JP2015132013A - Sputtering target and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sintered body target bonded (glued) to a support medium with proper bond strength, capable of heightening bond strength, and suppressing exfoliation or the like in operation of the target when being conveyed to or mounted on a sputtering device, further, even when being thermally affected during sputtering, capable of suppressing effectively occurrence of strain of the target, deformation of the target, crack or exfoliation from the support medium.SOLUTION: A sputtering target has a ground layer comprising copper or a copper alloy, and a laminated structure formed by bonding the ground layer and a support medium with indium or an indium alloy, on the surface of a ceramic sintered body whose roughness on the support medium side is within a prescribed range.

Description

The present invention relates to a sputtering target suitable for forming a film of ITO, IZO, IGZO or the like and a method for manufacturing the same. In particular, the present invention relates to a sputtering target such as ITO, IZO, and IGZO with little change in film characteristics from the initial stage to the end of sputtering of the target and a method for manufacturing the same.

An ITO (indium-tin composite oxide) film is widely used as a transparent electrode (conductive film) in a display device centering on a liquid crystal display. As a method for forming the ITO film, a method generally called physical vapor deposition such as vacuum vapor deposition or sputtering is used. In particular, the magnetron sputtering method is often used because of operability and coating stability.
Indium-zinc oxide (In ₂ O ₃ —ZnO: generally referred to as IZO) sputtering targets are widely used for transparent conductive thin films and gas sensors of liquid crystal display devices.

In addition, a thin film transistor having an active layer made of a silicon-based material for driving each pixel is used for a display element such as an active matrix type liquid crystal display device. However, as the pixel is miniaturized, the area occupied by the transistor increases. In recent years, thin film transistors using transparent oxide semiconductors have been developed due to the drawbacks such as a decrease in aperture ratio and the need for high-temperature film formation.
Transparent oxide semiconductors are attracting attention from the viewpoints of being capable of forming a uniform film over a large area by sputtering, high mobility, and the like. Among them, In—Ga—Zn—O containing indium, gallium, zinc, and oxygen as constituent elements. The mobility of an amorphous IGZO film made of a base material (hereinafter referred to as “IGZO”) is higher than that of amorphous silicon, and a field effect transistor using the amorphous IGZO film as an active layer is turned on / off. Since it has characteristics such as a large ratio and a low off-state current value, it is considered promising.

  A film is formed by sputtering, in which a cation such as Ar ions is physically collided with a target placed on a cathode, and the material constituting the target is released by the collision energy, so that a substrate on the anode side facing the target is released. This is done by stacking films having the same composition as the target material. The coating method by sputtering has a feature that it can be formed from a thin film of several nm to a thick film of several tens of μm at a stable film formation speed by adjusting processing time, supply power and the like. .

The sputtering target usually exists in a form of being placed on a support, but it may be flat or cylindrical. This target is usually manufactured from a sintered body, but it is necessary to bond (adhere) the support with an appropriate bonding strength.
When the bonding strength is weak, the target may be distorted, deformed, cracked, etc. due to the influence of the target operation, for example, when transported to or installed in a sputtering apparatus, or during sputtering. Depending on the case, it may peel off from the support.
The distortion and cracks of the target are accompanied by the occurrence of arcing during sputtering, causing variations in film formation due to sputtering, and there is a problem that the quality is deteriorated.

As described above, the bonding of the target to the support is important, but there are the following examples in the known art. In the following Patent Document 1, an inner peripheral surface of a target material 20 made of a cylindrical ceramic sintered body, or an inner peripheral surface of a target material made of a cylindrical ceramic sintered body and an outer periphery of a cylindrical support substrate 10 are disclosed. A first underlayer 30 made of nickel or copper is formed on both surfaces, a second underlayer 40 made of tin is formed on the first underlayer, and then the target material is made into a cylinder. It is disclosed that a target is manufactured by disposing them outside the shape support substrate and bonding them together with a bonding material.
This patent document 1 is intended to provide a sputtering target that can obtain a sufficient bonding rate and bonding strength and can significantly reduce the occurrence of cracks even under the influence of heat during sputtering, and a method for manufacturing the same. It is.

  Further, in Patent Document 2 below, in a sputtering target manufacturing method in which a sputtering target material and a backing plate are bonded by a soldering method, a solder film layer is formed at least on the sputtering target material bonding surface by an electroplating method. A method for manufacturing a sputtering target is disclosed. Also in this case, an object of the present invention is to provide a method for manufacturing a target having a high bonding strength and a small variation in bonding strength in a method for manufacturing a target in which a target material and a backing plate are bonded by a soldering method.

Further, in Patent Document 3 below, when a target material made of titanium or a titanium alloy is bonded to a backing plate material made of at least one of copper, copper alloy, titanium, and titanium alloy, nickel or titanium as a base treatment is used. A sputtering target soldering method is disclosed in which after copper is plated, both the target material and backing plate material are ultrasonically metallized and then joined with solder, and sputtering with extremely high bonding strength is disclosed. It is described that a target can be obtained.

However, Patent Documents 1 to 3 do not have sufficient bonding strength, and are affected by heat during the operation of the target, for example, when transported to or installed in a sputtering apparatus, or during sputtering, and the target is distorted. There has been a problem that the target is deformed, cracked, or peeled off from the support in some cases.

JP 2012-132065 A JP-A-11-106904 JP-A-8-67978

The present invention has been made paying attention to such a situation, and the sputtering target usually exists in a form of being placed on a support, but it may be flat or cylindrical. This target is usually manufactured by a sintered body, but this sintered body target is bonded (adhered) to the support with an appropriate bonding strength, the bonding strength is increased, and the target of the target at the time of transporting or mounting to the sputtering apparatus is increased. The object is to effectively suppress the occurrence of distortion of the target, deformation of the target, cracking, and peeling from the support even when peeling or the like in the operation is suppressed, or even when it is affected by heat during sputtering. Accordingly, an object of the present invention is to provide a sputtering target that suppresses generation of arcing and particles during sputtering, suppresses variations in film formation due to sputtering, and improves quality.

Based on this knowledge, the present invention provides the following inventions.
1) A sputtering target in which a ceramic sintered body and a support are joined, and the surface roughness Ra on the support side of the ceramic sintered body is 0.5 μm or more and 4.0 μm or less, and the surface thereof A laminated structure in which a base layer made of copper or a copper alloy containing copper at 80 at% or more is formed thereon, and the support and the base layer are joined by an indium alloy layer containing 80 at% or more indium or indium. A sputtering target comprising:

2) A sputtering target in which a ceramic sintered body and a support are joined, and the surface roughness Ra on the support side of the ceramic sintered body is 0.5 μm or more and 4.0 μm or less, and the surface thereof A first layer made of copper or a copper alloy containing copper at 80 at% or more and a second layer made of indium or an indium alloy containing 80 at% or more of indium are formed on the first layer. A sputtering target having a stacked structure in which a layer is bonded with indium or a bonding material of an indium alloy containing 80 at% or more of indium.

3) The sputtering target according to 1) or 2) above, wherein the support and the ceramic sintered body are flat plates.
4) The sputtering target according to 1) or 2) above, wherein the support is rod-shaped or cylindrical, and the ceramic sintered body is cylindrical.

5) The sputtering target according to any one of 1) to 4) above, wherein the surface of the sintered body on the support side further has fine grooves of 0.1 μm or more and 1 μm or less.
6) The sputtering target according to any one of 2) to 5) above, wherein the first layer is formed with a thickness of 5 to 20 μm and the second layer is formed with a thickness of 5 to 10 μm.

7) The sputtering target according to any one of 1) to 6) above, wherein the sintered body is a ceramic sintered body of ITO, IZO, or IGZO.
8) The sputtering target according to any one of 1) to 7) above, wherein the support is oxygen-free copper, copper alloy, Ti (including alloy) or SUS.

9) The sputtering strength according to any one of 2) to 8) above, wherein the peel strength between the first layer and the sintered body is 10 MPa or more after the heat treatment at 170 to 200 ° C. target.

  10) A method for producing a sputtering target in which a ceramic sintered body and a support are joined, wherein the surface roughness Ra on the support side of the ceramic sintered body is 0.5 μm or more and 4.0 μm or less, A base layer made of copper or a copper alloy containing 80 at% or more of copper was formed on the surface, and the support and the base layer were bonded together by an indium alloy layer containing 80 at% or more of indium or indium. A method of manufacturing a sputtering target, comprising forming a structure.

11) A method for producing a sputtering target in which a ceramic sintered body and a support are joined, wherein the surface roughness Ra on the support side of the ceramic sintered body is 0.5 μm or more and 4.0 μm or less, A first layer made of copper or a copper alloy containing 80 at% or more of copper is formed on the surface, and then a second layer made of indium or an indium alloy containing 80 at% or more of indium is formed on the surface. A method of manufacturing a sputtering target, comprising bonding a body and a second layer with a bonding material of indium or an indium alloy containing 80 at% or more of indium.

12) The method for producing a sputtering target according to 10) or 11) above, wherein the support and the ceramic sintered body are flat plates.
13) The method for producing a sputtering target as described in 10) or 11) above, wherein the support is rod-shaped or cylindrical, and the ceramic sintered body is cylindrical.

14) The above-mentioned 10) to 13), wherein the surface of the sintered body on the support side is electrolytically roughened to form fine grooves of 0.1 μm or more and 1 μm or less on the surface of the sintered body on the support side The manufacturing method of the sputtering target as described in any one of these.
15) The sputtering according to any one of 11) to 13) above, wherein the first layer is formed to a thickness of 5 to 20 μm and the second layer is formed to a thickness of 5 to 10 μm by plating. Target manufacturing method.

16) The method for producing a sputtering target according to any one of 10) to 15) above, wherein a ceramic sintered body of ITO, IZO or IGZO is used as the sintered body.

17) The method for producing a sputtering target according to any one of 10) to 16) above, wherein oxygen-free copper, copper alloy, Ti (including alloy) or SUS is used as the support.

18) Sputtering as described in any one of said 11) -14) characterized by making peeling strength between a 1st layer and a sintered compact into 10 Mpa or more after heat processing of 170-200 degreeC. Target manufacturing method.

As described above, according to the present invention, the sputtering target joins (adheres) the sintered body target to the support with an appropriate joining strength, increases the joining strength, and the target of the target at the time of transporting or mounting to the sputtering apparatus. Even when peeling or the like in the operation is suppressed, or even when receiving heat influence during sputtering, it is possible to effectively suppress the generation of distortion of the target, deformation of the target, cracks, and peeling from the support. As a result, the generation of arcing and particles during sputtering can be suppressed, variation in film formation due to sputtering can be generated, and a sputtering target with improved quality can be provided, and the sputtering target can be produced with high quality and efficiency. It has the effect that can be done.

It is explanatory drawing of the surface structure | tissue photograph of the ITO sintered compact which carried out the electrolytic roughening (degreasing) process, and the groove | channel formed in the structure | tissue inside. It is a surface structure photograph (4 types) of the ITO sintered compact processed by changing the current density of electrolytic roughening (degreasing).

One form of the sputtering target of the present invention is a sputtering target made of a ceramic sintered body bonded to a support. There are no particular restrictions on the material of the support (backing plate, backing tube), but usually copper alloys such as oxygen-free copper, Cu—Cr (Cr: 0.5-1.5 wt%) alloy, and Ti (including alloys) ) Or SUS can be preferably used.
The material of the sintered body is not particularly limited, but a ceramic sintered body such as ITO, IZO or IGZO is a suitable material.

As described above, joining a ceramic sintered body having a different material type and characteristics and a support, and producing a target, the problem is in the operation of the target during transportation to or mounting on the sputtering apparatus. The target is distorted due to peeling or the like, or affected by heat during sputtering, and the target is deformed, cracked, or peeled off from the support.
Even if no cracks are visible from the appearance, if there are internal strains, arcing and many particles are generated during sputtering, resulting in variations in film formation due to sputtering, and quality may deteriorate. .

The present invention provides a technique for solving the above problems. In this case, since the shape and usage of the target are diversified, it is necessary to prepare a target corresponding to the target. As one of the main forms of the present invention, the surface roughness Ra on the support side of the ceramic sintered body is 0.5 μm or more and 4.0 μm or less, and copper containing copper or copper at 80 at% or more on the surface By forming a base layer made of an alloy, joining the support and the base layer with indium or an indium alloy layer containing 80 at% or more of indium, and forming a sputtering target having a structure in which the target and the support are stacked. is there.
As a result, the bonding strength between the target and the base layer and between the covering layer and the support can be effectively increased.

Further, as another main form, the surface roughness Ra on the support side of the ceramic sintered body is set to 0.5 μm or more and 4.0 μm or less, and copper or copper is contained on the surface thereof by 80 at% or more. A first layer made of copper alloy and a second layer made of indium alloy containing indium or indium at 80 at% or more are formed thereon, and the support and the second layer contain indium or indium at 80 at% or more. And adopting a structure in which bonding is performed by a bonding material of indium alloy. Thus, a sputtering target having a structure in which a target made of a ceramic sintered body having a laminated structure and a support are laminated is obtained.

The former first layer is a layer usually formed by plating, and the latter second layer is a layer formed by a bonding material (bonding material). Both have very similar or the same material composition, but one is plating, and the other is a layer forming means using a bonding material (bonding material).
As described above, the bonding strength between the target and the base layer and between the covering layers (first layer and second layer) and between them and the support can be effectively increased. These layer structures have a function of improving adhesion to the support.

Conventionally, as disclosed in Patent Document 1, it is disclosed that the second layer is tin. However, an alloy is formed with indium, which is a general bonding material, and a low melting point is obtained depending on the composition ratio. It was found that the heat resistance was very inferior. Therefore, the present inventors have been able to overcome in terms of heat resistance by using indium or an indium alloy containing 80 at% or more of indium. Further, indium or an indium alloy containing 80 at% or more of indium as described above has very good wettability with an indium alloy containing 80 at% or more of indium or indium as a bonding material (bonding material), and bonding failure is also caused. It is reduced.

When the support and the sintered body are bonded, bonding using a bonding material, bonding by thermocompression bonding (including diffusion bonding), or the like can be used, and the bonding method is not particularly limited. As a suitable material for the bonding material, indium metal (including an indium alloy material containing 80 at% or more of indium such as an In—Sn alloy, an In—Ga alloy, an In—Cu alloy) can be given. The same material can be used for the bonding material used below.

As described above, in the past, metal plating was merely performed and sufficient bonding strength could not be obtained, but the surface roughness Ra of the surface of the sintered body should be 0.5 μm or more and 4.0 μm or less. Thus, the bonding strength with the layer formed thereon can be increased. If the surface roughness exceeds these values, the strength of the ceramic sintered body is affected and cracks may occur. On the other hand, if the roughness is lower than these values, the adhesiveness is lowered, which is not preferable.

Further, as a method for optimizing the surface roughness, there is a method of electrolytic roughening. Thereby, as shown in FIG.1 and FIG.2, the fine groove | channel of 0.1 micrometer or more and 1 micrometer or less can be formed. This further increases the bonding strength with the first layer. Fig. 2 is a photograph of the surface structure (4 types) of an ITO sintered body processed by changing the current density of electrolytic roughening (degreasing). One of the photographs was taken to form a roughened surface structure. FIG. 1 illustrates the groove formed.
1A is a structure photograph, and a schematic diagram B illustrates the groove of the structure photograph A, and a portion indicated by a dotted line in FIG. 1B corresponds to a groove at the particle interface (B in FIG. 1). Arrow part). FIG. 1C shows only the grooves after binarization. The grooves are indefinite and exist innumerably mainly along the particle interface.

Strictly defining this groove means that when an arbitrary point of the groove is fixed, the minimum width of the groove starting from this point is 0.1 μm or more and 1 μm or less. If the width of the groove is less than 0.1 μm, the effect is thin, and if it exceeds 1 μm, the strength may be lowered.
When electrolytic roughening (degreasing) is performed, grooves of 0.1 μm or more and 1 μm or less are formed as shown in FIG. Even if there is a groove of less than 0.1 μm or a small amount of grooves exceeding 1 μm, it is not particularly problematic as long as the groove is not less than 0.1 μm and not more than 1 μm. Will understand.

The details of the electrolytic roughening process will be described. A part of the surface texture is eluted by this process, and a groove having a width of 0.1 μm or more and 1 μm or less is formed. The portion that is likely to elute is mainly at the particle interface, but IGZO or the like partially elutes within the particle. As a result, when the structure is observed, there are many portions having a structure such as fins of the cooler. When evaluating the adhesion of the electroplated Cu film, when observing the surface structure on the back side of the peeled film (the part in close contact with the ceramic), it is observed that the electroplated Cu film is sufficiently in the groove. Therefore, a fine groove can be confirmed also from this.

As described above, even when transported to the sputtering apparatus or when the target is peeled off during the operation of the target, or even under the influence of heat during sputtering, the target is distorted, deformed, cracked, or peeled off from the support. Can be effectively suppressed. In addition, it is possible to provide a sputtering target in which generation of arcing and particles during sputtering is suppressed, variation in film formation due to sputtering is generated, and quality is improved.

The sputtering target of this invention can be used as the sputtering target which has arrange | positioned the flat ceramic target on the surface of the support body which consists of a flat backing plate.
Moreover, the sputtering target of this invention can be made into the sputtering target which has arrange | positioned the cylindrical ceramic target on the outer side or inner side of the support body which consists of a rod-shaped or cylindrical backing tube. Although this target is cylindrical, since the layer structure has the same layer structure as the flat plate target, the adhesion with the support plate can be improved, and the same effect as the flat plate target is obtained. .
The material of the rod-like or cylindrical support is not particularly limited, but oxygen-free copper, copper alloys such as Cu—Cr (Cr: 0.5-1.5 wt%) alloy, stainless steel ( SUS) and Ti (including alloys) are suitable materials. Hereinafter, when a rod-like or cylindrical support is used, the same material can be used.

The target material used in the present invention will be described in more detail. ITO (indium, tin, oxygen (In ₂ O ₃ —SnO ₂ -based material) as a constituent element), IZO (indium, zinc) , Oxygen (a composite oxide having In ₂ O ₃ —ZnO-based material) as a constituent element), or IGZO (indium, gallium, zinc, oxygen (In—Ga—Zn—O-based material) as a constituent element) A ceramic target such as a material is a suitable material.
However, it is not necessary to limit to these. For example, for ITO, the SnO ₂ content in ITO is ₂ to 36 wt. % Containing material, IZO, ZnO in IZO is 7 to 10.7 wt. For the material containing IGZO, In: Ga: Zn, a material of 2: 2: 1 (at%), or 5: 1: 4 (at%), or 5: 2: 3 (at%) is used. Can be used.

The thickness of the first layer is preferably 5 to 20 μm, and the thickness of the second layer is preferably 5 to 10 μm. To do is not particularly problematic.
When the thickness of the plating film becomes extremely thin, when a backing material such as a backing plate or backing tube and a ceramic material are joined with a bonding material, compressive stress remains on the target due to the difference in thermal expansion between them ( Coefficient of thermal expansion: support> ceramic material) If the thickness of the plating film becomes extremely thin, the plating film may be destroyed due to insufficient strength. On the other hand, when the plating film is thickened, defects that are not noticeable when the film is thin may become obvious, resulting in deterioration of characteristics. In addition, there is a concern that productivity and economic efficiency deteriorate due to the thick film.

Further, it is more desirable that the surface of the sintered body on which the first layer is laminated is subjected to an electrolytic roughening treatment, and the surface roughness is a rough surface in which Ra is 0.5 μm to 4 μm and Rz is 20 μm or less. It is good to do. Moreover, it is desirable to form fine grooves of 0.1 μm or more and 1 μm or less on the surface of the support. These are all factors that improve the adhesion between the support and the sputtering target. Moreover, about the said 1st layer, peeling strength with a sintered compact can achieve 10 Mpa or more after heat processing of 170-200 degreeC.

(Specific example of electrolytic degreasing “roughening treatment”)
Table 1 shows suitable electrolytic degreasing conditions (current density and treatment time). The amount of roughening is determined by the amount of coulomb, but in actual work it is managed by current density and processing time. When the current density is low, the formation of fine grooves does not proceed sufficiently and the adhesion of the first layer is lowered. On the other hand, if the current density is too high, the surface is roughened more than necessary, and some of the surface particles are degranulated, leading to a reduction in the strength of the surface texture. As a result, as in the case where the current density is low, the adhesiveness of the first layer is reduced, so it is necessary to adjust to an appropriate value.

(Copper electroplating method)
In the copper electroplating, copper plating is performed using a copper cyanide plating solution, a pyrophosphate copper plating solution, and a copper sulfate plating solution in the same manner as indium plating.

(Specific example of indium electroplating)
This is performed using a sulfamic acid-based indium plating solution.
Indium is used for the anode, a plating solution made of sulfamic acid is used as the plating solution, and the current density is 1.5 A / dm ² or less, the processing time is within 60 minutes, the temperature is room temperature, and the stirring is yes. Do.

  Hereinafter, a description will be given based on examples. In addition, a present Example is an example for making an understanding easy to the last, and is not restrict | limited at all by this example. In other words, the present invention is limited only by the scope of the claims, and includes various modifications other than the embodiments described in the present invention.

Example 1
Using a cylindrical ITO target material (inner diameter: φ135 mm, plate thickness: 10 mm, length: 224 mm), as shown in Table 5, the surface is roughened by combining sandblasting and etching, and Ra3. A rough surface of 88 μm and Rz 18.54 μm was obtained.
Copper electroplating was performed as the first layer, and indium electroplating was performed as the second layer. The film thickness of the first layer was 6 μm, and the film thickness of the second layer was 8 μm. The composition of the ITO target material is SnO ₂ content: 10.0 wt. %, Balance In ₂ O ₃ .

(Surface roughening method)
The surface roughening method will be described in detail.
The surface of the ITO target material was sandblasted and then subjected to aqua regia etching to obtain a rough surface with Ra 3.88 μm and Rz 18.54 μm. Although this is different from the electrolytic roughened surface, it is possible to improve the adhesion of the electric Cu plating film by providing a fine groove by aqua regia etching on a macro roughened surface by sandblasting.

(Sand blasting conditions are as follows.)
Air pressure: 4-5 kgf / cm ²
Nozzle distance: 100mm
Media: Alumina particles (Type: White Morundum Particle size: about 300μm)
(Aqua regia etching conditions are as follows.)
Treatment time: 5 minutes Treatment temperature: Room temperature (about 25 ° C)
Stirring: None

(Bonding work of cylindrical target (rotary target) ITO target material and backing tube)
Stainless steel (SUS) was used for the backing tube (BT). The roughening treatment and the multi-layer plating treatment were performed on the inner surface of a cylinder made of a plurality of ITO sintered bodies to be bonded.
A BT and a cylinder are installed in the bonding apparatus (the cylinder is arranged outside the BT). At this time, the division gaps and height positions (the positions of the end of the BT and the end of the cylinder) of each cylinder were adjusted, and the centering (adjusted so that the central axis of the BT and the cylinders coincided) was performed.

In order to prevent oxidation of the molten In metal, the rotary target assembly and the surrounding atmosphere were replaced with an inert gas. Thereafter, the entire rotary target assembly was heated to the bonding temperature.
Molten In metal was filled between the BT and the cylinder (filled to the extent that it would overflow to remove bubbles and metal oxide remaining inside).
Next, in a state where the molten In metal was sufficiently filled, the filling of the molten In metal was stopped, and the entire rotary target assembly was cooled to the room temperature level.
When the adhesion state was confirmed by ultrasonic flaw detection, the adhesion rate was 98%, and a good plating state could be obtained.

(Evaluation of adhesion of plating film: tensile test)
Next, adhesion evaluation and a tensile test of the plating film were performed.
The sample (size: 30 mm × 50 mm × 10 mm laminated plated) was subjected to heat treatment under the conditions of atmospheric air, 200 ° C. and 1 hour. Next, the tensile test column is bonded to the laminated plating surface with an epoxy adhesive, the sample is fixed to the tensile tester, the column is pulled up under the condition of 0.5 mm / sec, the maximum load value, The tensile strength of the multilayer plating film was calculated from the area of the part.
From this test, it was confirmed that the sample had a tensile strength of about 15 MPa. Table 2 shows the above materials, surface roughening, types of the first layer and second layer, and results.

(Example 2)
A cylindrical ITO target material (inner diameter: φ135 mm, plate thickness: 10 mm, length: 224 mm) was used, and the surface was subjected to electrolytic roughening as shown in Table 2, and the surface roughness was Ra 1.77 μm, A rough surface of Rz 11.35 μm was obtained. Moreover, a fine groove of 0.1 μm or more and 1 μm or less could be formed on the ITO surface. Next, electrolytic copper plating was performed as the first layer, and indium electroplating was performed as the second layer. The film thickness of the first layer was 8.2 μm, and the film thickness of the second layer was 7.5 μm. The composition of the ITO target material is SnO2 content: 10.0 wt. %, Balance In ₂ O ₃ .

(Electrolytic roughening treatment)
The conditions for the electrolytic roughening treatment are as follows. As electrolytic roughening conditions shown in Table 1, electrolytic roughening was performed with a current density of 11.3 A / dm ² and a treatment time of 1 min.

(Cylindrical (rotary target) IZO target material and backing tube bonding)
Ti (titanium) was used for the backing tube (BT). The bonding operation was the same as in Example 1.

When the adhesion state was confirmed by ultrasonic flaw detection, the adhesion rate was 98.8%, and a good plating state could be obtained. Moreover, as a result of conducting the same tensile test as in Example 1, it was confirmed that the sample had a tensile strength of about 17.8 MPa. The above materials, surface roughening, first layer and second layer types and results are similarly shown in Table 2 above.

(Example 3)
A cylindrical IZO target material (inner diameter: φ135 mm, plate thickness: 10 mm, length: 224 mm) is used, and electrolytic roughening is performed on the surface thereof as shown in Table 2, and the surface roughness is Ra 1.62 μm, A rough surface having an Rz of 10.71 μm was obtained. Moreover, a fine groove of 0.1 μm or more and 1 μm or less could be formed on the IZO surface.
Next, electrolytic copper plating was performed as the first layer, and indium electroplating was performed as the second layer. The film thickness of the first layer was 6.5 μm, and the film thickness of the second layer was 7.5 μm. The component composition of the IZO target material has a ZnO content of 10.7 wt. %, Balance In ₂ O ₃ .

(Electrolytic roughening treatment)
The conditions for the electrolytic roughening treatment are as follows. As electrolytic roughening conditions shown in Table 1, electrolytic roughening was performed with a current density of 11.3 A / dm ² and a treatment time of 1 min.

(Cylindrical (rotary target) IZO target material and backing tube bonding)
Ti (titanium) was used for the backing tube (BT). The bonding operation was the same as in Example 1.

When the adhesion state was confirmed by ultrasonic flaw detection, the adhesion rate was 97.5%, and a good plating state could be obtained. Moreover, as a result of conducting the same tensile test as in Example 1, it was confirmed that the sample had a tensile strength of about 17 MPa. The above materials, surface roughening, first layer and second layer types and results are similarly shown in Table 2 above.

Example 4
A cylindrical IGZO target material (inner diameter: φ135 mm, plate thickness: 10 mm, length: 224 mm) was used, and electrolytic roughening was performed on the surface thereof as shown in Table 2, and the surface roughness was Ra 3.27 μm, A rough surface having an Rz of 19.54 μm was obtained.
Moreover, a fine groove of 0.1 μm or more and 1 μm or less could be formed on the IGZO surface. Copper electroplating was performed as the first layer, and indium electroplating was performed as the second layer. The film thickness of the first layer was 7 μm, and the film thickness of the second layer was 7.4 μm. The component composition of the IGZO target material is Ga ₂ O ₃ content: 29.9 wt. %, ZnO content: 25.9%, the balance being In ₂ O ₃ .

(Electrolytic roughening treatment)
The conditions for the electrolytic roughening treatment are as follows. As electrolytic roughening conditions shown in Table 1, electrolytic roughening was performed with a current density of 1.13 A / dm ² and a treatment time of 10 minutes.

(Cylindrical (rotary target) IZO target material and backing tube bonding)
Oxygen-free copper was used for the backing tube (BT). The bonding operation was the same as in Example 1.

When the adhesion state was confirmed by ultrasonic flaw detection, the adhesion rate was 98.5%, and a good plating state could be obtained. Moreover, as a result of performing the same tensile test as Example 1, it was confirmed that the sample had a tensile strength of about 15 MPa. Table 2 shows the above materials, surface roughening, types of the first layer and the second layer, and the results.

(Comparative Example 1)
Using a cylindrical ITO target material (inner diameter: φ135 mm, plate thickness: 10 mm, length: 224 mm), roughening was performed to obtain a rough surface of Ra 2.75 μm and Rz 14.94 μm. Indium electroplating was performed on the surface. The component composition of the ITO target material is SnO ₂ content: 10 wt. %, Balance In ₂ O ₃ .

(Electrolytic roughening treatment)
The conditions for the roughening treatment are as follows. As electrolytic roughening conditions shown in Table 1, electrolytic roughening was performed with a current density of 0.75 A / dm ² and a treatment time of 15 minutes.

(Cylindrical (rotary target) IZO target material and backing tube bonding)
Stainless steel (SUS) was used for the backing tube (BT). The bonding operation was the same as in Example 1.

(Evaluation of adhesion of plating film: tensile test)
Next, adhesion evaluation and a tensile test of the plating film were performed. When the sample (laminated plating treatment) was heat-treated at 200 ° C. for 1 hour in an air atmosphere, swelling of the In plating film and defective film peeling were confirmed. Table 2 shows the above materials, surface roughening, types of the first layer and the second layer, and the results.
The reason for this failure is considered to be that the indium plating does not sufficiently enter the fine groove because the plating particles are large. Furthermore, it was considered that when heat treatment was performed assuming a bonding operation, moisture and air remaining in the fine groove portion were thermally expanded and the film was peeled off, resulting in poor expansion.

(Comparative Example 2)
A cylindrical ITO target material (inner diameter: φ135 mm, plate thickness: 10 mm, length: 224 mm) was used for roughening to obtain a rough surface of Ra 2.52 μm and Rz 15.93 μm. The surface was subjected to electrolytic copper plating. The component composition of the ITO target material is SnO ₂ content: 10 wt. %, Balance In ₂ O ₃ .

(Roughening treatment)
The conditions for the roughening treatment are the same as in Example 1.
(Electro copper plating)
The conditions for electrolytic copper plating are the same as in Example 1.

(Evaluation of adhesion of plating film: tensile test)
Next, adhesion evaluation and a tensile test of the plating film were performed.
The sample (laminated plating process) was heat-treated at 200 ° C. for 1 hour under atmospheric conditions. Next, the tensile test column is bonded to the laminated plating surface with an epoxy adhesive, the sample is fixed to the tensile tester, the column is pulled up under the condition of 0.5 mm / sec, the maximum load value, The tensile strength of the multilayer plating film was calculated from the area of the part.
From this test, it was confirmed that the sample had a tensile strength of about 20 MPa.

(Cylindrical (rotary target) IZO target material and backing plate bonding)
Ti (titanium) was used for the backing plate (BT). The bonding operation was the same as in Example 1.
When a bonding test was carried out using these cylinders, the wettability of In metal was poor and the cylinders could not be joined. Table 2 shows the above materials, surface roughening, types of the first layer and the second layer, and the results.

(Comparative Example 3)
Using a cylindrical ITO target material (inner diameter: φ135 mm, plate thickness: 10 mm, length: 224 mm), without roughening, copper electroplating as the first layer and indium electroplating as the second layer Carried out. The component composition of the ITO target material is SnO ₂ content: 10 wt. %, Balance In ₂ O ₃ .

(Evaluation of adhesion of plating film: tensile test)
Next, the adhesion evaluation of the plating film and the tensile test were carried out in the same manner as in Example 1. When the sample (laminated plating process) was heat-treated at 200 ° C. for 1 hour under atmospheric conditions, the adhesion between the ITO surface and the Cu plating film was insufficient, and peeling occurred on the entire surface. Table 2 shows the above materials, surface roughening, types of the first layer and the second layer, and the results.

(Comprehensive evaluation of examples and comparative examples)
As is clear from the comparison between the above examples and comparative examples, the surface of the plate-like or cylindrical sintered body has a predetermined roughness range, and copper or copper alloy containing 80 at% or more of copper on the surface. A second layer made of indium or an indium alloy containing 80 at% or more of indium is formed thereon, and bonded by a bonding material made of indium or an alloy of indium containing 80 at% or more of indium. It can be confirmed that the laminated body thus formed is bonded (adhered) to the sintered body and the support body with an appropriate bonding strength to increase the bonding strength.

The sputtering target of the present invention usually exists in a form of being placed on a support, but it may be flat or cylindrical. Bonding (adhering) the sintered body target to the support with an appropriate bonding strength, increasing the bonding strength, suppressing peeling in the operation of the target during transportation to or mounting on the sputtering device, or thermal effects during sputtering Even when it is received, the generation of distortion of the target, deformation of the target, cracks, and peeling from the support can be effectively suppressed. Accordingly, it is possible to provide a sputtering target that suppresses the occurrence of arcing and particles during sputtering, generates variations in film formation due to sputtering, and improves the quality, and thus has high industrial utility value.

Based on this knowledge, the present invention provides the following inventions.
1) A sputtering target in which a ceramic sintered body and a support are joined, and the surface roughness Ra on the support side of the ceramic sintered body is 0.5 μm or more and 4.0 μm or less, and further 0 A first layer made of a copper alloy having a fine groove of 1 μm or more and 1 μm or less and containing copper or copper at 80 at% or more on the surface thereof, and an indium alloy containing 80 at% or more of indium on the first layer; A sputtering target having a laminated structure in which a second layer is formed, and the support and the second layer are joined together by a joining material of indium or an indium alloy containing 80 at% or more of indium.

2) The sputtering target according to 1) above, wherein the support and the ceramic sintered body are flat plates.

3) The sputtering target according to 1) above, wherein the support is rod-shaped or cylindrical, and the ceramic sintered body is cylindrical.

4) The sputtering target according to 1) above, wherein the first layer is formed with a thickness of 5 to 20 μm and the second layer is formed with a thickness of 5 to 10 μm.
5) The sputtering target according to any one of 1) to 4) above, wherein the sintered body is a ceramic sintered body of ITO, IZO, or IGZO.

6) The sputtering target according to any one of 1) to 5) above, wherein the support is oxygen-free copper, copper alloy, Ti (including an alloy), or SUS.

7) The sputtering strength according to any one of 1) to 6) above, wherein the peel strength between the first layer and the sintered body is 10 MPa or more after the heat treatment at 170 to 200 ° C. target.

8) A method for producing a sputtering target in which a ceramic sintered body and a support are joined, wherein the surface roughness Ra on the support side of the ceramic sintered body is 0.5 μm or more and 4.0 μm or less, By electrolytically roughing the surface on the support side, a fine groove of 0.1 μm or more and 1 μm or less is formed on the surface on the support side of the sintered body, and copper or a copper alloy containing copper at least 80 at% on the surface A first layer is formed, and then a second layer made of indium or an indium alloy containing 80 at% or more of indium is formed on the surface thereof, and the support and the second layer are made of indium or indium of 80 at% or more. A method for producing a sputtering target, comprising joining with a contained indium alloy joining material.

9) The method for producing a sputtering target as described in 8) above, wherein the support and the ceramic sintered body are flat plates.

10) The method for producing a sputtering target according to 8) above, wherein the support is rod-shaped or cylindrical, and the ceramic sintered body is cylindrical.

11) The sputtering according to any one of 8) to 10) above, wherein the first layer is formed to a thickness of 5 to 20 μm and the second layer is formed to a thickness of 5 to 10 μm by plating. Target manufacturing method.

12) The method for producing a sputtering target according to any one of 8) to 11) above, wherein a ceramic sintered body of ITO, IZO or IGZO is used as the sintered body.

13) The method for producing a sputtering target according to any one of 8) to 12) above, wherein oxygen-free copper, copper alloy, Ti (including alloy) or SUS is used as the support.

14) Sputtering as described in any one of said 8) -13) characterized by making peeling strength between a 1st layer and a sintered compact into 10 Mpa or more after heat processing of 170-200 degreeC. Target manufacturing method.

Claims (18)

A sputtering target in which a ceramic sintered body and a support are joined, and the surface roughness Ra of the ceramic sintered body on the support side is 0.5 μm or more and 4.0 μm or less, on the surface thereof It has a laminated structure in which copper or a base layer made of a copper alloy containing 80 at% or more of copper and a support and the base layer are joined by an indium alloy layer containing 80 at% or more of indium or indium. Sputtering target. A sputtering target in which a ceramic sintered body and a support are joined, and the surface roughness Ra of the ceramic sintered body on the support side is 0.5 μm or more and 4.0 μm or less, on the surface thereof A first layer made of copper or a copper alloy containing 80 at% or more of copper, and a second layer made of indium alloy containing 80 at% or more of indium on it are further formed, and the support and the second layer, A sputtering target characterized by having a laminated structure formed by bonding with indium or a bonding material of indium alloy containing indium of 80 at% or more. The sputtering target according to claim 1 or 2, wherein the support and the ceramic sintered body are flat plates. The sputtering target according to claim 1 or 2, wherein the support is rod-shaped or cylindrical, and the ceramic sintered body is cylindrical. 5. The sputtering target according to claim 1, wherein the surface of the sintered body on the support side further has a fine groove of 0.1 μm or more and 1 μm or less.   The sputtering target according to any one of claims 2 to 5, wherein the first layer is formed with a thickness of 5 to 20 µm and the second layer is formed with a thickness of 5 to 10 µm. The sputtering target according to any one of claims 1 to 6, wherein the sintered body is a ceramic sintered body of ITO, IZO or IGZO. The sputtering target according to any one of claims 1 to 7, wherein the support is oxygen-free copper, copper alloy, Ti (including an alloy) or SUS. 9. The sputtering target according to claim 2, wherein the peel strength between the first layer and the sintered body is 10 MPa or more after the heat treatment at 170 to 200 ° C. 9. A method for producing a sputtering target in which a ceramic sintered body and a support are joined, wherein the surface roughness Ra of the ceramic sintered body on the support side is 0.5 μm or more and 4.0 μm or less, and the surface thereof A base layer made of copper or a copper alloy containing copper at 80 at% or more is formed thereon, and the support and the base layer are joined by an indium alloy layer containing 80 at% or more of indium or indium to form a laminated structure. A method for producing a sputtering target, comprising: forming a sputtering target. A method for producing a sputtering target in which a ceramic sintered body and a support are joined, wherein the surface roughness Ra of the ceramic sintered body on the support side is 0.5 μm or more and 4.0 μm or less, and the surface thereof A first layer made of copper or a copper alloy containing 80 at% or more of copper is formed thereon, and then a second layer made of indium or an indium alloy containing 80 at% or more of indium is formed thereon. A method for manufacturing a sputtering target, wherein the second layer is bonded to the second layer by a bonding material of indium or an indium alloy containing 80 at% or more of indium. The method for producing a sputtering target according to claim 10 or 11, wherein the support and the ceramic sintered body are flat plates. The method of manufacturing a sputtering target according to claim 10 or 11, wherein the support is rod-shaped or cylindrical, and the ceramic sintered body is cylindrical. The surface of the sintered body on the support side is electrolytically roughened to form fine grooves of 0.1 μm or more and 1 μm or less on the surface of the sintered body on the support side. The manufacturing method of the sputtering target of one term. 14. The sputtering target according to claim 11, wherein the first layer is formed to a thickness of 5 to 20 μm and the second layer is formed to a thickness of 5 to 10 μm by plating. Method. The method for manufacturing a sputtering target according to any one of claims 10 to 15, wherein a ceramic sintered body of ITO, IZO or IGZO is used as the sintered body. The method for producing a sputtering target according to any one of claims 10 to 16, wherein oxygen-free copper, copper alloy, Ti (including an alloy) or SUS is used as the support. The peel strength between the first layer and the sintered body is set to 10 MPa or more after the heat treatment at 170 to 200 ° C. The production of the sputtering target according to claim 11, Method.