JP2019137875A - Sputtering target, and manufacturing method of sputtering target - Google Patents

Abstract

To provide a sputtering target capable of suppressing generation of a crack at a manufacturing time and at a using time of the sputtering target, and depositing stably an oxide film (low reflectivity film) containing Fe and Mo; and to provide a manufacturing method of the sputtering target.SOLUTION: A sputtering target contains Fe and Mo as metal components, in which at least a part of the metal elements exists in the form of oxide, and further contains at least either or both of Mn and Mg as metal components, in which an atomic ratio (Mn+Mg)/Fe of the total content of Mn and Mg to the content of Fe is in the range of 0.05% or more and 5% or less.SELECTED DRAWING: None

Description

  The present invention relates to a sputtering target used for forming an oxide film and a method for manufacturing the sputtering target.

In recent years, a projected capacitive touch panel has been adopted as an input means for portable terminal devices and the like. In this type of touch panel, sensing electrodes are formed for touch position detection. This sensing electrode is usually formed by patterning, and an X electrode extending in the X direction and a Y electrode extending in the Y direction perpendicular to the X direction are formed on one surface of the transparent substrate. These are provided and arranged in a grid pattern.
Here, when a metal film is used for the electrode of the touch panel, the metal film has a metallic luster, so that the electrode pattern is visually recognized from the outside. For this reason, it is conceivable that the visibility of the electrode is lowered by forming a low reflectance film having a low visible light reflectance on the metal thin film.

In addition, color filters intended for color display are employed in flat panel displays typified by liquid crystal display devices and plasma displays. In this color filter, a black member called a black matrix is formed for the purpose of improving contrast and color purity and improving visibility.
The above-described low reflectance film can also be used as this black matrix (hereinafter referred to as “BM”).

Furthermore, in the solar cell panel, when sunlight is incident through a glass substrate or the like, a back electrode of the solar cell is formed on the opposite side. As the back electrode, a metal film such as molybdenum (Mo) or silver (Ag) is used. When the solar cell panel of such an aspect is seen from the back side, the metal film which is the back electrode will be visually recognized.
For this reason, it is conceivable to reduce the visibility of the back electrode by forming the above-described low reflectance film on the back electrode.

Note that the low reflectance film described above needs to be formed in accordance with the pattern shape of the electrode, and therefore has the same etching property as the metal film. Moreover, in order to suppress deterioration during use, excellent weather resistance is also required.
Therefore, for example, Patent Document 1 proposes an oxide film containing Fe and Mo suitable for the above-described low reflectivity film, and a sputtering target used when forming this oxide film.

  Here, the sputtering target described in Patent Document 1 has a Mo oxide phase and a Fe oxide phase, and the difference in thermal expansion coefficient between these Mo oxide phase and Fe oxide phase (linear expansion). In order to suppress the generation of cracks during the production and use of the sputtering target due to the difference in the coefficient, the sintering conditions are controlled to have the Fe—Mo—O composite oxide phase as the oxide phase. .

Japanese Patent Laid-Open No. 2006-191090

Recently, in order to cope with an increase in the size of a substrate on which a film is formed and an improvement in film formation efficiency, a large sputtering target or a cylindrical sputtering target is required. In such a large sputtering target or a cylindrical sputtering target, if a partial crack occurs, the entire sputtering target becomes unusable. It is requested to do.
In the sputtering target described in Patent Document 1, as described above, the Fe—Mo—O composite oxide phase is formed as the oxide phase to reduce cracking. Furthermore, in order to cope with the cylindrical shape, further measures against cracking are required.

  The present invention has been made in view of the above-described circumstances, and can sufficiently suppress the generation of cracks during the production and use of a sputtering target, and an oxide film (low reflectance film) containing Fe and Mo can be provided. It is an object of the present invention to provide a sputtering target capable of stably forming a film and a method for manufacturing the sputtering target.

  As a result of intensive studies by the present inventors in order to solve the above problems, as shown in the observation photograph of FIG. 4, the Fe oxide phase 11 (dark gray region in FIG. 4) and the Mo oxide phase 12 (FIG. It was confirmed that the Fe oxide phase 11 was cracked and progressed in the sputtering target having a thin gray region in FIG. For this reason, in order to suppress generation | occurrence | production of the crack at the time of manufacture and use of a sputtering target, the knowledge that it was effective to suppress generation | occurrence | production and progress of the crack in the Fe oxide phase 11 was acquired.

  This invention is made | formed based on the above-mentioned knowledge, Comprising: The sputtering target of this invention contains Fe and Mo as a metal component, And at least one part of the said metal component is a form of an oxide. Further, at least one or both of Mn and Mg are contained as a metal component, and the atomic ratio (Mn + Mg) / Fe of the total content of Mn and Mg to the content of Fe is 0.05% or more and 5% or less. It is characterized by being within the range.

According to the sputtering target of this structure, it contains at least one or both of Mn and Mg, and the atomic ratio (Mn + Mg) / Fe of the total content of Mn and Mg to the content of Fe is 0.05% or more and 5%. Since it is within the following range, the crack resistance of the Fe oxide phase is improved by Mn and Mg, and the occurrence and progress of cracks in the Fe oxide phase can be suppressed. Also, since Mn oxide and Mg oxide have a smaller difference in coefficient of thermal expansion from Mo oxide than Fe oxide, the presence of Mn and Mg in the Fe oxide phase results in the Fe oxide phase and Mo The difference in coefficient of thermal expansion with the oxide phase is reduced, and the occurrence of cracks due to thermal stress can be reduced.
Therefore, it becomes possible to suppress the generation of cracks during the production and use of the sputtering target.

Here, in the sputtering target of the present invention, the Fe content in the metal component is in the range of 20 atomic% to 95 atomic%, the Mo content is in the range of 5 atomic% to 80 atomic%, and It is preferable that
In this case, an oxide film having the above-described composition can be formed, and an oxide film having low visible light reflectance and excellent etching properties and weather resistance can be reliably formed.

Moreover, in the sputtering target of this invention, it is preferable to have a Fe-Mo-O complex oxide phase.
In this case, by having the Fe—Mo—O composite oxide phase, the Fe oxide phase and the Mo oxide phase are sufficiently reacted, and the density of the sputtering target can be improved. . Thereby, the number of vacancies in the sputtering target is reduced, the occurrence of abnormal discharge during sputtering can be suppressed, and the oxide film can be formed more stably.

In the sputtering target of the present invention, In may be further included as a metal component, and the In content in the metal component may be in the range of 0.1 atomic% to 23 atomic%.
In this case, it becomes possible to suppress generation | occurrence | production of the curvature at the time of manufacture of a sputtering target by containing In in the above-mentioned range. In addition, it is possible to maintain characteristics such as reflectance, etching property, and weather resistance of the formed oxide film.

  The manufacturing method of the sputtering target of this invention is a manufacturing method of the sputtering target which manufactures the above-mentioned sputtering target, Comprising: The total content of Mn and Mg is 0.05 mass% or more and 5 mass% with respect to Fe oxide powder. Fe oxide raw material powder containing at least one or both of Mn and Mg by mixing and heating the Fe oxide, Mn raw material, and Mg raw material so as to be within the following range, and then grinding. It is characterized by having a Fe oxide raw material powder forming step to be formed.

  According to the manufacturing method of the sputtering target having this configuration, since the Fe oxide raw material powder forming step of forming the Fe oxide raw material powder containing at least one or both of Mn and Mg is provided, at least one of Mn and Mg Or the Fe oxide phase containing both can be formed, and the crack resistance of the Fe oxide phase can be improved, and the occurrence and progress of cracks in the Fe oxide phase can be suppressed.

Here, in the manufacturing method of the sputtering target of this invention, the said sintering raw material powder formation process which mixes the said Fe oxide raw material powder and Mo oxide powder, and forms sintering raw material powder, and obtained sintering A sintering step of sintering the raw material powder.
In this case, since it includes a sintering step of sintering the sintered raw material powder formed by mixing the Fe oxide raw material powder and the Mo oxide powder, it contains at least one or both of Mn and Mg. A sputtering target having an Fe oxide phase and a Mo oxide phase can be accurately produced.

Moreover, in the manufacturing method of the sputtering target of this invention, in the said sintering raw material powder formation process, in addition to the said Fe oxide raw material powder and the said Mo oxide powder, at least one or both of metal Fe powder and metal Mo powder May be mixed.
In this case, even if the metal Fe powder and the metal Mo powder are mixed in the sintering raw material powder forming step, the sputtering includes the Fe oxide phase containing at least one or both of Mn and Mg, and the Mo oxide phase. The target can be accurately manufactured. Note that part of the metal Fe and metal Mo may remain as a metal phase in the sputtering target.

Furthermore, in the method for producing a sputtering target of the present invention, in the sintering raw material powder forming step, in addition to the Fe oxide raw material powder and the Mo oxide powder, at least one of In oxide powder and metal In powder or Both may be mixed.
In this case, in addition to the Fe oxide phase containing at least one or both of Mn and Mg, and the Mo oxide phase, it is possible to produce a sputtering target having an In oxide phase. A part of the metal In may remain as a metal phase.

Moreover, in the manufacturing method of the sputtering target of this invention, it is preferable that the sintering temperature in the said sintering process exists in the range of 840 degreeC or more and 950 degrees C or less.
In this case, since the sintering temperature in the sintering step is in the range of 840 ° C. or higher and 950 ° C. or lower, the Fe oxide raw material powder and the Mo oxide powder are sufficiently reacted in the sintering step. Thus, an Fe—Mo—O composite oxide phase can be formed, and the density of the sputtering target can be improved.

  According to the present invention, it is possible to sufficiently suppress the generation of cracks during the production and use of a sputtering target, and to stably form an oxide film (low reflectance film) containing Fe and Mo. A target and a method for manufacturing the sputtering target can be provided.

It is explanatory drawing which shows the structure | tissue of the sputtering target which concerns on one Embodiment of this invention. It is a flowchart which shows the manufacturing method of the sputtering target which concerns on one Embodiment of this invention. It is explanatory drawing which shows the structure | tissue of the sputtering target which concerns on other embodiment of this invention. It is an observation photograph which shows the generation | occurrence | production state of the crack in the conventional sputtering target.

  Below, the sputtering target which is embodiment of this invention, and the manufacturing method of a sputtering target are demonstrated with reference to attached drawing.

The sputtering target according to the present embodiment contains Fe and Mo as metal components, and at least a part of the metal components exists in the form of an oxide, and further contains at least one or both of Mn and Mg as metal components. Contains.
The atomic ratio (Mn + Mg) / Fe between the total content of Mn and Mg and the content of Fe is in the range of 0.05% to 5%.
In the present embodiment, the Fe content in the metal component is in the range of 20 atomic% to 95 atomic%, and the Mo content is in the range of 5 atomic% to 80 atomic%.

  Moreover, in the sputtering target which concerns on this embodiment, in addition to Fe, Mo, Mn, and Mg, you may contain In as a metal component. At this time, the content of In in the metal component is preferably in the range of 0.1 atomic% to 23 atomic%. In this case, it has an In oxide phase. In may also exist as a complex oxide phase with Fe and Mo.

Note that the oxide content in the sputtering target according to the present embodiment is preferably in the range of 70% to 95% by weight.
Here, by setting the oxide content in the sputtering target to 70% or more by mass ratio, the amount of oxygen in the formed film can be secured, and the reflectance of the film can be kept low. On the other hand, by setting the oxide content in the sputtering target to 95% or less by mass ratio, it is possible to suppress the metal component from being softened during the sintering and reduce the density improvement effect, and the density can be sufficiently improved. In addition, the sintering time can be shortened.

Here, in the sputtering target according to the present embodiment, as shown in FIG. 1, an Fe oxide phase 11, a Mo oxide phase 12, and an Fe—Mo—O composite oxide phase 13 are provided. It is said that.
In the present embodiment, the Fe oxide phase 11 has the Fe ₃ O ₄ phase as the main phase, and the Mo oxide phase 12 has the MoO ₂ phase as the main phase. Further, the Fe—Mo—O composite oxide phase 13 has a Fe ₂ Mo ₃ O ₈ phase as a main phase.
In the present embodiment, the Fe oxide phase 11 contains at least one or both of Mn and Mg.

  Below, in the sputtering target which is this embodiment, the atomic ratio of the total content of Mn and Mg and the content of Fe, the content of Fe in the metal component, the content of Mo, Fe-Mo-O complex oxidation The reason for defining the physical phase as described above will be described.

(Atomic ratio between the total content of Mn and Mg and the content of Fe)
In the sputtering target which is this embodiment, the crack resistance of the Fe oxide phase 11 can be improved by containing Mn and Mg as metal components. For this reason, in this embodiment, the total content of Mn and Mg is prescribed according to the content of Fe.
Here, when the atomic ratio (Mn + Mg) / Fe of the total content of Mn and Mg and the content of Fe is less than 0.05%, the crack resistance of the Fe oxide phase 11 can be sufficiently improved. It may not be possible. On the other hand, when the atomic ratio (Mn + Mg) / Fe of the total content of Mn and Mg to the content of Fe exceeds 5%, Mn and Mg are aggregated during sintering, and cracks start from this aggregate. May occur.

From the above, in the present embodiment, the atomic ratio (Mn + Mg) / Fe between the total content of Mn and Mg and the content of Fe is set in the range of 0.05% or more and 5% or less.
In order to further improve the cracking resistance of the Fe oxide phase 11, the lower limit of the atomic ratio (Mn + Mg) / Fe of the total content of Mn and Mg to the content of Fe should be 0.1% or more. Is preferable, and more preferably 0.5% or more. On the other hand, in order to further suppress the occurrence of cracks due to Mn or Mg aggregates, the upper limit of the atomic ratio (Mn + Mg) / Fe of the total content of Mn and Mg and the content of Fe is 4.5%. The content is preferably set to 4% or less, more preferably 4% or less.

(Fe content in metal component, Mo content)
The oxide film formed using the sputtering target according to the present embodiment has a composition equivalent to that of the above-described sputtering target.
Here, in the sputtering target of the present embodiment, the Fe content in the metal component is in the range of 20 atomic% to 95 atomic%, and the Mo content is in the range of 5 atomic% to 80 atomic%. By setting the inside, an visible light (wavelength of 400 to 800 nm) has an average reflectance of 30% or less, and an oxide film having a sufficiently low reflectance can be formed. In addition, an oxide film excellent in etching property and weather resistance can be formed.

  In order to form an oxide film having a sufficiently low reflectivity and particularly excellent in etching property and weather resistance, the lower limit of the Fe content in the metal component should be 20 atomic% or more. Preferably, it is more preferably 25 atomic% or more. Further, the upper limit of the Fe content in the metal component is preferably 90 atomic% or less, and more preferably 85 atomic% or less. Moreover, it is preferable that the minimum of content of Mo in a metal component shall be 10 atomic% or more, and it is more preferable to set it as 15 atomic% or more. Furthermore, the upper limit of the Mo content in the metal component is preferably 75 atomic percent or less, and more preferably 70 atomic percent or less.

(Fe-Mo-O complex oxide phase)
In the sputtering target of this embodiment, as shown in FIG. 1, an Fe—Mo—O composite oxide phase 13 is formed between the Fe oxide phase 11 and the Mo oxide phase 12.
The Fe—Mo—O composite oxide phase 13 is formed by a reaction between the Fe oxide raw material powder, which is a sintering raw material, and the Mo oxide powder. When this Fe—Mo—O composite oxide phase 13 is present, the Fe oxide raw material powder and the Mo oxide powder are sufficiently sintered, and the Fe oxide phase 11 and the Mo oxide phase 12 It is possible to suppress the generation of voids between the two and the density can be sufficiently improved. Moreover, since the Fe—Mo—O composite oxide phase 13 has a thermal expansion coefficient between the Fe oxide phase 11 and the Mo oxide phase 12, the occurrence of cracks due to the difference in the thermal expansion coefficient is suppressed. It becomes possible.
For this reason, in this embodiment, as shown in FIG. 1, it shall have the Fe-Mo-O complex oxide phase 13. As shown in FIG.

(In content)
By containing In as a metal component, the occurrence of warpage in the sputtering target can be suppressed. In particular, in the case where the Fe—Mo—O composite oxide phase 13 described above is included, since it tends to be warped, it is preferable to contain In.
By setting the In content as the metal component to 0.1 atomic% or more, an effect of suppressing the warpage of the sputtering target can be obtained. On the other hand, by setting the In content as the metal component to 23 atomic% or less, the density of the sputtering target can be suppressed from being lowered, the strength of the sputtering target can be secured, and the occurrence of cracks can be suppressed. Become.
Therefore, when In is positively contained, the In content as the metal component is in the range of 0.1 atomic% to 23 atomic%.
The lower limit of the In content as the metal component is preferably 1 atomic% or more, and the upper limit of the In content as the metal component is preferably 10 atomic% or less.

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

  In this embodiment, as shown in FIG. 2, Fe oxide raw material powder forming step S01 for forming Fe oxide raw material powder containing at least one or both of Mn and Mg, and the obtained Fe oxide raw material powder And a sintering material powder forming step S02 for mixing the Mo oxide powder to form a sintering material powder, and a sintering step S03 for pressure-sintering the obtained sintering material powder.

(Fe oxide raw material powder forming step S01)
The Fe oxide raw material powder in this embodiment contains at least one or both of Mn and Mg.
In this Fe oxide raw material powder forming step S01, Fe oxide, Mn so that the total content of Mn and Mg in the Fe oxide powder is within the range of 0.05 mass% to 5 mass%. By mixing and heating the raw material and the Mg raw material, and pulverizing and classifying the raw material, Fe oxide raw material powder having a predetermined particle diameter containing at least one or both of Mn and Mg is formed. In the present embodiment, the average particle size of the Fe oxide raw material powder is in the range of 0.1 μm or more and 20 μm or less.
Here, in this embodiment, Fe ₃ O ₄ is used as the Fe oxide, MnO ₂ is used as the Mn material, and MgO is used as the Mg material.

(Sintering raw material powder forming step S02)
Next, the above-described Fe oxide raw material powder and Mo oxide powder are mixed at a predetermined ratio to obtain a sintered raw material powder. In the present embodiment, MoO ₂ powder is used as the Mo oxide powder. Moreover, the average particle diameter of Mo oxide powder is made into the range of 0.1 micrometer or more and 20 micrometers or less.
Here, in the sintering raw material powder forming step S02, it is preferable to use a mixing device such as a ball mill.

(Sintering step S03)
Next, the above-mentioned sintered raw material powder is sintered by heating while applying pressure to obtain a sintered body. In this embodiment, sintering was performed using a hot press apparatus.
The sintering temperature in this sintering step S03 is in the range of 700 ° C. or more and 950 ° C. or less, the holding time at the sintering temperature is in the range of 2 hours or more and 5 hours or less, and the pressing pressure is in the range of 10 MPa or more and 50 MPa or less. did.
Here, the Fe—Mo—O composite oxide phase 13 can be formed by setting the sintering temperature in the sintering step S03 within the range of 840 ° C. or more and 950 ° C. or less.

(Machining process S04)
Next, the obtained sintered body is machined to have a predetermined size. Thereby, the sputtering target which is this embodiment is manufactured.

According to the sputtering target of the present embodiment configured as described above, it contains at least one or both of Mn and Mg, and the atomic ratio of the total content of Mn and Mg to the content of Fe (Mn + Mg) Since / Fe is in the range of 0.05% or more and 5% or less, the crack resistance of the Fe oxide phase 11 is improved by Mn and Mg, and the occurrence and progress of cracks in the Fe oxide phase 11 are suppressed. It becomes possible. Moreover, since the difference in thermal expansion coefficient between the Mn oxide and the Mg oxide and the Mo oxide is smaller than that of the Fe oxide, the occurrence of cracking due to thermal stress can be reduced.
Therefore, it is possible to sufficiently suppress the generation of cracks during the production and use of the sputtering target.

  In the present embodiment, the Fe content in the metal component is in the range of 20 atomic% to 95 atomic%, and the Mo content is in the range of 5 atomic% to 80 atomic%. Therefore, it is possible to reliably form an oxide film having a low visible light reflectance and excellent etching properties and weather resistance.

  Furthermore, in the present embodiment, since the Fe—Mo—O composite oxide phase 13 is included, the density of the sputtering target can be improved. Thereby, the number of vacancies in the sputtering target is reduced, the occurrence of abnormal discharge during sputtering can be suppressed, and the oxide film can be formed more stably.

  According to the manufacturing method of the sputtering target which is this embodiment, since it has Fe oxide raw material powder formation process S01 which forms Fe oxide raw material powder containing at least one or both of Mn and Mg, Mn and Mg It is possible to form the Fe oxide phase 11 containing at least one or both of the above, to improve the crack resistance of the Fe oxide phase 11 and to suppress the occurrence and progress of cracks in the Fe oxide phase 11 It becomes.

  Further, in the present embodiment, a sintered raw material powder forming step S02 for obtaining a sintered raw material powder by mixing Fe oxide raw material powder and Mo oxide powder containing at least one or both of Mn and Mg, and this sintering Since the sintering step S03 for pressure sintering the binder powder is provided, a sputtering target having the Fe oxide phase 11 containing at least one or both of Mn and Mg and the Mo oxide phase 12 is accurately obtained. Can be manufactured.

  Furthermore, in this embodiment, by setting the sintering temperature in the sintering step S03 within the range of 840 ° C. or more and 950 ° C. or less, the Fe oxide raw material powder and the Mo oxide powder are reacted in the sintering step S03. Thus, the Fe—Mo—O composite oxide phase 13 can be formed. Thereby, Fe oxide raw material powder and Mo oxide powder can fully be sintered, and the density of a sputtering target can be improved.

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 idea of the invention.
For example, in the present embodiment, as illustrated in FIG. 1, the description has been made on the assumption that the Fe oxide phase 11, the Mo oxide phase 12, and the Fe—Mo—O composite oxide phase 13 are included. Instead, as shown in FIG. 3, it may be composed of the Fe oxide phase 11 and the Mo oxide phase 12 without having the Fe—Mo—O composite oxide phase 13.

  Furthermore, in this embodiment, although it demonstrated as what uses the mixed powder which mixed Fe oxide raw material powder and Mo oxide powder as a sintering raw material, it is not limited to this, Sintering raw material powder formation process In addition to Fe oxide raw material powder and Mo oxide powder, at least one or both of metal Fe powder and metal Mo powder may be mixed. Furthermore, you may mix at least one or both of In oxide powder and metal In powder. In this case, the metal Fe phase, the metal Mo phase, and the metal In phase may remain in the sputtering target.

In the present embodiment, in the Fe oxide raw material powder forming step S01, MnO ₂ is used as the Mn raw material and MgO is used as the Mg raw material. However, the present invention is not limited to this. Mn raw material and Mg raw material may be used.

  Below, the result of the evaluation test evaluated about the effect of the sputtering target which concerns on this invention, and the manufacturing method of a sputtering target is demonstrated.

Fe ₃ O ₄ powder having a median diameter (d50) of 1 μm, MnO ₂ powder having a median diameter of 1 μm, and MgO powder having a median diameter of 1 μm are prepared, and a total of 2 kg so as to obtain the composition ratio shown in Table 1 Were weighed, put into a ball mill container together with 6 kg of φ5 mm zirconia balls, and mixed in a ball mill apparatus for 24 hours. The mixed powder was placed in an alumina crucible, heat-treated in a vacuum at 1000 ° C. for 1 hour, and the resulting sintered mass was ball milled. Then, classified with a sieve having an opening of 500 [mu] m, the median diameter (d50) was obtained _Fe 3 _{O 4} raw material powder containing at least one or both of 0.8μm Mn and Mg.

Then, Fe ₃ O ₄ raw material powder shown in Table 2, MoO ₂ powder with a median diameter of 5 μm, and In ₂ O ₃ powder with a median diameter of 0.3 μm are prepared, and the composition ratio shown in Table 2 is obtained. Were weighed and mixed using a ball mill apparatus to obtain a sintered raw material powder.
This sintered raw material powder was filled into a 135 mm × 215 mm carbon mold and sintered in vacuum under the conditions of the sintering temperature, pressure 20 MPa, and holding time 3 hours shown in Table 2.
And the obtained sintered compact was wet-grinded and processed into a size of 126 mm × 178 mm × 6 mmt. This was soldered to a backing plate using an In solder material.

  About the obtained sputtering target, the metal component in a sputtering target, a density, the presence or absence of a Fe-Mo-O composite oxide phase, the presence or absence of a crack, and the average reflectance of visible light of a deposited oxide film are as follows. Evaluated. The evaluation results are shown in Table 3.

(Metal component of sputtering target)
1 g of a measurement sample was collected from the obtained sintered body, and the metal components of Fe, Mo, In, Mn, and Mg were quantified using an ICP-AES apparatus. The total value of the obtained metal components was defined as the total metal component amount, and each metal component value was determined according to the following formula. Further, the atomic ratio (Mn + Mg) / Fe of the total content of Mn and Mg and the content of Fe was determined.
Metal component value (atomic%) = (Metal component quantitative value) / (Total metal component amount) × 100

(density)
The density was calculated from the dimensions and weight of the obtained processed sputtering target. The ratio obtained by dividing the dimensional density by the following calculated density is shown in Table 3 as “density”.
Calculated density (g / cm ³ ) = 100 / {Fe ₃ O ₄ charge (mass%) / Fe ₃ O ₄ density (g / cm ³ ) + MoO ₂ charge (mass%) / MoO ₂ density (g / cm ³ ) + In ₂ O ₃ charge (mass%) / In ₂ O ₃ density (g / cm ³ )}

(Presence or absence of Fe-Mo-O composite oxide phase)
1 g of a measurement sample was collected from the obtained sintered body, and the presence or absence of the Fe—Mo—O composite oxide phase was confirmed by XRD measurement. When a peak of Fe ₂ Mo ₃ O ₈ phase or FeMoO ₄ phase was detected, “Yes” is described in the column of “Fe—Mo—O phase” in Table 3, and the above-mentioned peak was not detected In this case, “None” is described in the “Fe—Mo—O phase” column of Table 3.

(Presence or absence of cracks)
A penetration inspection test was performed on the sintered body before the wet grinding process, the occurrence of cracks was evaluated, and the indication pattern was visually evaluated.

(Reflectance of oxide film)
Using a sputtering target, film formation by sputtering was performed under the following conditions.
Power supply: DC power supply Power: 914W
Gas flow rate: Ar, 50 sccm
Gas pressure: 0.67Pa
Target-substrate distance: 60mm
Substrate temperature: Room temperature Substrate: Glass substrate (Product name: Eagle XG)

Note that a silver film having a thickness of 200 nm was formed over a glass substrate, and an oxide film was formed over the silver film with a thickness of 50 nm using the above-described sputtering target.
As described above, the reflectance of the laminated film of the silver film and the oxide film formed on the glass substrate was measured. Using a spectrophotometer (U4100 manufactured by Hitachi, Ltd.), measurement was performed at a wavelength of 400 to 800 nm from the film-formed film side. The average value of the measured reflectance is shown in Table 3 as “average reflectance of film”.

In Comparative Example 1-3 in which the atomic ratio (Mn + Mg) / Fe of the total content of Mn and Mg and the content of Fe was less than 0.05%, cracks were confirmed in the sputtering target. This is presumably because the contents of Mn and Mg were small and the crack resistance of the Fe oxide phase could not be improved.
In Comparative Examples 4 and 5 in which the atomic ratio (Mn + Mg) / Fe of the total content of Mn and Mg to the content of Fe exceeds 5%, cracks were confirmed in the sputtering target. It is presumed that Mn and Mg aggregated and cracks due to the aggregate occurred.

On the other hand, in Example 1-19 of the present invention in which the atomic ratio (Mn + Mg) / Fe of the total content of Mn and Mg and the content of Fe was in the range of 0.05% or more and 5% or less, Cracks were not confirmed. It is estimated that the crack resistance of the Fe oxide phase was sufficiently improved by Mn and Mg.
Further, in Invention Examples 2, 3, 6-11, and 13-19 in which the sintering temperature was 840 ° C. or higher and 950 ° C. or lower, the Fe—Mo—O composite oxide phase was confirmed and the density increased. It is confirmed that
Furthermore, in this invention example 1-19, it is confirmed that the oxide film formed has a sufficiently low visible light reflectance.

  From the above, according to the present invention example, it is possible to suppress the generation of cracks during the production and use of the sputtering target, and to stably form an oxide film (low reflectance film) containing Fe and Mo. It was confirmed that a possible sputtering target and a method for producing the sputtering target can be provided.

11 Fe oxide phase 12 Mo oxide phase 13 Fe-Mo-O composite oxide phase

Claims (9)

As a metal component, Fe, Mo is contained, and at least a part of the metal component exists in the form of an oxide,
Furthermore, it contains at least one or both of Mn and Mg as a metal component, and the atomic ratio (Mn + Mg) / Fe of the total content of Mn and Mg to the content of Fe is in the range of 0.05% to 5%. A sputtering target characterized by being made.   2. The Fe content in the metal component is in the range of 20 atomic% to 95 atomic%, and the Mo content is in the range of 5 atomic% to 80 atomic%. A sputtering target according to 1.   It has a Fe-Mo-O complex oxide phase, The sputtering target of Claim 1 or Claim 2 characterized by the above-mentioned.   Furthermore, In is contained as a metal component, and the content of In in the metal component is in the range of 0.1 atomic% or more and 23 atomic% or less. The sputtering target according to item. It is a manufacturing method of the sputtering target which manufactures the sputtering target as described in any one of Claims 1-4, Comprising:
Fe oxide, Mn raw material, Mg raw material are mixed and heated so that the total content of Mn and Mg is within the range of 0.05% by mass or more and 5% by mass or less with respect to the Fe oxide powder, and then A method for producing a sputtering target comprising a Fe oxide raw material powder forming step of forming an Fe oxide raw material powder containing at least one or both of Mn and Mg by pulverization.   A sintering raw material powder forming step of forming the sintered raw material powder by mixing the Fe oxide raw material powder and the Mo oxide powder, and a sintering step of pressure-sintering the obtained sintered raw material powder. The method of manufacturing a sputtering target according to claim 5, wherein the sputtering target is provided.   The said sintering raw material powder formation process WHEREIN: In addition to the said Fe oxide raw material powder and the said Mo oxide powder, at least one or both of metallic Fe powder and metallic Mo powder are mixed. A method for manufacturing a sputtering target.   7. In the sintering raw material powder forming step, in addition to the Fe oxide raw material powder and the Mo oxide powder, at least one or both of In oxide powder and metal In powder are mixed. The manufacturing method of the sputtering target of Claim 7.   The method for producing a sputtering target according to any one of claims 6 to 8, wherein a sintering temperature in the sintering step is within a range of 840 ° C or higher and 950 ° C or lower.