KR20220087425A - oxide sputtering target - Google Patents

Abstract

One aspect of this oxide sputtering target is an oxide composed of a metal component and oxygen, wherein the metal component contains Al in an amount within the range of 0.3 mass% or more and 3.7 mass% or less, with the total content of the metal component being 100 mass%, Si contains 6.0 mass% or more and 14.5 mass% or less, and an M element consisting of one or two or more selected from Zr, Hf, and Y in a total amount within the range of 0.003 mass% or more and 0.1 mass% or less, and It consists of additional Zn and unavoidable impurities.

Description

oxide sputtering target

The present invention relates to an oxide sputtering target made of an oxide containing zinc, aluminum, and silicon as a metal component.

This application claims priority on the basis of Japanese Patent Application No. 2019-192591, filed in Japan on October 23, 2019 and Japanese Patent Application No. 2020-176125, filed on October 20, 2020 in Japan, the contents of which invoke it here

As a metal component, the oxide film containing zinc, aluminum, and silicon is various devices, such as a liquid crystal display element, an organic electroluminescent element, and a solar cell, as disclosed by patent documents 1 and 2, for example. WHEREIN: Water vapor|steam or atmosphere It is used as a barrier film protecting from gas.

Here, the oxide film mentioned above is formed into a film by sputtering using the sputtering target which consists of an oxide, as shown to the following patent documents 1 - 4, for example. In addition, as a sputtering target mentioned above, what makes a flat plate shape or a cylindrical shape is provided, for example.

Patent Documents 1 and 2 describe forming an oxide film using an oxide sputtering target containing zinc, aluminum, and silicon and having a ZnO phase and a complex oxide phase (Zn ₂ SiO ₄ phase).

Patent Document 3 describes that in an oxide sputtering target containing zinc, aluminum, and silicon, by limiting the particle size of the composite oxide phase (Zn ₂ SiO ₄ phase) to 5 µm or less, it is described that the occurrence of abnormal discharge is suppressed. .

Patent Document 4 describes that B ₂ O ₃ or MoO ₃ is added to an oxide sputtering target containing zinc, aluminum, and silicon.

By the way, when forming an oxide film into a film using the oxide sputtering target mentioned above, it is necessary to suppress generation|occurrence|production of the abnormal discharge at the time of sputtering.

Here, in Patent Document 3, the occurrence of abnormal discharge was suppressed by limiting the particle size of the composite oxide phase (Zn ₂ SiO ₄ phase) to 5 µm or less, but grain growth of the ZnO phase could not be suppressed.

Moreover, also in patent document 4, grain growth of a ZnO phase could not be suppressed.

Here, when the particle size of the ZnO phase was coarsened in an oxide sputtering target, when it used for a long time, there existed a possibility that the generation|occurrence|production of the abnormal discharge resulting from this particle could not be suppressed existed that it could generate|occur|produce a particle.

Moreover, in order to suppress the generation|occurrence|production of the abnormal discharge resulting from this particle, it was necessary to release the apparatus during use and to perform the cleaning operation|work of a sputtering target. For this reason, there existed a possibility that film-forming of an oxide film could not be performed efficiently.

Japanese Patent Laid-Open No. 2013-189657 Japanese Laid-Open Patent Publication No. 2015-163741 Japanese Patent Laid-Open No. 2014-055348 Japanese Patent Application Laid-Open No. 2014-141386

The present invention has been made in view of the above circumstances, and it is an object to provide an oxide sputtering target capable of suppressing the generation of particles even when used for a long period of time and capable of suppressing the occurrence of abnormal discharge caused by these particles. .

In order to solve the above problems, an oxide sputtering target according to an aspect of the present invention is an oxide composed of a metal component and oxygen, and the metal component has a total content of the metal component of 100 mass%, Al is 0.3 mass % or more and 3.7 mass% or less, Si in an amount in the range of 6.0 mass% or more and 14.5 mass% or less, and M element consisting of one or two or more selected from Zr, Hf and Y 0.003 mass% or more 0.1 It is characterized in that it is contained in a total amount within the range of mass% or less, and the balance consists of Zn and unavoidable impurities.

According to the oxide sputtering target of this configuration, the total content of the metal component is 100 mass%, Al and Si are contained in the above-mentioned ranges, and one or two or more selected from Zr, Hf, Y. The M element formed is contained in a total amount within the range of 0.003 mass% or more and 0.1 mass% or less.

The above-mentioned M element has the effect|action which suppresses the grain growth of ZnO, and can suppress small the particle size of the ZnO phase in an oxide sputtering target. Thereby, even when it is used for a long time, generation of particles can be suppressed, and it becomes possible to suppress the generation of abnormal discharge resulting from these particles.

In addition, the oxide sputtering target according to an aspect of the present invention is an oxide comprising a metal component, C, and oxygen, wherein the metal component and the C have a total content of the metal component and the C of 100 mass%, Al is contained in an amount within the range of 0.3 mass% to 3.7 mass%, Si in an amount within the range of 6.0 mass% to 14.5 mass%, and C in an amount within the range of 0.03 mass% to 1.0 mass%, the balance being Zn and unavoidable impurities.

Further, in one aspect of the present invention, Si is included in the metal component.

According to the oxide sputtering target having this configuration, the total content of the metal component and C is 100 mass%, Al and Si are contained in the above-mentioned ranges, and C is contained within the range of 0.03 mass% or more and 1.0 mass% or less. is supposed to contain.

C has the effect of suppressing the grain growth of ZnO, and can suppress the grain size of the ZnO phase in an oxide sputtering target small. Thereby, even when it is used for a long time, generation of particles can be suppressed, and it becomes possible to suppress the generation of abnormal discharge resulting from these particles.

In addition, the oxide sputtering target according to an aspect of the present invention is an oxide comprising a metal component, C, and oxygen, wherein the metal component and the C have a total content of the metal component and the C of 100 mass%, Al An amount within the range of 0.3 mass% to 3.7 mass%, Si in an amount within the range of 6.0 mass% to 14.5 mass%, and an M element consisting of one or two or more selected from Zr, Hf, and Y 0.003 mass % or more and 0.1 mass% or less, C is contained in an amount within the range of 0.03 mass% or more and 1.0 mass% or less, and the balance consists of Zn and unavoidable impurities.

According to the oxide sputtering target having this configuration, the total content of the metal component and C is 100 mass%, Al and Si are contained in the above-mentioned ranges, and one or two types selected from Zr, Hf, and Y The M element composed of the above is contained in a total amount within the range of 0.003 mass% or more and 0.1 mass% or less, and C is contained within the range of 0.03 mass% or more and 1.0 mass% or less.

The above-mentioned M element and C have the effect|action which suppresses the grain growth of ZnO, and can suppress the particle size of the ZnO phase in an oxide sputtering target small. Thereby, even when it is used for a long time, generation of particles can be suppressed, and it becomes possible to suppress the generation of abnormal discharge resulting from these particles.

Here, in the oxide sputtering target according to one aspect of the present invention, it is preferable that it has a ZnO phase and a Zn ₂ SiO ₄ phase, the average particle diameter of the ZnO phase is 5 μm or less, and the average particle diameter of the Zn ₂ SiO ₄ phase is 5 μm or less. .

In this case, since the average particle diameter of the Zn ₂ SiO ₄ phase is limited to 5 µm or less, the occurrence of abnormal discharge due to the Zn ₂ SiO ₄ phase can be suppressed. And, since the average particle diameter of the ZnO phase is limited to 5 µm or less, generation of particles can be suppressed even when used for a long time, and it becomes possible to suppress the occurrence of abnormal discharge caused by these particles.

Moreover, in the oxide sputtering target which concerns on one aspect of this invention, it has a ZnO phase and _a Zn2SiO4 phase, and _in the measurement range of 25000 micrometers, the diameter (equivalent to a circle|round|yen) is within the range of 10 micrometers or more and 25 micrometers or less. It is preferable that the number of ZnO phases is 10 or less.

In this case, the number of relatively coarse ZnO phases within the range of 10 μm or more and 25 μm or less in diameter (equivalent to circular diameter) is suppressed, and generation of particles can be suppressed even when used for a long time, and abnormal discharge caused by these particles is suppressed. It becomes possible to suppress the occurrence.

ADVANTAGE OF THE INVENTION According to one aspect of this invention, while being able to suppress generation|occurrence|production of an abnormal discharge, a specific resistance value is sufficiently low, and it becomes possible to provide the sputtering target in which DC sputtering is possible stably.

Below, the oxide sputtering target which is embodiment of this invention is demonstrated. In addition, the oxide sputtering target which is this embodiment is used when forming into a film the oxide film used as a gas barrier film.

The oxide sputtering target according to the first embodiment of the present invention consists of an oxide consisting of a metal component, oxygen, and an unavoidable impurity, wherein the metal component has a total content of the metal component of 100 mass%, and contains Al at 0.3 mass% or more 3.7 An amount within the range of mass% or less, an amount of Si within the range of 6.0 mass% or more and 14.5 mass% or less, and 0.003 mass% or more and 0.1 mass% or less of M element consisting of one or two or more selected from Zr, Hf, and Y It contains a total amount within the range of , and has a composition in which the balance consists of Zn and an unavoidable metal.

The oxide sputtering target according to the second embodiment of the present invention consists of a metal component, an oxide consisting of C and oxygen, and unavoidable impurities, wherein the metal component and C have a total content of the metal component and C of 100 mass%, and Al is contained in an amount within the range of 0.3 mass% to 3.7 mass%, Si in an amount within the range of 6.0 mass% to 14.5 mass%, and C in an amount within the range of 0.03 mass% to 1.0 mass%, the balance being Zn and an unavoidable metal.

The oxide sputtering target according to the third embodiment of the present invention consists of a metal component, an oxide composed of C and oxygen, and unavoidable impurities, wherein the metal component and C have a total content of the metal component and C of 100 mass%, and Al An amount within the range of 0.3 mass% to 3.7 mass%, Si in an amount within the range of 6.0 mass% to 14.5 mass%, and an M element consisting of one or two or more selected from Zr, Hf, and Y 0.003 mass % or more and 0.1 mass% or less, C is contained in an amount within the range of 0.03 mass% or more and 1.0 mass% or less, and the balance is composed of Zn and an unavoidable metal.

In the first embodiment, the unavoidable impurities are elements other than oxygen and metal components.

In the 2nd and 3rd embodiment, an unavoidable impurity is oxygen, C, and elements other than a metal component.

The unavoidable metal is an element whose content was specified, and a metal element other than Zn. In addition, it is assumed that semimetals, such as Si, are contained in a metal component. For this reason, semimetals are contained in an unavoidable metal.

Here, in the oxide sputtering target according to the first to third embodiments of the present invention, it has a ZnO phase and a Zn ₂ SiO ₄ phase, the average particle diameter of the ZnO phase is 5 μm or less, and the average particle diameter of the Zn ₂ SiO ₄ phase is 5 μm or less. it is preferable

Moreover, in the oxide sputtering target which is 1st - 3rd Embodiment of this invention, it has a ZnO phase and a Zn2SiO4 phase, In the measurement range of 25000 micrometers, _{WHEREIN :} The ZnO phase in the range of 10 micrometers or more and 25 micrometers or less in diameter. It is preferable that the number is 10 or less.

Below, the composition of the oxide sputtering target of this embodiment, the content of M element and C, the average particle size of the ZnO phase and Zn ₂ SiO ₄ phase, and the number of ZnO phases within the range of 10 µm or more and 25 µm or less in diameter are as described above. The reason for the same rule will be explained.

(Al)

In the present embodiment, the reason why the content of Al is within the range of 0.3 mass% or more and 3.7 mass% or less is shown below. If the Al content is less than 0.3 mass%, sufficient conductivity cannot be obtained, abnormal discharge occurs, and stable DC sputtering for a long time cannot be performed. When the content of Al exceeds 3.7 mass%, abnormal discharge resulting from the generated Al ₂ O ₃ and the complex oxide ZnAl ₂ O ₄ of ZnO occurs, and DC sputtering cannot be performed. The Al content is preferably 0.5 mass% or more and 2.9 mass% or less.

(Si)

In this embodiment, the reason why content of Si was made into the range of 6.0 mass % or more and 14.5 mass % or less is shown below. When the Si content is less than 6.0 mass%, a sufficient effect of increasing the transmittance cannot be obtained. Moreover, water vapor barrier property also falls. When the Si content exceeds 14.5 mass%, sufficient electrical conductivity cannot be obtained, abnormal discharge occurs, and stable DC sputtering for a long time cannot be performed. The content of Si is preferably 8.0 mass% or more and 12.0 mass% or less.

(M element)

The element M composed of one or two or more selected from Zr, Hf, and Y exists as an oxide or is dissolved in ZnO phase. Furthermore, the M element produces|generates a complex oxide. Thereby, the M element has an effect of inhibiting grain growth of the ZnO phase.

Here, if the total content of the element M composed of one or two or more selected from Zr, Hf, and Y is less than 0.003 mass%, the above-described effects cannot be obtained. On the other hand, when the total content of the M element composed of one or two or more selected from Zr, Hf, and Y exceeds 0.1 mass%, there is a fear that the M element itself may cause abnormal discharge.

From the above, in the present embodiment, the content of the element M composed of one or two or more selected from Zr, Hf, and Y is set to be in the range of 0.003 mass% or more and 0.1 mass% or less.

In addition, the lower limit of the content of the element M composed of one or two or more selected from Zr, Hf, and Y is preferably 0.004 mass% or more, more preferably 0.005 mass% or more, and most preferably 0.02 mass% or more. . On the other hand, the upper limit of the content of the element M composed of one or two or more selected from Zr, Hf, and Y is preferably 0.09 mass% or less, more preferably 0.08 mass% or less, and most preferably 0.008 mass% or less. .

(C)

C (carbon) has an effect of inhibiting grain growth of the ZnO phase due to the difference in atomic radius.

Here, if the total content of C is less than 0.03 mass%, the above-described effects cannot be obtained. On the other hand, when the content of C exceeds 1.0 mass%, there is a fear that the transmittance of the formed oxide film is lowered.

From the above, in this embodiment, the content of C is made into the range of 0.03 mass% or more and 1.0 mass% or less.

The lower limit of the C content is preferably 0.04 mass% or more, more preferably 0.05 mass% or more, and most preferably 0.1 mass% or more. On the other hand, the upper limit of the C content is preferably 0.9 mass% or less, more preferably 0.8 mass% or less, still more preferably 0.6 mass% or less, and most preferably 0.4 mass% or less.

Here, when the above-mentioned element M and C are co-added, the total content of the element M is within the range of 0.003 mass% or more and 0.1 mass% or less, and the content of C is within the range of 0.03 mass% or more and 1.0 mass% or less. do.

In addition, when the total content of M element is 0.08 mass% or more and 0.1 mass% or less, it is preferable that the content of C falls within the range of 0.03 mass% or more and 0.6 mass% or less. Moreover, when the content of C is 0.9 mass% or more and 1.0 mass% or less, it is preferable that the total content of the M element falls within the range of 0.03 mass% or more and 0.08 mass% or less.

(Average particle size of Zn ₂ SiO ₄ phase)

In the oxide sputtering target of this embodiment, when the average particle diameter of the Zn ₂ SiO ₄ phase is limited to 5 µm or less, it becomes possible to suppress the occurrence of an abnormal discharge resulting from the Zn ₂ SiO ₄ phase.

Moreover, it is preferable that it is 4.8 micrometers or less, as for the average particle diameter _{of Zn2SiO4} phase, it is more preferable that it is 3.5 micrometers or less, It is more preferable that it is 2.7 micrometers or less. Although the lower limit in particular of the average particle diameter _{of Zn2SiO4} phase is not restrict|limited, It becomes 2.0 micrometers or more substantially. It is thought that this originates in the maximum amount of carbon and M element added.

(Average particle diameter of ZnO phase)

In the oxide sputtering target of the present embodiment, when the average particle diameter of the ZnO phase is limited to 5 µm or less, the generation of particles can be suppressed even after long-term use, and the occurrence of abnormal discharge due to the particles can be suppressed. .

Further, the average particle diameter of the ZnO phase is preferably 4.9 µm or less, more preferably 3.5 µm or less, still more preferably 2.1 µm or less, and most preferably 1.0 µm or less. Although the lower limit in particular of the average particle diameter of a ZnO phase is not restrict|limited, It becomes 0.6 micrometer or more substantially. It is thought that this originates in the maximum amount of carbon and M element added.

(The number of ZnO phases within the range of 10 μm or more and 25 μm or less in diameter)

In the oxide sputtering target of this embodiment, in the measurement range of 25000 µm, when the number of ZnO phases in the range of 10 µm or more and 25 µm or less in diameter (equivalent to a circle) is 10 or less, there are many relatively coarse ZnO phases It does not exist, and generation|occurrence|production of a particle can be suppressed even if it uses for a long time, and it becomes possible to suppress generation|occurrence|production of the abnormal discharge resulting from a particle.

Moreover, in the measurement range of 25000 micrometers, it is preferable that it is 4 or less, and, as for the number of ZnO phases in the range of 10 micrometers or more and 25 micrometers or less in diameter (equivalent circle diameter), it is more preferable that it is two or less.

Moreover, it is preferable that the largest particle diameter of a ZnO phase is 25 micrometers or less.

Next, the manufacturing method of the oxide sputtering target which is this embodiment is demonstrated.

First, various raw material powders such as aluminum oxide powder (Al ₂ O ₃ powder), silicon oxide powder (SiO ₂ powder), and zinc oxide powder (ZnO powder) are prepared, and these are mixed to obtain a mixed raw material powder.

Here, in the oxide sputtering target of 1st Embodiment, the oxide powder of M element which consists of 1 type(s) or 2 or more types chosen from Zr, Hf, and Y is added. Or by using a zirconia ball in the mixing of the raw material powder by a subsequent ball mill, you may add Zr etc. using the abrasion of a zirconia ball.

Moreover, in the oxide sputtering target of 2nd Embodiment, carbon powder is added. Alternatively, a dispersing agent made of an organic substance or the like may be added to the mixed raw material powder as a carbon source.

In addition, in the oxide sputtering target of 3rd Embodiment, M element and C are added by the various methods mentioned above.

Here, when Zr or the like is added from zirconia balls, since the deterioration state of the zirconia balls greatly affects the amount of addition, variations in the amount of addition often occur, and selection by composition analysis is necessary after target production.

Moreover, when adding C with a dispersing agent etc., the mixed solution of a dispersing agent and raw material powder is dried and granulated by spray drying. Usually, the obtained powder may contain carbon by not carrying out a decarbonization process, although the decarburization process called a degreasing process is essential for decarbonization.

In addition, when adding Zr using the abrasion of zirconia balls, it is necessary to reduce the solvent as much as possible in order to promote wear, so it is effective to add a dispersant for the purpose of preventing solidification during mixing and forming a slurry. . At this time, you may utilize a dispersing agent as a carbon source.

When adding M elements such as C and Zr without using the abrasion of the zirconia balls, a dispersing agent may be added as a C source (carbon source). have. What is necessary is just to select an organic polymeric material which does not evaporate or decompose|disassemble by drying by a hot plate or spray drying, and remains as carbon at the time of hot pressing. In the case of a low molecular weight organic substance, it evaporates, decomposes/evaporates during the process, and cannot be effectively used as a C source in many cases. For this reason, it is preferable to use a high molecular weight organic substance. However, it is preferable to select a polymer organic material that uniformly diffuses into the solvent. As a dispersing agent, polycarboxylic acid is mentioned.

In addition, mixing of powder is not limited to a ball mill, It can implement with a mixer or a blender. For example, it can be mixed by a Henschel mixer, a rocking mixer, or a V-type mixer.

In addition, when spray-drying by adding a dispersing agent, pure water may be used as a solvent, and organic solvents, such as alcohol, may be used on the conditions which do not affect residual carbon.

Next, the mixed raw material powder is filled in a mold, heated while pressurized, and sintered to obtain a sintered body. Here, as a sintering means, the hot press method is employable.

Further, the sintering temperature is in the range of 900°C or more and 1250°C or less (preferably 1000°C or more and 1150°C or less), and the holding time at the sintering temperature is in the range of 2 hours or more and 9 hours or less (preferably 5 hours or more) do it with The pressing pressure is preferably in the range of 100 kgf/cm 2 or more and 350 kgf/cm 2 or less, more preferably 125 kgf/cm 2 or more and 350 kgf/cm 2 or less. Further, the atmosphere is preferably a vacuum atmosphere (50 Pa or less).

Next, the obtained sintered compact is machined. Thereby, the oxide sputtering target which is this embodiment is manufactured.

In the oxide sputtering target of this embodiment having the configuration as described above, the total content of the metal component and C is 100 mass%, Al and Si are contained in the above-mentioned ranges, and Zr, Hf, Y M element composed of one or two or more selected elements is contained within the range of 0.003 mass% or more and 0.1 mass% or less, and C is contained within the range of 0.03 mass% or more and 1.0 mass% or less, and in these M elements and C Thus, the grain growth of ZnO is suppressed.

For this reason, even when it is used for a long time, generation|occurrence|production of a particle can be suppressed and it becomes possible to suppress generation|occurrence|production of the abnormal discharge resulting from this particle.

Moreover, in this embodiment, when the average particle diameter of _the Zn2SiO4 phase is limited to ₅ micrometers or less, generation|occurrence|production _of the abnormal discharge resulting from this _Zn2SiO4 phase can be suppressed.

In addition, in this embodiment, when the average particle diameter of the ZnO phase is limited to 5 µm or less, the generation of particles can be suppressed even when used for a long time, and the occurrence of abnormal discharge caused by these particles can be suppressed. becomes

Moreover, in this embodiment, when the number of ZnO phases in the range of 10 micrometers or more and 25 micrometers or less in diameter in the measurement range of 25000 micrometers is 10 or less, the number of comparatively coarse ZnO phases is suppressed. For this reason, even when it is used for a long time, generation|occurrence|production of a particle can be suppressed and it becomes possible to suppress generation|occurrence|production of the abnormal discharge resulting from this particle.

As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably in the range which does not deviate from the technical requirement of the invention.

Example

Hereinafter, the result of the confirmation experiment performed in order to confirm the effectiveness of this embodiment is demonstrated.

<Invention Examples and Comparative Examples>

As the raw material powder, zinc oxide powder (ZnO powder: purity 99.9 mass% or more, average particle size 1 μm), silicon oxide powder (SiO ₂ powder: purity 99.9 mass% or more, average particle diameter 2 μm), aluminum oxide powder (Al ₂ O ₃ powder: purity 99.9 mass% or more, average particle diameter 0.2 μm), zirconium oxide powder (ZrO ₂ powder: purity 99.9 mass% or more, average particle diameter 1 μm/purity 99.9 mass% or more, particle diameter 20-30 nm), hafnium oxide powder (HfO ₂ powder: purity 99.9 mass% or more, average particle size 0.1 μm), yttrium oxide powder (Y ₂ O ₃ powder: purity 99.9 mass% or more, particle size 30-50 nm), carbon powder (C: purity 99.9 mass% or more) , a particle size of 20 to 50 nm) was prepared. A polycarboxylic acid was prepared as a dispersant. In addition, the value of the powder particle diameter of 0.1 micrometer or more is the measured value by the laser diffraction scattering method, and the value of the powder particle diameter of less than 100 nm is a value obtained by observing the particle|grains using the transmission microscope. The calculated particle size is the number-based median diameter D50.

And by the various manufacturing methods shown below, the M element which consists of 1 type or 2 or more types selected from Zr, Hf, Y, Al, Si, Zn, and C were added, and the oxide sputtering target was manufactured. The manufacturing method used is shown to Tables 1-4.

Moreover, the shape of an oxide sputtering target is shown to Tables 1-4. In Tables 1-4, the "disc plate" shape had the dimension of 152.4 mm diameter x 6 mm thickness. The "cylindrical" shape had dimensions of an outer diameter of 155 mm, an inner diameter of 135 mm, and an axial length of 600 mm. In detail, four things having an outer diameter of 155 mm, an inner diameter of 135 mm, and an axial direction length of 150 mm were connected, and the axial direction length was 600 mm.

(Manufacturing method 1)

The above-mentioned aluminum oxide powder, silicon oxide powder, zinc oxide powder, and the oxide powder of M element shown in Tables 1-4 were weighed and mixed, and the obtained powder was set as the weighed raw material powder.

In mixing, the weighed raw material powder and 4 times the amount (weight ratio) of zirconia balls (a ball of 5 mm in diameter and a ball of 10 mm in diameter are halved by weight) were placed in a pot of a 10 L ball mill. Alcohol was used as a solvent. Alcohol in an amount of 96 mass% based on 100 mass% of the powder was put into the pot so that the slurry had a sufficient viscosity. The mixture was pulverized at a rotation speed of 73 rpm for 24 hours.

The obtained mixed powder was dried with a hot plate. Then, it was assembled by sieving a sieve of a scale size: 500 μm, and vacuum drying was performed.

It vacuum hot-pressed with the temperature (HP temperature) and time (holding time) of Tables 1-4, and the pressure of 200 kgf/cm<2>, and it was set as the sintered compact.

(Manufacturing method 2)

(1) Not using the oxide powder of element M, and (2) adjusting the ball mill conditions (mixing time) to set the Zr content to the value shown in Tables 1 to 4, except for the same as in Manufacturing Method 1 and a sintered compact was obtained.

(Manufacturing method 3)

A sintered body was obtained in the same manner as in Production Method 1, except that the carbon powder was weighed instead of the oxide powder of the M element, and the carbon powder, aluminum oxide powder, silicon oxide powder, and zinc oxide powder were mixed to obtain a weighed raw material powder. .

(Manufacturing method 4)

A sintered body was obtained in the same manner as in Production Method 1, except that (1) no oxide powder of element M was used, and (2) a dispersant was used as a carbon source and the powder was wet-mixed and dried under the following conditions. .

The weighed raw material powder and 4 times the amount (weight ratio) of zirconia balls (a ball having a diameter of 5 mm and a ball having a diameter of 10 mm in half by weight) were placed in a pot of a 100 L ball mill. So that the zirconia balls are not worn, pure water in an amount of 20 mass% or more based on 100 mass% of the powder weight was put into the pot. At this time, the dispersant was put into the pot. It was set as the amount of C shown in Tables 1-4 by adjusting the addition amount of this dispersing agent. And it wet-mixed for 18 hours with the ball mill apparatus, and obtained the mixed powder.

The obtained mixed powder was dried by spray drying. In addition, in order to make carbon remain|survive in a sintered compact, the degreasing|degreasing performed normally was not implemented.

(Manufacturing method 5)

A sintered body was obtained in the same manner as in Production Method 1, except that the carbon powder was weighed and the carbon powder, aluminum oxide powder, silicon oxide powder, zinc oxide powder, and M element oxide powder were mixed to obtain a weighed raw material powder.

(Manufacturing method 6)

(1) Weighing carbon powder instead of oxide powder of element M and mixing carbon powder, aluminum oxide powder, silicon oxide powder, and zinc oxide powder to obtain a weighed raw material powder, and (2) ball mill conditions (mixing) time), except having made content of Zr into the value shown to Tables 1-4, it carried out similarly to manufacturing method 1, and obtained the sintered compact.

(Manufacturing method 7)

A sintered compact was obtained in the same manner as in Production Method 1 except that the powder was wet-mixed and dried under the following conditions using a dispersant as a carbon source.

The weighed raw material powder and 4 times the amount (weight ratio) of zirconia balls (a ball having a diameter of 5 mm and a ball having a diameter of 10 mm in half by weight) were placed in a pot of a 100 L ball mill. So that the zirconia balls are not worn, pure water in an amount of 20 mass% or more based on 100 mass% of the powder weight was put into the pot. At this time, the dispersant was put into the pot. It was set as the amount of C shown in Tables 1-4 by adjusting the addition amount of this dispersing agent. And it wet-mixed for 18 hours with the ball mill apparatus, and obtained the mixed powder.

The obtained mixed powder was dried by spray drying. In addition, in order to contain carbon in a sintered compact, the degreasing performed normally was not implemented.

(Manufacturing method 8)

(1) that an oxide powder of element M was not used, (2) that the powder was wet-mixed and dried under the following conditions using a dispersant as a carbon source, and (3) ball mill conditions (mixing time) were adjusted By doing so, except having made content of Zr into the value shown in Tables 1-4, it carried out similarly to manufacturing method 1, and obtained the sintered compact.

The weighed raw material powder and 4 times the amount (weight ratio) of zirconia balls (a ball having a diameter of 5 mm and a ball having a diameter of 10 mm in half by weight) were placed in a pot of a 100 L ball mill. Pure water in an amount of 15 mass% based on 100 mass% of the powder weight was put into the pot. At this time, the dispersant was put into the pot. It was set as the amount of C shown in Tables 1-4 by adjusting the addition amount of this dispersing agent. And content of Zr was made into the value shown to Tables 1-4 by adjusting ball mill conditions (mixing time).

The obtained mixed powder was dried by spray drying. In addition, in order to contain carbon in a sintered compact, the degreasing performed normally was not implemented.

<Conventional Example 1>

(1) No oxide powder of element M used, (2) Wet-mixed with a ball mill for 48 hours, and (3) Dry the obtained mixed powder with a hot plate, and then granulated by sieving with a grid size of 250 μm Except having carried out, it carried out similarly to manufacturing method 1, and obtained the sintered compact. In the above (2), wet mixing was performed under the same conditions as in Production Method 1 except for the time of 48 hours.

<Conventional Example 2>

First, each raw material powder of zinc oxide and silicon oxide mentioned above was weighed so that it might become ZnO:SiO2= ₂ :1 (molar ratio). Each of these weighed raw material powders and three times the amount (weight ratio) of zirconia balls (a ball having a diameter of 5 mm and a ball having a diameter of 10 mm in half by weight) were placed in a poly container (port of a ball mill). In addition, alcohol as a solvent was placed in a poly container. It was wet-mixed for 16 hours with the ball mill apparatus, and the mixed powder was obtained.

Next, the obtained mixed powder was dried and then granulated. Then, it was fired at 1200°C for 5 hours in the air to obtain a pre-fired body (composite oxide of Zn and Si: Zn ₂ SiO ₄ ). This pre-fired body and five times the amount (weight ratio) of zirconia balls (a ball having a diameter of 5 mm and a ball having a diameter of 10 mm in half by weight) were placed in a poly container. Moreover, alcohol as a solvent was put into the poly container. Wet grinding was carried out for 24 hours with a ball mill apparatus.

After wet grinding, the pre-fired body was dried and granulated. The obtained pre-baked powder (composite oxide powder of Zn and Si) (Formula: Zn ₂ SiO ₄ , D50 = 12 µm), the zinc oxide powder and the aluminum oxide powder described above were weighed so as to have a predetermined ratio.

Each of the weighed raw material powders and five times the amount (weight ratio) of zirconia balls (a ball having a diameter of 5 mm and a ball having a diameter of 10 mm in half by weight) were placed in a poly container. Moreover, alcohol as a solvent was put into the poly container. Wet mixing was carried out for 24 hours with a ball mill apparatus.

Then, the obtained mixed powder was dried and then granulated. And the temperature (HP temperature) and time (holding time) of Table 4, and vacuum hot pressing was carried out at the pressure of 200 kgf/cm<2>, and it was set as the sintered compact.

<Conventional example 3>

The above-mentioned aluminum oxide powder, silicon oxide powder, and zinc oxide powder were weighed so that the content ratio after sintering might become the ratio shown in Table 4.

Each of the weighed raw material powders and five times the amount (weight ratio) of zirconia balls (a ball having a diameter of 5 mm and a ball having a diameter of 10 mm in half by weight) were placed in a poly container. In addition, alcohol as a solvent was placed in a poly container. Wet mixing was carried out for 24 hours with a ball mill apparatus.

Then, the obtained mixed powder was dried and then granulated. And the temperature (HP temperature) and time (holding time) of Table 4, and vacuum hot pressing was carried out at the pressure of 200 kgf/cm<2>, and it was set as the sintered compact.

<Conventional example 4>

Wet pulverization, drying, granulation, and calcination of the raw material powder were carried out in the same manner as in Conventional Example 2 except for calcining in the atmosphere at 1000° C. for 5 hours, followed by pre-calcined powder (composite oxide powder of Zn and Si) (Formula: Zn ₂ SiO ₄ , D50 = 12 μm) was obtained.

The content ratio of the obtained pre-fired powder (composite oxide powder of Zn and Si) (chemical formula: Zn ₂ SiO ₄ , D50 = 12 µm), the zinc oxide powder and aluminum oxide powder described above after sintering is shown in Table 4 It was weighed so that it became this.

Each of the weighed raw material powders and five times the amount (weight ratio) of zirconia balls (a ball having a diameter of 5 mm and a ball having a diameter of 10 mm in half by weight) were placed in a poly container. Moreover, alcohol as a solvent was put into the poly container. Wet mixing was carried out for 24 hours with a ball mill apparatus.

Next, the obtained mixed powder was dried and then granulated. Then, it was fired at 1000°C for 5 hours in the air to obtain a preliminary fired body. This pre-fired body and five times the amount (weight ratio) of zirconia balls (a ball having a diameter of 5 mm and a ball having a diameter of 10 mm in half by weight) were placed in a poly container. In addition, alcohol as a solvent was put in a poly container. It was wet-milled for 24 hours with a ball mill apparatus.

Next, the obtained mixed powder was pressed at a pressure of 500 kgf/cm 2 at room temperature. Then, the green compact was baked in an oxygen atmosphere at 1400°C for 5 hours to obtain a sintered compact.

<Conventional Example 5>

In addition to zinc oxide powder, aluminum oxide powder, and silicon oxide powder, boron oxide powder (B ₂ O ₃ , purity 99.9 mass% or more, average particle diameter 1 µm) was weighed so that the content ratio after sintering would be the ratio shown in Table 4 , A sintered compact was obtained in the same manner as in Conventional Example 3 except that the weighed raw material powder was obtained.

<Conventional example 6>

Molybdenum oxide powder (MoO ₃ , purity 99.9 mass% or more, average particle size 2.5 µm) together with zinc oxide powder, aluminum oxide powder, and silicon oxide powder is weighed so that the content ratio after sintering becomes the ratio shown in Table 4 A sintered compact was obtained in the same manner as in Conventional Example 3 except that one raw material powder was obtained.

Each obtained sintered compact was machined to predetermined dimensions, and various oxide sputtering targets were obtained. About these, the following items were evaluated.

<composition>

A measurement sample was collected from the obtained sputtering target, and quantitative analysis was performed on each element by ICP emission spectroscopy. From the obtained composition analysis value, content of each metal component was converted so that the total content of metal component might be set to 100 mass %. The results are shown in Tables 1-4.

<relative density>

The weight and dimension of the obtained oxide sputtering target were measured, and the volume density was calculated|required. Next, the relative density (%) was calculated by dividing the volume density by the theoretical density rho _fn (unit: g/cm 3 ). In addition, about the theoretical density (rho) _fn , it calculated|required by the formula shown below based on the theoretical density of a raw material and the weight % measured.

The theoretical density ρ _fn is calculated from the theoretical density and blending ratio of single elements or single molecules of the raw material. Compounds may be formed from single elements or single molecules of the raw material during sintering, but the theoretical density of the compound is not taken into account. For this reason, a relative density may exceed 100 %.

<X-ray diffraction analysis>

A sample for measuring an X-ray diffraction pattern was taken from the obtained sputtering target, and an X-ray diffraction pattern (XRD pattern) was measured under the following conditions. Regarding the ZnO phase, the area index of the characteristic peak was confirmed with PDF card number: 00-01-1136. Regarding the Zn ₂ SiO ₄ phase, the area index of the characteristic peak was confirmed with PDF card number: 01-83-2270. Accordingly, the presence or absence of the ZnO phase and the Zn ₂ SiO ₄ phase was confirmed.

Device: Rigaku Electric Co., Ltd. (RINT-Ultima/PC)

Province (管球): Cu

Tube voltage: 40 kV

Tube current: 50 mA

Scanning range (2θ): 4˚ ∼ 80˚

Slit size: Divergence (DS) 2/3 degree, Scattering (SS) 2/3 degree, light reception (RS) 0.8 mm

Measuring step width: 0.02 degrees in 2θ

Scan speed: 2 degrees per minute

Sample table rotation speed: 30 rpm

<Average particle size/number of coarse ZnO>

EBSD (Electron BackScatter Diffraction) image data and EDS (Energy Dispersive X-ray Spectroscopy) spectrum were simultaneously acquired from the obtained oxide sputtering target. From the result of the EDS spectrum, the measurement area was separated into a Si detection area and a non-Si detection area on the image data. The Si detection region was defined as the Zn ₂ SiO ₄ phase, and the Si non-detection region was defined as the ZnO phase. From the image data of EBSD, the grain size of the crystal grains of each phase was computed as an equivalent-circle diameter (diameter of a perfect circle corresponding to the area of a crystal grain). The number average crystal grain size in each phase region was calculated. The number average crystal grain size is the number-based median diameter D50.

In addition, the number of coarse ZnO was confirmed by counting the coarse grains in the region defined as the ZnO phase. Specifically, in the measurement range of 25000 µm 2 , the number of ZnO crystal grains having an equivalent circle diameter of 10 µm or more and 25 µm or less was measured.

Apparatus: FE-SEM SU-60 & EBSD (Hikari) sysem manufactured by Hitachi High-Technologies

Acceleration voltage: 15 kV

Magnification: 1000 times

Measurement step: 0.2

<Measurement of the number of abnormal discharges>

The obtained oxide sputtering target was brazed to an oxygen-free copper backing plate or backing tube, and this was attached to a magnetron type DC sputtering apparatus. Subsequently, film formation by the sputtering method was performed continuously for 60 minutes on the following sputtering conditions. During this film formation, the number of abnormal discharges was counted using the arc counter attached to the power supply of the DC sputtering apparatus.

In detail, the number of times of abnormal discharge from the start of film formation to the time point of lapse of 60 minutes was counted. The number of abnormal discharges is described in the item "initial" in the table. Moreover, the frequency|count of the abnormal discharge between the time of 12-hour film-forming and the time of a further 60 minutes elapsed was counted. The frequency of the abnormal discharge was described in the item "after 12 hours" in the table.

Reached vacuum degree: 5 × 10 ^-5 Pa

Ar gas pressure: 0.3 Pa

Sputter output: Disc shape: DC500W

Cylindrical: DC3000W

<DC sputtering>

It was confirmed whether or not a discharge occurred when an electric current was passed under the sputtering conditions described above. In the item "DC sputtering" in the table, the case of discharging was described as "probable", and the case of not discharging was described as "impossible".

<Membrane Characteristics>

The obtained oxide sputtering target was brazed to an oxygen-free copper backing plate or backing tube, and this was attached to the DC sputtering apparatus of a magnetron type. Next, an oxide film of a predetermined thickness was formed under the following sputtering conditions.

Sputter output: Disc shape: DC500W

Cylindrical: DC3000W

Reached vacuum degree: 1 × 10 ^-4 Pa

Sputter temperature: 100℃

Ar gas: 0.67 Pa

(Water Vapor Transmittance)

A 50-nm-thick oxide film was formed on the 120-micrometer-thick, 100-mmx100-mm size PET substrate under the conditions mentioned above.

About this oxide film, using the Mocon method, using PERMATRAN-WMODEL3.33 by mcon, based on JIS K7129, the water vapor transmission rate (water vapor barrier property) was measured on the conditions of 40 degreeC and 90 %RH.

(Visible light transmittance)

On the glass substrate (EAGLE XG) of thickness 0.7mm and 20 mm x 20 mm size, the 50-nm-thick oxide film was formed into a film on the conditions mentioned above.

About this oxide film, the transmittance|permeability of the light in the wavelength range of 380 nm - 750 nm was measured with the spectrophotometer (Nippon Spectroscopy company V-550).

In Conventional Example 1, no element M powder and no carbon powder were added, the amount of Zr was less than 0.001 mass% (lower limit of quantitation), and no incorporation of Zr from the zirconia balls was confirmed. Accordingly, the average particle diameter of the ZnO phase increased, and the number of coarse ZnO phases increased. For this reason, many abnormal discharges occurred due to the particles after the lapse of 12 hours.

In Conventional Example 2, a powder of a complex oxide of Zn and Si (Zn ₂ SiO ₄ ) was used, but M element powder and carbon powder were not added, and the amount of Zr was less than 0.001 mass%. Mixing was not confirmed. Accordingly, the average particle diameter of the ZnO phase increased, and the number of coarse ZnO phases increased. For this reason, many abnormal discharges occurred due to the particles after the lapse of 12 hours.

In Conventional Example 3, M element powder and carbon powder were not added, the amount of Zr was less than 0.001 mass%, and mixing of Zr from the zirconia balls was not confirmed. Accordingly, the average particle diameter of the ZnO phase increased, and the number of coarse ZnO phases increased. For this reason, many abnormal discharges occurred due to the particles after the lapse of 12 hours.

In Conventional Example 4, although the sintering conditions were changed using the powder of the composite oxide of Zn and Si (Zn ₂ SiO ₄ ), direct current sputtering could not be performed. For this reason, other evaluation was stopped.

In the prior art example 5, although boron oxide powder was added, abnormal discharge occurred frequently from the initial stage of sputtering, and sputter|spatter film formation could not be carried out stably. Moreover, in the oxide film formed into a film, water vapor barrier property also became low. Also, the relative density was lowered.

In the conventional example 6, although molybdenum oxide powder was added, abnormal discharge occurred frequently from the initial stage of sputtering, and sputter|spatter film formation could not be carried out stably. Moreover, the oxide film formed into a film WHEREIN: The water vapor barrier property was also low, and the visible light transmittance also became low. Also, the relative density was lowered.

In Comparative Examples 1 and 3, the total content of M element exceeded 0.1 msass%, and many abnormal discharges occurred in the initial stage.

In Comparative Examples 2 and 4, the total content of M element was less than 0.003 msass%, coarsening of the ZnO phase could not be suppressed, and a large number of abnormal discharges occurred due to particles after 12 hours had elapsed.

In Comparative Example 5, M element was not contained, the C content exceeded 1.0 mass%, and many abnormal discharges occurred in the initial stage. Moreover, the visible light transmittance of the oxide film formed into a film fell.

In Comparative Example 6, M element was not contained, the C content was less than 0.03 msass%, coarsening of the ZnO phase could not be suppressed, and after 12 hours had elapsed, many abnormal discharges were caused due to particles.

In Comparative Example 7, M element and carbon were contained, the total content of M element exceeded 0.1 mass%, and the C content exceeded 1.0 mass%, and a large number of abnormal discharges occurred in the initial stage. Moreover, the visible light transmittance of the oxide film formed into a film fell.

In Comparative Example 8, M element and carbon were contained, and the total content of M element exceeded 0.1 mass%, and many abnormal discharges occurred in the initial stage.

In Comparative Example 9, M element and carbon were contained, the total content of M element was less than 0.003 mass%, and the content of C was less than 0.03 mass%, and coarsening of the ZnO phase could not be suppressed, and after 12 hours Afterwards, a lot of abnormal discharge occurred due to the particles.

In Comparative Example 10, the C content was more than 1.0 mass%, and many abnormal discharges occurred in the initial stage. Moreover, the visible light transmittance of the oxide film formed into a film fell.

In Comparative Example 11, the M element and carbon were contained, and the total content of the M element exceeded 0.1 mass%, and many abnormal discharges occurred in the initial stage.

On the other hand, in Examples 1-28, an M element consisting of one or two or more selected from Zr, Hf, and Y: 0.003 mass% or more and 0.1 mass% or less, and C: 0.03 mass% or more and 1.0 mass% or less Among them, either one or both are included. The coarsening of the ZnO phase was suppressed, and generation|occurrence|production of the abnormal discharge was fully suppressed even after 12 hours passed. Moreover, there were few initial abnormal discharges, and DC sputtering was able to perform stably. Moreover, the water vapor barrier property and visible light transmittance of the oxide film formed into a film were excellent.

As mentioned above, according to this embodiment, it was confirmed that generation|occurrence|production of a particle can be suppressed even when it uses for a long time, and it was confirmed that the oxide sputtering target which can suppress generation|occurrence|production of the abnormal discharge resulting from this particle can be provided.

The oxide sputtering target of this embodiment is suitably applied to the process of manufacturing an oxide film containing zinc, aluminum, and silicon, which is used as a barrier film of various devices such as liquid crystal display elements, organic EL elements, and solar cells, by sputtering method. can

Claims (5)

An oxide composed of a metal component and oxygen, wherein the metal component contains an amount within the range of 0.3 mass% or more and 3.7 mass% or less of Al and 6.0 mass% or more and 14.5 mass% of Si with a total content of the metal component of 100 mass%. % or less, the M element consisting of one or two or more selected from Zr, Hf, and Y is contained in a total amount within the range of 0.003 mass% or more and 0.1 mass% or less, the balance being Zn and unavoidable impurities Oxide sputtering target, characterized in that. An oxide comprising a metal component, C and oxygen, wherein the metal component and the C are in an amount within the range of 0.3 mass% or more and 3.7 mass% or less of Al, assuming that the total content of the metal component and the C is 100 mass%, An oxide sputtering target comprising Si in an amount within the range of 6.0 mass% or more and 14.5 mass% or less, and C in an amount within the range of 0.03 mass% or more and 1.0 mass% or less, the balance being Zn and unavoidable impurities. An oxide comprising a metal component, C and oxygen, wherein the metal component and the C are in an amount within the range of 0.3 mass% or more and 3.7 mass% or less of Al, assuming that the total content of the metal component and the C is 100 mass%, The amount of Si in the range of 6.0 mass% to 14.5 mass%, the total amount of M element consisting of one or two or more selected from Zr, Hf, and Y within the range of 0.003 mass% to 0.1 mass%, and 0.03 to C Oxide sputtering target characterized by containing in an amount within the range of mass % or more and 1.0 mass % or less, and the balance consists of Zn and an unavoidable impurity. 4. The method according to any one of claims 1 to 3,
It has a ZnO phase and _a Zn2SiO4 phase, the average particle diameter of a ZnO phase is ₅ micrometers or less, _The average particle diameter of a Zn2SiO4 phase is ₅ micrometers or less, The oxide sputtering target characterized by the above-mentioned. 5. The method according to any one of claims 1 to 4,
An oxide sputtering target having a ZnO phase and a Zn ₂ SiO ₄ phase, wherein the number of ZnO phases in the range of 10 μm or more and 25 μm or less in diameter (equivalent to a circle diameter) is 10 or less in a measurement range of 25000 μm 2 .