WO2020044798A1 - Oxide sputtering target and production method for oxide sputtering target - Google Patents
Oxide sputtering target and production method for oxide sputtering target Download PDFInfo
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- WO2020044798A1 WO2020044798A1 PCT/JP2019/027168 JP2019027168W WO2020044798A1 WO 2020044798 A1 WO2020044798 A1 WO 2020044798A1 JP 2019027168 W JP2019027168 W JP 2019027168W WO 2020044798 A1 WO2020044798 A1 WO 2020044798A1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
Definitions
- the present invention relates to an oxide sputtering target composed of an oxide containing zirconium, silicon and indium as metal components, and a method for producing the oxide sputtering target.
- a shield layer is provided in order to prevent a malfunction due to charging of a liquid crystal element or an organic EL element.
- the above-described shield layer is required to have an action of causing a touch signal to reach a sensor portion inside the panel while eliminating external noise.
- the shield layer is also required to have high visible light transmittance in order to ensure the visibility of the display panel.
- Patent Document 1 proposes a transparent conductive film mainly containing indium tin oxide (ITO) as the above-mentioned shield layer.
- ITO indium tin oxide
- a transparent conductive film containing indium tin oxide (ITO) as a main component has a low transmittance with respect to visible light, so that the transparent conductive film looks yellowish and visibility may be deteriorated.
- ITO indium tin oxide
- Patent Documents 2 to 4 propose an oxide sputtering target used when forming an oxide film containing zirconium, silicon, and indium as metal components.
- the oxide sputtering target disclosed in Patent Documents 2-4 is mainly intended for forming a dielectric layer and a protective layer of an optical disk as an information recording medium, and the target sputtering surface is comparatively large.
- a shield layer such as an in-cell touch panel
- Patent Documents 2 to 4 when a large-sized sputtering target is manufactured, sintering becomes insufficient, and variations in density and oxygen concentration occur, and cracks and warpages occur. There is a possibility that a sputter film cannot be stably formed.
- the present invention has been made in view of the above-described circumstances, and has an oxide sputtering target capable of stably forming a sputter film even when a target sputtering surface is relatively large, and an oxide sputtering target having the same structure.
- An object of the present invention is to provide a method for manufacturing a target.
- the oxide sputtering target of the present invention is an oxide sputtering target composed of an oxide containing zirconium, silicon, and indium as a metal component, and has a variation in density in a target sputtering surface. It is characterized in that it is within 3% and the variation in density in the thickness direction is within 5%.
- the oxide sputtering target of the present invention since it is composed of an oxide containing zirconium, silicon and indium as the metal component, it has a high resistance, and has excellent visible light transmittance, and is suitable for the shield layer. This makes it possible to form an oxide film. Since the variation in the density within the target sputtering surface is set to 3% or less, the sputtering is stable on the entire target sputtering surface during the sputtering film formation, and the oxide film can be stably formed. In addition, since the variation in the density in the thickness direction is within 5%, an oxide film can be formed stably even when sputtering proceeds.
- the variation of the specific resistance in the target sputtering surface is within 10% and the variation of the specific resistance in the thickness direction is within 10%.
- the variation in the specific resistance within the target sputtering surface is set to be within 10%, it is possible to suppress occurrence of abnormal discharge during sputtering.
- the variation in the specific resistance in the thickness direction is set to be within 10%, the oxide film can be stably formed even when the sputtering proceeds.
- the area of the target sputtering surface may be 0.02 m 2 or more. In this case, since the area of the target sputtering surface is relatively large at 0.02 m 2 or more, an oxide film can be formed over a large-area substrate.
- the oxide sputtering target may have a flat plate shape or a cylindrical shape.
- the method for producing an oxide sputtering target of the present invention is a method for producing an oxide sputtering target comprising an oxide containing zirconium, silicon and indium as metal components, comprising zirconium oxide powder, silicon oxide powder and indium oxide powder. And a sintering step of sintering the obtained sintering material powder to obtain a sintered body.
- the bonding step is characterized by heating while introducing oxygen, maintaining the temperature in a temperature range of 1200 ° C. or more and 1400 ° C. or less for 3 hours or more, and then heating and maintaining the temperature to a temperature exceeding 1400 ° C.
- sintering is performed at 1200 ° C. or higher at which sintering of indium oxide in the sintering raw material powder is started, and sintering is performed by forming a composite oxide. Since the temperature is maintained in the temperature range of 1400 ° C. or less for 3 hours or more, it is possible to allow oxygen gas to permeate into the inside while maintaining the gap channel between the sintering raw material powders during sintering. Then, by heating and holding the temperature to a temperature exceeding 1400 ° C., sintering can be progressed uniformly, and a sintered body having a small variation in density can be obtained.
- the median diameter (D50) of the sintering raw material powder is in a range of 0.05 ⁇ m or more and 1.2 ⁇ m or less.
- the median diameter (D50) of the sintering raw material powder is relatively small in the range of 0.05 ⁇ m or more and 1.2 ⁇ m or less, the amount of shrinkage during sintering can be suppressed low, and large-sized oxide sputtering Even when the target is manufactured, generation of cracks and warpage can be suppressed, and the manufacturing yield can be improved.
- an oxide sputtering target that can stably form a sputter film even when the target sputtering surface is relatively large, and a method for manufacturing the oxide sputtering target.
- FIG. 1 is a cross-sectional view of an oxide sputtering target according to one embodiment of the present invention. It is a flow figure showing the manufacturing method of the oxide sputtering target concerning one embodiment of the present invention.
- 4 is a temperature chart of a sintering step in the method for manufacturing an oxide sputtering target according to one embodiment of the present invention.
- It is a top view of the oxide sputtering target which is other embodiment of this invention.
- It is sectional drawing of the oxide sputtering target which is other embodiment of this invention.
- the oxide sputtering target according to the present embodiment forms an oxide film suitable as a shield layer provided for preventing static electricity in a display panel such as a liquid crystal display panel, an organic EL display panel, and a touch panel. It is used at the time.
- the oxide sputtering target according to the present embodiment is composed of an oxide containing zirconium, silicon and indium as metal components.
- the oxide sputtering target of the present embodiment has a composite oxide phase containing at least a part of the above-described metal elements and an indium oxide phase.
- the sputtering surface is a rectangular flat-plate type sputtering target having a rectangular shape, and the area of the target sputtering surface is 0.02 m 2 or more.
- the variation in density in the target sputtering surface is set to 3% or less, and the variation in density in the thickness direction is set to 5% or less.
- the average value (average density) of the densities measured at a plurality of locations is set to 5.5 g / cm 3 or more.
- the variation of the specific resistance in the target sputtering surface is set to 10% or less, and the variation of the specific resistance in the thickness direction is set to 10% or less.
- the average value of the specific resistance measured at a plurality of locations is set to 1.0 ⁇ 10 ⁇ 2 ⁇ ⁇ cm or less.
- the composition of the oxide, the phase configuration, the variation in the density in the target sputtering surface, the variation in the density in the thickness direction, the variation in the specific resistance in the target sputtering surface, the thickness The reason why the variation in the specific resistance in the direction is defined as described above will be described.
- the oxide sputtering target according to the present embodiment is composed of an oxide containing zirconium, silicon and indium as the metal component. In an oxide sputtering target having such a composition, it is possible to form an oxide film having a sufficiently high resistance value and excellent transmittance of visible light.
- the Zr content is in the range of 2 mass% to 27 mass%
- the In content is in the range of 65 mass% to 95 mass%
- the Si content is It is preferable that it is in the range of 0.5 mass% or more and 15 mass% or less and is an unavoidable impurity metal element.
- the content of Zr is 2 mass% or more, the durability of the formed oxide film can be improved, and the hardness is increased and the oxide film is resistant to scratches.
- the content of Zr is 27 mass% or less, the increase in the refractive index can be suppressed, and the occurrence of unnecessary reflection can be suppressed, so that the visible light transmittance of the formed oxide film decreases. Can be suppressed.
- the lower limit of the Zr content is preferably 5 mass% or more, and the upper limit of the Zr content is preferably 20 mass% or less.
- the In content is 65 mass% or more, the conductivity of the oxide sputtering target can be secured, and an oxide film can be formed by direct current (DC) sputtering.
- DC direct current
- the In content is 95 mass% or less, a decrease in the transmittance of the formed oxide film at short wavelengths can be suppressed, and visibility can be secured.
- the lower limit of the In content is preferably 75 mass% or more, and the upper limit of the In content is preferably 90 mass% or less.
- the Si content is 0.5 mass% or more, the flexibility of the oxide sputtering target can be ensured, and the crack resistance of the film is improved.
- the content of Si is set to 15 mass% or less, a decrease in the conductivity of the film can be suppressed, and an oxide film can be formed by direct current (DC) sputtering.
- DC direct current
- the oxide sputtering target according to the present embodiment has a composite oxide phase containing at least a part of the above-described metal elements and an indium oxide phase.
- the presence of the indium oxide phase lowers the resistance value of the oxide sputtering target according to the present embodiment, so that an oxide film can be formed by direct current (DC) sputtering.
- DC direct current
- Density variation If the density varies in the target sputtering surface, abnormal discharge may occur during sputtering film formation.
- the area of the target sputtering surface is relatively large, that is, 0.02 m 2 or more, the density in the target sputtering surface tends to vary. Therefore, in the present embodiment, the variation in density within the target sputtering surface is set to within 3%.
- the variation in the density in the thickness direction is set to 5% or less.
- the variation in the density of the oxide sputtering target is caused by the center part (1) where the diagonal lines intersect and the four corner parts (2), (3), (4), and (5).
- a sample was taken from the block, and as shown in FIG. 1B, these five blocks were divided into three ( ⁇ ), ( ⁇ ), and ( ⁇ ) blocks in the thickness direction (divided into three), for a total of 15 blocks. Were sampled, and the density of each sample was measured.
- the variation in density in the target sputtering surface was calculated as follows. From the maximum value and the minimum value of the density in each block in the thickness direction for the five blocks in the target sputtering surface, the target in one block in the thickness direction (for example, five samples of ⁇ 1 to ⁇ 5) is obtained by the above equation. The variation in the density within the sputtering surface is calculated, and the average value of the variation in the density of the three blocks ( ⁇ 1 to ⁇ 5 / ⁇ 1 to ⁇ 5 / ⁇ 1 to ⁇ 5) in the thickness direction is calculated as “the variation in the density within the target sputtering surface”.
- the density variation in the same horizontal plane is calculated from the maximum value and the minimum value of the density by the above equation, and further, the average value of the density variations calculated in each of the same horizontal planes Is referred to as “density variation in the target sputtering surface”.
- the maximum value and the minimum value of the density of each block in the target sputtering surface are calculated from the maximum value and the minimum value of one block in the target sputtering surface by the above equation.
- the dispersion of the density in the thickness direction in one block (for example, three samples of ⁇ 1 to ⁇ 1) is calculated, and the five blocks ( ⁇ 1 to ⁇ 1 / ⁇ 2 to ⁇ 2 / ⁇ 3 to ⁇ 3 / ⁇ 4 to ⁇ 4 / ⁇ 5) in the target sputtering surface are calculated.
- the average value of the density variations of ⁇ 5) was defined as "density variation in the thickness direction".
- the variation of the density in the same vertical direction is calculated from the maximum value and the minimum value of the density by the above equation, and the average value of the density variations calculated in the same vertical direction is calculated. Is referred to as “density variation in the thickness direction”.
- the average value (average density) of the densities measured for the 15 samples described above is 5.5 g / cm 3 or more.
- the average density is preferably 6.0 g / cm 3 or more, and more preferably 6.2 g / cm 3 or more.
- the variation of the specific resistance in the thickness direction is set to within 10%.
- the variation in the specific resistance of the oxide sputtering target is caused by the center part (1) where the diagonal lines intersect and the five corner parts (2), (3), (4), and (5).
- a sample was taken from one block, and as shown in FIG. 1B, these five blocks were divided into three (three) in the thickness direction, and a total of 15 samples were taken. It was measured.
- the variation in the specific resistance in the target sputtering surface was calculated as follows. From the maximum value and the minimum value of the specific resistance of each block in the thickness direction for the five blocks in the target sputtering surface, the above equation is used to calculate the value in one block in the thickness direction (for example, five samples of ⁇ 1 to ⁇ 5). The variation of the specific resistance in the target sputtering surface is calculated, and the average value of the specific resistance variation of the three blocks ( ⁇ 1 to ⁇ 5 / ⁇ 1 to ⁇ 5 / ⁇ 1 to ⁇ 5) in the thickness direction is calculated as “the specific ratio in the target sputtering surface. Resistance variation ".
- the variation of the specific resistance in the same horizontal plane is calculated from the maximum value and the minimum value of the specific resistance by the above equation, and the variation of the specific resistance calculated in each of the same horizontal planes is calculated.
- the average value of was determined as “variation in specific resistance in the target sputtering surface”.
- the maximum value and the minimum value of the specific resistance of each block in the target sputtering surface are calculated according to the above equation.
- the specific resistance in the thickness direction of one block eg, three samples of ⁇ 1 to ⁇ 1
- the five blocks ⁇ 1 to ⁇ 1 / ⁇ 2 to ⁇ 2 / ⁇ 3 to ⁇ 3 / ⁇ 4 to The average value of the variation in specific resistance of ⁇ 4 / ⁇ 5 to ⁇ 5) was defined as “variation in specific resistance in the thickness direction”.
- the variation of the specific resistance in the same vertical direction is calculated from the maximum value and the minimum value of the specific resistance by the above equation, and the variation of the specific resistance calculated in the same vertical direction is further calculated. Is referred to as “variation in specific resistance in the thickness direction”.
- the average value (average specific resistance) of the specific resistances measured for the above-described 15 samples is 1.0 ⁇ 10 ⁇ 2 ⁇ ⁇ cm or less.
- the average specific resistance is preferably 8.5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less, and more preferably 7.5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less.
- zirconium oxide powder (ZrO 2 powder), silicon oxide powder (SiO 2 powder) and indium oxide powder (In 2 O 3 powder) are prepared.
- Zirconium oxide powder (ZrO 2 powder), silicon oxide powder (SiO 2 powder) and indium oxide powder (In 2 O 3 powder) each have a purity of 99.9% by mass or more and an average particle diameter of 0.1 ⁇ m or more and 20 ⁇ m or more. It is preferable to be within the following range.
- the purity of the ZrO 2 powder was calculated by measuring the contents of Fe 2 O 3 , SiO 2 , TiO 2 , and Na 2 O, with the balance being ZrO 2 .
- the ZrO 2 powder of the present embodiment may contain HfO 2 at a maximum of 2.5%.
- the oxide powders are weighed so as to have a predetermined composition ratio, and mixed using a pulverizer / mixer to form a sintering raw material powder.
- the sintering raw material powder preferably has a median diameter (D50) in the range of 0.05 ⁇ m to 1.2 ⁇ m.
- the obtained sintering raw material powder is filled into a molding die and pressed to obtain a molded body having a predetermined shape.
- a pressing method a press, CIP, or the like is used.
- the pressurizing pressure at this time is preferably in the range of 20 MPa or more and 300 MPa or less.
- the temperature may be room temperature, but in order to improve the strength of the molded body, press forming at a temperature in the range of 900 ° C. or more and 950 ° C. or less promotes neck formation and improves the strength of the molded body. I do.
- a pressure may be formed by adding a binder to the sintering raw material powder.
- This compact is placed in a firing apparatus having an oxygen introduction function, and is heated and sintered while introducing oxygen.
- the amount of introduced oxygen is preferably in the range of 3 L / min to 10 L / min. Further, it is preferable that the heating rate be in the range of 50 ° C./h or more and 200 ° C./h or less.
- the temperature is maintained in a temperature range of 1200 ° C. or more and 1400 ° C. or less for 3 hours or more, and thereafter, a temperature exceeding 1400 ° C. (for example, 1500 ° C. or more) Heat and hold until the sintering of the compact proceeds.
- a temperature of 1200 ° C. or more which is the temperature at which sintering of indium oxide powder in the sintering raw material powder is started, and 1400 ° C. or less, at which sintering proceeds due to formation of a composite oxide, for 3 hours or more.
- the upper limit of the holding time in the temperature range of 1200 ° C. to 1400 ° C. is not limited, but is preferably 15 hours or less from the viewpoint of working efficiency. Thereafter, by heating and holding to a temperature exceeding 1400 ° C., the sintering of the molded body proceeds uniformly.
- the oxide sputtering target of the present embodiment is manufactured.
- an oxide film suitable as a shield layer for an in-cell type touch panel or the like is formed by sputtering using the oxide sputtering target of the present embodiment.
- the oxide sputtering target according to the present embodiment has a low resistance value due to the presence of the indium oxide phase, so that an oxide film can be formed by direct current (DC) sputtering.
- the formed oxide film has a composite oxide phase as a whole, has a sufficiently high resistance value, and is particularly suitable as a shield layer.
- the metal component is formed of an oxide containing zirconium, silicon, and indium, the resistance value is high, and visible.
- An oxide film having excellent light transmittance and suitable for a shield layer can be formed.
- the variation in the density within the target sputtering surface is set to 3% or less, the sputtering is stable on the entire target sputtering surface during the sputtering film formation, and the oxide film can be stably formed.
- the variation in the density in the thickness direction is within 5%, an oxide film can be formed stably even when sputtering proceeds.
- the oxide sputtering target of the present embodiment since the variation in the specific resistance within the target sputtering surface is within 10%, the occurrence of abnormal discharge during sputtering can be suppressed. Further, in the oxide sputtering target of the present embodiment, since the variation in the specific resistance in the thickness direction is within 10%, the oxide film is stably formed even when sputtering proceeds. be able to.
- the oxide sputtering target of this embodiment has a relatively large target sputtering surface area of 0.02 m 2 or more, an oxide film can be formed on a large-area substrate.
- a sputter film can be stably formed.
- the sintering of indium oxide in the sintering raw material powder is started at 1200 ° C. or higher, and the composite oxide is Since the sintering is maintained at a temperature range of 1400 ° C. or less for 3 hours or more in which sintering proceeds by forming, oxygen gas is uniformly injected into the molded body while maintaining a gap channel between the sintering raw material powders during sintering. It is possible to penetrate. By heating and maintaining the temperature in this state up to a temperature exceeding 1400 ° C., sintering can be progressed uniformly in the molded body, and a sintered body in which variation in density is sufficiently suppressed can be obtained. It becomes possible.
- the median diameter of the sintering raw material powder is in the range of 0.05 ⁇ m or more and 1.2 ⁇ m or less in the sintering raw material powder forming step S01, the amount of shrinkage during sintering is suppressed to be low. Therefore, even when a large-sized oxide sputtering target is manufactured, generation of cracks and warpage can be suppressed, and manufacturing yield can be improved.
- FIGS. 1A and 1B a rectangular flat plate type sputtering target having a rectangular target sputtering surface has been described.
- the present invention is not limited to this.
- a disk-shaped sputtering target having a circular target sputtering surface may be used.
- a cylindrical sputtering target having a cylindrical target sputtering surface may be used.
- Samples were taken from five blocks of the outer peripheral portions (2), (3), (4), and (5), and as shown in FIG. 4B, these five blocks were placed in the thickness direction ( ⁇ ), ( ⁇ ). ) And ( ⁇ ) are divided into three (divided into three), and a total of 15 samples are collected. The density of each sample in the same horizontal plane or the same vertical direction and the ratio in the same horizontal plane or the same vertical direction are obtained.
- the resistance was measured, and the density variation in the target sputtering surface, the density variation in the thickness direction, and the specific resistance variation in the target sputtering surface, and the thickness were measured by the method described in the above-described embodiment. Variation in resistivity in the direction, it is preferable to calculate the.
- the lower end portion A, the center portion B, and the upper end portion C in the axial direction each have a circumferential direction.
- Samples were taken from a total of 12 blocks at positions (1), (2), (3), and (4) at intervals (90 ° intervals), and these 12 blocks were removed as shown in FIG. 5C. Divide into three ( ⁇ ), ( ⁇ ), and ( ⁇ ) blocks in the thickness direction (radial direction), and collect a total of 36 samples. Each sample is in the same horizontal plane or the same.
- the density in the vertical direction and the specific resistance in the same horizontal plane or in the same vertical direction were measured, and the density variation in the target sputtering surface (in the cylindrical surface) and the density in the thickness direction were determined by the method described in the section of the above embodiment.
- target Resistivity variation in the sputtering plane (the cylindrical surface) it is preferable to the ratio calculated variation in resistance, a in the thickness direction.
- ⁇ Oxide sputtering target As raw material powders, indium oxide powder (In 2 O 3 powder: purity 99.9% by mass or more, average particle size 1 ⁇ m) and silicon oxide powder (SiO 2 powder: purity 99.8% by mass or more, average particle size 2 ⁇ m) And zirconium oxide powder (ZrO 2 powder: purity 99.9% by mass or more, average particle size 2 ⁇ m).
- the purity of the ZrO 2 powder was calculated by measuring the contents of Fe 2 O 3 , SiO 2 , TiO 2 , and Na 2 O, with the balance being ZrO 2 .
- the ZrO 2 powder of the present embodiment may contain HfO 2 at a maximum of 2.5% by mass. And these were weighed so that it might become a compounding ratio shown in Table 1.
- each weighed raw material powder was wet-pulverized using a basket mill using zirconia balls having a diameter of 2 mm as a grinding medium or a bead mill using zirconia balls having a diameter of 0.5 mm as a grinding medium. Mixed. The obtained slurry was dried, and the zirconia balls were removed with a 250 ⁇ m sieve to obtain a sintering raw material powder. Table 1 shows the median diameter (D50) of the obtained sintering raw material powder.
- the median diameter was determined by preparing 100 mL of an aqueous solution having a sodium hexametaphosphate concentration of 0.2%, adding 10 mg of the mixed powder to the aqueous solution, and using a laser diffraction scattering method (measurement apparatus: manufactured by Nikkiso Co., Ltd., Microtrac MT3000). The distribution was measured. A cumulative particle size distribution curve was created from the obtained particle size distribution to obtain a median diameter (D50).
- press molding or CIP molding was performed using a molding die having a size of 165 mm ⁇ 298 mm.
- the conditions for press molding were 920 ° C. and a pressure of 25 MPa, and the conditions for CIP molding were room temperature (25 ° C.) and a pressure of 100 MPa.
- press molding or CIP molding was performed using a mold having an outer diameter of 205 mm, an inner diameter of 165 mm, and a height of 200 mm.
- the conditions for press molding were 920 ° C. and a pressure of 25 MPa, and the conditions for CIP molding were room temperature (25 ° C.) and a pressure of 100 MPa.
- the obtained molded body is charged into a firing device having an oxygen introduction function (internal volume of 27,000 cm 3 ), and is heated and sintered while introducing oxygen.
- the introduced amount of oxygen was 6 L / min.
- the rate of temperature rise was 120 ° C./h.
- the temperature was maintained under the conditions shown in Table 1, and then the main firing was performed under the firing conditions shown in Table 1, to obtain a sintered body.
- the obtained sintered body is subjected to wet grinding to have a size of 126 mm ⁇ 178 mm ⁇ 6 mmt in a rectangular flat plate type sputtering target, and an outer diameter of 155 mm, an inner diameter of 135 mm and a height of 150 mm in a cylindrical type sputtering target. Four pieces were used to make the length 600 mm.
- Table 2 shows the evaluation results.
- Metal component composition A sample was cut out from the prepared oxide sputtering target, pulverized, pretreated with an acid, and analyzed for metal components of Zr, Si, and In by ICP-AES. The content of each metal component with respect to the content was calculated and is shown in Table 2.
- the variation in the density within the target sputtering surface was calculated as follows. From the maximum value and the minimum value of the density for each block in the thickness direction for the five blocks in the target sputtering surface, the same horizontal plane in one block in the thickness direction (target sputtering surface) The variation in the density in (in) was calculated, and the average value of the three blocks in the thickness direction was defined as the variation in the density in the target sputtering surface.
- the variation in density in the thickness direction was calculated as follows. For the three blocks in the thickness direction, from the maximum value and the minimum value of the density of each block in the target sputtering surface, the same vertical direction (thickness) in one block in the target sputtering surface is obtained by the equation described in the embodiment. The variation in the density in the thickness direction was calculated, and the average value of the five blocks in the target sputtering surface was defined as the variation in the density in the thickness direction.
- the X axis is an arbitrary end face direction
- the Y axis is an end face direction perpendicular to the X axis
- the variation in the density within the target sputtering surface was calculated as follows. From the maximum value and the minimum value of the density in each block in the thickness direction for 12 blocks in the target sputtering surface, the same horizontal plane in one block in the thickness direction (target sputtering surface) The variation in the density in (in) was calculated, and the average value of the three blocks in the thickness direction was defined as the variation in the density in the target sputtering surface.
- the variation in density in the thickness direction was calculated as follows. For the three blocks in the thickness direction, from the maximum value and the minimum value of the density of each block in the target sputtering surface, the same vertical direction (thickness) in one block in the target sputtering surface is obtained by the equation described in the embodiment. The variation in the density in the thickness direction was calculated, and the average value of the 12 blocks in the target sputtering surface was defined as the variation in the density in the thickness direction.
- a low resistivity meter (Loresta manufactured by Mitsubishi Chemical Co., Ltd.) was used for 15 blocks similar to the sample for density measurement for the rectangular flat plate type sputtering target and for 36 blocks for the cylindrical type sputtering target. -GP) using the four-probe method. The measurement was performed at a temperature of 23 ⁇ 5 ° C. and a humidity of 50 ⁇ 20%. Then, similarly to the variation of the density, the variation of the specific resistance in the target sputtering surface and the variation of the specific resistance in the thickness direction were calculated. Table 2 shows the average value of the specific resistance.
- the obtained oxide sputtering target was soldered to a backing plate or a backing tube using In solder, and then mounted on a magnetron sputtering device. Then, using a magnetron sputtering apparatus, an Ar gas was used as a sputtering gas, a flow rate was set to 50 sccm, a pressure was set to 0.67 Pa, and an input power of 5 W / cm 2 was used to perform sputtering for 1 hour. The number of abnormal discharges was measured by the arc count function. In this embodiment, RPG-50 (manufactured by mks) was used as a power supply device.
- the number of abnormal discharges during 1 hour from the start of sputtering is defined as “initial”, and the number of abnormal discharges during 1 hour from the time when the depth of the deepest portion of the erosion portion reaches 5 mm is defined as “final”.
- initial The number of abnormal discharges during 1 hour from the start of sputtering
- final the number of abnormal discharges during 1 hour from the time when the depth of the deepest portion of the erosion portion reaches 5 mm.
- Comparative Example 1 which was held at 1000 ° C. for 5 hours in the sintering process, the variation in the density in the target sputtering surface, the variation in the density in the thickness direction, and the variation in the specific resistance in the thickness direction were large. The number has increased.
- Comparative Example 2 which was held at 1450 ° C. for 5 hours in the sintering step, the density variation in the target sputtering surface, the density variation in the thickness direction, the specific resistance variation in the target sputtering surface, and the ratio in the thickness direction The variation in resistance was large, and the number of abnormal discharges at the end increased.
- Comparative Example 3 held at 1300 ° C. for 1 hour in the sintering process, the variation in density, the variation in density in the thickness direction, and the variation in specific resistance in the thickness direction in the target sputtering surface were large, and abnormal discharge at the end The number has increased.
- Example 1-12 of the present invention in which the temperature was kept in the temperature range of 1200 ° C. to 1400 ° C. for 3 hours or more in the sintering step, the density variation in the target sputtering surface and the density variation in the thickness direction.
- the dispersion of the specific resistance in the target sputtering surface and the dispersion of the specific resistance in the thickness direction were small, the number of abnormal discharges was small, and the sputtering film could be stably formed.
- an oxide sputtering target capable of stably forming a sputter film even when the target sputtering surface is relatively large, and a method for manufacturing this oxide sputtering target It was confirmed that it could be provided.
- an oxide sputtering target that can stably form a sputter film even when the target sputtering surface is relatively large, and a method for manufacturing the oxide sputtering target.
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Abstract
This oxide sputtering target comprises an oxide that contains zirconium, silicon, and indium as metal components. The oxide sputtering target is characterized in that variation of density in a target sputtering surface is 3% or less and variation of density in the thickness direction is 5% or less.
Description
本発明は、金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物からなる酸化物スパッタリングターゲット、及び、この酸化物スパッタリングターゲットの製造方法に関するものである。
本願は、2018年8月27日に日本に出願された特願2018-158101号、および、2019年7月4日に日本に出願された特願2019-125596号について優先権を主張し、それらの内容をここに援用する。 The present invention relates to an oxide sputtering target composed of an oxide containing zirconium, silicon and indium as metal components, and a method for producing the oxide sputtering target.
This application claims the priority of Japanese Patent Application No. 2018-158101 filed in Japan on August 27, 2018 and Japanese Patent Application No. 2019-125596 filed in Japan on Jul. 4, 2019. The contents of the above are incorporated herein.
本願は、2018年8月27日に日本に出願された特願2018-158101号、および、2019年7月4日に日本に出願された特願2019-125596号について優先権を主張し、それらの内容をここに援用する。 The present invention relates to an oxide sputtering target composed of an oxide containing zirconium, silicon and indium as metal components, and a method for producing the oxide sputtering target.
This application claims the priority of Japanese Patent Application No. 2018-158101 filed in Japan on August 27, 2018 and Japanese Patent Application No. 2019-125596 filed in Japan on Jul. 4, 2019. The contents of the above are incorporated herein.
液晶ディスプレイ、有機ELディスプレイ、及び、タッチパネル等のディスプレイパネルにおいては、液晶素子や有機EL素子等の帯電による誤動作を防止するために、シールド層を配設している。特に、インセル型のタッチパネルにおいては、上述のシールド層には、外部からのノイズは排除しながら、タッチ信号をパネル内部のセンサー部分に到達させる作用も求められる。
また、このシールド層においては、ディスプレイパネルの視認性を確保するために、可視光の透過性が高いことも求められる。 In a display panel such as a liquid crystal display, an organic EL display, and a touch panel, a shield layer is provided in order to prevent a malfunction due to charging of a liquid crystal element or an organic EL element. In particular, in the in-cell type touch panel, the above-described shield layer is required to have an action of causing a touch signal to reach a sensor portion inside the panel while eliminating external noise.
The shield layer is also required to have high visible light transmittance in order to ensure the visibility of the display panel.
また、このシールド層においては、ディスプレイパネルの視認性を確保するために、可視光の透過性が高いことも求められる。 In a display panel such as a liquid crystal display, an organic EL display, and a touch panel, a shield layer is provided in order to prevent a malfunction due to charging of a liquid crystal element or an organic EL element. In particular, in the in-cell type touch panel, the above-described shield layer is required to have an action of causing a touch signal to reach a sensor portion inside the panel while eliminating external noise.
The shield layer is also required to have high visible light transmittance in order to ensure the visibility of the display panel.
例えば、特許文献1においては、上述のシールド層として、酸化インジウムスズ(ITO)を主成分とした透明導電膜が提案されている。
ところで、酸化インジウムスズ(ITO)を主成分とした透明導電膜においては、可視光での透過率が低いために、黄色味が掛かっているように見えてしまい、視認性が劣化するおそれがあった。 For example,Patent Document 1 proposes a transparent conductive film mainly containing indium tin oxide (ITO) as the above-mentioned shield layer.
By the way, a transparent conductive film containing indium tin oxide (ITO) as a main component has a low transmittance with respect to visible light, so that the transparent conductive film looks yellowish and visibility may be deteriorated. Was.
ところで、酸化インジウムスズ(ITO)を主成分とした透明導電膜においては、可視光での透過率が低いために、黄色味が掛かっているように見えてしまい、視認性が劣化するおそれがあった。 For example,
By the way, a transparent conductive film containing indium tin oxide (ITO) as a main component has a low transmittance with respect to visible light, so that the transparent conductive film looks yellowish and visibility may be deteriorated. Was.
そこで、上述のシールド層として、金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物膜を適用することが考えられる。
例えば、特許文献2~4には、金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物膜を成膜する際に用いられる酸化物スパッタリングターゲットが提案されている。 Therefore, it is conceivable to apply an oxide film containing zirconium, silicon and indium as metal components as the above-mentioned shield layer.
For example,Patent Documents 2 to 4 propose an oxide sputtering target used when forming an oxide film containing zirconium, silicon, and indium as metal components.
例えば、特許文献2~4には、金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物膜を成膜する際に用いられる酸化物スパッタリングターゲットが提案されている。 Therefore, it is conceivable to apply an oxide film containing zirconium, silicon and indium as metal components as the above-mentioned shield layer.
For example,
ところで、特許文献2-4に開示された酸化物スパッタリングターゲットは、主に、情報記録媒体である光ディスクの誘電体層及び保護層を成膜することを想定したものであり、ターゲットスパッタ面が比較的小さいものであった。
インセル型のタッチパネル等のシールド層を成膜する際には、ターゲットスパッタ面の面積が大きい大型のスパッタリングターゲットや円筒型スパッタリングターゲットを用いることが好ましい。
上述の特許文献2~4においては、大型のスパッタリングターゲットを製造した場合に、焼成が不十分となって、密度のばらつきや酸素濃度のばらつきが発生したり、割れや反りが生じたりして、安定してスパッタ成膜を行うことができないおそれがあった。 By the way, the oxide sputtering target disclosed in Patent Documents 2-4 is mainly intended for forming a dielectric layer and a protective layer of an optical disk as an information recording medium, and the target sputtering surface is comparatively large. Was small.
When a shield layer such as an in-cell touch panel is formed, it is preferable to use a large sputtering target or a cylindrical sputtering target having a large target sputtering surface area.
In the above-mentionedPatent Documents 2 to 4, when a large-sized sputtering target is manufactured, sintering becomes insufficient, and variations in density and oxygen concentration occur, and cracks and warpages occur. There is a possibility that a sputter film cannot be stably formed.
インセル型のタッチパネル等のシールド層を成膜する際には、ターゲットスパッタ面の面積が大きい大型のスパッタリングターゲットや円筒型スパッタリングターゲットを用いることが好ましい。
上述の特許文献2~4においては、大型のスパッタリングターゲットを製造した場合に、焼成が不十分となって、密度のばらつきや酸素濃度のばらつきが発生したり、割れや反りが生じたりして、安定してスパッタ成膜を行うことができないおそれがあった。 By the way, the oxide sputtering target disclosed in Patent Documents 2-4 is mainly intended for forming a dielectric layer and a protective layer of an optical disk as an information recording medium, and the target sputtering surface is comparatively large. Was small.
When a shield layer such as an in-cell touch panel is formed, it is preferable to use a large sputtering target or a cylindrical sputtering target having a large target sputtering surface area.
In the above-mentioned
この発明は、前述した事情に鑑みてなされたものであって、ターゲットスパッタ面が比較的大きくても、安定してスパッタ成膜を行うことが可能な酸化物スパッタリングターゲット、及び、この酸化物スパッタリングターゲットの製造方法を提供することを目的とする。
The present invention has been made in view of the above-described circumstances, and has an oxide sputtering target capable of stably forming a sputter film even when a target sputtering surface is relatively large, and an oxide sputtering target having the same structure. An object of the present invention is to provide a method for manufacturing a target.
上記課題を解決するために、本発明の酸化物スパッタリングターゲットは、金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物からなる酸化物スパッタリングターゲットであって、ターゲットスパッタ面内における密度のばらつきが3%以内とされ、厚さ方向における密度のばらつきが5%以内とされていることを特徴としている。
In order to solve the above problems, the oxide sputtering target of the present invention is an oxide sputtering target composed of an oxide containing zirconium, silicon, and indium as a metal component, and has a variation in density in a target sputtering surface. It is characterized in that it is within 3% and the variation in density in the thickness direction is within 5%.
本発明の酸化物スパッタリングターゲットによれば、金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物で構成されているので、抵抗が高く、かつ、可視光の透過性に優れ、シールド層に適した酸化物膜を成膜することが可能となる。
そして、ターゲットスパッタ面内における密度のばらつきが3%以内とされているので、スパッタ成膜時においてターゲットスパッタ面全体でスパッタが安定し、酸化物膜を安定して成膜することができる。
また、厚さ方向における密度のばらつきが5%以内とされているので、スパッタが進行した場合であっても、酸化物膜を安定して成膜することができる。 According to the oxide sputtering target of the present invention, since it is composed of an oxide containing zirconium, silicon and indium as the metal component, it has a high resistance, and has excellent visible light transmittance, and is suitable for the shield layer. This makes it possible to form an oxide film.
Since the variation in the density within the target sputtering surface is set to 3% or less, the sputtering is stable on the entire target sputtering surface during the sputtering film formation, and the oxide film can be stably formed.
In addition, since the variation in the density in the thickness direction is within 5%, an oxide film can be formed stably even when sputtering proceeds.
そして、ターゲットスパッタ面内における密度のばらつきが3%以内とされているので、スパッタ成膜時においてターゲットスパッタ面全体でスパッタが安定し、酸化物膜を安定して成膜することができる。
また、厚さ方向における密度のばらつきが5%以内とされているので、スパッタが進行した場合であっても、酸化物膜を安定して成膜することができる。 According to the oxide sputtering target of the present invention, since it is composed of an oxide containing zirconium, silicon and indium as the metal component, it has a high resistance, and has excellent visible light transmittance, and is suitable for the shield layer. This makes it possible to form an oxide film.
Since the variation in the density within the target sputtering surface is set to 3% or less, the sputtering is stable on the entire target sputtering surface during the sputtering film formation, and the oxide film can be stably formed.
In addition, since the variation in the density in the thickness direction is within 5%, an oxide film can be formed stably even when sputtering proceeds.
本発明の酸化物スパッタリングターゲットにおいては、ターゲットスパッタ面内における比抵抗のばらつきが10%以内とされ、厚さ方向における比抵抗のばらつきが10%以内とされていることが好ましい。
この場合、ターゲットスパッタ面内における比抵抗のばらつきが10%以内とされているので、スパッタ時における異常放電の発生を抑制することができる。
また、厚さ方向における比抵抗のばらつきが10%以内とされているので、スパッタが進行した場合であっても、酸化物膜を安定して成膜することができる。 In the oxide sputtering target of the present invention, it is preferable that the variation of the specific resistance in the target sputtering surface is within 10% and the variation of the specific resistance in the thickness direction is within 10%.
In this case, since the variation in the specific resistance within the target sputtering surface is set to be within 10%, it is possible to suppress occurrence of abnormal discharge during sputtering.
Further, since the variation in the specific resistance in the thickness direction is set to be within 10%, the oxide film can be stably formed even when the sputtering proceeds.
この場合、ターゲットスパッタ面内における比抵抗のばらつきが10%以内とされているので、スパッタ時における異常放電の発生を抑制することができる。
また、厚さ方向における比抵抗のばらつきが10%以内とされているので、スパッタが進行した場合であっても、酸化物膜を安定して成膜することができる。 In the oxide sputtering target of the present invention, it is preferable that the variation of the specific resistance in the target sputtering surface is within 10% and the variation of the specific resistance in the thickness direction is within 10%.
In this case, since the variation in the specific resistance within the target sputtering surface is set to be within 10%, it is possible to suppress occurrence of abnormal discharge during sputtering.
Further, since the variation in the specific resistance in the thickness direction is set to be within 10%, the oxide film can be stably formed even when the sputtering proceeds.
また、本発明の酸化物スパッタリングターゲットにおいては、ターゲットスパッタ面の面積が0.02m2以上であってもよい。
この場合、ターゲットスパッタ面の面積が0.02m2以上と比較的大きいことから、大面積の基板に酸化物膜を成膜することが可能となる。酸化物スパッタリングターゲットは、平板形状であってもよいし、円筒型形状であってもよい。 In the oxide sputtering target of the present invention, the area of the target sputtering surface may be 0.02 m 2 or more.
In this case, since the area of the target sputtering surface is relatively large at 0.02 m 2 or more, an oxide film can be formed over a large-area substrate. The oxide sputtering target may have a flat plate shape or a cylindrical shape.
この場合、ターゲットスパッタ面の面積が0.02m2以上と比較的大きいことから、大面積の基板に酸化物膜を成膜することが可能となる。酸化物スパッタリングターゲットは、平板形状であってもよいし、円筒型形状であってもよい。 In the oxide sputtering target of the present invention, the area of the target sputtering surface may be 0.02 m 2 or more.
In this case, since the area of the target sputtering surface is relatively large at 0.02 m 2 or more, an oxide film can be formed over a large-area substrate. The oxide sputtering target may have a flat plate shape or a cylindrical shape.
本発明の酸化物スパッタリングターゲットの製造方法は、金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物からなる酸化物スパッタリングターゲットの製造方法であって、酸化ジルコニウム粉、酸化ケイ素粉および酸化インジウム粉を混合した酸化物を含む焼結原料粉を得る焼結原料粉形成工程と、得られた前記焼結原料粉を焼結して焼結体を得る焼結工程と、を有し、前記焼結工程では、酸素を導入しながら加熱し、1200℃以上1400℃以下の温度範囲で3時間以上保持した後、1400℃を超える温度にまで加熱して保持することを特徴としている。
The method for producing an oxide sputtering target of the present invention is a method for producing an oxide sputtering target comprising an oxide containing zirconium, silicon and indium as metal components, comprising zirconium oxide powder, silicon oxide powder and indium oxide powder. And a sintering step of sintering the obtained sintering material powder to obtain a sintered body. The bonding step is characterized by heating while introducing oxygen, maintaining the temperature in a temperature range of 1200 ° C. or more and 1400 ° C. or less for 3 hours or more, and then heating and maintaining the temperature to a temperature exceeding 1400 ° C.
この構成の酸化物スパッタリングターゲットの製造方法によれば、焼結工程において、焼結原料粉中の酸化インジウムの焼結が開始される1200℃以上で、かつ、複合酸化物の形成によって焼結が進行する1400℃以下の温度範囲で3時間以上保持するので、焼結時に焼結原料粉同士の間の隙間チャンネルを保った状態で酸素ガスを内部に浸透させることが可能となる。
そして、その後、1400℃を超える温度にまで加熱して保持することで、均一に焼結を進行させることができ、密度のばらつきの小さい焼結体を得ることが可能となる。 According to the method for manufacturing an oxide sputtering target having this configuration, in the sintering step, sintering is performed at 1200 ° C. or higher at which sintering of indium oxide in the sintering raw material powder is started, and sintering is performed by forming a composite oxide. Since the temperature is maintained in the temperature range of 1400 ° C. or less for 3 hours or more, it is possible to allow oxygen gas to permeate into the inside while maintaining the gap channel between the sintering raw material powders during sintering.
Then, by heating and holding the temperature to a temperature exceeding 1400 ° C., sintering can be progressed uniformly, and a sintered body having a small variation in density can be obtained.
そして、その後、1400℃を超える温度にまで加熱して保持することで、均一に焼結を進行させることができ、密度のばらつきの小さい焼結体を得ることが可能となる。 According to the method for manufacturing an oxide sputtering target having this configuration, in the sintering step, sintering is performed at 1200 ° C. or higher at which sintering of indium oxide in the sintering raw material powder is started, and sintering is performed by forming a composite oxide. Since the temperature is maintained in the temperature range of 1400 ° C. or less for 3 hours or more, it is possible to allow oxygen gas to permeate into the inside while maintaining the gap channel between the sintering raw material powders during sintering.
Then, by heating and holding the temperature to a temperature exceeding 1400 ° C., sintering can be progressed uniformly, and a sintered body having a small variation in density can be obtained.
本発明の酸化物スパッタリングターゲットの製造方法においては、前記焼結原料粉のメディアン径(D50)が0.05μm以上1.2μm以下の範囲内であることが好ましい。
この場合、前記焼結原料粉のメディアン径(D50)が0.05μm以上1.2μm以下の範囲内と比較的小さいため、焼結時における収縮量を低く抑えることができ、大型の酸化物スパッタリングターゲットを製造した場合であっても、割れや反りの発生を抑制することができ、製造歩留まりの向上を図ることができる。 In the method for manufacturing an oxide sputtering target of the present invention, it is preferable that the median diameter (D50) of the sintering raw material powder is in a range of 0.05 μm or more and 1.2 μm or less.
In this case, since the median diameter (D50) of the sintering raw material powder is relatively small in the range of 0.05 μm or more and 1.2 μm or less, the amount of shrinkage during sintering can be suppressed low, and large-sized oxide sputtering Even when the target is manufactured, generation of cracks and warpage can be suppressed, and the manufacturing yield can be improved.
この場合、前記焼結原料粉のメディアン径(D50)が0.05μm以上1.2μm以下の範囲内と比較的小さいため、焼結時における収縮量を低く抑えることができ、大型の酸化物スパッタリングターゲットを製造した場合であっても、割れや反りの発生を抑制することができ、製造歩留まりの向上を図ることができる。 In the method for manufacturing an oxide sputtering target of the present invention, it is preferable that the median diameter (D50) of the sintering raw material powder is in a range of 0.05 μm or more and 1.2 μm or less.
In this case, since the median diameter (D50) of the sintering raw material powder is relatively small in the range of 0.05 μm or more and 1.2 μm or less, the amount of shrinkage during sintering can be suppressed low, and large-sized oxide sputtering Even when the target is manufactured, generation of cracks and warpage can be suppressed, and the manufacturing yield can be improved.
本発明によれば、ターゲットスパッタ面が比較的大きくても、安定してスパッタ成膜を行うことが可能な酸化物スパッタリングターゲット、及び、この酸化物スパッタリングターゲットの製造方法を提供することができる。
According to the present invention, it is possible to provide an oxide sputtering target that can stably form a sputter film even when the target sputtering surface is relatively large, and a method for manufacturing the oxide sputtering target.
以下に、本発明の実施形態である酸化物スパッタリングターゲット、及び、酸化物スパッタリングターゲットの製造方法について添付した図面を参照して説明する。
本実施形態に係る酸化物スパッタリングターゲットは、液晶ディスプレイパネル、有機ELディスプレイパネル、及び、タッチパネル等のディスプレイパネルにおいて、帯電防止のために配設されるシールド層として適した酸化物膜を成膜する際に用いられるものである。 Hereinafter, an oxide sputtering target according to an embodiment of the present invention and a method for manufacturing the oxide sputtering target will be described with reference to the accompanying drawings.
The oxide sputtering target according to the present embodiment forms an oxide film suitable as a shield layer provided for preventing static electricity in a display panel such as a liquid crystal display panel, an organic EL display panel, and a touch panel. It is used at the time.
本実施形態に係る酸化物スパッタリングターゲットは、液晶ディスプレイパネル、有機ELディスプレイパネル、及び、タッチパネル等のディスプレイパネルにおいて、帯電防止のために配設されるシールド層として適した酸化物膜を成膜する際に用いられるものである。 Hereinafter, an oxide sputtering target according to an embodiment of the present invention and a method for manufacturing the oxide sputtering target will be described with reference to the accompanying drawings.
The oxide sputtering target according to the present embodiment forms an oxide film suitable as a shield layer provided for preventing static electricity in a display panel such as a liquid crystal display panel, an organic EL display panel, and a touch panel. It is used at the time.
本実施形態に係る酸化物スパッタリングターゲットは、金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物で構成されている。本実施形態の酸化物スパッタリングターゲットにおいては、上述の金属元素の少なくとも一部を含む複合酸化物相と酸化インジウム相とを有している。
本実施形態では、図1Aおよび図1Bに示すように、スパッタ面が矩形状をなす矩形平板型スパッタリングターゲットとされており、ターゲットスパッタ面の面積が0.02m2以上とされている。 The oxide sputtering target according to the present embodiment is composed of an oxide containing zirconium, silicon and indium as metal components. The oxide sputtering target of the present embodiment has a composite oxide phase containing at least a part of the above-described metal elements and an indium oxide phase.
In this embodiment, as shown in FIGS. 1A and 1B, the sputtering surface is a rectangular flat-plate type sputtering target having a rectangular shape, and the area of the target sputtering surface is 0.02 m 2 or more.
本実施形態では、図1Aおよび図1Bに示すように、スパッタ面が矩形状をなす矩形平板型スパッタリングターゲットとされており、ターゲットスパッタ面の面積が0.02m2以上とされている。 The oxide sputtering target according to the present embodiment is composed of an oxide containing zirconium, silicon and indium as metal components. The oxide sputtering target of the present embodiment has a composite oxide phase containing at least a part of the above-described metal elements and an indium oxide phase.
In this embodiment, as shown in FIGS. 1A and 1B, the sputtering surface is a rectangular flat-plate type sputtering target having a rectangular shape, and the area of the target sputtering surface is 0.02 m 2 or more.
そして、本実施形態に係る酸化物スパッタリングターゲットにおいては、ターゲットスパッタ面内における密度のばらつきが3%以内とされ、厚さ方向における密度のばらつきが5%以内とされている。
本実施形態においては、複数の箇所で測定した密度の平均値(平均密度)が5.5g/cm3以上とされている。 In the oxide sputtering target according to the present embodiment, the variation in density in the target sputtering surface is set to 3% or less, and the variation in density in the thickness direction is set to 5% or less.
In the present embodiment, the average value (average density) of the densities measured at a plurality of locations is set to 5.5 g / cm 3 or more.
本実施形態においては、複数の箇所で測定した密度の平均値(平均密度)が5.5g/cm3以上とされている。 In the oxide sputtering target according to the present embodiment, the variation in density in the target sputtering surface is set to 3% or less, and the variation in density in the thickness direction is set to 5% or less.
In the present embodiment, the average value (average density) of the densities measured at a plurality of locations is set to 5.5 g / cm 3 or more.
さらに、本実施形態に係る酸化物スパッタリングターゲットにおいては、ターゲットスパッタ面内における比抵抗のばらつきが10%以内とされ、厚さ方向における比抵抗のばらつきが10%以内とされている。
本実施形態においては、複数の箇所で測定した比抵抗の平均値(平均比抵抗)が1.0×10-2Ω・cm以下とされている。 Furthermore, in the oxide sputtering target according to the present embodiment, the variation of the specific resistance in the target sputtering surface is set to 10% or less, and the variation of the specific resistance in the thickness direction is set to 10% or less.
In the present embodiment, the average value of the specific resistance measured at a plurality of locations (average specific resistance) is set to 1.0 × 10 −2 Ω · cm or less.
本実施形態においては、複数の箇所で測定した比抵抗の平均値(平均比抵抗)が1.0×10-2Ω・cm以下とされている。 Furthermore, in the oxide sputtering target according to the present embodiment, the variation of the specific resistance in the target sputtering surface is set to 10% or less, and the variation of the specific resistance in the thickness direction is set to 10% or less.
In the present embodiment, the average value of the specific resistance measured at a plurality of locations (average specific resistance) is set to 1.0 × 10 −2 Ω · cm or less.
以下に、本実施形態の酸化物スパッタリングターゲットにおいて、酸化物の組成、相構成、ターゲットスパッタ面内における密度のばらつき、厚さ方向における密度のばらつき、ターゲットスパッタ面内における比抵抗のばらつき、厚さ方向における比抵抗のばらつきを、上述のように規定した理由を示す。
Hereinafter, in the oxide sputtering target of the present embodiment, the composition of the oxide, the phase configuration, the variation in the density in the target sputtering surface, the variation in the density in the thickness direction, the variation in the specific resistance in the target sputtering surface, the thickness The reason why the variation in the specific resistance in the direction is defined as described above will be described.
(酸化物組成)
本実施形態である酸化物スパッタリングターゲットにおいては、金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物で構成されている。このような組成の酸化物スパッタリングターゲットにおいては、抵抗値が十分に高く、かつ、可視光の透過性に優れた酸化物膜を成膜することが可能となる。
本実施形態においては、金属成分の合計を100mass%として、Zrの含有量が2mass%以上27mass%以下の範囲内、Inの含有量が65mass%以上95mass%以下の範囲内、Siの含有量が0.5mass%以上15mass%以下の範囲内、及び不可避不純物金属元素とされていることが好ましい。 (Oxide composition)
The oxide sputtering target according to the present embodiment is composed of an oxide containing zirconium, silicon and indium as the metal component. In an oxide sputtering target having such a composition, it is possible to form an oxide film having a sufficiently high resistance value and excellent transmittance of visible light.
In the present embodiment, assuming that the total of the metal components is 100 mass%, the Zr content is in the range of 2 mass% to 27 mass%, the In content is in the range of 65 mass% to 95 mass%, and the Si content is It is preferable that it is in the range of 0.5 mass% or more and 15 mass% or less and is an unavoidable impurity metal element.
本実施形態である酸化物スパッタリングターゲットにおいては、金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物で構成されている。このような組成の酸化物スパッタリングターゲットにおいては、抵抗値が十分に高く、かつ、可視光の透過性に優れた酸化物膜を成膜することが可能となる。
本実施形態においては、金属成分の合計を100mass%として、Zrの含有量が2mass%以上27mass%以下の範囲内、Inの含有量が65mass%以上95mass%以下の範囲内、Siの含有量が0.5mass%以上15mass%以下の範囲内、及び不可避不純物金属元素とされていることが好ましい。 (Oxide composition)
The oxide sputtering target according to the present embodiment is composed of an oxide containing zirconium, silicon and indium as the metal component. In an oxide sputtering target having such a composition, it is possible to form an oxide film having a sufficiently high resistance value and excellent transmittance of visible light.
In the present embodiment, assuming that the total of the metal components is 100 mass%, the Zr content is in the range of 2 mass% to 27 mass%, the In content is in the range of 65 mass% to 95 mass%, and the Si content is It is preferable that it is in the range of 0.5 mass% or more and 15 mass% or less and is an unavoidable impurity metal element.
Zrの含有量を2mass%以上とした場合には、成膜した酸化物膜の耐久性を向上させることができるとともに、硬度が硬くなり、ひっかき傷に強くなる。一方、Zrの含有量を27mass%以下とした場合には、屈折率が増大することを抑制でき、不要な反射の発生を抑制できるので、成膜した酸化物膜の可視光の透過率が低下することを抑制できる。
金属成分の合計を100mass%として、Zrの含有量の下限は5mass%以上とすることが好ましく、Zrの含有量の上限は20mass%以下とすることが好ましい。 When the content of Zr is 2 mass% or more, the durability of the formed oxide film can be improved, and the hardness is increased and the oxide film is resistant to scratches. On the other hand, when the content of Zr is 27 mass% or less, the increase in the refractive index can be suppressed, and the occurrence of unnecessary reflection can be suppressed, so that the visible light transmittance of the formed oxide film decreases. Can be suppressed.
Assuming that the total of the metal components is 100 mass%, the lower limit of the Zr content is preferably 5 mass% or more, and the upper limit of the Zr content is preferably 20 mass% or less.
金属成分の合計を100mass%として、Zrの含有量の下限は5mass%以上とすることが好ましく、Zrの含有量の上限は20mass%以下とすることが好ましい。 When the content of Zr is 2 mass% or more, the durability of the formed oxide film can be improved, and the hardness is increased and the oxide film is resistant to scratches. On the other hand, when the content of Zr is 27 mass% or less, the increase in the refractive index can be suppressed, and the occurrence of unnecessary reflection can be suppressed, so that the visible light transmittance of the formed oxide film decreases. Can be suppressed.
Assuming that the total of the metal components is 100 mass%, the lower limit of the Zr content is preferably 5 mass% or more, and the upper limit of the Zr content is preferably 20 mass% or less.
Inの含有量を65mass%以上とした場合には、酸化物スパッタリングターゲットの導電性を確保でき、直流(DC)スパッタによって酸化物膜を成膜することが可能となる。一方、Inの含有量を95mass%以下とした場合には、成膜した酸化物膜の短波長の透過率が低下することを抑制でき、視認性を確保することができる。
金属成分の合計を100mass%として、Inの含有量の下限は75mass%以上とすることが好ましく、Inの含有量の上限は90mass%以下とすることが好ましい。 When the In content is 65 mass% or more, the conductivity of the oxide sputtering target can be secured, and an oxide film can be formed by direct current (DC) sputtering. On the other hand, when the In content is 95 mass% or less, a decrease in the transmittance of the formed oxide film at short wavelengths can be suppressed, and visibility can be secured.
Assuming that the total of the metal components is 100 mass%, the lower limit of the In content is preferably 75 mass% or more, and the upper limit of the In content is preferably 90 mass% or less.
金属成分の合計を100mass%として、Inの含有量の下限は75mass%以上とすることが好ましく、Inの含有量の上限は90mass%以下とすることが好ましい。 When the In content is 65 mass% or more, the conductivity of the oxide sputtering target can be secured, and an oxide film can be formed by direct current (DC) sputtering. On the other hand, when the In content is 95 mass% or less, a decrease in the transmittance of the formed oxide film at short wavelengths can be suppressed, and visibility can be secured.
Assuming that the total of the metal components is 100 mass%, the lower limit of the In content is preferably 75 mass% or more, and the upper limit of the In content is preferably 90 mass% or less.
Siの含有量を0.5mass%以上とした場合には、酸化物スパッタリングターゲットの柔軟性を確保でき、膜の割れ耐性が向上する。一方、Siの含有量を15mass%以下とした場合には、膜の導電性が低下することを抑制でき、直流(DC)スパッタによって酸化物膜を成膜することが可能となる。
金属成分の合計を100mass%として、Siの含有量の下限は2mass%以上とすることが好ましく、Siの含有量の上限は7mass%以下とすることが好ましい。 When the Si content is 0.5 mass% or more, the flexibility of the oxide sputtering target can be ensured, and the crack resistance of the film is improved. On the other hand, when the content of Si is set to 15 mass% or less, a decrease in the conductivity of the film can be suppressed, and an oxide film can be formed by direct current (DC) sputtering.
Assuming that the total of the metal components is 100 mass%, the lower limit of the Si content is preferably 2 mass% or more, and the upper limit of the Si content is preferably 7 mass% or less.
金属成分の合計を100mass%として、Siの含有量の下限は2mass%以上とすることが好ましく、Siの含有量の上限は7mass%以下とすることが好ましい。 When the Si content is 0.5 mass% or more, the flexibility of the oxide sputtering target can be ensured, and the crack resistance of the film is improved. On the other hand, when the content of Si is set to 15 mass% or less, a decrease in the conductivity of the film can be suppressed, and an oxide film can be formed by direct current (DC) sputtering.
Assuming that the total of the metal components is 100 mass%, the lower limit of the Si content is preferably 2 mass% or more, and the upper limit of the Si content is preferably 7 mass% or less.
(相構成)
本実施形態である酸化物スパッタリングターゲットにおいては、上述の金属元素の少なくとも一部を含む複合酸化物相と酸化インジウム相とを有している。
酸化インジウム相が存在することにより、本実施形態である酸化物スパッタリングターゲットの抵抗値が低くなり、直流(DC)スパッタによって酸化物膜を成膜することが可能となる。 (Phase composition)
The oxide sputtering target according to the present embodiment has a composite oxide phase containing at least a part of the above-described metal elements and an indium oxide phase.
The presence of the indium oxide phase lowers the resistance value of the oxide sputtering target according to the present embodiment, so that an oxide film can be formed by direct current (DC) sputtering.
本実施形態である酸化物スパッタリングターゲットにおいては、上述の金属元素の少なくとも一部を含む複合酸化物相と酸化インジウム相とを有している。
酸化インジウム相が存在することにより、本実施形態である酸化物スパッタリングターゲットの抵抗値が低くなり、直流(DC)スパッタによって酸化物膜を成膜することが可能となる。 (Phase composition)
The oxide sputtering target according to the present embodiment has a composite oxide phase containing at least a part of the above-described metal elements and an indium oxide phase.
The presence of the indium oxide phase lowers the resistance value of the oxide sputtering target according to the present embodiment, so that an oxide film can be formed by direct current (DC) sputtering.
(密度のばらつき)
ターゲットスパッタ面内において密度のばらつきが生じると、スパッタ成膜時に異常放電が発生するおそれがある。特に、本実施形態では、ターゲットスパッタ面の面積が0.02m2以上と比較的大面積のため、ターゲットスパッタ面内の密度のばらつきが生じやすい傾向にある。そこで、本実施形態においては、ターゲットスパッタ面内における密度のばらつきを3%以内としている。 (Density variation)
If the density varies in the target sputtering surface, abnormal discharge may occur during sputtering film formation. In particular, in the present embodiment, since the area of the target sputtering surface is relatively large, that is, 0.02 m 2 or more, the density in the target sputtering surface tends to vary. Therefore, in the present embodiment, the variation in density within the target sputtering surface is set to within 3%.
ターゲットスパッタ面内において密度のばらつきが生じると、スパッタ成膜時に異常放電が発生するおそれがある。特に、本実施形態では、ターゲットスパッタ面の面積が0.02m2以上と比較的大面積のため、ターゲットスパッタ面内の密度のばらつきが生じやすい傾向にある。そこで、本実施形態においては、ターゲットスパッタ面内における密度のばらつきを3%以内としている。 (Density variation)
If the density varies in the target sputtering surface, abnormal discharge may occur during sputtering film formation. In particular, in the present embodiment, since the area of the target sputtering surface is relatively large, that is, 0.02 m 2 or more, the density in the target sputtering surface tends to vary. Therefore, in the present embodiment, the variation in density within the target sputtering surface is set to within 3%.
また、厚さ方向における密度のばらつきが生じると、スパッタが進行してターゲットスパッタ面が消耗した際に、スパッタ成膜時に異常放電が発生するおそれがある。そこで、本実施形態においては、厚さ方向における密度のばらつきを5%以内としている。
本実施形態において、同一水平面内または同一鉛直方向の密度のばらつきは、複数の箇所で測定した密度の最大値と最小値から、以下の式で定義した。
密度のばらつき = (最大値-最小値)/(最大値+最小値) ×100(%) In addition, if the density varies in the thickness direction, abnormal discharge may occur during sputtering deposition when sputtering proceeds and the target sputtering surface is consumed. Therefore, in the present embodiment, the variation in the density in the thickness direction is set to 5% or less.
In the present embodiment, the variation in the density in the same horizontal plane or in the same vertical direction is defined by the following formula from the maximum and minimum values of the density measured at a plurality of locations.
Variation in density = (maximum value-minimum value) / (maximum value + minimum value) x 100 (%)
本実施形態において、同一水平面内または同一鉛直方向の密度のばらつきは、複数の箇所で測定した密度の最大値と最小値から、以下の式で定義した。
密度のばらつき = (最大値-最小値)/(最大値+最小値) ×100(%) In addition, if the density varies in the thickness direction, abnormal discharge may occur during sputtering deposition when sputtering proceeds and the target sputtering surface is consumed. Therefore, in the present embodiment, the variation in the density in the thickness direction is set to 5% or less.
In the present embodiment, the variation in the density in the same horizontal plane or in the same vertical direction is defined by the following formula from the maximum and minimum values of the density measured at a plurality of locations.
Variation in density = (maximum value-minimum value) / (maximum value + minimum value) x 100 (%)
酸化物スパッタリングターゲットの密度のばらつきは、図1Aに示すように、対角線が交差する中心部(1)と、4つの角部(2)、(3)、(4)、(5)の5つのブロックから試料を採取し、図1Bに示すように、これら5つのブロックを厚さ方向に(α)、(β)、(γ)のブロックに3分割(三等分)して、合計15個の試料を採取し、それぞれの試料の密度を測定した。
As shown in FIG. 1A, the variation in the density of the oxide sputtering target is caused by the center part (1) where the diagonal lines intersect and the four corner parts (2), (3), (4), and (5). A sample was taken from the block, and as shown in FIG. 1B, these five blocks were divided into three (α), (β), and (γ) blocks in the thickness direction (divided into three), for a total of 15 blocks. Were sampled, and the density of each sample was measured.
ターゲットスパッタ面内の密度のばらつきについては、以下のように算出した。ターゲットスパッタ面内の5ブロックについて、厚さ方向の1つのブロック毎における密度の最大値及び最小値から、上記式によって、厚さ方向の1つのブロック(例えば、α1~α5の5試料)におけるターゲットスパッタ面内の密度のばらつきを算出し、厚さ方向の3つのブロック(α1~α5/β1~β5/γ1~γ5)の密度のばらつきの平均値を、「ターゲットスパッタ面内の密度のばらつき」とした。
すなわち、同一水平面内にある5ブロックについて、密度の最大値と最小値から、上記式によって同一水平面内の密度のばらつきを算出し、さらにそれぞれの同一水平面内において算出された密度のばらつきの平均値を、「ターゲットスパッタ面内の密度ばらつき」とした。 The variation in density in the target sputtering surface was calculated as follows. From the maximum value and the minimum value of the density in each block in the thickness direction for the five blocks in the target sputtering surface, the target in one block in the thickness direction (for example, five samples of α1 to α5) is obtained by the above equation. The variation in the density within the sputtering surface is calculated, and the average value of the variation in the density of the three blocks (α1 to α5 / β1 to β5 / γ1 to γ5) in the thickness direction is calculated as “the variation in the density within the target sputtering surface”. And
That is, for the five blocks in the same horizontal plane, the density variation in the same horizontal plane is calculated from the maximum value and the minimum value of the density by the above equation, and further, the average value of the density variations calculated in each of the same horizontal planes Is referred to as “density variation in the target sputtering surface”.
すなわち、同一水平面内にある5ブロックについて、密度の最大値と最小値から、上記式によって同一水平面内の密度のばらつきを算出し、さらにそれぞれの同一水平面内において算出された密度のばらつきの平均値を、「ターゲットスパッタ面内の密度ばらつき」とした。 The variation in density in the target sputtering surface was calculated as follows. From the maximum value and the minimum value of the density in each block in the thickness direction for the five blocks in the target sputtering surface, the target in one block in the thickness direction (for example, five samples of α1 to α5) is obtained by the above equation. The variation in the density within the sputtering surface is calculated, and the average value of the variation in the density of the three blocks (α1 to α5 / β1 to β5 / γ1 to γ5) in the thickness direction is calculated as “the variation in the density within the target sputtering surface”. And
That is, for the five blocks in the same horizontal plane, the density variation in the same horizontal plane is calculated from the maximum value and the minimum value of the density by the above equation, and further, the average value of the density variations calculated in each of the same horizontal planes Is referred to as “density variation in the target sputtering surface”.
また、厚さ方向の密度のばらつきについては、厚さ方向の3つのブロックについて、ターゲットスパッタ面内の1つのブロック毎における密度の最大値及び最小値から、上記式によって、ターゲットスパッタ面内の1つのブロック(例えば、α1~γ1の3試料)における厚さ方向の密度のばらつきを算出し、ターゲットスパッタ面内の5つのブロック(α1~γ1/α2~γ2/α3~γ3/α4~γ4/α5~γ5)の密度ばらつきの平均値を、「厚さ方向の密度のばらつき」とした。
すなわち、同一鉛直方向にある3ブロックについて、密度の最大値と最小値から、上記式によって同一鉛直方向の密度のばらつきを算出し、さらにそれぞれの同一鉛直方向において算出された密度のばらつきの平均値を「厚さ方向の密度ばらつき」とした。 Further, regarding the variation in the density in the thickness direction, for the three blocks in the thickness direction, the maximum value and the minimum value of the density of each block in the target sputtering surface are calculated from the maximum value and the minimum value of one block in the target sputtering surface by the above equation. The dispersion of the density in the thickness direction in one block (for example, three samples of α1 to γ1) is calculated, and the five blocks (α1 to γ1 / α2 to γ2 / α3 to γ3 / α4 to γ4 / α5) in the target sputtering surface are calculated. The average value of the density variations of ~ 5) was defined as "density variation in the thickness direction".
That is, for the three blocks in the same vertical direction, the variation of the density in the same vertical direction is calculated from the maximum value and the minimum value of the density by the above equation, and the average value of the density variations calculated in the same vertical direction is calculated. Is referred to as “density variation in the thickness direction”.
すなわち、同一鉛直方向にある3ブロックについて、密度の最大値と最小値から、上記式によって同一鉛直方向の密度のばらつきを算出し、さらにそれぞれの同一鉛直方向において算出された密度のばらつきの平均値を「厚さ方向の密度ばらつき」とした。 Further, regarding the variation in the density in the thickness direction, for the three blocks in the thickness direction, the maximum value and the minimum value of the density of each block in the target sputtering surface are calculated from the maximum value and the minimum value of one block in the target sputtering surface by the above equation. The dispersion of the density in the thickness direction in one block (for example, three samples of α1 to γ1) is calculated, and the five blocks (α1 to γ1 / α2 to γ2 / α3 to γ3 / α4 to γ4 / α5) in the target sputtering surface are calculated. The average value of the density variations of ~ 5) was defined as "density variation in the thickness direction".
That is, for the three blocks in the same vertical direction, the variation of the density in the same vertical direction is calculated from the maximum value and the minimum value of the density by the above equation, and the average value of the density variations calculated in the same vertical direction is calculated. Is referred to as “density variation in the thickness direction”.
本実施形態である酸化物スパッタリングターゲットにおいては、上述した15個の試料で測定した密度の平均値(平均密度)が5.5g/cm3以上とされている。平均密度は6.0g/cm3以上であることが好ましく、6.2g/cm3以上であることがさらに好ましい。
In the oxide sputtering target according to the present embodiment, the average value (average density) of the densities measured for the 15 samples described above is 5.5 g / cm 3 or more. The average density is preferably 6.0 g / cm 3 or more, and more preferably 6.2 g / cm 3 or more.
(比抵抗のばらつき)
ターゲットスパッタ面内において比抵抗のばらつきが生じると、スパッタ成膜時に異常放電が発生するおそれがある。特に、本実施形態では、ターゲットスパッタ面の面積が0.02m2以上と比較的大面積のため、ターゲットスパッタ面内の比抵抗のばらつきが生じやすい傾向にある。そこで、本実施形態においては、ターゲットスパッタ面内における比抵抗のばらつきを10%以内としている。 (Dispersion of specific resistance)
If a variation in specific resistance occurs in the target sputtering surface, abnormal discharge may occur during sputtering film formation. In particular, in the present embodiment, since the area of the target sputtering surface is relatively large, that is, 0.02 m 2 or more, the specific resistance tends to vary in the target sputtering surface. Therefore, in the present embodiment, the variation of the specific resistance in the target sputtering surface is set to 10% or less.
ターゲットスパッタ面内において比抵抗のばらつきが生じると、スパッタ成膜時に異常放電が発生するおそれがある。特に、本実施形態では、ターゲットスパッタ面の面積が0.02m2以上と比較的大面積のため、ターゲットスパッタ面内の比抵抗のばらつきが生じやすい傾向にある。そこで、本実施形態においては、ターゲットスパッタ面内における比抵抗のばらつきを10%以内としている。 (Dispersion of specific resistance)
If a variation in specific resistance occurs in the target sputtering surface, abnormal discharge may occur during sputtering film formation. In particular, in the present embodiment, since the area of the target sputtering surface is relatively large, that is, 0.02 m 2 or more, the specific resistance tends to vary in the target sputtering surface. Therefore, in the present embodiment, the variation of the specific resistance in the target sputtering surface is set to 10% or less.
また、厚さ方向において比抵抗のばらつきが生じると、スパッタが進行してターゲットスパッタ面が消耗した際に、スパッタ成膜時に異常放電が発生するおそれがある。そこで、本実施形態においては、厚さ方向における比抵抗のばらつきを10%以内としている。
本実施形態において、同一水平面内または同一鉛直方向の比抵抗のばらつきは、複数の箇所で測定した比抵抗の最大値と最小値から、以下の式で定義した。
比抵抗のばらつき = (最大値-最小値)/(最大値+最小値) ×100(%) In addition, when a variation in specific resistance occurs in the thickness direction, abnormal discharge may occur during sputtering deposition when sputtering proceeds and the target sputtering surface is consumed. Thus, in the present embodiment, the variation of the specific resistance in the thickness direction is set to within 10%.
In the present embodiment, the variation in the specific resistance in the same horizontal plane or in the same vertical direction is defined by the following formula from the maximum and minimum values of the specific resistance measured at a plurality of locations.
Variation in specific resistance = (maximum value-minimum value) / (maximum value + minimum value) x 100 (%)
本実施形態において、同一水平面内または同一鉛直方向の比抵抗のばらつきは、複数の箇所で測定した比抵抗の最大値と最小値から、以下の式で定義した。
比抵抗のばらつき = (最大値-最小値)/(最大値+最小値) ×100(%) In addition, when a variation in specific resistance occurs in the thickness direction, abnormal discharge may occur during sputtering deposition when sputtering proceeds and the target sputtering surface is consumed. Thus, in the present embodiment, the variation of the specific resistance in the thickness direction is set to within 10%.
In the present embodiment, the variation in the specific resistance in the same horizontal plane or in the same vertical direction is defined by the following formula from the maximum and minimum values of the specific resistance measured at a plurality of locations.
Variation in specific resistance = (maximum value-minimum value) / (maximum value + minimum value) x 100 (%)
酸化物スパッタリングターゲットの比抵抗のばらつきは、図1Aに示すように、対角線が交差する中心部(1)と、4つの角部(2)、(3)、(4)、(5)の5つのブロックから試料を採取し、図1Bに示すように、これら5つのブロックを厚さ方向に3分割(三等分)して、合計15個の試料を採取し、それぞれの試料の比抵抗を測定した。
As shown in FIG. 1A, the variation in the specific resistance of the oxide sputtering target is caused by the center part (1) where the diagonal lines intersect and the five corner parts (2), (3), (4), and (5). A sample was taken from one block, and as shown in FIG. 1B, these five blocks were divided into three (three) in the thickness direction, and a total of 15 samples were taken. It was measured.
ターゲットスパッタ面内の比抵抗のばらつきについては、以下のように算出した。ターゲットスパッタ面内の5ブロックについて、厚さ方向の1つのブロック毎における比抵抗の最大値及び最小値から、上記式によって、厚さ方向の1つのブロック(例えば、α1~α5の5試料)におけるターゲットスパッタ面内の比抵抗のばらつきを算出し、厚さ方向の3つのブロック(α1~α5/β1~β5/γ1~γ5)の比抵抗のばらつきの平均値を、「ターゲットスパッタ面内の比抵抗のばらつき」とした。
すなわち、同一水平面内にある5ブロックについて、比抵抗の最大値と最小値から、上記式によって同一水平面内の比抵抗のばらつきを算出し、さらにそれぞれの同一水平面内において算出された比抵抗のばらつきの平均値を、「ターゲットスパッタ面内の比抵抗のばらつき」とした。 The variation in the specific resistance in the target sputtering surface was calculated as follows. From the maximum value and the minimum value of the specific resistance of each block in the thickness direction for the five blocks in the target sputtering surface, the above equation is used to calculate the value in one block in the thickness direction (for example, five samples of α1 to α5). The variation of the specific resistance in the target sputtering surface is calculated, and the average value of the specific resistance variation of the three blocks (α1 to α5 / β1 to β5 / γ1 to γ5) in the thickness direction is calculated as “the specific ratio in the target sputtering surface. Resistance variation ".
That is, for the five blocks in the same horizontal plane, the variation of the specific resistance in the same horizontal plane is calculated from the maximum value and the minimum value of the specific resistance by the above equation, and the variation of the specific resistance calculated in each of the same horizontal planes is calculated. The average value of was determined as “variation in specific resistance in the target sputtering surface”.
すなわち、同一水平面内にある5ブロックについて、比抵抗の最大値と最小値から、上記式によって同一水平面内の比抵抗のばらつきを算出し、さらにそれぞれの同一水平面内において算出された比抵抗のばらつきの平均値を、「ターゲットスパッタ面内の比抵抗のばらつき」とした。 The variation in the specific resistance in the target sputtering surface was calculated as follows. From the maximum value and the minimum value of the specific resistance of each block in the thickness direction for the five blocks in the target sputtering surface, the above equation is used to calculate the value in one block in the thickness direction (for example, five samples of α1 to α5). The variation of the specific resistance in the target sputtering surface is calculated, and the average value of the specific resistance variation of the three blocks (α1 to α5 / β1 to β5 / γ1 to γ5) in the thickness direction is calculated as “the specific ratio in the target sputtering surface. Resistance variation ".
That is, for the five blocks in the same horizontal plane, the variation of the specific resistance in the same horizontal plane is calculated from the maximum value and the minimum value of the specific resistance by the above equation, and the variation of the specific resistance calculated in each of the same horizontal planes is calculated. The average value of was determined as “variation in specific resistance in the target sputtering surface”.
また、厚さ方向の比抵抗のばらつきについては、厚さ方向の3つのブロックについて、ターゲットスパッタ面内の1つのブロック毎における比抵抗の最大値及び最小値から、上記式によって、ターゲットスパッタ面内の1つのブロック(例えば、α1~γ1の3試料)における厚さ方向の比抵抗のばらつきを算出し、ターゲットスパッタ面内の5つのブロック(α1~γ1/α2~γ2/α3~γ3/α4~γ4/α5~γ5)の比抵抗のばらつきの平均値を、「厚さ方向の比抵抗のばらつき」とした。
すなわち、同一鉛直方向にある3ブロックについて、比抵抗の最大値と最小値から、上記式によって同一鉛直方向の比抵抗のばらつきを算出し、さらにそれぞれの同一鉛直方向において算出された比抵抗のばらつきの平均値を「厚さ方向の比抵抗のばらつき」とした。 Further, regarding the variation of the specific resistance in the thickness direction, for the three blocks in the thickness direction, the maximum value and the minimum value of the specific resistance of each block in the target sputtering surface are calculated according to the above equation. Of the specific resistance in the thickness direction of one block (eg, three samples of α1 to γ1) is calculated, and the five blocks (α1 to γ1 / α2 to γ2 / α3 to γ3 / α4 to The average value of the variation in specific resistance of γ4 / α5 to γ5) was defined as “variation in specific resistance in the thickness direction”.
That is, for the three blocks in the same vertical direction, the variation of the specific resistance in the same vertical direction is calculated from the maximum value and the minimum value of the specific resistance by the above equation, and the variation of the specific resistance calculated in the same vertical direction is further calculated. Is referred to as “variation in specific resistance in the thickness direction”.
すなわち、同一鉛直方向にある3ブロックについて、比抵抗の最大値と最小値から、上記式によって同一鉛直方向の比抵抗のばらつきを算出し、さらにそれぞれの同一鉛直方向において算出された比抵抗のばらつきの平均値を「厚さ方向の比抵抗のばらつき」とした。 Further, regarding the variation of the specific resistance in the thickness direction, for the three blocks in the thickness direction, the maximum value and the minimum value of the specific resistance of each block in the target sputtering surface are calculated according to the above equation. Of the specific resistance in the thickness direction of one block (eg, three samples of α1 to γ1) is calculated, and the five blocks (α1 to γ1 / α2 to γ2 / α3 to γ3 / α4 to The average value of the variation in specific resistance of γ4 / α5 to γ5) was defined as “variation in specific resistance in the thickness direction”.
That is, for the three blocks in the same vertical direction, the variation of the specific resistance in the same vertical direction is calculated from the maximum value and the minimum value of the specific resistance by the above equation, and the variation of the specific resistance calculated in the same vertical direction is further calculated. Is referred to as “variation in specific resistance in the thickness direction”.
本実施形態である酸化物スパッタリングターゲットにおいては、上述した15個の試料で測定した比抵抗の平均値(平均比抵抗)が1.0×10-2Ω・cm以下とされている。平均比抵抗は8.5×10-3Ω・cm以下であることが好ましく、7.5×10-3Ω・cm以下であることがさらに好ましい。
In the oxide sputtering target according to the present embodiment, the average value (average specific resistance) of the specific resistances measured for the above-described 15 samples is 1.0 × 10 −2 Ω · cm or less. The average specific resistance is preferably 8.5 × 10 −3 Ω · cm or less, and more preferably 7.5 × 10 −3 Ω · cm or less.
次に、上述した本実施形態である酸化物スパッタリングターゲットの製造方法について、図2及び図3を参照して説明する。
Next, a method for manufacturing the oxide sputtering target according to the above-described embodiment will be described with reference to FIGS.
(焼結原料粉形成工程S01)
まず、酸化ジルコニウム粉(ZrO2粉)、酸化ケイ素粉(SiO2粉)および酸化インジウム粉(In2O3粉)を準備する。
酸化ジルコニウム粉(ZrO2粉)、酸化ケイ素粉(SiO2粉)および酸化インジウム粉(In2O3粉)は、それぞれ、純度が99.9質量%以上、平均粒子径が0.1μm以上20μm以下の範囲内であることが好ましい。ZrO2粉の純度は、Fe2O3、SiO2、TiO2、Na2Oの含有量を測定し、残部がZrO2であるとして算出されたものである。本実施形態のZrO2粉においては、HfO2を最大で2.5%含有することがある。 (Sintering raw material powder forming step S01)
First, zirconium oxide powder (ZrO 2 powder), silicon oxide powder (SiO 2 powder) and indium oxide powder (In 2 O 3 powder) are prepared.
Zirconium oxide powder (ZrO 2 powder), silicon oxide powder (SiO 2 powder) and indium oxide powder (In 2 O 3 powder) each have a purity of 99.9% by mass or more and an average particle diameter of 0.1 μm or more and 20 μm or more. It is preferable to be within the following range. The purity of the ZrO 2 powder was calculated by measuring the contents of Fe 2 O 3 , SiO 2 , TiO 2 , and Na 2 O, with the balance being ZrO 2 . The ZrO 2 powder of the present embodiment may contain HfO 2 at a maximum of 2.5%.
まず、酸化ジルコニウム粉(ZrO2粉)、酸化ケイ素粉(SiO2粉)および酸化インジウム粉(In2O3粉)を準備する。
酸化ジルコニウム粉(ZrO2粉)、酸化ケイ素粉(SiO2粉)および酸化インジウム粉(In2O3粉)は、それぞれ、純度が99.9質量%以上、平均粒子径が0.1μm以上20μm以下の範囲内であることが好ましい。ZrO2粉の純度は、Fe2O3、SiO2、TiO2、Na2Oの含有量を測定し、残部がZrO2であるとして算出されたものである。本実施形態のZrO2粉においては、HfO2を最大で2.5%含有することがある。 (Sintering raw material powder forming step S01)
First, zirconium oxide powder (ZrO 2 powder), silicon oxide powder (SiO 2 powder) and indium oxide powder (In 2 O 3 powder) are prepared.
Zirconium oxide powder (ZrO 2 powder), silicon oxide powder (SiO 2 powder) and indium oxide powder (In 2 O 3 powder) each have a purity of 99.9% by mass or more and an average particle diameter of 0.1 μm or more and 20 μm or more. It is preferable to be within the following range. The purity of the ZrO 2 powder was calculated by measuring the contents of Fe 2 O 3 , SiO 2 , TiO 2 , and Na 2 O, with the balance being ZrO 2 . The ZrO 2 powder of the present embodiment may contain HfO 2 at a maximum of 2.5%.
これらの酸化物粉末を、所定の組成比となるように秤量し、粉砕混合装置を用いて混合し、焼結原料粉を形成する。
焼結原料粉は、メディアン径(D50)を0.05μm以上1.2μm以下の範囲内とすることが好ましい。 These oxide powders are weighed so as to have a predetermined composition ratio, and mixed using a pulverizer / mixer to form a sintering raw material powder.
The sintering raw material powder preferably has a median diameter (D50) in the range of 0.05 μm to 1.2 μm.
焼結原料粉は、メディアン径(D50)を0.05μm以上1.2μm以下の範囲内とすることが好ましい。 These oxide powders are weighed so as to have a predetermined composition ratio, and mixed using a pulverizer / mixer to form a sintering raw material powder.
The sintering raw material powder preferably has a median diameter (D50) in the range of 0.05 μm to 1.2 μm.
(成形工程S02)
次に、得られた焼結原料粉を、成形型に充填して加圧することによって、所定形状の成形体を得る。加圧方法としては、プレスやCIP等が用いられる。このときの加圧圧力は20MPa以上300MPa以下の範囲内とすることが好ましい。また、温度は常温でもよいが、成形体強度を向上させる場合には、900℃以上950℃以下の範囲の温度でプレス成形を行った方が、ネック形成が促進され、成形体の強度が向上する。また、焼結原料粉にバインダーを添加して加圧成形してもよい。 (Molding step S02)
Next, the obtained sintering raw material powder is filled into a molding die and pressed to obtain a molded body having a predetermined shape. As a pressing method, a press, CIP, or the like is used. The pressurizing pressure at this time is preferably in the range of 20 MPa or more and 300 MPa or less. The temperature may be room temperature, but in order to improve the strength of the molded body, press forming at a temperature in the range of 900 ° C. or more and 950 ° C. or less promotes neck formation and improves the strength of the molded body. I do. Further, a pressure may be formed by adding a binder to the sintering raw material powder.
次に、得られた焼結原料粉を、成形型に充填して加圧することによって、所定形状の成形体を得る。加圧方法としては、プレスやCIP等が用いられる。このときの加圧圧力は20MPa以上300MPa以下の範囲内とすることが好ましい。また、温度は常温でもよいが、成形体強度を向上させる場合には、900℃以上950℃以下の範囲の温度でプレス成形を行った方が、ネック形成が促進され、成形体の強度が向上する。また、焼結原料粉にバインダーを添加して加圧成形してもよい。 (Molding step S02)
Next, the obtained sintering raw material powder is filled into a molding die and pressed to obtain a molded body having a predetermined shape. As a pressing method, a press, CIP, or the like is used. The pressurizing pressure at this time is preferably in the range of 20 MPa or more and 300 MPa or less. The temperature may be room temperature, but in order to improve the strength of the molded body, press forming at a temperature in the range of 900 ° C. or more and 950 ° C. or less promotes neck formation and improves the strength of the molded body. I do. Further, a pressure may be formed by adding a binder to the sintering raw material powder.
(焼結工程S03)
この成形体を、酸素導入機能を有する焼成装置内に装入し、酸素を導入しながら加熱して焼結する。このとき、酸素の導入量は3L/分以上10L/分以下の範囲内とすることが好ましい。また、昇温速度は50℃/h以上200℃/h以下の範囲内とすることが好ましい。 (Sintering step S03)
This compact is placed in a firing apparatus having an oxygen introduction function, and is heated and sintered while introducing oxygen. At this time, the amount of introduced oxygen is preferably in the range of 3 L / min to 10 L / min. Further, it is preferable that the heating rate be in the range of 50 ° C./h or more and 200 ° C./h or less.
この成形体を、酸素導入機能を有する焼成装置内に装入し、酸素を導入しながら加熱して焼結する。このとき、酸素の導入量は3L/分以上10L/分以下の範囲内とすることが好ましい。また、昇温速度は50℃/h以上200℃/h以下の範囲内とすることが好ましい。 (Sintering step S03)
This compact is placed in a firing apparatus having an oxygen introduction function, and is heated and sintered while introducing oxygen. At this time, the amount of introduced oxygen is preferably in the range of 3 L / min to 10 L / min. Further, it is preferable that the heating rate be in the range of 50 ° C./h or more and 200 ° C./h or less.
そして、本実施形態では、焼結工程S03においては、図3に示すように、1200℃以上1400℃以下の温度範囲で3時間以上保持し、その後、1400℃を超える温度(例えば1500℃以上)まで加熱して保持し、成形体の焼結を進行させる。
焼結原料粉中の酸化インジウム粉の焼結が開始される温度である1200℃以上で、かつ、複合酸化物の形成によって焼結が進行する1400℃以下の温度範囲で3時間以上保持することにより、焼結時に焼結原料粉同士の間の隙間チャンネルを保った状態で酸素ガスを、成形体の内部に均一に浸透させることが可能となる。焼結工程S03において、1200℃以上1400℃以下の温度範囲での保持時間の上限に制限はないが、作業効率の観点から15時間以下とすることが好ましい。
その後、1400℃を超える温度にまで加熱して保持することで、成形体の焼結が均一に進行することになる。 Then, in the present embodiment, in the sintering step S03, as shown in FIG. 3, the temperature is maintained in a temperature range of 1200 ° C. or more and 1400 ° C. or less for 3 hours or more, and thereafter, a temperature exceeding 1400 ° C. (for example, 1500 ° C. or more) Heat and hold until the sintering of the compact proceeds.
Maintain at a temperature of 1200 ° C. or more, which is the temperature at which sintering of indium oxide powder in the sintering raw material powder is started, and 1400 ° C. or less, at which sintering proceeds due to formation of a composite oxide, for 3 hours or more. Thereby, it is possible to uniformly infiltrate the oxygen gas into the inside of the compact while maintaining the gap channel between the sintering raw material powders at the time of sintering. In the sintering step S03, the upper limit of the holding time in the temperature range of 1200 ° C. to 1400 ° C. is not limited, but is preferably 15 hours or less from the viewpoint of working efficiency.
Thereafter, by heating and holding to a temperature exceeding 1400 ° C., the sintering of the molded body proceeds uniformly.
焼結原料粉中の酸化インジウム粉の焼結が開始される温度である1200℃以上で、かつ、複合酸化物の形成によって焼結が進行する1400℃以下の温度範囲で3時間以上保持することにより、焼結時に焼結原料粉同士の間の隙間チャンネルを保った状態で酸素ガスを、成形体の内部に均一に浸透させることが可能となる。焼結工程S03において、1200℃以上1400℃以下の温度範囲での保持時間の上限に制限はないが、作業効率の観点から15時間以下とすることが好ましい。
その後、1400℃を超える温度にまで加熱して保持することで、成形体の焼結が均一に進行することになる。 Then, in the present embodiment, in the sintering step S03, as shown in FIG. 3, the temperature is maintained in a temperature range of 1200 ° C. or more and 1400 ° C. or less for 3 hours or more, and thereafter, a temperature exceeding 1400 ° C. (for example, 1500 ° C. or more) Heat and hold until the sintering of the compact proceeds.
Maintain at a temperature of 1200 ° C. or more, which is the temperature at which sintering of indium oxide powder in the sintering raw material powder is started, and 1400 ° C. or less, at which sintering proceeds due to formation of a composite oxide, for 3 hours or more. Thereby, it is possible to uniformly infiltrate the oxygen gas into the inside of the compact while maintaining the gap channel between the sintering raw material powders at the time of sintering. In the sintering step S03, the upper limit of the holding time in the temperature range of 1200 ° C. to 1400 ° C. is not limited, but is preferably 15 hours or less from the viewpoint of working efficiency.
Thereafter, by heating and holding to a temperature exceeding 1400 ° C., the sintering of the molded body proceeds uniformly.
(機械加工工程S04)
次に、上述の焼結体に対して旋盤加工等の機械加工を行い、所定サイズの酸化物スパッタリングターゲットを得る。 (Machining process S04)
Next, machining such as lathing is performed on the above-described sintered body to obtain an oxide sputtering target having a predetermined size.
次に、上述の焼結体に対して旋盤加工等の機械加工を行い、所定サイズの酸化物スパッタリングターゲットを得る。 (Machining process S04)
Next, machining such as lathing is performed on the above-described sintered body to obtain an oxide sputtering target having a predetermined size.
上述の工程により、本実施形態である酸化物スパッタリングターゲットが製造されることになる。
に よ り Through the above steps, the oxide sputtering target of the present embodiment is manufactured.
そして、本実施形態である酸化物スパッタリングターゲットを用いて、スパッタ成膜することにより、インセル型のタッチパネル等のシールド層として適した酸化物膜が成膜される。
本実施形態である酸化物スパッタリングターゲットは、上述のように、酸化インジウム相が存在することによって抵抗値が低く、直流(DC)スパッタによって酸化物膜を成膜することが可能となる。
一方、成膜された酸化物膜は、全体が複合酸化物相となっており、抵抗値が十分に高くなり、シールド層として特に適している。 Then, an oxide film suitable as a shield layer for an in-cell type touch panel or the like is formed by sputtering using the oxide sputtering target of the present embodiment.
As described above, the oxide sputtering target according to the present embodiment has a low resistance value due to the presence of the indium oxide phase, so that an oxide film can be formed by direct current (DC) sputtering.
On the other hand, the formed oxide film has a composite oxide phase as a whole, has a sufficiently high resistance value, and is particularly suitable as a shield layer.
本実施形態である酸化物スパッタリングターゲットは、上述のように、酸化インジウム相が存在することによって抵抗値が低く、直流(DC)スパッタによって酸化物膜を成膜することが可能となる。
一方、成膜された酸化物膜は、全体が複合酸化物相となっており、抵抗値が十分に高くなり、シールド層として特に適している。 Then, an oxide film suitable as a shield layer for an in-cell type touch panel or the like is formed by sputtering using the oxide sputtering target of the present embodiment.
As described above, the oxide sputtering target according to the present embodiment has a low resistance value due to the presence of the indium oxide phase, so that an oxide film can be formed by direct current (DC) sputtering.
On the other hand, the formed oxide film has a composite oxide phase as a whole, has a sufficiently high resistance value, and is particularly suitable as a shield layer.
以上のような構成とされた本実施形態である酸化物スパッタリングターゲットによれば、金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物で構成されているので、抵抗値が高く、かつ、可視光の透過率に優れ、シールド層に適した酸化物膜を成膜することが可能となる。
According to the oxide sputtering target of the present embodiment having the above-described configuration, since the metal component is formed of an oxide containing zirconium, silicon, and indium, the resistance value is high, and visible. An oxide film having excellent light transmittance and suitable for a shield layer can be formed.
そして、ターゲットスパッタ面内における密度のばらつきが3%以内とされているので、スパッタ成膜時においてターゲットスパッタ面全体でスパッタが安定し、酸化物膜を安定して成膜することができる。
また、厚さ方向における密度のばらつきが5%以内とされているので、スパッタが進行した場合であっても、酸化物膜を安定して成膜することができる。 Since the variation in the density within the target sputtering surface is set to 3% or less, the sputtering is stable on the entire target sputtering surface during the sputtering film formation, and the oxide film can be stably formed.
In addition, since the variation in the density in the thickness direction is within 5%, an oxide film can be formed stably even when sputtering proceeds.
また、厚さ方向における密度のばらつきが5%以内とされているので、スパッタが進行した場合であっても、酸化物膜を安定して成膜することができる。 Since the variation in the density within the target sputtering surface is set to 3% or less, the sputtering is stable on the entire target sputtering surface during the sputtering film formation, and the oxide film can be stably formed.
In addition, since the variation in the density in the thickness direction is within 5%, an oxide film can be formed stably even when sputtering proceeds.
さらに、本実施形態の酸化物スパッタリングターゲットは、ターゲットスパッタ面内における比抵抗のばらつきが10%以内とされているので、スパッタ時における異常放電の発生を抑制することができる。
また、本実施形態の酸化物スパッタリングターゲットは、厚さ方向における比抵抗のばらつきが10%以内とされているので、スパッタが進行した場合であっても、酸化物膜を安定して成膜することができる。 Furthermore, in the oxide sputtering target of the present embodiment, since the variation in the specific resistance within the target sputtering surface is within 10%, the occurrence of abnormal discharge during sputtering can be suppressed.
Further, in the oxide sputtering target of the present embodiment, since the variation in the specific resistance in the thickness direction is within 10%, the oxide film is stably formed even when sputtering proceeds. be able to.
また、本実施形態の酸化物スパッタリングターゲットは、厚さ方向における比抵抗のばらつきが10%以内とされているので、スパッタが進行した場合であっても、酸化物膜を安定して成膜することができる。 Furthermore, in the oxide sputtering target of the present embodiment, since the variation in the specific resistance within the target sputtering surface is within 10%, the occurrence of abnormal discharge during sputtering can be suppressed.
Further, in the oxide sputtering target of the present embodiment, since the variation in the specific resistance in the thickness direction is within 10%, the oxide film is stably formed even when sputtering proceeds. be able to.
さらに、本実施形態の酸化物スパッタリングターゲットは、ターゲットスパッタ面の面積が0.02m2以上と比較的大きいことから、大面積の基板に酸化物膜を成膜することが可能となる。また、このような大型の酸化物スパッタリングターゲットであっても、上述のように密度のばらつきが規定されているので、安定してスパッタ成膜を行うことができる。
Furthermore, since the oxide sputtering target of this embodiment has a relatively large target sputtering surface area of 0.02 m 2 or more, an oxide film can be formed on a large-area substrate. In addition, even with such a large oxide sputtering target, since the variation in density is specified as described above, a sputter film can be stably formed.
また、本実施形態である酸化物スパッタリングターゲットの製造方法によれば、焼結工程S03において、焼結原料粉中の酸化インジウムの焼結が開始される1200℃以上で、かつ、複合酸化物の形成によって焼結が進行する1400℃以下の温度範囲で3時間以上保持するので、焼結時に焼結原料粉同士の間の隙間チャンネルを保った状態で酸素ガスを、成形体の内部に均一に浸透させることが可能となる。そして、この状態で1400℃を超える温度にまで加熱して保持することで、成形体において均一に焼結を進行させることができ、密度のばらつきが十分に抑制された焼結体を得ることが可能となる。
Further, according to the method for manufacturing an oxide sputtering target of the present embodiment, in the sintering step S03, the sintering of indium oxide in the sintering raw material powder is started at 1200 ° C. or higher, and the composite oxide is Since the sintering is maintained at a temperature range of 1400 ° C. or less for 3 hours or more in which sintering proceeds by forming, oxygen gas is uniformly injected into the molded body while maintaining a gap channel between the sintering raw material powders during sintering. It is possible to penetrate. By heating and maintaining the temperature in this state up to a temperature exceeding 1400 ° C., sintering can be progressed uniformly in the molded body, and a sintered body in which variation in density is sufficiently suppressed can be obtained. It becomes possible.
また、本実施形態においては、焼結原料粉形成工程S01において、焼結原料粉のメディアン径を0.05μm以上1.2μm以下の範囲内としているので、焼結時における収縮量を低く抑えることができ、大型の酸化物スパッタリングターゲットを製造した場合であっても、割れや反りの発生を抑制することができ、製造歩留まりの向上を図ることができる。
Further, in the present embodiment, since the median diameter of the sintering raw material powder is in the range of 0.05 μm or more and 1.2 μm or less in the sintering raw material powder forming step S01, the amount of shrinkage during sintering is suppressed to be low. Therefore, even when a large-sized oxide sputtering target is manufactured, generation of cracks and warpage can be suppressed, and manufacturing yield can be improved.
以上、本発明の実施形態について説明したが、本発明はこれに限定されることはなく、その発明の技術的思想を逸脱しない範囲で適宜変更可能である。
例えば、本実施形態では、図1Aおよび図1Bに示すように、ターゲットスパッタ面が矩形状をなす矩形平板型スパッタリングターゲットとして説明したが、これに限定されることはなく、図4Aおよび図4Bに示すように、ターゲットスパッタ面が円形をなす円板型スパッタリングターゲットとしてもよい。また、図5A~図5Cに示すように、ターゲットスパッタ面が円筒面とされた円筒型スパッタリングターゲットであってもよい。 As described above, the embodiments of the present invention have been described, but the present invention is not limited thereto, and can be appropriately changed without departing from the technical idea of the present invention.
For example, in the present embodiment, as shown in FIGS. 1A and 1B, a rectangular flat plate type sputtering target having a rectangular target sputtering surface has been described. However, the present invention is not limited to this. As shown, a disk-shaped sputtering target having a circular target sputtering surface may be used. Further, as shown in FIGS. 5A to 5C, a cylindrical sputtering target having a cylindrical target sputtering surface may be used.
例えば、本実施形態では、図1Aおよび図1Bに示すように、ターゲットスパッタ面が矩形状をなす矩形平板型スパッタリングターゲットとして説明したが、これに限定されることはなく、図4Aおよび図4Bに示すように、ターゲットスパッタ面が円形をなす円板型スパッタリングターゲットとしてもよい。また、図5A~図5Cに示すように、ターゲットスパッタ面が円筒面とされた円筒型スパッタリングターゲットであってもよい。 As described above, the embodiments of the present invention have been described, but the present invention is not limited thereto, and can be appropriately changed without departing from the technical idea of the present invention.
For example, in the present embodiment, as shown in FIGS. 1A and 1B, a rectangular flat plate type sputtering target having a rectangular target sputtering surface has been described. However, the present invention is not limited to this. As shown, a disk-shaped sputtering target having a circular target sputtering surface may be used. Further, as shown in FIGS. 5A to 5C, a cylindrical sputtering target having a cylindrical target sputtering surface may be used.
ターゲットスパッタ面が円形をなす円板型スパッタリングターゲットにおいては、図4Aに示すように、スパッタ面がなす円の中心(1)、及び、円の中心を通過するとともに互いに直交する2本の直線上の外周部分(2)、(3)、(4)、(5)の5つのブロックから試料を採取し、図4Bに示すように、これら5つのブロックを厚さ方向に(α)、(β)、(γ)のブロックに3分割(三等分)して、合計15個の試料を採取し、それぞれの試料の同一水平面内または同一鉛直方向の密度及び同一水平面内または同一鉛直方向の比抵抗を測定し、上述の実施形態の欄に記載した方法によって、ターゲットスパッタ面内における密度のばらつき、厚さ方向における密度のばらつき、及び、ターゲットスパッタ面内における比抵抗のばらつき、厚さ方向における比抵抗のばらつき、を算出することが好ましい。
As shown in FIG. 4A, in the disk-shaped sputtering target having a target sputtering surface having a circular shape, as shown in FIG. 4A, the center (1) of the circle formed by the sputtering surface and the two straight lines which pass through the center of the circle and are orthogonal to each other. Samples were taken from five blocks of the outer peripheral portions (2), (3), (4), and (5), and as shown in FIG. 4B, these five blocks were placed in the thickness direction (α), (β). ) And (γ) are divided into three (divided into three), and a total of 15 samples are collected. The density of each sample in the same horizontal plane or the same vertical direction and the ratio in the same horizontal plane or the same vertical direction are obtained. The resistance was measured, and the density variation in the target sputtering surface, the density variation in the thickness direction, and the specific resistance variation in the target sputtering surface, and the thickness were measured by the method described in the above-described embodiment. Variation in resistivity in the direction, it is preferable to calculate the.
また、ターゲットスパッタ面が円筒面とされた円筒型スパッタリングターゲットにおいては、図5A,図5Bに示すように、軸方向の下端部A、中央部B、上端部Cにおいて、それぞれ円周方向に等間隔(90°間隔)の(1)、(2)、(3)、(4)の位置の合計12個のブロックから試料を採取し、図5Cに示すように、これらの12個のブロックを厚さ方向(径方向)に(α)、(β)、(γ)のブロックに3分割(三等分)して、合計36個の試料を採取し、それぞれの試料の同一水平面内または同一鉛直方向の密度及び同一水平面内または同一鉛直方向の比抵抗を測定し、上述の実施形態の欄に記載した方法によって、ターゲットスパッタ面内(円筒面内)における密度のばらつき、厚さ方向における密度のばらつき、及び、ターゲットスパッタ面内(円筒面内)における比抵抗のばらつき、厚さ方向における比抵抗のばらつき、を算出することが好ましい。
In a cylindrical sputtering target having a target sputtering surface of a cylindrical surface, as shown in FIGS. 5A and 5B, the lower end portion A, the center portion B, and the upper end portion C in the axial direction each have a circumferential direction. Samples were taken from a total of 12 blocks at positions (1), (2), (3), and (4) at intervals (90 ° intervals), and these 12 blocks were removed as shown in FIG. 5C. Divide into three (α), (β), and (γ) blocks in the thickness direction (radial direction), and collect a total of 36 samples. Each sample is in the same horizontal plane or the same. The density in the vertical direction and the specific resistance in the same horizontal plane or in the same vertical direction were measured, and the density variation in the target sputtering surface (in the cylindrical surface) and the density in the thickness direction were determined by the method described in the section of the above embodiment. And target Resistivity variation in the sputtering plane (the cylindrical surface), it is preferable to the ratio calculated variation in resistance, a in the thickness direction.
以下に、本発明の有効性を確認するために行った確認実験の結果について説明する。
結果 The following describes the results of confirmation experiments performed to confirm the effectiveness of the present invention.
<酸化物スパッタリングターゲット>
原料粉末として、酸化インジウム粉末(In2O3粉末:純度99.9質量%以上、平均粒径1μm)と、酸化シリコン粉末(SiO2粉末:純度99.8質量%以上、平均粒径2μm)と、酸化ジルコニウム粉末(ZrO2粉末:純度99.9質量%以上、平均粒径2μm)と、を準備した。ZrO2粉の純度は、Fe2O3、SiO2、TiO2、Na2Oの含有量を測定し、残部がZrO2であるとして算出されたものである。本実施形態のZrO2粉においては、HfO2を最大で2.5質量%含有することがある。そして、これらを、表1に示す配合比となるように、秤量した。 <Oxide sputtering target>
As raw material powders, indium oxide powder (In 2 O 3 powder: purity 99.9% by mass or more,average particle size 1 μm) and silicon oxide powder (SiO 2 powder: purity 99.8% by mass or more, average particle size 2 μm) And zirconium oxide powder (ZrO 2 powder: purity 99.9% by mass or more, average particle size 2 μm). The purity of the ZrO 2 powder was calculated by measuring the contents of Fe 2 O 3 , SiO 2 , TiO 2 , and Na 2 O, with the balance being ZrO 2 . The ZrO 2 powder of the present embodiment may contain HfO 2 at a maximum of 2.5% by mass. And these were weighed so that it might become a compounding ratio shown in Table 1.
原料粉末として、酸化インジウム粉末(In2O3粉末:純度99.9質量%以上、平均粒径1μm)と、酸化シリコン粉末(SiO2粉末:純度99.8質量%以上、平均粒径2μm)と、酸化ジルコニウム粉末(ZrO2粉末:純度99.9質量%以上、平均粒径2μm)と、を準備した。ZrO2粉の純度は、Fe2O3、SiO2、TiO2、Na2Oの含有量を測定し、残部がZrO2であるとして算出されたものである。本実施形態のZrO2粉においては、HfO2を最大で2.5質量%含有することがある。そして、これらを、表1に示す配合比となるように、秤量した。 <Oxide sputtering target>
As raw material powders, indium oxide powder (In 2 O 3 powder: purity 99.9% by mass or more,
秤量した各原料粉末を、表1に示すように、直径2mmのジルコニアボールを粉砕媒体としたバスケットミル装置、あるいは、直径0.5mmのジルコニアボールを粉砕媒体としたビーズミル装置を用いて、湿式粉砕混合した。
得られたスラリーを乾燥させ、250μmの篩いでジルコニアボールを除去し、焼結原料粉を得た。得られた焼結原料粉のメディアン径(D50)を表1に示す。
メディアン径は、ヘキサメタリン酸ナトリウム濃度0.2%の水溶液を100mL調製し、この水溶液に混合粉末を10mg加え、レーザー回折散乱法(測定装置:日機装株式会社製、Microtrac MT3000)を用いて、粒子径分布を測定した。得られた粒子径分布から累積粒度分布曲線を作成し、メディアン径(D50)を得た。 As shown in Table 1, each weighed raw material powder was wet-pulverized using a basket mill using zirconia balls having a diameter of 2 mm as a grinding medium or a bead mill using zirconia balls having a diameter of 0.5 mm as a grinding medium. Mixed.
The obtained slurry was dried, and the zirconia balls were removed with a 250 μm sieve to obtain a sintering raw material powder. Table 1 shows the median diameter (D50) of the obtained sintering raw material powder.
The median diameter was determined by preparing 100 mL of an aqueous solution having a sodium hexametaphosphate concentration of 0.2%, adding 10 mg of the mixed powder to the aqueous solution, and using a laser diffraction scattering method (measurement apparatus: manufactured by Nikkiso Co., Ltd., Microtrac MT3000). The distribution was measured. A cumulative particle size distribution curve was created from the obtained particle size distribution to obtain a median diameter (D50).
得られたスラリーを乾燥させ、250μmの篩いでジルコニアボールを除去し、焼結原料粉を得た。得られた焼結原料粉のメディアン径(D50)を表1に示す。
メディアン径は、ヘキサメタリン酸ナトリウム濃度0.2%の水溶液を100mL調製し、この水溶液に混合粉末を10mg加え、レーザー回折散乱法(測定装置:日機装株式会社製、Microtrac MT3000)を用いて、粒子径分布を測定した。得られた粒子径分布から累積粒度分布曲線を作成し、メディアン径(D50)を得た。 As shown in Table 1, each weighed raw material powder was wet-pulverized using a basket mill using zirconia balls having a diameter of 2 mm as a grinding medium or a bead mill using zirconia balls having a diameter of 0.5 mm as a grinding medium. Mixed.
The obtained slurry was dried, and the zirconia balls were removed with a 250 μm sieve to obtain a sintering raw material powder. Table 1 shows the median diameter (D50) of the obtained sintering raw material powder.
The median diameter was determined by preparing 100 mL of an aqueous solution having a sodium hexametaphosphate concentration of 0.2%, adding 10 mg of the mixed powder to the aqueous solution, and using a laser diffraction scattering method (measurement apparatus: manufactured by Nikkiso Co., Ltd., Microtrac MT3000). The distribution was measured. A cumulative particle size distribution curve was created from the obtained particle size distribution to obtain a median diameter (D50).
得られた焼結原料粉を加圧成形して成形体を得た。矩形平板型スパッタリングターゲットにおいては、165mm×298mmサイズの成形型を用い、プレス成形もしくはCIP成形を実施した。プレス成形の条件は、温度920℃、加圧圧力25MPaとし、CIP成形の条件は、常温(25℃)、加圧圧力100MPaとした。
円筒型スパッタリングターゲットにおいては、外径205mm、内径165mm、高さ200mmの成形型を用い、プレス成形もしくはCIP成形を実施した。プレス成形の条件は、温度920℃、加圧圧力25MPaとし、CIP成形の条件は、常温(25℃)、加圧圧力100MPaとした。 The obtained sintering raw material powder was compacted to obtain a compact. In the rectangular flat plate type sputtering target, press molding or CIP molding was performed using a molding die having a size of 165 mm × 298 mm. The conditions for press molding were 920 ° C. and a pressure of 25 MPa, and the conditions for CIP molding were room temperature (25 ° C.) and a pressure of 100 MPa.
In the cylindrical sputtering target, press molding or CIP molding was performed using a mold having an outer diameter of 205 mm, an inner diameter of 165 mm, and a height of 200 mm. The conditions for press molding were 920 ° C. and a pressure of 25 MPa, and the conditions for CIP molding were room temperature (25 ° C.) and a pressure of 100 MPa.
円筒型スパッタリングターゲットにおいては、外径205mm、内径165mm、高さ200mmの成形型を用い、プレス成形もしくはCIP成形を実施した。プレス成形の条件は、温度920℃、加圧圧力25MPaとし、CIP成形の条件は、常温(25℃)、加圧圧力100MPaとした。 The obtained sintering raw material powder was compacted to obtain a compact. In the rectangular flat plate type sputtering target, press molding or CIP molding was performed using a molding die having a size of 165 mm × 298 mm. The conditions for press molding were 920 ° C. and a pressure of 25 MPa, and the conditions for CIP molding were room temperature (25 ° C.) and a pressure of 100 MPa.
In the cylindrical sputtering target, press molding or CIP molding was performed using a mold having an outer diameter of 205 mm, an inner diameter of 165 mm, and a height of 200 mm. The conditions for press molding were 920 ° C. and a pressure of 25 MPa, and the conditions for CIP molding were room temperature (25 ° C.) and a pressure of 100 MPa.
そして、得られた成形体を、酸素導入機能を有する焼成装置内(装置内容積27000cm3)に装入し、酸素を導入しながら加熱して焼結する。このとき、酸素の導入量は6L/分とした。また、昇温速度は120℃/hとした。
そして、焼結の昇温時において、表1に示す条件で温度保持を行い、その後、表1に示す焼成条件で本焼成し、焼結体を得た。 Then, the obtained molded body is charged into a firing device having an oxygen introduction function (internal volume of 27,000 cm 3 ), and is heated and sintered while introducing oxygen. At this time, the introduced amount of oxygen was 6 L / min. The rate of temperature rise was 120 ° C./h.
Then, at the time of raising the temperature of the sintering, the temperature was maintained under the conditions shown in Table 1, and then the main firing was performed under the firing conditions shown in Table 1, to obtain a sintered body.
そして、焼結の昇温時において、表1に示す条件で温度保持を行い、その後、表1に示す焼成条件で本焼成し、焼結体を得た。 Then, the obtained molded body is charged into a firing device having an oxygen introduction function (internal volume of 27,000 cm 3 ), and is heated and sintered while introducing oxygen. At this time, the introduced amount of oxygen was 6 L / min. The rate of temperature rise was 120 ° C./h.
Then, at the time of raising the temperature of the sintering, the temperature was maintained under the conditions shown in Table 1, and then the main firing was performed under the firing conditions shown in Table 1, to obtain a sintered body.
得られた焼結体に対して湿式研削加工を施し、矩形平板型スパッタリングターゲットにおいては、126mm×178mm×6mmtのサイズとし、円筒型スパッタリングターゲットにおいては、外径155mm、内径135mm、高さ150mmのものを4個用いて、長さ600mmとした。
The obtained sintered body is subjected to wet grinding to have a size of 126 mm × 178 mm × 6 mmt in a rectangular flat plate type sputtering target, and an outer diameter of 155 mm, an inner diameter of 135 mm and a height of 150 mm in a cylindrical type sputtering target. Four pieces were used to make the length 600 mm.
得られた酸化物スパッタリングターゲットについて、以下の項目について評価した。評価結果を表2に示す。
The following items were evaluated for the obtained oxide sputtering target. Table 2 shows the evaluation results.
(金属成分組成)
作製された酸化物スパッタリングターゲットからサンプルを切り出して粉砕し、酸で前処理した後、ICP-AESによってZr,Si,Inの金属成分を分析し、得られた結果から、上述の全金属成分の含有量に対する各金属成分の含有量を計算し、表2に示した。 (Metal component composition)
A sample was cut out from the prepared oxide sputtering target, pulverized, pretreated with an acid, and analyzed for metal components of Zr, Si, and In by ICP-AES. The content of each metal component with respect to the content was calculated and is shown in Table 2.
作製された酸化物スパッタリングターゲットからサンプルを切り出して粉砕し、酸で前処理した後、ICP-AESによってZr,Si,Inの金属成分を分析し、得られた結果から、上述の全金属成分の含有量に対する各金属成分の含有量を計算し、表2に示した。 (Metal component composition)
A sample was cut out from the prepared oxide sputtering target, pulverized, pretreated with an acid, and analyzed for metal components of Zr, Si, and In by ICP-AES. The content of each metal component with respect to the content was calculated and is shown in Table 2.
(焼結体の粒子径)
作製された酸化物スパッタリングターゲットからサンプルを切り出し、湿式研磨にて研磨加工を行った後、電子プローブマイクロアナライザ(EPMA)装置を用いて倍率3000倍のCOMPO像を3枚撮影し、それぞれの画像に対して任意の線分3本を引き、それぞれに対して横切った粒子の数を計測した。線分の長さを粒子の数で割ることで、それぞれの線分における焼結体の粒子径を計算した。これを3枚の画像に対して行って、得られた9個の粒子径の平均値を表2に示した。 (Sintered particle size)
A sample was cut out from the prepared oxide sputtering target, polished by wet polishing, and three COMPO images at a magnification of 3000 were photographed using an electron probe microanalyzer (EPMA) device. On the other hand, three arbitrary line segments were drawn, and the number of particles crossing each line was measured. By dividing the length of the line segment by the number of particles, the particle diameter of the sintered body in each line segment was calculated. This was performed on three images, and the average value of the obtained nine particle diameters is shown in Table 2.
作製された酸化物スパッタリングターゲットからサンプルを切り出し、湿式研磨にて研磨加工を行った後、電子プローブマイクロアナライザ(EPMA)装置を用いて倍率3000倍のCOMPO像を3枚撮影し、それぞれの画像に対して任意の線分3本を引き、それぞれに対して横切った粒子の数を計測した。線分の長さを粒子の数で割ることで、それぞれの線分における焼結体の粒子径を計算した。これを3枚の画像に対して行って、得られた9個の粒子径の平均値を表2に示した。 (Sintered particle size)
A sample was cut out from the prepared oxide sputtering target, polished by wet polishing, and three COMPO images at a magnification of 3000 were photographed using an electron probe microanalyzer (EPMA) device. On the other hand, three arbitrary line segments were drawn, and the number of particles crossing each line was measured. By dividing the length of the line segment by the number of particles, the particle diameter of the sintered body in each line segment was calculated. This was performed on three images, and the average value of the obtained nine particle diameters is shown in Table 2.
(密度、及び、密度のばらつき)
矩形平板型スパッタリングターゲットにおいては、X軸を126mm方向、Y軸を178mm方向とし、中心を(X,Y)=(0mm,0mm)座標とした際に、(-58mm,+84mm)、(-58mm,-84mm)、(0mm,0mm)、(+58mm,+84mm)、(+58mm,-84mm)のそれぞれ5点を中心とした10mm×10mm×6mmtのブロックに切断した。得られた10mm×10mm×6mmtのブロック5個を、厚み方向に3分割(三等分)した合計15個の試料について寸法密度を測定した。そして、これら15個の試料の密度の平均値を表2に示した。 (Density and density variation)
In the rectangular flat plate type sputtering target, when the X axis is in the direction of 126 mm, the Y axis is in the direction of 178 mm, and the center is (X, Y) = (0 mm, 0 mm), the coordinates are (−58 mm, +84 mm), (−58 mm). , -84 mm), (0 mm, 0 mm), (+58 mm, +84 mm), and (+58 mm, -84 mm). The dimensional density was measured for a total of 15 samples obtained by dividing the obtained 5 blocks of 10 mm × 10 mm × 6 mmt into three (three) in the thickness direction. Table 2 shows the average values of the densities of these 15 samples.
矩形平板型スパッタリングターゲットにおいては、X軸を126mm方向、Y軸を178mm方向とし、中心を(X,Y)=(0mm,0mm)座標とした際に、(-58mm,+84mm)、(-58mm,-84mm)、(0mm,0mm)、(+58mm,+84mm)、(+58mm,-84mm)のそれぞれ5点を中心とした10mm×10mm×6mmtのブロックに切断した。得られた10mm×10mm×6mmtのブロック5個を、厚み方向に3分割(三等分)した合計15個の試料について寸法密度を測定した。そして、これら15個の試料の密度の平均値を表2に示した。 (Density and density variation)
In the rectangular flat plate type sputtering target, when the X axis is in the direction of 126 mm, the Y axis is in the direction of 178 mm, and the center is (X, Y) = (0 mm, 0 mm), the coordinates are (−58 mm, +84 mm), (−58 mm). , -84 mm), (0 mm, 0 mm), (+58 mm, +84 mm), and (+58 mm, -84 mm). The dimensional density was measured for a total of 15 samples obtained by dividing the obtained 5 blocks of 10 mm × 10 mm × 6 mmt into three (three) in the thickness direction. Table 2 shows the average values of the densities of these 15 samples.
ターゲットスパッタ面内の密度のばらつきについては、次のように算出した。ターゲットスパッタ面内の5ブロックについて、厚さ方向の1つのブロック毎における密度の最大値及び最小値から、実施形態に記載した式によって、厚さ方向の1つのブロックにおける同一水平面内(ターゲットスパッタ面内)の密度のばらつきを算出し、厚さ方向の3つのブロックの平均値を、ターゲットスパッタ面内の密度のばらつきとした。
密度 The variation in the density within the target sputtering surface was calculated as follows. From the maximum value and the minimum value of the density for each block in the thickness direction for the five blocks in the target sputtering surface, the same horizontal plane in one block in the thickness direction (target sputtering surface) The variation in the density in (in) was calculated, and the average value of the three blocks in the thickness direction was defined as the variation in the density in the target sputtering surface.
厚さ方向の密度のばらつきについては、次のように算出した。厚さ方向の3つのブロックについて、ターゲットスパッタ面内の1つのブロック毎における密度の最大値及び最小値から、実施形態に記載した式によって、ターゲットスパッタ面内の1つのブロックにおける同一鉛直方向(厚さ方向)の密度のばらつきを算出し、ターゲットスパッタ面内の5つのブロックの平均値を、厚さ方向の密度のばらつきとした。
密度 The variation in density in the thickness direction was calculated as follows. For the three blocks in the thickness direction, from the maximum value and the minimum value of the density of each block in the target sputtering surface, the same vertical direction (thickness) in one block in the target sputtering surface is obtained by the equation described in the embodiment. The variation in the density in the thickness direction was calculated, and the average value of the five blocks in the target sputtering surface was defined as the variation in the density in the thickness direction.
円筒型スパッタリングターゲットにおいては、円筒型スパッタリングターゲットの片方の端面を下側にして置き、軸線に直交する平面において、X軸を任意の端面方向、Y軸をX軸と垂直に交差する端面方向、Z軸を軸線向とし、中心を(X,Y,Z)=(0mm,0mm,0mm)座標とした際に、(-72.5mm,0mm,-70mm)、(+72.5mm,0mm,-70mm)、(0mm,-72.5mm、-70mm)、(0mm,+72.5mm,-70mm)、(-72.5mm,0mm,0mm)、(+72.5mm,0mm,0mm)、(0mm,-72.5mm,0mm)、(0mm,+72.5mm,0mm)、(-72.5mm,0mm,+70mm)、(+72.5mm,0mm,+70mm)、(0mm,-72.5mm,+70mm)、(0mm,+72.5mm,+70mm)のそれぞれ12点を中心とした10mm×10mm×10mmtのブロックに切断した。得られた10mm×10mm×10mmtのブロック12個を厚み方向に3分割(三等分)した合計36個の試料について、寸法密度を測定した。そして、これら36個の試料の密度の平均値を表2に示した。
In the cylindrical sputtering target, one end face of the cylindrical sputtering target is placed on the lower side, and in a plane perpendicular to the axis, the X axis is an arbitrary end face direction, the Y axis is an end face direction perpendicular to the X axis, When the Z axis is the axis direction and the center is (X, Y, Z) = (0 mm, 0 mm, 0 mm) coordinates, (−72.5 mm, 0 mm, −70 mm), (+72.5 mm, 0 mm, − 70mm), (0mm, -72.5mm, -70mm), (0mm, + 72.5mm, -70mm), (-72.5mm, 0mm, 0mm), (+ 72.5mm, 0mm, 0mm), (0mm, -72.5mm, 0mm), (0mm, + 72.5mm, 0mm), (-72.5mm, 0mm, + 70mm), (+ 72.5mm, 0mm, + 70mm), (0mm, 72.5mm, + 70mm), cut (0mm, + 72.5mm, the block of 10mm × 10mm × 10mmt around the 12 points each + 70 mm). The dimensional density was measured for a total of 36 samples obtained by dividing the obtained 12 blocks of 10 mm × 10 mm × 10 mmt into three (three) in the thickness direction. Table 2 shows average values of the densities of these 36 samples.
ターゲットスパッタ面内の密度のばらつきについては、次のように算出した。ターゲットスパッタ面内の12ブロックについて、厚さ方向の1つのブロック毎における密度の最大値及び最小値から、実施形態に記載した式によって、厚さ方向の1つのブロックにおける同一水平面内(ターゲットスパッタ面内)の密度のばらつきを算出し、厚さ方向の3つのブロックの平均値を、ターゲットスパッタ面内の密度のばらつきとした。
密度 The variation in the density within the target sputtering surface was calculated as follows. From the maximum value and the minimum value of the density in each block in the thickness direction for 12 blocks in the target sputtering surface, the same horizontal plane in one block in the thickness direction (target sputtering surface) The variation in the density in (in) was calculated, and the average value of the three blocks in the thickness direction was defined as the variation in the density in the target sputtering surface.
厚さ方向の密度のばらつきについては、次のように算出した。厚さ方向の3つのブロックについて、ターゲットスパッタ面内の1つのブロック毎における密度の最大値及び最小値から、実施形態に記載した式によって、ターゲットスパッタ面内の1つのブロックにおける同一鉛直方向(厚さ方向)の密度のばらつきを算出し、ターゲットスパッタ面内の12のブロックの平均値を、厚さ方向の密度のばらつきとした。
密度 The variation in density in the thickness direction was calculated as follows. For the three blocks in the thickness direction, from the maximum value and the minimum value of the density of each block in the target sputtering surface, the same vertical direction (thickness) in one block in the target sputtering surface is obtained by the equation described in the embodiment. The variation in the density in the thickness direction was calculated, and the average value of the 12 blocks in the target sputtering surface was defined as the variation in the density in the thickness direction.
(比抵抗、及び、比抵抗のばらつき)
得られた酸化物スパッタリングターゲットについて、矩形平板型スパッタリングターゲットについては密度測定用のサンプルと同様の15ブロックについて、円筒型スパッタリングターゲットについては36ブロックについて、三菱化学株式会社製の低抵抗率計(Loresta-GP)を用い、四探針法で測定した。測定時の温度は23±5℃、湿度は50±20%にて測定した。
そして、密度のばらつきと同様に、ターゲットスパッタ面内の比抵抗のばらつき、厚さ方向の比抵抗のばらつきを算出した。
また、比抵抗の平均値を表2に示した。 (Specific resistance and variation of specific resistance)
Regarding the obtained oxide sputtering target, a low resistivity meter (Loresta manufactured by Mitsubishi Chemical Co., Ltd.) was used for 15 blocks similar to the sample for density measurement for the rectangular flat plate type sputtering target and for 36 blocks for the cylindrical type sputtering target. -GP) using the four-probe method. The measurement was performed at a temperature of 23 ± 5 ° C. and a humidity of 50 ± 20%.
Then, similarly to the variation of the density, the variation of the specific resistance in the target sputtering surface and the variation of the specific resistance in the thickness direction were calculated.
Table 2 shows the average value of the specific resistance.
得られた酸化物スパッタリングターゲットについて、矩形平板型スパッタリングターゲットについては密度測定用のサンプルと同様の15ブロックについて、円筒型スパッタリングターゲットについては36ブロックについて、三菱化学株式会社製の低抵抗率計(Loresta-GP)を用い、四探針法で測定した。測定時の温度は23±5℃、湿度は50±20%にて測定した。
そして、密度のばらつきと同様に、ターゲットスパッタ面内の比抵抗のばらつき、厚さ方向の比抵抗のばらつきを算出した。
また、比抵抗の平均値を表2に示した。 (Specific resistance and variation of specific resistance)
Regarding the obtained oxide sputtering target, a low resistivity meter (Loresta manufactured by Mitsubishi Chemical Co., Ltd.) was used for 15 blocks similar to the sample for density measurement for the rectangular flat plate type sputtering target and for 36 blocks for the cylindrical type sputtering target. -GP) using the four-probe method. The measurement was performed at a temperature of 23 ± 5 ° C. and a humidity of 50 ± 20%.
Then, similarly to the variation of the density, the variation of the specific resistance in the target sputtering surface and the variation of the specific resistance in the thickness direction were calculated.
Table 2 shows the average value of the specific resistance.
(異常放電)
得られた酸化物スパッタリングターゲットをバッキングプレート又はバッキングチューブにInはんだを用いてはんだ付けし、マグネトロンスパッタ装置に装着した。そして、マグネトロンスパッタ装置により、スパッタガスとしてArガスを用いて、流量50sccm,圧力0.67Paとし、投入電力として5W/cm2の電力にて1時間のスパッタを行い、DC電源装置に備えられているアークカウント機能により、異常放電の回数を計測した。
本実施例では、電源装置として、RPG-50(mks社製)を使用した。スパッタ開始から1hの間の異常放電の回数を「初期」とし、スパッタを継続して行いエロージョン部の最も深い部分の深さが5mmに達した時点から1hの間の異常放電の回数を「終期」として、表2に記載した。 (Abnormal discharge)
The obtained oxide sputtering target was soldered to a backing plate or a backing tube using In solder, and then mounted on a magnetron sputtering device. Then, using a magnetron sputtering apparatus, an Ar gas was used as a sputtering gas, a flow rate was set to 50 sccm, a pressure was set to 0.67 Pa, and an input power of 5 W / cm 2 was used to perform sputtering for 1 hour. The number of abnormal discharges was measured by the arc count function.
In this embodiment, RPG-50 (manufactured by mks) was used as a power supply device. The number of abnormal discharges during 1 hour from the start of sputtering is defined as “initial”, and the number of abnormal discharges during 1 hour from the time when the depth of the deepest portion of the erosion portion reaches 5 mm is defined as “final”. In Table 2.
得られた酸化物スパッタリングターゲットをバッキングプレート又はバッキングチューブにInはんだを用いてはんだ付けし、マグネトロンスパッタ装置に装着した。そして、マグネトロンスパッタ装置により、スパッタガスとしてArガスを用いて、流量50sccm,圧力0.67Paとし、投入電力として5W/cm2の電力にて1時間のスパッタを行い、DC電源装置に備えられているアークカウント機能により、異常放電の回数を計測した。
本実施例では、電源装置として、RPG-50(mks社製)を使用した。スパッタ開始から1hの間の異常放電の回数を「初期」とし、スパッタを継続して行いエロージョン部の最も深い部分の深さが5mmに達した時点から1hの間の異常放電の回数を「終期」として、表2に記載した。 (Abnormal discharge)
The obtained oxide sputtering target was soldered to a backing plate or a backing tube using In solder, and then mounted on a magnetron sputtering device. Then, using a magnetron sputtering apparatus, an Ar gas was used as a sputtering gas, a flow rate was set to 50 sccm, a pressure was set to 0.67 Pa, and an input power of 5 W / cm 2 was used to perform sputtering for 1 hour. The number of abnormal discharges was measured by the arc count function.
In this embodiment, RPG-50 (manufactured by mks) was used as a power supply device. The number of abnormal discharges during 1 hour from the start of sputtering is defined as “initial”, and the number of abnormal discharges during 1 hour from the time when the depth of the deepest portion of the erosion portion reaches 5 mm is defined as “final”. In Table 2.
焼結工程において、1000℃で5時間保持した比較例1においては、ターゲットスパッタ面内における密度のばらつき、厚さ方向の密度のばらつき、厚さ方向の比抵抗のばらつきが大きく、終期の異常放電回数が多くなった。
焼結工程において、1450℃で5時間保持した比較例2においては、ターゲットスパッタ面内における密度のばらつき、厚さ方向の密度のばらつき、ターゲットスパッタ面内における比抵抗のばらつき、厚さ方向の比抵抗のばらつきが大きく、終期の異常放電回数が多くなった。
焼結工程において、1300℃で1時間保持した比較例3においては、ターゲットスパッタ面内における密度のばらつき、厚さ方向の密度のばらつき、厚さ方向の比抵抗のばらつきが大きく、終期の異常放電回数が多くなった。 In Comparative Example 1, which was held at 1000 ° C. for 5 hours in the sintering process, the variation in the density in the target sputtering surface, the variation in the density in the thickness direction, and the variation in the specific resistance in the thickness direction were large. The number has increased.
In Comparative Example 2, which was held at 1450 ° C. for 5 hours in the sintering step, the density variation in the target sputtering surface, the density variation in the thickness direction, the specific resistance variation in the target sputtering surface, and the ratio in the thickness direction The variation in resistance was large, and the number of abnormal discharges at the end increased.
In Comparative Example 3 held at 1300 ° C. for 1 hour in the sintering process, the variation in density, the variation in density in the thickness direction, and the variation in specific resistance in the thickness direction in the target sputtering surface were large, and abnormal discharge at the end The number has increased.
焼結工程において、1450℃で5時間保持した比較例2においては、ターゲットスパッタ面内における密度のばらつき、厚さ方向の密度のばらつき、ターゲットスパッタ面内における比抵抗のばらつき、厚さ方向の比抵抗のばらつきが大きく、終期の異常放電回数が多くなった。
焼結工程において、1300℃で1時間保持した比較例3においては、ターゲットスパッタ面内における密度のばらつき、厚さ方向の密度のばらつき、厚さ方向の比抵抗のばらつきが大きく、終期の異常放電回数が多くなった。 In Comparative Example 1, which was held at 1000 ° C. for 5 hours in the sintering process, the variation in the density in the target sputtering surface, the variation in the density in the thickness direction, and the variation in the specific resistance in the thickness direction were large. The number has increased.
In Comparative Example 2, which was held at 1450 ° C. for 5 hours in the sintering step, the density variation in the target sputtering surface, the density variation in the thickness direction, the specific resistance variation in the target sputtering surface, and the ratio in the thickness direction The variation in resistance was large, and the number of abnormal discharges at the end increased.
In Comparative Example 3 held at 1300 ° C. for 1 hour in the sintering process, the variation in density, the variation in density in the thickness direction, and the variation in specific resistance in the thickness direction in the target sputtering surface were large, and abnormal discharge at the end The number has increased.
これに対して、焼結工程において、1200℃以上1400℃以下の温度範囲で3時間以上保持した本発明例1-12においては、ターゲットスパッタ面内における密度のばらつき、厚さ方向の密度のばらつき、ターゲットスパッタ面内における比抵抗のばらつき、厚さ方向の比抵抗のばらつきが小さく、異常放電回数が少なく、安定してスパッタ成膜を行うことができた。
On the other hand, in Example 1-12 of the present invention in which the temperature was kept in the temperature range of 1200 ° C. to 1400 ° C. for 3 hours or more in the sintering step, the density variation in the target sputtering surface and the density variation in the thickness direction In addition, the dispersion of the specific resistance in the target sputtering surface and the dispersion of the specific resistance in the thickness direction were small, the number of abnormal discharges was small, and the sputtering film could be stably formed.
以上のことから、本発明例によれば、ターゲットスパッタ面が比較的大きくても、安定してスパッタ成膜を行うことが可能な酸化物スパッタリングターゲット、及び、この酸化物スパッタリングターゲットの製造方法を提供可能であることが確認された。
From the above, according to the example of the present invention, an oxide sputtering target capable of stably forming a sputter film even when the target sputtering surface is relatively large, and a method for manufacturing this oxide sputtering target It was confirmed that it could be provided.
本発明によれば、ターゲットスパッタ面が比較的大きくても、安定してスパッタ成膜を行うことが可能な酸化物スパッタリングターゲット、及び、この酸化物スパッタリングターゲットの製造方法を提供することができる。
According to the present invention, it is possible to provide an oxide sputtering target that can stably form a sputter film even when the target sputtering surface is relatively large, and a method for manufacturing the oxide sputtering target.
Claims (5)
- 金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物からなる酸化物スパッタリングターゲットであって、
ターゲットスパッタ面内における密度のばらつきが3%以内とされ、厚さ方向における密度のばらつきが5%以内とされていることを特徴とする酸化物スパッタリングターゲット。 As a metal component, zirconium, an oxide sputtering target composed of an oxide containing silicon and indium,
An oxide sputtering target, wherein the variation in density in the target sputtering surface is within 3% and the variation in density in the thickness direction is within 5%. - ターゲットスパッタ面内における比抵抗のばらつきが10%以内とされ、厚さ方向における比抵抗のばらつきが10%以内とされていることを特徴とする請求項1に記載の酸化物スパッタリングターゲット。 2. The oxide sputtering target according to claim 1, wherein a variation in specific resistance in a target sputtering surface is within 10%, and a variation in specific resistance in a thickness direction is within 10%.
- ターゲットスパッタ面の面積が0.02m2以上であることを特徴とする請求項1又は請求項2に記載の酸化物スパッタリングターゲット。 3. The oxide sputtering target according to claim 1, wherein the area of the target sputtering surface is 0.02 m 2 or more. 4.
- 金属成分として、ジルコニウム、ケイ素およびインジウムを含有した酸化物からなる酸化物スパッタリングターゲットの製造方法であって、
酸化ジルコニウム粉、酸化ケイ素粉および酸化インジウム粉を混合した焼結原料粉を得る焼結原料粉形成工程と、得られた前記焼結原料粉を焼結して焼結体を得る焼結工程と、を有し、
前記焼結工程では、酸素を導入しながら加熱し、1200℃以上1400℃以下の温度範囲で3時間以上保持した後、1400℃を超える温度にまで加熱して保持することを特徴とする酸化物スパッタリングターゲットの製造方法。 As a metal component, zirconium, a method for producing an oxide sputtering target consisting of an oxide containing silicon and indium,
A sintering material powder forming step of obtaining a sintering material powder obtained by mixing zirconium oxide powder, silicon oxide powder and indium oxide powder, and a sintering step of sintering the obtained sintering material powder to obtain a sintered body; , And
In the sintering step, the oxide is heated while introducing oxygen, held at a temperature in a range of 1200 ° C. to 1400 ° C. for 3 hours or more, and then heated to a temperature exceeding 1400 ° C. and held. A method for manufacturing a sputtering target. - 前記焼結原料粉のメディアン径(D50)が0.05μm以上1.2μm以下の範囲内であることを特徴とする請求項4に記載の酸化物スパッタリングターゲットの製造方法。 The method for producing an oxide sputtering target according to claim 4, wherein a median diameter (D50) of the sintering raw material powder is in a range of 0.05 μm or more and 1.2 μm or less.
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