between a mold release agent and a core, and between a mold release agent and a sintered compact has shown. It was seen. Discoloration that darkened between the release agent and the capsule container, or between the release agent and the core, was confirmed on the surface of the contact area of the release agent. Similarly, a dark color change was confirmed between the release agent and the sintered body on the surface where the release agent contacted. When the release agent was subjected to EDX analysis and EPMA analysis, the release agent contained SUS304-derived components (iron, chromium, nickel), which are the materials of the capsule container and the core, and sintered body-derived components (indium, Gallium and zinc) were detected.
From these results, since the release agent used in Comparative Examples 1-4 and 1-7 reacts with the material to be sintered in the sintering temperature region, and between the capsule container and the core, It seems that it was unsuitable as a mold. Furthermore, since the relative density of the release agent after the capsule HIP treatment was 100%, the release agent could not perform the desired function, and stress was applied to the sintered body, resulting in cracks. it is conceivable that.
Further, for Comparative Examples 1-5, 6, and 8, molybdenum foil, stainless steel foil, and nickel foil were used, but since the thickness after the sintering treatment was less than 1 mm, the sintered body was subjected to the capsule HIP treatment. It is considered that the stress applied to the film could not be sufficiently relaxed and a crack occurred.

  In Comparative Example 1-9, gas was generated during capsule HIP treatment, and the capsule expanded, so that capsule HIP treatment could not be performed.

[2. (When using a hollow capsule)
[Example 2-1]
(Raw material adjustment)
Indium oxide powder tap density of ^{_{1.62g / cm 3 (In 2 O}} 3, Maresan metal Ltd., average particle size: 0.56 .mu.m) and oxide tap density of 1.39 g / cm ³ Gallium powder (Ga ₂ O ₃ , manufactured by Yamanaka Futec Co., Ltd., average particle diameter: 1.5 μm) and zinc oxide powder (ZnO, manufactured by Hakusui Tech Co., Ltd., average particles having a tap density of 1.02 g / cm ³ ) (Diameter: 1.5 μm) was weighed so that the atomic ratio of indium element, gallium element, and zinc element was 1: 1: 1, and dry mixing was performed with a super mixer at 3000 rpm for 60 minutes.

The resulting mixture was heated from room temperature to 1400 ° C. at a temperature rising rate of 10 ° C./min in an air atmosphere using an electric furnace (manufactured by Kitahama Corporation), and calcined at 1400 ° C. for 12 hours, The mixture was lightly pulverized by hand in a mortar to obtain a mixed powder after calcining. The obtained mixed powder corresponds to “sintered material 2A” in the present specification.
The mixed powder (ceramic powder) after calcination had a tap density of 4.32 g / cm ³ .

(Raw material filling)
As the capsule container, a hollow capsule as shown in FIG. 4 was used. The used capsule container is a stainless steel (SUS304) container main body (diameter: 184 mm, height 700 mm, thickness: 2.5 mm cylindrical container) having a through hole (diameter 128 mm) in the center of the bottom. A cylindrical member (diameter: 128 mm, height 700 mm) made of stainless steel (SUS304) is joined to the through hole. The “container body” and the “cylindrical member” correspond to the description in the description of the “hollow capsule”.

The release agent was stuffed into the bottom of the hollow capsule container until the height reached 4 mm.
As the release agent, aluminum oxide powder (Al ₂ O ₃ : manufactured by Sumitomo Chemical Co., Ltd., purity 99.9%, average particle diameter 45 μm) was used.

Next, a paper cylinder (diameter: 176 mm, height: 692 mm) is set up as a first partition in the capsule container, and a release agent is provided between the inner wall of the capsule container and the first partition (space width: 4 mm). Was pressed and filled.
Similarly, a paper cylinder (diameter: 136 mm, height: 692 mm) is set up as the second partition in the capsule container, and is separated between the second partition and the cylindrical member (space width: 4 mm). The mold was packed and filled.

  Next, the space between the first partition and the second partition was filled while applying vibration until there was no volume change of the obtained mixed powder.

Note that the theoretical density of the sintered body is described in the JCPDS card as single crystal information of InGaZnO ₄ (JCPDS card number: 381104) having a composition ratio In: Ga: Zn = 1: 1: 1. The single crystal theoretical density (6.379 g / cm ³ ) described in the JCPDS card was employed.

  On the filled mixed powder, a release agent was squeezed into a height of 4 mm to remove the paper cylinder.

For the mixed powder filled in the capsule container, the relative density (relative density before sintering) obtained from the tap density of the mixed powder and the theoretical density of mixed powder 6.379 g / cm ³ is 67.7%. there were.
The filling rate of the mixed powder with respect to the volume of the container body determined from the volume of the mixed powder and the relative density before sintering of the mixed powder was 47.8%.
As for the release agent, the relative density after sintering was 77% and the relative density before sintering was 28%, and the true relative density of the release agent was 36.4%. Using this true relative density, the filling rate of the release agent with respect to the volume of the container body determined from the volume of the release agent and the true relative density of the release agent was 10.7%.
The total filling factor of the mixed powder and the release agent was 58.5%.

Next, an exhaust pipe was welded to the upper lid of the capsule container, and then the upper lid and the capsule container were welded. In order to confirm the soundness of the welded part of the capsule container, a He leak test was performed. The amount of leakage at this time was set to 1 × 10 ⁻⁶ Torr · L / second or less (where 1 Torr = 133.32 Pa).

Next, the inside of the capsule container is depressurized over 7 hours while being heated to 550 ° C., the inside of the capsule container is confirmed to be 1.33 × 10 ⁻² Pa or less, the exhaust pipe is closed, and the capsule container is sealed did.

  Next, the sealed capsule container was placed in a HIP device (manufactured by Kobe Steel, Ltd.), and capsule HIP treatment was performed. The sintering process in the capsule HIP process was performed at 1200 ° C. for 4 hours under a pressure medium of argon (Ar) gas (purity: 99.9%) having a pressure of 118 MPa. In the cooling process in the capsule HIP process, the cooling is performed at a cooling rate of 100 ° C./hour until the temperature in the HIP apparatus reaches 200 ° C., and then the natural cooling is performed to manufacture the cylindrical target material of Example 2-1. The method was carried out.

About Example 2-2 to 2-19 and Comparative Examples 2-1 to 2-9, the point which changed mainly about the mold release agent is shown below.
In Examples 2-2 to 2-19 and Comparative Examples 2-1 to 2-9, the size and dimensions of the capsule container are slightly different from those in Example 2-1. Moreover, the diameter of a 1st partition and a 2nd partition differs also with the magnitude | size change of a capsule container.
In Example 2-20, the mixed powder (sintered material) is different from Example 2-1.

(Example 2-2)
The manufacturing method of the cylindrical target material of Example 2-2 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the alumina ball used in Example 1-2.

(Example 2-3)
The method for producing the cylindrical target material of Example 2-3 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the porous alumina ball in Example 1-3.

(Example 2-4)
The capsule container used was a stainless steel (SUS304) cylindrical body (diameter: 128 mm) on a stainless steel (SUS304) container body (diameter: 180 mm, height 700 mm, thickness: 2.5 mm cylindrical container). , 700 mm in height) are joined.

A release agent was coated on the entire inner surface and upper lid of the capsule container until a thickness of 3 mm was formed to form a coating film. The material of the coating film is inorganic paint thermopreg H (composition of inorganic paint = Al ₂ O ₃ : 81 mass%, SiO ₂ : 13.9 mass%, ZrO ₂ : 5.1 mass%. Shin Nippon Thermal Ceramics Co., Ltd.) Made).

  The thickness of the coating film was determined by measuring the combined thickness of the capsule container wall and the coating film using calipers after the formation of the coating film, and subtracting the thickness of the capsule container wall.

  Next, the capsule container was filled with the obtained mixed powder until it reached a height of 894 mm while applying vibration until there was no volume change.

  Thereafter, the cylindrical target material manufacturing method of Example 2-4 was carried out in the same manner as in Example 2-1.

(Example 2-5)
The method for producing a cylindrical target material of Example 2-5 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the ceramic cocoon used in Example 1-5.

(Example 2-6)
The release agent was changed to a laminate of the ceramic paper and SUS foil used in Example 1-6, and the SUS foil was placed on the mixed powder side, and the partitions (first partition, second partition) Except not using it, it carried out similarly to Example 2-1, and implemented the manufacturing method of the cylindrical target material of Example 2-6.

(Example 2-7)
The release agent was changed to the one obtained by overlapping the ceramic blanket used in Example 1-7 and the SUS foil, and the SUS foil was arranged on the mixed powder side, and the partitions (first partition, second partition) Except not using it, it carried out similarly to Example 2-1, and implemented the manufacturing method of the cylindrical target material of Example 2-7.

(Example 2-8)
As a release agent, an alumina molded body having the following shape and size was used. As the alumina molded body, an alumina powder formed by CIP and fired at normal pressure and 1200 ° C. was used. The relative density of the alumina molded body was about 70%.
Alumina compact 31E: cylindrical shape (annular) with a diameter of 185 mm, an inner diameter of 125 mm, and a thickness of 5 mm
Alumina molded body 31F: cylindrical shape with outer diameter 185mm, inner diameter 175mm, height 690mm Alumina molded body 31G: cylindrical shape with outer diameter 135mm, inner diameter 125mm, height 690mm Alumina molded body 31H: diameter 185mm, inner diameter 125mm, thickness 5mm Cylindrical shape (annular)

The alumina molded body 31E was used as a mold release agent that fills the bottom of the container body 21 in the step shown in FIG.
The alumina molded body 31F was used as a release agent disposed on the container main body 21 side in the step shown in FIG.
The alumina molded body 31G was used as a mold release agent disposed on the inner wall 21b side in the step shown in FIG.
In the step shown in FIG. 5C, the alumina molded body 31H was used as a mold release agent for further filling the filled material to be sintered 2A.

  Cylindrical target of Example 2-8 in the same manner as in Example 1-1, except that the release agent was changed to the above-mentioned alumina molded body and no partition (first partition, second partition) was used. The manufacturing method of material was implemented.

(Example 2-9)
Same as Example 2-1 except that the release agent was changed to one in which the molybdenum sheets used in Example 1-9 were stacked and that no partitions (first partition, second partition) were used. Then, the manufacturing method of the cylindrical target material of Example 2-9 was carried out.

(Example 2-10)
Same as Example 2-1 except that the release agent was changed to a stack of two tungsten sheets used in Example 1-10 and that no partition (first partition, second partition) was used. Then, the manufacturing method of the cylindrical target material of Example 2-10 was carried out.

(Example 2-11)
The release agent was the same as in Example 2-1, except that the tantalum sheet used in Example 1-11 was changed to a stack of two and that no partition (first partition, second partition) was used. Then, the manufacturing method of the cylindrical target material of Example 2-11 was carried out.

(Example 2-12)
The method for producing a cylindrical target material of Example 2-12 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the titanium nitride powder used in Example 1-12.

(Example 2-13)
A method for producing a cylindrical target material of Example 2-13 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the chromium oxide powder used in Example 1-13.

(Example 2-14)
The method for producing the cylindrical target material of Example 2-14 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the zirconium oxide powder used in Example 1-14.

(Example 2-15)
The method for producing a cylindrical target material of Example 2-15 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the zirconia balls used in Example 1-15.

(Example 2-16)
The method for producing the cylindrical target material of Example 2-16 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the tantalum powder used in Example 1-16.

(Example 2-17)
The manufacturing method of the cylindrical target material of Example 2-17 was implemented like Example 2-1, except having changed the mold release agent into the niobium powder used in Example 1-17.

(Example 2-18)
The method for producing the cylindrical target material of Example 2-18 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the molybdenum powder used in Example 1-18.

(Example 2-19)
Except that the release agent was changed to tungsten powder (powder diameter is 43 μm or less, High Purity Chemical Laboratory), in the same manner as in Example 2-1, a method for producing a cylindrical target material of Example 2-19 Carried out.

[Example 2-20]
(Raw material adjustment)
Zinc oxide powder (ZnO: manufactured by Hakusuitec Co., Ltd., purity 99.9%, primary particle size 1.5 μm) was calcined at 1200 ° C. for 10 hours in the atmosphere. The temperature was raised from room temperature to 1200 ° C. at a rate of 10 ° C./min. After calcination, coarse pulverization was performed using a hammer mill to obtain a calcined zinc oxide powder.
The tap density of the obtained calcined zinc oxide powder was measured to be 3.91 g / cm ³ .

The obtained zinc oxide powder after calcination, titanium monoxide powder (TiO (II): manufactured by Furuuchi Chemical Co., Ltd., purity 99.9%, primary particle size 1 μm or less), and aluminum oxide powder (Al ₂ O) ₃ : Sumitomo Chemical Co., Ltd., purity 99.9%, primary particle size 0.5 μm) was used.
Weigh so that the atomic ratio of zinc, titanium, and aluminum is Zn: Ti: Al = 98.2: 1.0: 0.8, and perform dry mixing in the same manner as in Example 2-1 to mix. A powder was obtained. The obtained mixed powder corresponds to “sintered material 2A” in the present specification.
The tap density of the obtained mixed powder (ceramic powder) was 3.91 g / cm ³ .

A method for producing a cylindrical target material of Example 2-20 was carried out in the same manner as in Example 2-1, except that the mixed powder thus obtained was used.
In addition, about the mixed powder with which the capsule container was filled, the relative density (relative density before sintering) calculated | required from the tap density of mixed powder and the theoretical density 5.6g / cm < ³ > of mixed powder is 69.8. %Met.
Moreover, the filling rate of the mixed powder with respect to the volume of the container main body determined from the volume of the mixed powder and the relative density before sintering of the mixed powder was 49.3%.
Moreover, the total filling factor of the mixed powder and the release agent was 60.0%.

(Comparative Example 2-1)
The method for producing the cylindrical target material of Comparative Example 2-1 was carried out in the same manner as in Example 2-1, except that no release agent was used and no partition (first partition, second partition) was used. did.
(Comparative Example 2-2)
The release agent was changed to the alumina ball used in Example 1-2, and it was not filled between the mixed powder and the container body, but was filled only between the mixed powder and the cylindrical member, and Except not using a 1st partition, it carried out similarly to Example 2-1, and implemented the manufacturing method of the cylindrical target material of the comparative example 2-2.

(Comparative Example 2-3)
Comparative Example 2 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the ceramic blanket used in Comparative Example 1-2 and that the partitions (first partition and second partition) were not used. -3 cylindrical target material manufacturing method was carried out.

(Comparative Example 2-4)
A method for producing a cylindrical target material of Comparative Example 2-4 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the titanium oxide powder used in Comparative Example 1-4.

(Comparative Example 2-5)
Comparative Example 2 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the molybdenum foil used in Comparative Example 1-5, and no partition (first partition, second partition) was used. The manufacturing method of -5 cylindrical target material was implemented.

(Comparative Example 2-6)
Comparative Example 2 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the SUS foil used in Comparative Example 1-6, and the partition (first partition, second partition) was not used. The manufacturing method of 6 cylindrical target materials was implemented.

(Comparative Example 2-7)
The method for producing the cylindrical target material of Comparative Example 2-7 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the nickel powder used in Comparative Example 1-7.

(Comparative Example 2-8)
Comparative Example 2 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the nickel foil used in Comparative Example 1-8 and that the partitions (first partition and second partition) were not used. The manufacturing method of -8 cylindrical target material was implemented.

(Comparative Example 2-9)
A method for producing a cylindrical target material of Comparative Example 2-9 was carried out in the same manner as in Example 2-1, except that the release agent was changed to the titanium carbide used in Comparative Example 1-9.

The results of Examples 2-1 to 2-20 are shown in Tables 7 to 9, and the results of Comparative Examples 2-1 to 2-9 are shown in Tables 10 to 12.
Tables 7 and 10 show the size and material of the capsule container used, and the size of the paper cylinder used as the first partition and the second partition. In Tables 7 and 10, “outer diameter” refers to the diameter of the inner space of the container body. In Tables 7 and 10, “inner diameter” refers to the diameter of a cylindrical member (reference numeral 21b in FIG. 5).
“R1”, “R2”, “R1-2d”, and “R2 + 2d” shown in Tables 7 and 10 correspond to the dimensions shown in FIG.
Tables 8 and 11 collectively show information on the release agents used.
Tables 9 and 12 collectively show information on the material to be sintered and the obtained sintered body (cylindrical target material).

  For Examples 2-1 to 2-20, after the capsule HIP treatment, the metal capsule container was removed, and the state of the release agent was observed.

  First, the release agent filled on the outer peripheral side of the capsule container with respect to the obtained sintered body (IGZO sintered body, TAZO sintered body) and the inner peripheral side of the capsule container with respect to the sintered body The released release agent was powdery before the capsule HIP treatment, but was solid after the treatment. This solid release agent was not discolored on the contact surface between the capsule container and the sintered body, and could be easily peeled off from both.

  The density of the peeled solid release agent was determined by a length measurement method, and the relative density of the release agent after the capsule HIP treatment was determined by the method described above. In Examples 2-1 to 2-20, the release agent did not sufficiently sinter and remained at a low density.

  On the other hand, the relative density of the obtained IGZO sintered body and TAZO sintered body is 100.0%, and various sintered bodies were observed with an electron microscope. It was a body.

  About various obtained sintered compacts, various surface sintered bodies (IGZO sintered compacts, TAZO sintered compacts) are obtained by surface grinding, peripheral grinding and surface polishing so that the outer surface and the inner surface become cylindrical. A cylindrical target material as a forming material could be obtained. The obtained cylindrical target material was processed into an outer diameter of 153 mm, an inner diameter of 135 mm, and a length of 530 mm.

  Thereby, according to the manufacturing method of the cylindrical target material of the present invention, it is confirmed that a cylindrical target material having a length of 500 mm or more and a relative density of 100% can be obtained without cracking or chipping. did it.

  The obtained cylindrical target material is a set of five, and a Ti backing tube having an outer diameter of 133 mm, an inner diameter of 125 mm, and a length of 2940 mm is inserted into the through hole, and the cylindrical target material is backed by In solder. The tube was joined. The interval between the target materials (the length of the divided portion) was 0.2 mm.

Thus, it was confirmed that various targets having a relative density of 100% can be produced without causing cracks and chips using the target material produced by the method for producing a cylindrical target material of the present invention.
A cylindrical sputtering target material and a target formed therefrom were obtained.

On the other hand, in Comparative Examples 2-1 to 2-8, after the capsule HIP treatment, since the obtained sintered body had many cracks, it could not be processed into a sputtering target as a cylindrical target material. It was.
Moreover, about Comparative Examples 2-1 to 2-3, the trace which the container material and the sintered compact reacted at the contact location of a capsule container and a sintered compact has been confirmed.
About Comparative Examples 2-1 and 2-2, EDX analysis and EPMA analysis were performed in the contact location of a capsule container and a sintered compact. As a result of analysis, iron, chromium, and nickel, which are components of the capsule container (SUS304), were detected within a depth range of 2 to 3 mm from the surface of the sintered body. Moreover, the discoloration which became dark on the contact location surface of a sintered compact was confirmed.

The comparative example 2-3 is considered as follows.
A ceramic blanket that is a non-woven fabric has many gaps. Therefore, in the filling process, the mixed powder passes through the gap of the ceramic blanket and comes into contact with the capsule container, and in part, the part where “the release agent is not interposed between the capsule container and the mixed powder”, that is, the capsule container It is considered that a part where the mixed powder and the mixed powder are in direct contact has occurred. In such a portion, it is considered that the mold release agent cannot perform a desired function, and stress is applied to the sintered body to cause a crack.

Moreover, about Comparative Examples 2-4 and 2-7, the trace which reacted between the mold release agent and the capsule container and between the mold release agent and the sintered compact was seen. Between the release agent and the capsule container, a discoloration darkened on the surface of the release agent contact portion was confirmed. Similarly, a dark color change was confirmed between the release agent and the sintered body on the surface where the release agent contacted. When the release agent was subjected to EDX analysis and EPMA analysis, SUS304-derived components (iron, chromium, nickel) and sintered body-derived components (indium, gallium, zinc), which are the materials of the capsule container, were included in the release agent. ) Was detected.
From these results, the release agent used in Comparative Examples 2-4 and 2-7 is unsuitable as a release agent because it reacts with the material to be sintered in the sintering temperature region and with the capsule container. It is thought that it was. Furthermore, since the relative density of the release agent after the capsule HIP treatment was 100%, the release agent could not perform the desired function, and stress was applied to the sintered body, resulting in cracks. it is conceivable that.
In Comparative Examples 2-5, 6, and 8, molybdenum foil, stainless steel foil, and nickel foil were used, but the thickness after sintering was less than 1 mm. It is considered that the stress applied to the film could not be sufficiently relaxed and a crack occurred.

  In Comparative Example 2-9, gas was generated during capsule HIP treatment, and the capsule expanded, so that capsule HIP treatment could not be performed.

  From the above, it was confirmed that the method for producing a cylindrical target of the present invention is useful.

DESCRIPTION OF SYMBOLS 1 ... Sputtering target, 2 ... Cylindrical target material, 2a ... Through-hole, 2A ... Material to be sintered, 2x ... Inner wall, 3 ... Backing tube, 3a ... Through-hole, 3x ... Outer wall, 4 ... Bonding layer, 7th 1 partition (partition), 8 ... 2nd partition (partition), 10 ... capsule container, 11 ... container body, 11a ... outer wall part, 11b ... inner wall part, 11c ... bottom part, 11x ... inner wall surface, 12 ... middle core, 12x ... surface, 15 ... lid, 19 ... space, 20 ... capsule container, 21 ... container body, 21a ... outer wall, 21b ... inner wall, 21c ... bottom, 21d ... through hole, 21x ... inner wall, 23 ... through hole, 25 ... Lid, 29 ... Space, 31 ... Release agent, 32 ... Coating film, 301 ... Flange

Claims (12)

A method for producing a cylindrical target material having a cylindrical shape and comprising a ceramic sintered body,
A filling step of filling a capsule container with a material to be sintered which is a forming material of the ceramic sintered body;
A sintering step of sintering the material to be sintered while pressurizing the capsule container,
The capsule container is a cylindrical metal container having a bottom;
In the filling step, a cylindrical core is disposed in the capsule container coaxially with the capsule container and filled with the material to be sintered, and further between the capsule container and the material to be sintered, and A mold release agent is always interposed between the core and the material to be sintered,
The release agent has a reactivity between the material to be sintered in the sintering temperature region of the sintering step, and a reactivity between the material to be sintered and the capsule container and the material to be sintered. Lower than the reactivity between the core and the core,
The amount of the mold release agent is a method for producing a cylindrical target material in which the thickness of the mold release agent after the sintering treatment is controlled to be 1 mm or more. In the filling step, the capsule material is filled with the powder of the material to be sintered and the powder of the release agent in a state where a partition for partitioning the material to be sintered and the release agent is provided in the capsule vessel. ,
The partition is formed between a space formed between an inner wall surface of the capsule container and a surface of the partition facing the inner wall surface, and a surface of the core and the surface of the partition facing the surface. The method for producing a cylindrical target material according to claim 1, wherein the space to be formed is provided so as to be filled with the amount of the release agent.   In the filling step, a coating material containing the release agent and a solvent is applied to the inside of the capsule container and the surface of the core, and the solvent is removed by drying to form a coating film, and then the sintered body The manufacturing method of the cylindrical target material of Claim 1 with which a material is filled. A method for producing a cylindrical target material having a cylindrical shape and comprising a ceramic sintered body,
A filling step of filling a capsule container with a material to be sintered which is a forming material of the ceramic sintered body;
A sintering step of sintering the material to be sintered while pressurizing the capsule container,
The capsule container is a metal container having a cylindrical outer wall portion, a cylindrical inner wall portion provided coaxially with the outer wall portion, and an annular bottom portion connecting the outer wall portion and the inner wall portion. Yes,
In the filling step, the capsule material is filled with the material to be sintered, and a release agent is always interposed between the capsule container and the material to be sintered,
The mold release agent has a lower reactivity with the material to be sintered in the sintering temperature region of the sintering step than a reactivity between the material to be sintered and the capsule container. ,
The amount of the mold release agent is a method for producing a cylindrical target material in which the thickness of the mold release agent after the sintering treatment is controlled to be 1 mm or more. In the filling step, the capsule material is filled with the powder of the material to be sintered and the powder of the release agent in a state where a partition for partitioning the material to be sintered and the release agent is provided in the capsule vessel. ,
The partition is controlled and provided so that the space formed between the inner wall surface of the capsule container and the surface of the partition facing the inner wall surface can be filled with the amount of the release agent. 5. A method for producing a cylindrical target material according to 4.   In the filling step, the coating material containing the mold release agent and the solvent is applied to the inside of the capsule container, and after the solvent is dried and removed to form a coating film, the material to be sintered is filled. 5. A method for producing a cylindrical target material according to 4.   The manufacturing method of the cylindrical target material of Claim 1 or 4 which uses what shape | molded the said mold release agent in the sheet form as the said mold release agent in the said filling process.   The method for producing a cylindrical target material according to any one of claims 1 to 7, wherein a metal having a melting point higher than a temperature at which the sintering process is performed is used as the mold release agent.   The method for producing a cylindrical target material according to claim 8, wherein the release agent has a relative density of 85% or less after the sintering treatment.   The production of the cylindrical target material according to any one of claims 1 to 7, wherein a metal oxide is used as the mold release agent and a relative density after the sintering treatment is 85% or less. Method.   The method for producing a cylindrical target material according to claim 10, wherein the release agent includes alumina powder.   A cylindrical target material having a relative density of 100%.

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