TWI568705B - Conductive oxide sintered body and manufacturing method thereof - Google Patents

Description

Conductive oxide sintered body and method of producing the same

The present invention relates to a target for forming an optical film which does not contain sulfur, has low bulk resistance, can be subjected to IDC sputtering, and has a low refractive index, and a method for producing the same.

Conventionally, ZnS-SiO ₂ which is mainly used for the protective layer of a phase change optical information recording medium is widely used because of its excellent optical properties, thermal properties, and adhesion to a recording layer. . However, today, for rewritable optical discs represented by Blue-Ray, there is a strong demand for an increase in the number of overwrites, a large capacity, and a high-speed recording.

One of the causes of deterioration in the number of times of overwriting of the optical information recording medium is that the sulfur component of ZnS-SiO ₂ is diffused to the recording layer sandwiched by the protective layer ZnS-SiO ₂ . Further, in order to increase the capacity and record at high speed, a pure Ag or Ag alloy having high reflectance and high heat conduction characteristics is used for the reflective layer, but such a reflective layer is also disposed with the protective layer ZnS-SiO _{2 .} Contact.

Therefore, in this case as well, the sulfur component is diffused from the ZnS-SiO ₂ to cause corrosion deterioration of the pure Ag or Ag alloy reflective layer, which is a cause of deterioration of characteristics such as reflectance of the optical information recording medium.

As a countermeasure against the diffusion of the sulfur components, an intermediate layer mainly composed of nitride or carbide is provided between the reflective layer and the protective layer, and between the recording layer and the protective layer. However, this method will increase the number of layers, and the problem of reduced production and increased costs will occur. In order to solve the above problems, it has been studied to replace a protective layer material with a material which does not contain a sulfide and contains only an oxide, and which has optical characteristics equal to or higher than that of ZnS-SiO ₂ and amorphous stability.

Further, since a ceramic target such as ZnS-SiO ₂ has a high bulk resistance value, it cannot be formed by a DC sputtering apparatus, and a high frequency sputtering (RF) apparatus is usually used. However, this high-frequency sputtering (RF) device is not only expensive in itself, but also has many disadvantages such as poor sputtering efficiency, large power consumption, complicated control, and slow film formation speed. Moreover, when high electric power is applied in order to raise the film formation speed, there exists a problem that the temperature of a board|substrate raises, and it deforms the polycarbonate substrate. Furthermore, the reduction in yield and the increase in cost due to the thick ZnS-SiO ₂ film thickness are also problems.

From the above, a sintered body target capable of DC sputtering has been proposed, in which ZnO, that is, a sulfur-free component is used, in order to form a transparent conductive film, an element having a positive trivalent or higher valence is separately formed. It is added to ZnO (for example, refer to Patent Document 1). However, in this case, the low bulk resistance value and the low refractive index are not sufficiently achieved.

Further, a transparent conductive film and a sintered body for producing the transparent conductive film have been proposed, which are manufactured by various combinations of Group I, Group III, and Group IV elements by high frequency or DC magnetron sputtering. (Refer to Patent Document 2). However, the purpose of this technique is not to achieve the purpose of lowering the resistance of the target, and it is also impossible to sufficiently achieve both the low bulk resistance value and the low refractive index.

Further, a ZnO sputtering target (see Patent Document 3) has been proposed, in which at least one of the added elements is dissolved in ZnO. This is based on the solid solution of the added element, so there is a limit to the composition of the component, so there is a problem that the optical properties are also limited.

In view of the above problems, the applicant of the present invention completed the invention of the following Patent Document 4, that is, providing an Al ₂ O ₃ : 0.2 to 3.0 at%, MgO and/or SiO ₂ : 1 to 27 at%, and remaining A part of ZnO is a sputtering target having a low refractive index and a low bulk resistance, whereby the target and film forming properties can be greatly improved.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2-149459

Patent Document 2: Japanese Laid-Open Patent Publication No. Hei 8-264022

Patent Document 3: Japanese Patent Laid-Open No. Hei 11-322332

Patent Document 4: Japanese Patent No. 4828529

Although the above-mentioned Patent Document 4 is a sputtering target capable of forming a low refractive index film, when the composition of the composition is adjusted to lower the refractive index, low bulk resistance cannot be obtained, and DC sputtering cannot be performed. Accordingly, the present invention provides a sintered body which can form a low refractive index film by DC sputtering and a method of manufacturing the same. Thereby, the film formation speed can be improved, and the yield of forming a low refractive index film can be greatly improved.

In order to solve the problem, the inventors of the present invention have conducted intensive studies, and as a result, have obtained the following findings: even in a composition region having a low refractive index, sintering can be performed in an inert gas or a vacuum atmosphere to obtain a low bulk resistance. Perform DC sputtering. As a result, it is possible to obtain a high-speed film formation by DC sputtering, improve the characteristics of the optical information recording medium, and improve the productivity.

The present invention is based on this insight and is:

1) A sintered body composed of zinc (Zn), aluminum (Al), magnesium (Mg) and/or cerium (Si), and oxygen (O), and the content of Al is 0.1 to 3.0 mol in terms of Al ₂ O _{3 .} The total content of %, Mg and/or Si is 27 to 70 mol% in terms of MgO and/or SiO ₂ , and the remainder is the content of Zn in terms of ZnO.

2) The sintered body according to item 1 above, having a bulk resistance of 10 Ω. Below cm.

3) The sintered body according to the above item 1 or 2, which has a relative density of 90% or more.

The sintered body according to any one of the above items 1 to 3, further comprising a metal forming an oxide having a melting point of 1000 ° C or less, the content of the metal forming the oxide being 0.1 to 5 wt % in terms of oxide weight .

The sintered body according to item 4 above, wherein the oxide is selected from the group consisting of B ₂ O ₃ , P ₂ O ₅ , K ₂ O, V ₂ O ₅ , Sb ₂ O ₃ , TeO ₂ , Ti ₂ O ₃ One or more materials selected from the group consisting of PbO, Bi ₂ O ₃ and MoO ₃ .

The sintered body according to any one of the above items 1 to 5, which is used as a sputtering target.

7) A film obtained by sputtering using the sintered body of the above item 6, wherein the refractive index is 2.0 or less.

8) A method for producing a sintered body, wherein the Al ₂ O ₃ powder is 0.1 to 3.0 mol%, the MgO and/or SiO ₂ powder is 27 to 70 mol%, and the balance is ZnO powder, and the total amount is 100 mol%. The raw material powder is adjusted, and the raw material powder is sintered at a temperature of 1050 ° C or higher and 1500 ° C or lower in an inert gas or a vacuum atmosphere.

(9) The method for producing a sintered body according to the above item 8, wherein 0.1 to 5 wt% of an oxide powder having a melting point of 1000 ° C or less is further added to prepare a raw material powder.

According to the above, the present invention has an excellent effect of providing a sintered body capable of forming a low refractive index film by DC sputtering and a method for producing the same. Further, it is possible to provide a sputtering target which is particularly suitable for use in a film for an optical information recording medium (especially as a protective film, a reflective layer, or a semi-transmissive film layer). As described above, it has an excellent effect of improving the characteristics of the optical information recording medium, reducing the equipment cost, and greatly improving the yield achieved by increasing the film formation speed.

The present invention is a sintered body containing zinc (Zn), aluminum (Al), magnesium (Mg) and/or cerium (Si), and oxygen (0) as constituent elements, characterized in that the Al content is converted in terms of Al ₂ O ₃ 0.1 to 3.0 mol%, the total content of Mg and/or Si is 27 to 70 mol% in terms of MgO and/or SiO ₂ , and the remainder is Zn in terms of ZnO, and has low bulk resistance capable of DC sputtering. .

When the raw material is adjusted, the remaining portion is made of ZnO, and the ratio of each oxide is adjusted to have a total composition of 100 mol%. Therefore, the Zn content can be obtained from the remaining portion of ZnO.

Further, in the present invention, the content of each metal in the sintered body is specified in terms of oxide, but a part or all of each metal in the sintered body is compounded. The form of the oxide exists. Further, in the component analysis of the sintered body which is generally used, the content of each metal is not measured by measuring the content of each oxide.

The sintered body of the present invention is characterized in that an oxide of Al in an amount of 0.1 to 3.0 mol% in terms of Al ₂ O _{3 is} added in order to impart conductivity. Addition of an Al oxide exceeding this range makes it difficult to impart desired conductivity.

Further, the sintered body of the present invention is characterized in that an oxide of Mg and/or Si is added in order to lower the refractive index. MgO and SiO ₂ can be added separately or in combination, and both methods can be used for the purpose of the invention. In general, when MgO and/or SiO ₂ is 27 mol% or more, the bulk resistance value becomes high, and DC sputtering becomes difficult. However, according to the present invention, even if MgO and/or SiO ₂ is 27 mol% or more, A bulk resistance value to the extent that DC sputtering can be performed is obtained. On the other hand, when it exceeds 70 mol%, it is difficult to maintain low bulk resistance, which is not preferable.

Further, the sintered body of the present invention has a bulk resistance value which is capable of DC sputtering, and is preferably 10 Ω. Below cm. Better at 1 Ω. Below cm.

Further, the sintered body of the present invention preferably has a relative density of 90% or more. By setting the relative density to 90% or more, the film thickness uniformity of the film formed by sputtering can be improved.

Further, the present invention is characterized in that it contains 0.1 to 5 wt% of a metal in terms of oxide, and the metal forms an oxide having a melting point of 1000 ° C or lower. By adding an oxide having a melting point of 1000 ° C or less, it is possible to sinter at a low temperature and increase the density, and it is possible to perform stable sputtering without abnormal discharge. As the low melting point oxide, in particular, it is selected from the group consisting of B ₂ O ₃ , P ₂ O ₅ , K ₂ O, V ₂ O ₅ , Sb ₂ O ₃ , TeO ₂ , Ti ₂ O ₃ , PbO, Bi ₂ O ₃ The material in MoO ₃ is effective. If the content is less than 0.1% by weight, the above effects cannot be sufficiently obtained. If it exceeds 5% by weight, the properties are affected by the composition, which is not preferable.

The sintered body sputtering target of the present invention is suitable for industrially producing a low refractive index having a refractive index of 2.00 or less with respect to light having a wavelength of 550 nm or less. Optical film for optical discs. In particular, a target for forming a protective layer, a reflective layer or a semi-transmissive layer of an optical information recording medium can be used.

When the sputtering target of the present invention is produced, the raw material Al ₂ O ₃ powder is 0.1 to 3.0 mol%, the MgO and/or SiO ₂ powder is 27 to 70 mol%, and the remainder is ZnO powder, which becomes 100 mol%. In the manner, the basic raw material powder is adjusted, and then the mixed powder is sintered at a temperature of 1050 ° C or more and 1500 ° C or less.

A particularly important point in the present invention is the sintering in an inert gas or vacuum environment. A portion of ZnO can be depleted by sintering in an inert gas or vacuum environment. Conductivity can be obtained by the lack of oxygen, and a sintered body having a low bulk resistance value capable of DC sputtering can be produced. The ambient gas is argon gas, nitrogen gas or the like, and can be generally used as a so-called inert atmosphere gas.

Further, the Al ₂ O ₃ powder as a raw material and the ZnO powder may be previously mixed and calcined in advance, and then the pre-sintered Al ₂ O ₃ -ZnO powder (AZO powder) may be mixed with MgO and/or SiO _{2 .} The powder is sintered. When only MgO and/or SiO ₂ powder is added, Al ₂ O ₃ reacts with MgO and/or SiO ₂ to easily become a spinel, and the bulk resistance value tends to increase. Therefore, in order to achieve lower bulk resistance of the sintered body, pre-sintered Al ₂ O ₃ -ZnO powder (AZO powder) is preferably used for sintering.

It is further proposed that the Al ₂ O ₃ powder as a raw material and the ZnO powder are previously mixed and pre-fired to form an AZO powder, and the MgO powder as a raw material is mixed with the SiO ₂ powder in the same manner and calcined, and then The MgO-SiO ₂ calcined powder was mixed with the calcined Al ₂ O ₃ -ZnO powder (AZO powder) for sintering. This is because the spinel and petrochemical can be further suppressed and the low bulk resistance can be achieved.

In the present invention, 0.1 to 5 wt% of a low-melting oxide powder having a melting point of 1000 ° C or less may be further added thereto. Further, it is also effective to mix the low-melting oxide powder in the pre-calcined powder which has been previously mixed and calcined.

The present invention is a sintered body having such a composition, which can maintain electrical conductivity and can form a film by DC sputtering (DC sputtering). DC sputtering Compared with RF sputtering, the film formation speed is fast and the sputtering efficiency is good, so it is excellent and can significantly increase the yield. Moreover, the DC sputtering device has the advantages of being cheap, easy to control, and low in power consumption. Since the thickness of the protective film itself can be made thin, the effect of improving productivity and preventing heating of the substrate can be further exhibited.

Example

Hereinafter, description will be given based on examples and comparative examples. In addition, this embodiment is only an example and is not limited by this illustration. That is, the present invention is limited only by the scope of the patent application, and includes various modifications other than the embodiments included in the invention.

(Example 1)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as The basic raw materials were adjusted so that the ratio of the basic raw materials was 100 mol% as shown in Table 1, and then B ₂ O ₃ powder having an average particle diameter of 5 μm or less of ₃ N was blended in the ratio shown in Table 1 to the basic material. A raw material, wherein the B ₂ O ₃ powder is a low melting point oxide having a melting point of 1000 ° C or less. Then, after mixing them, hot pressing (HP) was performed at a temperature of 1050 ° C in an argon atmosphere. The pressure of hot pressing was 220 kg/cm ² .

After sintering, the sintered body is machined into a target shape by mechanical processing. The density of the sintered body target is 100.0%, and the volume resistance is 3.2×10 ^-3 Ω. Cm (3.2 mΩ.cm). In addition, the density indicated in the present specification means relative density. The relative density is obtained by first measuring the density of the target of the obtained composite oxide with respect to the theoretical density of the target obtained from the density of the raw material, and then determining the relative density from each density. Since it is not a simple mixture of raw materials, as shown in Table 1, there is an example in which the relative density exceeds 100%.

Use the above-mentioned finished 6吋 The target of size is sputtered. The sputtering conditions were DC sputtering, sputtering power of 500 W, Ar-2% O ₂ mixed gas pressure of 0.5 Pa, and film formation to a film thickness of 1500 Å. The film formation speed reaches 2.8Å/sec, which can be used for stable DC sputtering and has good sputtering properties. The refractive index (wavelength 550 nm) of the film-forming sample was 1.92, the volume resistivity was 2E+05 (2 × 10 ⁵ Ω·cm), and the extinction coefficient (λ = 450 nm): <0.01. The conditions and results of these conditions are summarized in Table 1.

(Example 2)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as The basic raw materials were adjusted so that the ratio of the basic raw materials was 100 mol% as shown in Table 1, and then B ₂ O ₃ powder having an average particle diameter of 5 μm or less of ₃ N was blended in the ratio shown in Table 1 to the basic material. A raw material, wherein the B ₂ O ₃ powder is a low melting point oxide having a melting point of 1000 ° C or less. Then, after mixing them, hot pressing (HP) was performed at a temperature of 1050 ° C in an argon atmosphere. The pressure of hot pressing was 220 kg/cm ² .

After sintering, the sintered body is machined into a target shape by mechanical processing. The density of the sintered body target is 99.5%, and the volume resistance is 2.9×10 ^-3 Ω. Cm (2.9 mΩ.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1. As a result, it can be used for stable DC sputtering and has good sputtering properties. The refractive index (wavelength 550 nm) of the film-forming sample was 1.90, the volume resistivity was 6E+04 (6 × 10 ⁴ Ω·cm), and the extinction coefficient (λ = 450 nm): <0.01.

(Example 3)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as The basic raw materials were adjusted so that the ratio of the basic raw materials was 100 mol% as shown in Table 1, and then B ₂ O ₃ powder having an average particle diameter of 5 μm or less of ₃ N was blended in the ratio shown in Table 1 to the basic material. A raw material, wherein the B ₂ O ₃ powder is a low melting point oxide having a melting point of 1000 ° C or less. Then, after mixing them, hot pressing (HP) was performed at a temperature of 1050 ° C in an argon atmosphere. The pressure of hot pressing was 220 kg/cm ² .

After sintering, the sintered body is machined into a target shape by mechanical processing. The density of the sintered body target is 99.8%, and the bulk resistance is 3.0×10 ^-3 Ω. Cm (3.0 mΩ.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1. As a result, it can be used for stable DC sputtering and has good sputtering properties. The refractive index (wavelength 550 nm) of the film-forming sample was 1.93, the volume resistivity was 4E+05 (4 × 10 ⁵ Ω·cm), and the extinction coefficient (λ = 450 nm): <0.01.

(Example 4)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as The basic raw materials were adjusted so that the ratio of the basic raw materials was 100 mol% as shown in Table 1, and then B ₂ O ₃ powder having an average particle diameter of 5 μm or less of ₃ N was blended in the ratio shown in Table 1 to the basic material. A raw material, wherein the B ₂ O ₃ powder is a low melting point oxide having a melting point of 1000 ° C or less. Then, after mixing them, hot pressing (HP) was performed at a temperature of 1050 ° C in an argon atmosphere. The pressure of hot pressing was 220 kg/cm ² .

After sintering, the sintered body is machined into a target shape by mechanical processing. The density of the sintered body target is 107.9%, and the volume resistance is 3.7×10 ^-1 Ω. Cm (0.37 Ω.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1. As a result, it can be used for stable DC sputtering and has good sputtering properties. The refractive index (wavelength 550 nm) of the film-forming sample was 1.70, the volume resistivity was 8E+08 (8 × 10 ⁸ Ω·cm), and the extinction coefficient (λ = 450 nm): <0.01.

(Example 5)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as The basic raw materials were adjusted so that the ratio of the basic raw materials was 100 mol% as shown in Table 1, and then B ₂ O ₃ powder having an average particle diameter of 5 μm or less of ₃ N was blended in the ratio shown in Table 1 to the basic material. A raw material, wherein the B ₂ O ₃ powder is a low melting point oxide having a melting point of 1000 ° C or less. Then, after mixing them, hot pressing (HP) was performed at a temperature of 1050 ° C in an argon atmosphere. The pressure of hot pressing was 220 kg/cm ² .

After sintering, the sintered body is machined into a target shape by mechanical processing. The density of the sintered body target is 98.1%, and the volume resistance is 9.0×10 ^-1 Ω. Cm (0.9 Ω.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1. As a result, it can be used for stable DC sputtering and has good sputtering properties. The refractive index (wavelength 550 nm) of the film-forming sample was 1.83, the volume resistivity was 4E+05 (4 × 10 ⁸ Ω·cm), and the extinction coefficient (λ = 450 nm): <0.01.

(Example 6)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as The basic raw materials were adjusted so that the ratio of the basic raw materials was 100 mol% as shown in Table 1, and then B ₂ O ₃ powder having an average particle diameter of 5 μm or less of ₃ N was blended in the ratio shown in Table 1 to the basic material. A raw material, wherein the B ₂ O ₃ powder is a low melting point oxide having a melting point of 1000 ° C or less. Then, after mixing them, hot pressing (HP) was performed at a temperature of 1050 ° C in an argon atmosphere. The pressure of hot pressing was 220 kg/cm ² .

After sintering, the sintered body is machined into a target shape by mechanical processing. The sintered body target has a density of 101.5% and a bulk resistance of 2.8×10 ^-3 Ω. Cm (2.8 mΩ.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1. As a result, it can be used for stable DC sputtering and has good sputtering properties. The refractive index (wavelength 550 nm) of the film-forming sample was 1.88, the volume resistivity was 5E+07 (5 × 10 ⁷ Ω·cm), and the extinction coefficient (λ = 450 nm): <0.01.

(Example 7)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as The basic raw materials and the ratio of the basic raw materials were adjusted so that the total amount was 100 mol% as shown in Table 1. Then, after mixing them, hot pressing (HP) was performed at 1200 ° C in an argon atmosphere. The pressure of hot pressing was 220 kg/cm ² .

After sintering, the sintered body is machined into a target shape by mechanical processing. The density of the sintered body target is 97.8%, and the volume resistance is 1.6×10 ^-3 Ω. Cm (1.6 mΩ.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1. As a result, it can be used for stable DC sputtering and has good sputtering properties. The refractive index (wavelength 550 nm) of the film-forming sample was 1.92, the volume resistivity was 2E+05 (2 × 10 ⁵ Ω·cm), and the extinction coefficient (λ = 450 nm): <0.01.

(Example 8)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as The basic raw materials were adjusted so that the ratio of the basic raw materials was 100 mol% as shown in Table 1, and then B ₂ O ₃ powder having an average particle diameter of 5 μm or less of ₃ N was blended in the ratio shown in Table 1 to the basic material. A raw material, wherein the B ₂ O ₃ powder is a low melting point oxide having a melting point of 1000 ° C or less. Next, after mixing them, it sintered at 1400 degreeC in argon atmosphere.

After sintering, the sintered body is machined into a target shape by mechanical processing. The sintered body target has a density of 94.5% and a bulk resistance of 3.0×10 ^-3 Ω. Cm (3.0 mΩ.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1. As a result, it can be used for stable DC sputtering and has good sputtering properties. The refractive index (wavelength 550 nm) of the film-forming sample was 1.92, the volume resistivity was 3E+05 (3 × 10 ⁵ Ω·cm), and the extinction coefficient (λ = 450 nm): <0.01.

(Comparative Example 1)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as The basic raw materials were adjusted so that the ratio of the basic raw materials was 100 mol% as shown in Table 1, and then B ₂ O ₃ powder having an average particle diameter of 5 μm or less of ₃ N was blended in the ratio shown in Table 1 to the basic material. A raw material, wherein the B ₂ O ₃ powder is a low melting point oxide having a melting point of 1000 ° C or less. Then, after mixing them, it was sintered at 1200 ° C under the atmosphere.

After sintering, the sintered body is machined into a target shape by mechanical processing. The sintered body target has a density of 90.9% and a bulk resistance of more than 1×10 ³ Ω. The value of cm (1 kΩ.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1, but stable DC sputtering could not be performed.

(Comparative Example 2)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as The basic raw materials were adjusted so that the ratio of the basic raw materials was 100 mol% as shown in Table 1, and then B ₂ O ₃ powder having an average particle diameter of 5 μm or less of ₃ N was blended in the ratio shown in Table 1 to the basic material. A raw material, wherein the B ₂ O ₃ powder is a low melting point oxide having a melting point of 1000 ° C or less. Then, after mixing them, hot pressing (HP) was performed at a temperature of 1050 ° C in an argon atmosphere. The pressure of hot pressing was 220 kg/cm ² .

After sintering, the sintered body is machined into a target shape by mechanical processing. The density of the sintered body target is 98.7%, but the bulk resistance is more than 1 × 10 ³ Ω. The value of cm (1 kΩ.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1, but stable DC sputtering could not be performed. Further, the refractive index (wavelength: 550 nm) of the film-forming sample was 1.67.

(Example 9)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as The basic raw material was adjusted so that the ratio of the basic composition was 100 mol% as shown in Table 1, and then B ₂ O ₃ powder having an average particle diameter of 5 μm or less of ₃ N was blended in the ratio shown in Table 1 to the basic A raw material, wherein the B ₂ O ₃ powder is a low melting point oxide having a melting point of 1000 ° C or less. Then, after mixing them, hot pressing (HP) was performed at a temperature of 1050 ° C in an argon atmosphere. The pressure of hot pressing was 220 kg/cm ² .

After sintering, the sintered body is machined into a target shape by mechanical processing. The density of the sintered body target is 99.2%, and the volume resistance is 3.0×10 ^-3 Ω. Cm (3.0 mΩ.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1. As a result, it can be used for stable DC sputtering and has good sputtering properties. The refractive index (wavelength 550 nm) of the film-forming sample was 1.93, the volume resistivity was 3E+05 (3 × 10 ⁵ Ω·cm), and the extinction coefficient (λ = 450 nm): <0.01.

(Embodiment 10)

ZnO powder of 5 μm or less, 3N or less, MgO powder having an average particle diameter of 5 μm or less, and Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as a basic raw material, and the ratio of the basic raw material is adjusted. The total amount shown in Figure 1 is 100 mol%, and then a B ₂ O ₃ powder having an average particle diameter of 5 μm or less of ₃ N is blended in the ratio shown in Table 1 to the base material, wherein the B ₂ O ₃ powder has a melting point of 1000. Low melting point oxide below °C. Next, these powders were adjusted to the blend ratio shown in Table 1, and after mixing, they were subjected to hot pressing (HP) at a temperature of 1,050 ° C in an argon atmosphere. The pressure of hot pressing was 220 kg/cm ² .

After sintering, the sintered body is machined into a target shape by mechanical processing. The density of the sintered body target is 99.6%, and the volume resistance is 2.0×10 ^-3 Ω. Cm (2.0 mΩ.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1. As a result, it can be used for stable DC sputtering and has good sputtering properties. The refractive index (wavelength 550 nm) of the film-forming sample was 1.93, the volume resistivity was 9E+04 (9×10 ⁴ Ω·cm), and the extinction coefficient (λ=450 nm): <0.01.

(Example 11)

ZnO powder of 5 μm or less, 3N or less, Al ₂ O ₃ powder having an average particle diameter of 5 μm or less, and SiO ₂ powder having an average particle diameter of 5 μm or less, which is equivalent to 3N, are used as a basic raw material, and the ratio of the basic raw material is adjusted. The total amount shown in Table 1 was 100 mol%, and then a B ₂ O ₃ powder having an average particle diameter of 5 μm or less corresponding to 3 N was blended in the base material in a ratio shown in Table 1, wherein the B ₂ O ₃ powder was a melting point at Low melting point oxide below 1000 °C. Then, after mixing them, hot pressing (HP) was performed at a temperature of 1050 ° C in an argon atmosphere. The pressure of hot pressing was 220 kg/cm ² .

After sintering, the sintered body is machined into a target shape by mechanical processing. The density of the sintered body target is 99.3%, and the volume resistance is 4.0×10 ^-3 Ω. Cm (4.0 mΩ.cm). Also, using the above-mentioned finished 6吋 The target of the size was sputtered under the same conditions as in Example 1. As a result, it can be used for stable DC sputtering and has good sputtering properties. The refractive index (wavelength 550 nm) of the film-forming sample was 1.92, volume resistivity: 6E+07 (6 × 10 ⁷ Ω·cm), extinction coefficient (λ = 450 nm): <0.01.

Industrial availability

The present invention is characterized in that even in the case of adjusting the composition for lowering the refractive index, by sintering in an inert gas or a vacuum atmosphere, the low body resistance of the sintered body can be achieved, and stable DC sputtering can be performed. plating. Therefore, it has the remarkable effect of the following DC sputtering characteristics, that is, the controllability of sputtering can be made easy, the film formation speed can be improved, and the sputtering efficiency can be improved. Further, it is possible to reduce the unevenness of particles (dust) and protrusions and quality which occur at the time of sputtering at the time of film formation, and to improve mass productivity.

The sintered body sputtering target of the present invention is extremely suitable for forming a film for an optical film, an organic EL television, an electrode for a touch panel, a seed layer of a hard disk, or the like.

Claims (7)

A sintered body composed of zinc (Zn), aluminum (Al), magnesium (Mg), and/or bismuth (Si), and oxygen (O), and the content of Al is 0.1 to 3.0 mol% in terms of Al ₂ O ₃ . The total content of Mg and/or Si is 27 to 70 mol% in terms of MgO and/or SiO ₂ , and the remainder is a content of Zn in terms of ZnO, and contains a metal forming an oxide having a melting point of 1000 ° C or less. The content of the metal is 0.1 to 5 wt% in terms of oxide weight, and the bulk resistance of the sintered body is 10 Ω‧ cm or less. The sintered body of the first aspect of the patent application has a relative density of 90% or more. The sintered body according to claim 1 or 2, wherein the oxide is selected from the group consisting of B ₂ O ₃ , P ₂ O ₅ , K ₂ O, V ₂ O ₅ , Sb ₂ O ₃ , TeO ₂ , Ti ₂ One or more materials of O ₃ , PbO, Bi ₂ O ₃ , and MoO ₃ . The sintered body according to any one of claims 1 to 3, which is used as a sputtering target. A film obtained by sputtering using a sintered body of the fourth aspect of the patent application has a refractive index of 2.0 or less. A method for producing a sintered body, wherein the Al ₂ O ₃ powder is 0.1 to 3.0 mol%, the MgO and/or SiO ₂ powder is 27 to 70 mol%, and the balance is ZnO powder, and the total amount is 100 mol%. The raw material powder is sintered at a temperature of 1050 ° C or higher and 1500 ° C or lower in an inert gas or a vacuum atmosphere. The method for producing a sintered body according to claim 6, wherein 0.1 to 5 wt% of an oxide powder having a melting point of 1000 ° C or less is further added to prepare a raw material powder.