WO2016024526A1 - Oxide sintered body and sputtering target - Google Patents
Oxide sintered body and sputtering target Download PDFInfo
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- WO2016024526A1 WO2016024526A1 PCT/JP2015/072389 JP2015072389W WO2016024526A1 WO 2016024526 A1 WO2016024526 A1 WO 2016024526A1 JP 2015072389 W JP2015072389 W JP 2015072389W WO 2016024526 A1 WO2016024526 A1 WO 2016024526A1
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- sintered body
- oxide sintered
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- sputtering
- oxygen
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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
- C04B35/453—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 based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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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 sintered body containing zinc, niobium and oxygen as constituent elements, and a sputtering target comprising the sintered body.
- Niobium oxide target which is a general high refractive index material, cannot obtain the conductivity of the target capable of DC discharge in the atmospheric pressure sintering method, so by reducing the sintered body under high temperature and pressure conditions, The conductivity of the sintered body is increased (for example, see Patent Document 1).
- composite oxide sintered bodies made of zinc, aluminum, and titanium have been reported as high refractive index targets (see, for example, Patent Document 3).
- the zinc oxide target containing titanium achieves a high refractive index of 2.0 or more, and it is said that a complex oxide sintered body having a stable DC discharge performance with less arcing is obtained. .
- An object of the present invention is to provide an oxide sintered body used for a sputtering target that has a low abnormal discharge phenomenon even during high power film formation, has a high film formation rate, and can obtain a high refractive index film. is there.
- the present inventors diligently studied the conductive mechanism of a composite oxide sintered body composed of a ZnO phase and a Zn 3 Nb 2 O 8 phase.
- the Zn 3 Nb 2 O 8 phase is a material with extremely low conductivity, while the ZnO phase has a small amount of niobium substituted into the ZnO crystal phase, resulting in slight conductivity.
- the inventors have used a high-density sintered body obtained by appropriately arranging a ZnO crystal phase having a predetermined particle size in a composite oxide phase as a sputtering target, thereby generating arcing during sputtering. We have achieved excellent discharge characteristics with no variation in thin film characteristics.
- the present invention (1) In an oxide sintered body having zinc, niobium and oxygen as constituent elements, when the zinc and niobium contents are Zn and Nb, respectively, the atomic ratio of Nb / (Zn + Nb) is 0.064 to An oxide sintered body characterized by being 0.334, a relative density exceeding 98%, and a bulk resistance value of 1.0 to 5000 ⁇ ⁇ cm. (2) The oxide sintered body according to (1), wherein the average particle diameter of the ZnO crystal phase in the oxide sintered body is 1.5 ⁇ m or more and 6 ⁇ m or less. (3) The oxide sintered body according to (1) or (2), wherein the amount of oxygen deficiency in the oxide sintered body is 5% or less.
- the oxide sintered body according to any one of (1) to (5) which has a cylindrical shape with an area of a target surface of 486 cm 2 or more.
- the content of zinc and niobium is Zn and Nb, respectively, and Nb / (Zn + Nb) is 0.064 in atomic ratio. It is an oxide sintered body having a relative density exceeding 98% and a bulk resistance value of 1.0 to 5000 ⁇ ⁇ cm.
- the oxide sintered body of the present invention has zinc and niobium as constituent elements.
- Nb / (Zn + Nb) is 0.064 in atomic ratio. It is characterized by -0.334.
- Nb / (Zn + Nb) is preferably 0.133 to 0.290, and more preferably 0.208 to 0.248.
- Nb / (Zn + Nb) is less than 0.064, the refractive index of the film obtained by sputtering decreases, and when Nb / (Zn + Nb) exceeds 0.334, the Zn 3 Nb 2 O 8 phase increases. Then, the resistivity becomes high.
- the oxide sintered body of the present invention is characterized in that the relative density exceeds 98%. This is because when the relative density is 98% or less in this material, the frequency of arcing increases when used as a sputtering target.
- the oxide sintered body of the present invention When used as a sputtering target, it can stably perform DC discharge, so that the bulk resistance value must be 1.0 to 5000 ⁇ ⁇ cm, and 15 to 3000 ⁇ ⁇ cm. It is preferably 30 to 850 ⁇ ⁇ cm.
- the variation width of the resistivity at any 10 points in the oxide sintered body is preferably within 70%, and more preferably within 50%.
- the variation width in the present invention is a value represented by (Rmax ⁇ Rmin) / Rmax ⁇ 100 [%], where Rmax is the maximum value of 10 measured points and Rmin is the minimum value.
- the oxide sintered body of the present invention includes a ZnO phase that is a conductive phase and a Zn 3 Nb 2 O 8 phase that is an insulating phase, and the Zn 3 Nb 2 O 8 phase is not finely and uniformly dispersed. This is because a large variation in resistance value is produced in the sintered body, which may cause severe abnormal discharge during sputtering.
- the oxide sintered body of the present invention has a feature that the amount of oxygen deficiency is smaller than that of the conventional one. In a target having a large amount of oxygen vacancies, it is necessary to introduce oxygen as a sputtering gas at the time of sputtering, which causes a problem that the film formation rate is rapidly reduced by the introduction of oxygen.
- the oxide sintered body of the present invention can realize excellent permeability and low absorption characteristics even in a state where the amount of introduced oxygen is extremely small, and a remarkable improvement effect of the film forming rate can be obtained.
- the oxide sintered body of the present invention since the ZnO phase as the conductive phase and the Zn 3 Nb 2 O 8 phase as the insulating phase coexist, the sputtering current concentrates on the ZnO, and oxygen vacancies in the sintered body A large amount is not preferable because ZnO is reduced and easily becomes metal Zn.
- the oxygen deficiency of the sintered body in the present application includes the stoichiometric value [wt%] of the oxygen content calculated as containing oxygen equal to the stoichiometric composition and the analytical value [wt%] measured by analysis. ],
- the oxygen deficiency is expressed by the following equation (1).
- the stoichiometric value [wt%] of the formula oxygen content is When the molar ratio of ZnO represented by ZnO / (ZnO + Nb 2 O 5 ) is x, ((M O ⁇ 1 ⁇ x + M O ⁇ 5 ⁇ (1-x)) / (M ZnO ⁇ x + MNb2O5 ⁇ (1-x))) ⁇ 100 (2)
- M Nb2O5 is the molecular weight of Nb 2 O 5
- the oxygen deficiency is preferably 5% or less.
- the average particle diameter of the ZnO phase in the oxide sintered body is preferably 1.5 ⁇ m or more and 6 ⁇ m or less. If the particle diameter of the ZnO phase that plays a role as a conductive path becomes too small, the Zn 3 Nb 2 O 8 phase that is an insulating phase easily enters the grain boundary portion, and the conductivity of the entire target is significantly deteriorated. This is because stable DC sputtering cannot be performed. In addition, if the particle size of the ZnO phase becomes too large, it is not preferable because it causes an increase in resistance variation, cracks in the sintered body, and a reduction in density.
- the maximum intensity of the diffraction peak existing when the incident angle (2 ⁇ ) in X-ray diffraction is 32.3 ° to 33.8 ° is I 1 , 35.8 ° to 37. It is preferable that the value of the diffraction intensity ratio I 2 / I 1 is 0.65 or more when the maximum intensity of the diffraction peak existing between 3 ° is I 2 .
- the peak existing between 32.3 ° and 33.8 ° corresponds to the diffraction peak corresponding to the Zn 3 Nb 2 O 8 phase in the composite oxide sintered body, and 35.8 ° to 37.37.
- the peak existing between 3 ° is a peak corresponding to the ZnO phase. This is because in the composite oxide sintered body of the present invention, the particle size of the ZnO phase is relatively larger than that of the Zn 3 Nb 2 O 8 phase.
- the input load to the target is normalized by the power density (W / cm 2 ) obtained by dividing the input power by the target area.
- the general power density in normal production is about 1 to 2.5 W / cm 2 , but in the present invention, it becomes a high-quality target material with extremely little arcing even under high power conditions of 4 W / cm 2 or more. An oxide sintered body is obtained.
- the method for producing an oxide sintered body according to the present invention uses a zinc oxide powder and a niobium pentoxide powder as a raw material powder, and the atomic ratio of elements is Nb / Nb when the content of zinc and niobium is Zn and Nb respectively.
- the obtained molded body is fired and held in an oxidizing atmosphere at a temperature of 1150 to 1300 ° C. for 0.5 to 5 hours. It is characterized by.
- the raw material powder is preferably an oxide powder of zinc oxide or niobium pentoxide.
- the purity of each raw material powder is preferably 99.9% or more, more preferably 99.99% or more. If impurities are included, it causes abnormal grain growth in the firing process.
- Nb / (Zn + Nb) is 0.064 to 0.334 when the atomic ratio of the elements of the zinc oxide powder and the niobium pentoxide powder is Zn and Nb, respectively. It is preferable to mix so that Nb / (Zn + Nb) is 0.133 to 0.290, and so that Nb / (Zn + Nb) is 0.208 to 0.248. It is more preferable.
- the physical properties of the zinc oxide powder are particularly important factors because they are related to the particle size and uniform dispersibility of the ZnO phase responsible for conductivity in the sintered body of the present invention.
- a ZnO raw material powder having a BET value in the range of 2.2 to 10 m 2 / g is used.
- the pulverization / mixing process is performed using a powder having a BET value larger than 10 m 2 / g, the particle size of the ZnO phase of the obtained sintered body is reduced, and the conductivity of the target is deteriorated.
- the deterioration of conductivity causes an increase in the number of arcing generated during sputtering, and a problem that DC discharge becomes impossible occurs particularly when the conductivity is poor. Furthermore, since the formability deteriorates due to the refinement of the raw material and causes a reduction in density, it is not preferable. In addition, if the pulverization / mixing process is performed using a powder having a BET value smaller than 2.2 m 2 / g, unevenness increases when mixing the raw materials, which causes variation in resistance value and low density, which is not preferable. .
- Niobium pentoxide powder having a BET value of 6 to 14 m 2 / g is used in consideration of the grinding and mixing process.
- the pulverization / mixing process is performed using a powder having a BET value larger than 14 m 2 / g, the conductive path of the ZnO phase is easily cut in the obtained sintered body, and the conductivity of the target is deteriorated.
- the pulverization / mixing step which is the next step, it is important to prevent the ZnO powder from being excessively pulverized while improving the mixing property with the niobium pentoxide powder.
- the ratio (B N / B Z ) between the BET value of the ZnO powder to be used and B Z , and the BET value B N of the niobium pentoxide powder is in the range of 0.8 to 3.6.
- the solid content concentration in the slurry is 35% to 65%, more preferably 55% to 65%. If the solid content concentration becomes too high, the processing ability is lowered, and desired powder physical properties cannot be obtained. In particular, zinc oxide tends to cause an increase in viscosity and greatly impairs the mixing property with other raw materials, so it is important to adjust it within an appropriate range.
- zirconia beads are used in consideration of prevention of impurities from being mixed into the raw material due to wear.
- the bead diameter is in the range of ⁇ 0.2 mm to ⁇ 0.3 mm.
- the total amount of beads charged into the mill is in the range of 4.5 to 5.5 kg, and the bead filling rate relative to the mill volume is in the range of 70 to 75%.
- the slurry temperature also needs to be strictly controlled.
- the mill inlet slurry temperature is controlled to 12 ° C. or lower, preferably 9 ° C. or lower, and constantly controlled so that the slurry outlet slurry temperature is 18 ° C. or lower.
- the type of the dispersant is not particularly limited, but it is important to keep the slurry viscosity change below a certain level. For this reason, the addition amount in the present invention needs to be larger than a general addition amount, and is preferably 1.0 wt% or more and 3.5 wt% or less with respect to the input powder amount.
- Efficient slurry supply into the mill is 0.4 L / min to 1.0 L / min for 1 to 2 passes, which is a heavy burden on the mill, and 1.5 L / min to 2.4 L / min thereafter. It is preferable because it can be processed.
- the peripheral speed of the mill is preferably set to a slightly low range of 2.5 m / sec to 5.5 m / sec.
- the slurry viscosity may rise due to some factor even under the same conditions.
- the amount of the dispersant is appropriately added within the above range, and the slurry viscosity is always 2200 mPa ⁇ s or less. Therefore, it is necessary to obtain stable powder properties.
- the mixed powder necessary to obtain the composite oxide sintered body of the present invention can be obtained by suppressing the number of grinding passes into the mill to 20 or less.
- the slurry after the wet mixing treatment can be used as it is in a wet molding method such as cast molding, but in the case of dry molding, the powder fluidity is high and the compact density is uniform. It is desirable to use a dry granulated powder. Although it does not limit about the granulation method, spray granulation, fluidized bed granulation, rolling granulation, stirring granulation, etc. can be used. In particular, it is desirable to use spray granulation which is easy to operate and can be processed in large quantities.
- the molding method is not particularly limited, and a molding method capable of molding the raw material powder into a desired shape can be appropriately selected. Examples thereof include a press molding method, a casting molding method, and an injection molding method.
- the molding pressure is not particularly limited as long as it does not cause cracks in the molded body and can be handled, but it is preferable to increase the molding density as much as possible. Therefore, it is also possible to use a method such as cold isostatic pressing (CIP) molding.
- CIP pressure is preferably for 1 ton / cm 2 or more to obtain a sufficient consolidation effect, more preferably 2 ton / cm 2 or more, especially preferably 2 ⁇ 3ton / cm 2.
- the firing atmosphere can be either an air atmosphere or an oxygen atmosphere which is an oxidizing atmosphere.
- Oxygen deficiency of the oxide sintered body is the oxygen present in the sintered body fired in a hot press or non-oxidizing atmosphere because it can be fired in the air atmosphere without requiring special atmosphere control. Less than the amount of deficiency.
- the control of oxygen deficiency is closely related to the rate of temperature rise and fall, the holding time, and the holding temperature particularly in a high temperature range, and is thus fired and held at a temperature of 1150 ° C. to 1300 ° C. for 0.5 to 5 hours. It is necessary.
- the temperature increase rate from 950 ° C. to 1050 ° C. is 200 to 350 ° C./h
- the cooling rate from the firing holding temperature to 900 ° C. is 350 ° C./h or more.
- the obtained sintered body is formed into a desired shape such as a plate shape, a circular shape, or a cylindrical shape by using a machining machine such as a surface grinder, a cylindrical grinder, a lathe, a cutting machine, or a machining center. To grind. Furthermore, a sputtering target using the sintered body of the present invention as a target material is obtained by bonding (bonding) a backing plate made of oxygen-free copper, titanium, or the like to the backing tube or backing tube using indium solder or the like as necessary. Can do.
- the size of the sintered body is not particularly limited, but since the sintered body according to the present invention has high strength, a large target can be manufactured.
- a large-sized sintered body having a length of 310 mm ⁇ width of 310 mm (target surface area 961 cm 2 ) or more can be produced.
- a large-sized sintered body having an outer diameter of 91 mm ⁇ ⁇ 170 mm (target surface area 486 cm 2 ) or more can be produced.
- the area of the target surface said here means the area of the sintered compact surface by the side of sputtering.
- the area of the surface of the sintered body on the side to be sputtered in each sintered body is the largest in the area of the target surface in the multi-divided target. is there.
- the oxide sintered body of the present invention When the oxide sintered body of the present invention is used as a sputtering target, even when a high power is applied, the occurrence of abnormal discharge (arcing) and cracking of the target are small, and stable DC discharge is possible. Moreover, since the strength of the sintered body is high, processing becomes easy, and a large target can be manufactured with high yield. Furthermore, since the amount of oxygen in the target is higher than that of the conventional hot press method, the amount of oxygen introduced during sputtering can be reduced, and not only can a high film formation rate be realized, but also a film with extremely excellent light transmission can be obtained. Can do.
- the true density of the sintered body was calculated assuming that all the Nb 2 O 5 phases in the sintered body reacted as the Zn 3 Nb 2 O 8 phase, and the weight a [g] of the ZnO phase and Zn 3 Nb 2 Using the weight b [g] of the O 8 phase and each true density 5.606 [g / cm 3 ], 5.734 [g / cm 3 ], the calculation was made from the arithmetic average represented by the following formula. .
- Sputtering was performed by changing the input power using this target, and the arcing measurement, the evaluation of the stability of the DC discharge, and the film formed under the following conditions were evaluated.
- Example 1 The powdered physical properties of zinc oxide powder and niobium oxide powder (purity 99.9% or more) shown in Table 1 were weighed so that the ratio of Nb / (Zn + Nb) was 0.248. The weighed powder was slurried with 10 kg of pure water, and 3 wt% of the polyacrylate dispersant was added to the total powder amount to prepare a slurry with a solid content concentration of 60%. Filled with 75% ⁇ 0.3mm zirconia beads in a 2.5L bead mill device, and circulated and pulverized and mixed the slurry in the mill at a mill peripheral speed of 5.0m / sec and a slurry supply rate of 2.0L / min. Processed.
- the temperature was controlled within the range of the slurry supply tank temperature of 8-9 ° C. and the slurry outlet temperature of 14-16 ° C., and the number of circulations (passes) in the mill was 5. Thereafter, the obtained slurry was spray-dried, the dried powder was passed through a 300 ⁇ m sieve, and a 120 mm ⁇ 120 mm ⁇ 8 mmt molded body was produced at a pressure of 300 kg / cm 2 by a press molding method, and then 2 ton / cm 2 . CIP-treated with pressure.
- Examples 2 to 11, Comparative Examples 1 to 12 The same method as in Example 1 except that the powder and composition used were changed to the contents shown in Table 2 (Example 4 has a molded body size of 310 mm ⁇ 310 mm ⁇ 6 mmt, Example 5 has a body size of 77 mm inner diameter ⁇ 91 mm outer diameter) The shape was changed to a cylindrical shape of ⁇ 170 mmL). Next, each compact was fired under the conditions shown in Table 2. Table 2 shows the evaluation results of the obtained sintered body.
- the resistivity of the thin film obtained in each of Examples 1 to 11 was measured by a four-terminal method using a Loresta HP MCP-T410 (manufactured by Mitsubishi Yuka). All the thin film resistors were high resistance films of 10 5 ⁇ or more.
- Example 13 A molded body was produced in the same manner as in Example 1, and then fired in the same manner as in Example 1 except that the firing atmosphere was changed to a nitrogen atmosphere.
- Table 2 shows the evaluation results of the obtained sintered body. Moreover, generation
- Example 2 Using the same composition as in Example 1 and a powder produced by the same method, a molded body was produced. Next, the compact was filled in a graphite hot press mold and sintered by holding it at 1000 ° C. for 1 hour under vacuum in a hot press apparatus. The hot press pressure was 19.6 MPa. The density of the obtained sintered body was 5.485 g / cm 3 and the relative density was 95.7%. Table 3 shows the evaluation results of the obtained sintered body.
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Abstract
The purpose of the present invention is to provide an oxide sintered body for use as a sputtering target that enables stable DC sputtering, has a high rate of film formation, and in which few abnormal electrical discharge phenomena occur even during high-power film formation. This oxide sintered body contains, as constituent elements, zinc, niobium, and oxygen in an atomic ratio Nb/(Zn + Nb), where Zn represents the zinc content and Nb represents the niobium content, of 0.064–0.334, and has a relative density greater than 98% and a bulk resistance value of 1.0–5000 Ω∙cm.
Description
本発明は、亜鉛、ニオブ及び酸素を構成元素とする酸化物焼結体及び当該焼結体を含んでなるスパッタリングターゲットに関するものである。
The present invention relates to an oxide sintered body containing zinc, niobium and oxygen as constituent elements, and a sputtering target comprising the sintered body.
近年、携帯型ディスプレイや建材ガラスにおいて屈折率調整用として高屈折率膜が採用されつつある。高屈折率材料として一般的な酸化ニオブターゲットは、常圧焼結法ではＤＣ放電が可能なターゲットの導電性が得られないため、高温、加圧条件下で焼結体を還元することにより、焼結体の導電性を高めている（例えば、特許文献１参照）。
In recent years, high refractive index films are being adopted for refractive index adjustment in portable displays and building glass. Niobium oxide target, which is a general high refractive index material, cannot obtain the conductivity of the target capable of DC discharge in the atmospheric pressure sintering method, so by reducing the sintered body under high temperature and pressure conditions, The conductivity of the sintered body is increased (for example, see Patent Document 1).
また、酸化ニオブに亜鉛を添加することで、抵抗率が下がることも報告されている（例えば、特許文献２参照）。
It has also been reported that the resistivity decreases by adding zinc to niobium oxide (see, for example, Patent Document 2).
しかしながら、いずれの方法もホットプレス法で製造しなければならないため、大型のターゲットの製造においては巨大なプレス機構が必要となるため、現実的なプロセスではなく、ターゲットサイズは小型品に限定されている。また、ホットプレス法は還元雰囲気下での焼結であるため、ターゲット内の酸素欠損量が多くなる傾向がある。酸素欠損量の多いターゲットでは、高い透過性を得るためにスパッタリング時にスパッタガスとして酸素を導入する必要があり、酸素の導入によって成膜レートが低下するという問題も生じている。
However, since both methods must be manufactured by the hot press method, a large press mechanism is required for manufacturing a large target, so this is not a realistic process, and the target size is limited to a small product. Yes. Moreover, since the hot press method is sintering in a reducing atmosphere, the amount of oxygen deficiency in the target tends to increase. In a target having a large amount of oxygen vacancies, it is necessary to introduce oxygen as a sputtering gas at the time of sputtering in order to obtain high permeability, and there is a problem that the film formation rate is lowered by the introduction of oxygen.
また、高屈折率ターゲットとして、亜鉛、アルミニウム、チタンより成る複合酸化物焼結体も報告されている（例えば、特許文献３参照）。チタンを含有した酸化亜鉛系ターゲットは、屈折率２．０以上の高屈折率を実現すると共に、アーキング発生の少ない、安定なＤＣ放電性能を有する複合酸化物焼結体が得られるとされている。
Also, composite oxide sintered bodies made of zinc, aluminum, and titanium have been reported as high refractive index targets (see, for example, Patent Document 3). The zinc oxide target containing titanium achieves a high refractive index of 2.0 or more, and it is said that a complex oxide sintered body having a stable DC discharge performance with less arcing is obtained. .
しかしながら、近年では高パワー負荷を投入可能な円筒ターゲットの採用等が進んでおり、従来想定していなかった高パワーを投入した成膜が主流になりつつある。したがって、高パワー投入時においてもアーキング発生やターゲット割れのない、安定なＤＣ放電が可能な高屈折率ターゲットに対する必要性が高まっている。
However, in recent years, the adoption of a cylindrical target capable of supplying a high power load is progressing, and film formation using a high power, which has not been assumed in the past, is becoming mainstream. Therefore, there is an increasing need for a high refractive index target capable of stable DC discharge without causing arcing and target cracking even when high power is applied.
本発明の目的は、高パワー成膜時においても異常放電現象が少なく、高成膜レートであり、高屈折率膜を得ることができるスパッタリングターゲットに用いられる酸化物焼結体を提供することである。
An object of the present invention is to provide an oxide sintered body used for a sputtering target that has a low abnormal discharge phenomenon even during high power film formation, has a high film formation rate, and can obtain a high refractive index film. is there.
本発明者らは、ＺｎＯ相とＺｎ３Ｎｂ２Ｏ８相よりなる複合酸化物焼結体の導電機構について鋭意検討を行った。複合酸化物を形成する結晶相の内、Ｚｎ３Ｎｂ２Ｏ８相は導電性の極めて低い材料である一方、ＺｎＯ相は微量のニオブがＺｎＯ結晶相に固溶置換し、僅かの導電性を示す。本発明者らは、所定の粒径を有するＺｎＯ結晶相を複合酸化物相内に適切に配することにより得られた高密度焼結体をスパッタリングターゲットとして用いることにより、スパッタリング中のアーキング発生や薄膜特性のバラツキのない、優れた放電特性を実現するに至った。
The present inventors diligently studied the conductive mechanism of a composite oxide sintered body composed of a ZnO phase and a Zn 3 Nb 2 O 8 phase. Among the crystal phases forming the composite oxide, the Zn 3 Nb 2 O 8 phase is a material with extremely low conductivity, while the ZnO phase has a small amount of niobium substituted into the ZnO crystal phase, resulting in slight conductivity. Show. The inventors have used a high-density sintered body obtained by appropriately arranging a ZnO crystal phase having a predetermined particle size in a composite oxide phase as a sputtering target, thereby generating arcing during sputtering. We have achieved excellent discharge characteristics with no variation in thin film characteristics.
すなわち、本発明は、
（１）構成元素として、亜鉛、ニオブ及び酸素を有する酸化物焼結体において、亜鉛、ニオブの含有量をそれぞれＺｎ、Ｎｂとしたときに、原子比でＮｂ／（Ｚｎ＋Ｎｂ）が０．０６４～０．３３４であり、相対密度が９８％を超え、バルク抵抗値が１．０～５０００Ω・ｃｍであることを特徴とする酸化物焼結体。
（２）酸化物焼結体中のＺｎＯ結晶相の平均粒径が１．５μｍ以上６μｍ以下であることを特徴とする（１）に記載の酸化物焼結体。
（３）酸化物焼結体の酸素欠損量が５％以下であることを特徴とする（１）または（２）に記載の酸化物焼結体。
（４）酸化物焼結体の抵抗率のばらつき幅が７０％以内であることを特徴とする（１）～（３）のいずれかに記載の酸化物焼結体。
（５）Ｘ線回折における入射角（２θ）が、３２．３°～３３．８°の間に存在する回折ピークの最大強度をＩ１、３５．８°～３７．３°の間に存在する回折ピークの最大強度をＩ２とした時の、回折強度比Ｉ２／Ｉ１の値が０．６５以上であることを特徴とする（１）～（４）のいずれかに記載の酸化物焼結体。
（６）ターゲット面の面積が９６１ｃｍ２以上である平板形状であることを特徴とする（１）～（５）のいずれかに記載の酸化物焼結体。
（７）ターゲット面の面積が４８６ｃｍ２以上である円筒形状であることを特徴とする（１）～（５）のいずれかに記載の酸化物焼結体。
（８）（１）から（７）のいずれかに記載の酸化物焼結体をターゲット材として用いることを特徴とするスパッタリングターゲット。
（９）（８）に記載のスパッタリングターゲットを用いてスパッタリング法で成膜したことを特徴とする薄膜。
に関するものである。 That is, the present invention
(1) In an oxide sintered body having zinc, niobium and oxygen as constituent elements, when the zinc and niobium contents are Zn and Nb, respectively, the atomic ratio of Nb / (Zn + Nb) is 0.064 to An oxide sintered body characterized by being 0.334, a relative density exceeding 98%, and a bulk resistance value of 1.0 to 5000 Ω · cm.
(2) The oxide sintered body according to (1), wherein the average particle diameter of the ZnO crystal phase in the oxide sintered body is 1.5 μm or more and 6 μm or less.
(3) The oxide sintered body according to (1) or (2), wherein the amount of oxygen deficiency in the oxide sintered body is 5% or less.
(4) The oxide sintered body according to any one of (1) to (3), wherein the variation range of resistivity of the oxide sintered body is within 70%.
(5) The maximum intensity of the diffraction peak where the incident angle (2θ) in X-ray diffraction is between 32.3 ° and 33.8 ° is between I 1 and 35.8 ° to 37.3 °. The oxidation according to any one of (1) to (4), wherein the value of the diffraction intensity ratio I 2 / I 1 is 0.65 or more when the maximum intensity of the diffraction peak is I 2 Sintered product.
(6) The oxide sintered body according to any one of (1) to (5), wherein the area of the target surface is a flat plate shape of 961 cm 2 or more.
(7) The oxide sintered body according to any one of (1) to (5), which has a cylindrical shape with an area of a target surface of 486 cm 2 or more.
(8) A sputtering target using the oxide sintered body according to any one of (1) to (7) as a target material.
(9) A thin film formed by sputtering using the sputtering target according to (8).
It is about.
（１）構成元素として、亜鉛、ニオブ及び酸素を有する酸化物焼結体において、亜鉛、ニオブの含有量をそれぞれＺｎ、Ｎｂとしたときに、原子比でＮｂ／（Ｚｎ＋Ｎｂ）が０．０６４～０．３３４であり、相対密度が９８％を超え、バルク抵抗値が１．０～５０００Ω・ｃｍであることを特徴とする酸化物焼結体。
（２）酸化物焼結体中のＺｎＯ結晶相の平均粒径が１．５μｍ以上６μｍ以下であることを特徴とする（１）に記載の酸化物焼結体。
（３）酸化物焼結体の酸素欠損量が５％以下であることを特徴とする（１）または（２）に記載の酸化物焼結体。
（４）酸化物焼結体の抵抗率のばらつき幅が７０％以内であることを特徴とする（１）～（３）のいずれかに記載の酸化物焼結体。
（５）Ｘ線回折における入射角（２θ）が、３２．３°～３３．８°の間に存在する回折ピークの最大強度をＩ１、３５．８°～３７．３°の間に存在する回折ピークの最大強度をＩ２とした時の、回折強度比Ｉ２／Ｉ１の値が０．６５以上であることを特徴とする（１）～（４）のいずれかに記載の酸化物焼結体。
（６）ターゲット面の面積が９６１ｃｍ２以上である平板形状であることを特徴とする（１）～（５）のいずれかに記載の酸化物焼結体。
（７）ターゲット面の面積が４８６ｃｍ２以上である円筒形状であることを特徴とする（１）～（５）のいずれかに記載の酸化物焼結体。
（８）（１）から（７）のいずれかに記載の酸化物焼結体をターゲット材として用いることを特徴とするスパッタリングターゲット。
（９）（８）に記載のスパッタリングターゲットを用いてスパッタリング法で成膜したことを特徴とする薄膜。
に関するものである。 That is, the present invention
(1) In an oxide sintered body having zinc, niobium and oxygen as constituent elements, when the zinc and niobium contents are Zn and Nb, respectively, the atomic ratio of Nb / (Zn + Nb) is 0.064 to An oxide sintered body characterized by being 0.334, a relative density exceeding 98%, and a bulk resistance value of 1.0 to 5000 Ω · cm.
(2) The oxide sintered body according to (1), wherein the average particle diameter of the ZnO crystal phase in the oxide sintered body is 1.5 μm or more and 6 μm or less.
(3) The oxide sintered body according to (1) or (2), wherein the amount of oxygen deficiency in the oxide sintered body is 5% or less.
(4) The oxide sintered body according to any one of (1) to (3), wherein the variation range of resistivity of the oxide sintered body is within 70%.
(5) The maximum intensity of the diffraction peak where the incident angle (2θ) in X-ray diffraction is between 32.3 ° and 33.8 ° is between I 1 and 35.8 ° to 37.3 °. The oxidation according to any one of (1) to (4), wherein the value of the diffraction intensity ratio I 2 / I 1 is 0.65 or more when the maximum intensity of the diffraction peak is I 2 Sintered product.
(6) The oxide sintered body according to any one of (1) to (5), wherein the area of the target surface is a flat plate shape of 961 cm 2 or more.
(7) The oxide sintered body according to any one of (1) to (5), which has a cylindrical shape with an area of a target surface of 486 cm 2 or more.
(8) A sputtering target using the oxide sintered body according to any one of (1) to (7) as a target material.
(9) A thin film formed by sputtering using the sputtering target according to (8).
It is about.
以下、本発明を詳細に説明する。
Hereinafter, the present invention will be described in detail.
本発明は、構成元素として、亜鉛、ニオブ及び酸素を有する酸化物焼結体において、亜鉛、ニオブの含有量をそれぞれＺｎ、Ｎｂとしたときに、原子比でＮｂ／（Ｚｎ＋Ｎｂ）が０．０６４～０．３３４であり、相対密度が９８％を超え、かつバルク抵抗値が１．０～５０００Ω・ｃｍである酸化物焼結体である。
In the oxide sintered body having zinc, niobium and oxygen as constituent elements, the content of zinc and niobium is Zn and Nb, respectively, and Nb / (Zn + Nb) is 0.064 in atomic ratio. It is an oxide sintered body having a relative density exceeding 98% and a bulk resistance value of 1.0 to 5000 Ω · cm.
本発明の酸化物焼結体は、構成元素として亜鉛及びニオブを有しており、亜鉛、ニオブの含有量をそれぞれＺｎ、Ｎｂとしたときに、原子比でＮｂ／（Ｚｎ＋Ｎｂ）が０．０６４～０．３３４であることを特徴としている。Ｎｂ／（Ｚｎ＋Ｎｂ）は０．１３３～０．２９０であることが好ましく、０．２０８～０．２４８であることがより好ましい。Ｎｂ／（Ｚｎ＋Ｎｂ）が０．０６４未満だと、スパッタリングして得られる膜の屈折率が低下してしまい、Ｎｂ／（Ｚｎ＋Ｎｂ）が０．３３４を超えると、Ｚｎ３Ｎｂ２Ｏ８相が増加し、抵抗率が高くなってしまう。
The oxide sintered body of the present invention has zinc and niobium as constituent elements. When the contents of zinc and niobium are Zn and Nb, respectively, Nb / (Zn + Nb) is 0.064 in atomic ratio. It is characterized by -0.334. Nb / (Zn + Nb) is preferably 0.133 to 0.290, and more preferably 0.208 to 0.248. When Nb / (Zn + Nb) is less than 0.064, the refractive index of the film obtained by sputtering decreases, and when Nb / (Zn + Nb) exceeds 0.334, the Zn 3 Nb 2 O 8 phase increases. Then, the resistivity becomes high.
また、本発明の酸化物焼結体は、相対密度が９８％を超えるものであることを特徴とする。本材料では、相対密度が９８％以下であると、スパッタリングターゲットとして用いた場合にアーキング発生の頻度が上昇するためである。
Further, the oxide sintered body of the present invention is characterized in that the relative density exceeds 98%. This is because when the relative density is 98% or less in this material, the frequency of arcing increases when used as a sputtering target.
本発明の酸化物焼結体は、スパッタリングターゲットとして使用する場合、安定的にＤＣ放電を行えるため、バルク抵抗値が１．０～５０００Ω・ｃｍであることが必要であり、１５～３０００Ω・ｃｍであることが好ましく、３０～８５０Ω・ｃｍであることがより好ましい。
When the oxide sintered body of the present invention is used as a sputtering target, it can stably perform DC discharge, so that the bulk resistance value must be 1.0 to 5000 Ω · cm, and 15 to 3000 Ω · cm. It is preferably 30 to 850 Ω · cm.
また、酸化物焼結体中の任意の１０点における抵抗率のばらつき幅が７０％以内であることが好ましく、５０％以内であることがより好ましい。本発明におけるばらつき幅とは、測定した１０点の内の最大値をＲｍａｘ、最小値をＲｍｉｎとした時、（Ｒｍａｘ―Ｒｍｉｎ）／Ｒｍａｘ×１００〔％〕で表される値である。本発明の酸化物焼結体は、導電相であるＺｎＯ相と絶縁相であるＺｎ３Ｎｂ２Ｏ８相を含んでおり、Ｚｎ３Ｎｂ２Ｏ８相が微細かつ均一に分散していないと、焼結体中に大きな抵抗値のばらつきを生じてしまい、スパッタリング時に激しい異常放電を引き起こすおそれがあるためである。
Moreover, the variation width of the resistivity at any 10 points in the oxide sintered body is preferably within 70%, and more preferably within 50%. The variation width in the present invention is a value represented by (Rmax−Rmin) / Rmax × 100 [%], where Rmax is the maximum value of 10 measured points and Rmin is the minimum value. The oxide sintered body of the present invention includes a ZnO phase that is a conductive phase and a Zn 3 Nb 2 O 8 phase that is an insulating phase, and the Zn 3 Nb 2 O 8 phase is not finely and uniformly dispersed. This is because a large variation in resistance value is produced in the sintered body, which may cause severe abnormal discharge during sputtering.
本発明の酸化物焼結体は、従来のものと比べて酸素欠損量が少ないという特徴を有している。酸素欠損量の多いターゲットでは、スパッタリング時にスパッタガスとして酸素を導入する必要があるため、酸素の導入によって成膜レートが急激に低下するという問題が生じる。しかし、本発明の酸化物焼結体は導入酸素量を極めて少なくした状態でも優れた透過性、低吸収特性を実現することができ、成膜速度も顕著な改善効果が得られる。さらに、本発明の酸化物焼結体は、導電相であるＺｎＯ相と絶縁相であるＺｎ３Ｎｂ２Ｏ８相が共存するため、スパッタ電流がＺｎＯに集中し、焼結体中の酸素欠損量が多いとＺｎＯが還元され金属Ｚｎに成り成り易く好ましくない。
The oxide sintered body of the present invention has a feature that the amount of oxygen deficiency is smaller than that of the conventional one. In a target having a large amount of oxygen vacancies, it is necessary to introduce oxygen as a sputtering gas at the time of sputtering, which causes a problem that the film formation rate is rapidly reduced by the introduction of oxygen. However, the oxide sintered body of the present invention can realize excellent permeability and low absorption characteristics even in a state where the amount of introduced oxygen is extremely small, and a remarkable improvement effect of the film forming rate can be obtained. Furthermore, in the oxide sintered body of the present invention, since the ZnO phase as the conductive phase and the Zn 3 Nb 2 O 8 phase as the insulating phase coexist, the sputtering current concentrates on the ZnO, and oxygen vacancies in the sintered body A large amount is not preferable because ZnO is reduced and easily becomes metal Zn.
本願における焼結体の酸素欠損量は、化学量論組成に等しい酸素が含有しているとして計算された酸素含有量の量論値［ｗｔ％］と、分析により測定された分析値［ｗｔ％］との比より、酸素欠損量として下記（１）式により表される。
（（量論値［ｗｔ％］－分析値［ｗｔ％］）／量論値［ｗｔ％］）×１００［％］ ・・・（１）式
酸素含有量の量論値［ｗｔ％］は、ＺｎＯ／（ＺｎＯ＋Ｎｂ２Ｏ５）で表されるＺｎＯのモル比をｘとしたとき、
（（ＭＯ×１×ｘ＋ＭＯ×５×（１－ｘ））／（ＭＺｎＯ×ｘ＋ＭＮｂ２Ｏ５×（１－ｘ）））×１００ ・・・（２）式 により算出される。
ここで、ＭＯは酸素の原子量でＭＯ＝１６、ＭＺｎＯはＺｎＯの分子量でＭＺｎＯ＝８１．３８、ＭＮｂ２Ｏ５はＮｂ２Ｏ５の分子量であり、ＭＮｂ２Ｏ５＝２６５．８１を用いる。本願発明の焼結体においては、酸素欠損量が５％以下であることが好ましい。 The oxygen deficiency of the sintered body in the present application includes the stoichiometric value [wt%] of the oxygen content calculated as containing oxygen equal to the stoichiometric composition and the analytical value [wt%] measured by analysis. ], The oxygen deficiency is expressed by the following equation (1).
((Stoichiometric value [wt%] − analytical value [wt%]) / stoichiometric value [wt%]) × 100 [%] (1) The stoichiometric value [wt%] of the formula oxygen content is When the molar ratio of ZnO represented by ZnO / (ZnO + Nb 2 O 5 ) is x,
((M O × 1 × x + M O × 5 × (1-x)) / (M ZnO × x + MNb2O5 × (1-x))) × 100 (2)
Here, M O is the atomic weight of oxygen and M O = 16, M ZnO is the molecular weight of ZnO and M ZnO = 81.38, M Nb2O5 is the molecular weight of Nb 2 O 5 , and M Nb2O5 = 265.81 is used. In the sintered body of the present invention, the oxygen deficiency is preferably 5% or less.
（（量論値［ｗｔ％］－分析値［ｗｔ％］）／量論値［ｗｔ％］）×１００［％］ ・・・（１）式
酸素含有量の量論値［ｗｔ％］は、ＺｎＯ／（ＺｎＯ＋Ｎｂ２Ｏ５）で表されるＺｎＯのモル比をｘとしたとき、
（（ＭＯ×１×ｘ＋ＭＯ×５×（１－ｘ））／（ＭＺｎＯ×ｘ＋ＭＮｂ２Ｏ５×（１－ｘ）））×１００ ・・・（２）式 により算出される。
ここで、ＭＯは酸素の原子量でＭＯ＝１６、ＭＺｎＯはＺｎＯの分子量でＭＺｎＯ＝８１．３８、ＭＮｂ２Ｏ５はＮｂ２Ｏ５の分子量であり、ＭＮｂ２Ｏ５＝２６５．８１を用いる。本願発明の焼結体においては、酸素欠損量が５％以下であることが好ましい。 The oxygen deficiency of the sintered body in the present application includes the stoichiometric value [wt%] of the oxygen content calculated as containing oxygen equal to the stoichiometric composition and the analytical value [wt%] measured by analysis. ], The oxygen deficiency is expressed by the following equation (1).
((Stoichiometric value [wt%] − analytical value [wt%]) / stoichiometric value [wt%]) × 100 [%] (1) The stoichiometric value [wt%] of the formula oxygen content is When the molar ratio of ZnO represented by ZnO / (ZnO + Nb 2 O 5 ) is x,
((M O × 1 × x + M O × 5 × (1-x)) / (M ZnO × x + MNb2O5 × (1-x))) × 100 (2)
Here, M O is the atomic weight of oxygen and M O = 16, M ZnO is the molecular weight of ZnO and M ZnO = 81.38, M Nb2O5 is the molecular weight of Nb 2 O 5 , and M Nb2O5 = 265.81 is used. In the sintered body of the present invention, the oxygen deficiency is preferably 5% or less.
本発明の酸化物焼結体は、酸化物焼結体中のＺｎＯ相の平均粒径が１．５μｍ以上６μｍ以下であることが好ましい。導電パスとしての役割を担うＺｎＯ相の粒径が小さくなり過ぎると、その粒界部分に絶縁相であるＺｎ３Ｎｂ２Ｏ８相が入り込み易くなり、ターゲット全体の導電性が著しく悪化するため、安定なＤＣスパッタリングが行えなくなるためである。また、ＺｎＯ相の粒径が大きくなり過ぎると、抵抗値のバラツキの増大や、焼結体の割れや低密度化の原因となるため、好ましくない。
In the oxide sintered body of the present invention, the average particle diameter of the ZnO phase in the oxide sintered body is preferably 1.5 μm or more and 6 μm or less. If the particle diameter of the ZnO phase that plays a role as a conductive path becomes too small, the Zn 3 Nb 2 O 8 phase that is an insulating phase easily enters the grain boundary portion, and the conductivity of the entire target is significantly deteriorated. This is because stable DC sputtering cannot be performed. In addition, if the particle size of the ZnO phase becomes too large, it is not preferable because it causes an increase in resistance variation, cracks in the sintered body, and a reduction in density.
本発明の酸化物焼結体は、Ｘ線回折における入射角（２θ）が、３２．３°～３３．８°の間に存在する回折ピークの最大強度をＩ１、３５．８°～３７．３°の間に存在する回折ピークの最大強度をＩ２とした時の、回折強度比Ｉ２／Ｉ１の値が０．６５以上であることが好ましい。３２．３°～３３．８°の間に存在するピークは、複合酸化物焼結体内のＺｎ３Ｎｂ２Ｏ８相に相当する回折ピークに対応するものであり、３５．８°～３７．３°の間に存在するピークはＺｎＯ相に対応するピークである。本願発明の複合酸化物焼結体内においては、ＺｎＯ相の粒径がＺｎ３Ｎｂ２Ｏ８相よりも相対的に大きくなるためである。
In the oxide sintered body of the present invention, the maximum intensity of the diffraction peak existing when the incident angle (2θ) in X-ray diffraction is 32.3 ° to 33.8 ° is I 1 , 35.8 ° to 37. It is preferable that the value of the diffraction intensity ratio I 2 / I 1 is 0.65 or more when the maximum intensity of the diffraction peak existing between 3 ° is I 2 . The peak existing between 32.3 ° and 33.8 ° corresponds to the diffraction peak corresponding to the Zn 3 Nb 2 O 8 phase in the composite oxide sintered body, and 35.8 ° to 37.37. The peak existing between 3 ° is a peak corresponding to the ZnO phase. This is because in the composite oxide sintered body of the present invention, the particle size of the ZnO phase is relatively larger than that of the Zn 3 Nb 2 O 8 phase.
ターゲットへの投入負荷は、投入電力をターゲット面積で割った電力密度（Ｗ／ｃｍ２）で規格化される。通常生産における一般的な電力密度は１～２．５Ｗ／ｃｍ２程度であるが、本発明においては４Ｗ／ｃｍ２以上の高パワー条件においてもアーキング発生の極めて少ない、高品質なターゲット材料となる酸化物焼結体が得られる。
The input load to the target is normalized by the power density (W / cm 2 ) obtained by dividing the input power by the target area. The general power density in normal production is about 1 to 2.5 W / cm 2 , but in the present invention, it becomes a high-quality target material with extremely little arcing even under high power conditions of 4 W / cm 2 or more. An oxide sintered body is obtained.
本発明の酸化物焼結体の製造方法は、酸化亜鉛粉末及び五酸化ニオブ粉末を原料粉末として、元素の原子比が、亜鉛、ニオブの含有量をそれぞれＺｎ、Ｎｂとしたときに、Ｎｂ／（Ｚｎ＋Ｎｂ）が０．０６４～０．３３４となるように混合し、成形した後、得られた成形体を酸化性雰囲気で１１５０～１３００℃の温度にて０．５～５時間焼成保持することを特徴とする。
The method for producing an oxide sintered body according to the present invention uses a zinc oxide powder and a niobium pentoxide powder as a raw material powder, and the atomic ratio of elements is Nb / Nb when the content of zinc and niobium is Zn and Nb respectively. After mixing and molding so that (Zn + Nb) is 0.064 to 0.334, the obtained molded body is fired and held in an oxidizing atmosphere at a temperature of 1150 to 1300 ° C. for 0.5 to 5 hours. It is characterized by.
以下、本発明の酸化物焼結体の製造方法について、工程毎に説明する。
Hereinafter, the manufacturing method of the oxide sintered body of the present invention will be described for each step.
（１）原料混合工程
原料粉末は取り扱い性を考慮すると酸化亜鉛、五酸化ニオブの各酸化物粉末が好ましい。各原料粉末の純度は９９．９％以上が好ましく、より好ましくは９９．９９％以上である。不純物が含まれると、焼成工程における異常粒成長の原因となる。 (1) Raw material mixing step In consideration of handleability, the raw material powder is preferably an oxide powder of zinc oxide or niobium pentoxide. The purity of each raw material powder is preferably 99.9% or more, more preferably 99.99% or more. If impurities are included, it causes abnormal grain growth in the firing process.
原料粉末は取り扱い性を考慮すると酸化亜鉛、五酸化ニオブの各酸化物粉末が好ましい。各原料粉末の純度は９９．９％以上が好ましく、より好ましくは９９．９９％以上である。不純物が含まれると、焼成工程における異常粒成長の原因となる。 (1) Raw material mixing step In consideration of handleability, the raw material powder is preferably an oxide powder of zinc oxide or niobium pentoxide. The purity of each raw material powder is preferably 99.9% or more, more preferably 99.99% or more. If impurities are included, it causes abnormal grain growth in the firing process.
本工程において、酸化亜鉛粉末及び五酸化ニオブ粉末の元素の原子比が、亜鉛、ニオブの含有量をそれぞれＺｎ、Ｎｂとしたときに、Ｎｂ／（Ｚｎ＋Ｎｂ）が０．０６４～０．３３４となるように混合する必要があり、Ｎｂ／（Ｚｎ＋Ｎｂ）が０．１３３～０．２９０となるように混合することが好ましく、Ｎｂ／（Ｚｎ＋Ｎｂ）が０．２０８～０．２４8となるように混合することがより好ましい。
In this step, Nb / (Zn + Nb) is 0.064 to 0.334 when the atomic ratio of the elements of the zinc oxide powder and the niobium pentoxide powder is Zn and Nb, respectively. It is preferable to mix so that Nb / (Zn + Nb) is 0.133 to 0.290, and so that Nb / (Zn + Nb) is 0.208 to 0.248. It is more preferable.
酸化亜鉛粉末の物性は、本発明の焼結体中で導電性を担うＺｎＯ相の粒径や均一分散性に関わることから、特に重要な因子である。本発明においては、次工程である粉砕・混合工程を考慮し、ＺｎＯ原料粉末のＢＥＴ値が２．２～１０ｍ２／ｇの範囲の粉末を用いる。ＢＥＴ値が１０ｍ２／ｇより大きい粉末を用いて粉砕・混合処理を行うと、得られる焼結体のＺｎＯ相の粒径が小さくなり、ターゲットの導電性が悪化するため好ましくない。導電性の悪化は、スパッタリング中に発生するアーキング数の増加原因となり、特に導電性が悪い場合にはＤＣ放電が不可能となる問題が発生する。さらに、原料の微細化により成形性が悪化し、低密度化の原因にもなるため、好ましくない。また、ＢＥＴ値が２．２ｍ２／ｇよりも小さい粉末を用いて粉砕・混合処理を行うと、原料混合時にムラが大きくなり、抵抗値のバラツキおよび低密度化の原因となるため、好ましくない。
The physical properties of the zinc oxide powder are particularly important factors because they are related to the particle size and uniform dispersibility of the ZnO phase responsible for conductivity in the sintered body of the present invention. In the present invention, in consideration of the next pulverization / mixing step, a ZnO raw material powder having a BET value in the range of 2.2 to 10 m 2 / g is used. When the pulverization / mixing process is performed using a powder having a BET value larger than 10 m 2 / g, the particle size of the ZnO phase of the obtained sintered body is reduced, and the conductivity of the target is deteriorated. The deterioration of conductivity causes an increase in the number of arcing generated during sputtering, and a problem that DC discharge becomes impossible occurs particularly when the conductivity is poor. Furthermore, since the formability deteriorates due to the refinement of the raw material and causes a reduction in density, it is not preferable. In addition, if the pulverization / mixing process is performed using a powder having a BET value smaller than 2.2 m 2 / g, unevenness increases when mixing the raw materials, which causes variation in resistance value and low density, which is not preferable. .
五酸化ニオブ粉末についても粉砕・混合工程を考慮し、ＢＥＴ値が６～１４ｍ２／ｇのものを使用する。ＢＥＴ値が１４ｍ２／ｇより大きい粉末を用いて粉砕・混合処理を行うと、得られる焼結体中でＺｎＯ相の導電パスが切断され易くなり、ターゲットの導電性が悪化するため好ましくない。また、ＢＥＴ比表面積が６ｍ２／ｇよりも小さい粉末を用いて粉砕・混合処理を行うと、焼結体の密度低下の原因となったり、焼結体に割れが発生し易くなるため、好ましくない。
Niobium pentoxide powder having a BET value of 6 to 14 m 2 / g is used in consideration of the grinding and mixing process. When the pulverization / mixing process is performed using a powder having a BET value larger than 14 m 2 / g, the conductive path of the ZnO phase is easily cut in the obtained sintered body, and the conductivity of the target is deteriorated. Further, it is preferable to perform pulverization / mixing treatment using a powder having a BET specific surface area of less than 6 m 2 / g because it causes a decrease in density of the sintered body or cracks are likely to occur in the sintered body. Absent.
更に、次工程である粉砕・混合工程においては、五酸化ニオブ粉末との混合性を高めつつ、ＺｎＯ粉末が過度に粉砕されること防ぐことが重要となる。本組成範囲においては、使用するＺｎＯ粉末のＢＥＴ値をＢＺ、五酸化ニオブ粉末のＢＥＴ値ＢＮとした場合の両者の比（ＢＮ／ＢＺ）が０．８～３．６の範囲とすることで混合性を高めることが出来、焼結体の導電性を改善されると共に、焼結性を高め高密度焼結体を得ることが可能となる。
Furthermore, in the pulverization / mixing step, which is the next step, it is important to prevent the ZnO powder from being excessively pulverized while improving the mixing property with the niobium pentoxide powder. In this composition range, the ratio (B N / B Z ) between the BET value of the ZnO powder to be used and B Z , and the BET value B N of the niobium pentoxide powder is in the range of 0.8 to 3.6. As a result, the mixing property can be improved, the conductivity of the sintered body can be improved, the sinterability can be improved, and a high-density sintered body can be obtained.
上記粉末の混合は、適切な粉砕・混合装置にて所定の条件下にて行なう必要がある。ターゲット中の導電性にムラの発生を抑制し、高密度焼結体を得るためには、各原料が均一に分散されている必要があるが、前述のとおり、ＺｎＯ粉末、五酸化ニオブ粉末共に過度の粉砕は好ましくないため、十分な注意が必要である。例えば、ミル容積２Ｌのビーズミル装置にて粉末２５ｋｇを処理する場合、下記の条件で行うことが好ましい。
It is necessary to mix the above powder under a predetermined condition with an appropriate crushing and mixing apparatus. In order to suppress the occurrence of unevenness in the conductivity in the target and obtain a high-density sintered body, it is necessary that each raw material is uniformly dispersed. As described above, both ZnO powder and niobium pentoxide powder are used. Excessive pulverization is not preferable, so sufficient care is required. For example, when processing 25 kg of powder in a bead mill apparatus having a mill volume of 2 L, it is preferable to carry out under the following conditions.
スラリー中の固形分濃度は３５％～６５％、より好ましくは５５％～６５％とする。固形分濃度が高くなり過ぎると処理能力が低下し、所望する粉末物性値が得られない。特に酸化亜鉛は粘度上昇の原因となり易く、他の原料との混合性を大きく損ねる原因となることから、適正範囲内に調整することが重要である。粉砕メディアは、摩耗による原料への不純物混入防止も考慮し、ジルコニアビーズを用いる。ビーズ径はφ０．２ｍｍ～φ０．３ｍｍの範囲内とする。ミルに投入するビーズの総量は４．５～５．５ｋｇの範囲とし、ミル容積に対するビーズ充填率としては７０～７５％の範囲とする。スラリー温度も厳密に管理する必要があり、ミル入口スラリー温度を１２℃以下、好ましくは９℃以下に管理すると共に、ミル出口のスラリー温度を１８℃以下となるように常時管理する。分散剤の種類は特に問わないが、スラリー粘度変化を一定以下に抑えることが重要である。このため、本発明における添加量は一般的な添加量よりも多くする必要があり、投入粉末量に対して１．０ｗｔ％以上３．５ｗｔ％以下とすることが好ましい。ミル内へのスラリー供給量はミルへの負担の大きい１～２パスまでは０．４Ｌ／ｍｉｎ～１．０Ｌ／ｍｉｎとし、その後は１．５Ｌ／ｍｉｎ～２．４Ｌ／ｍｉｎとすると効率的に処理が出来るため、好ましい。過度の粉砕を防止するため、ミルの周速は２．５ｍ／ｓｅｃ～５．５ｍ／ｓｅｃの範囲とやや低めに設定することが好ましい。処理のバッチによっては同一条件であってもスラリー粘度が何らかの要因によって上昇することがあるが、この場合は分散剤量を上記範囲内の内で適宜追添加し、スラリー粘度を常に２２００ｍＰａ・ｓ以下とすることで、安定した粉末物性を得るために必要である。
The solid content concentration in the slurry is 35% to 65%, more preferably 55% to 65%. If the solid content concentration becomes too high, the processing ability is lowered, and desired powder physical properties cannot be obtained. In particular, zinc oxide tends to cause an increase in viscosity and greatly impairs the mixing property with other raw materials, so it is important to adjust it within an appropriate range. As the grinding media, zirconia beads are used in consideration of prevention of impurities from being mixed into the raw material due to wear. The bead diameter is in the range of φ0.2 mm to φ0.3 mm. The total amount of beads charged into the mill is in the range of 4.5 to 5.5 kg, and the bead filling rate relative to the mill volume is in the range of 70 to 75%. The slurry temperature also needs to be strictly controlled. The mill inlet slurry temperature is controlled to 12 ° C. or lower, preferably 9 ° C. or lower, and constantly controlled so that the slurry outlet slurry temperature is 18 ° C. or lower. The type of the dispersant is not particularly limited, but it is important to keep the slurry viscosity change below a certain level. For this reason, the addition amount in the present invention needs to be larger than a general addition amount, and is preferably 1.0 wt% or more and 3.5 wt% or less with respect to the input powder amount. Efficient slurry supply into the mill is 0.4 L / min to 1.0 L / min for 1 to 2 passes, which is a heavy burden on the mill, and 1.5 L / min to 2.4 L / min thereafter. It is preferable because it can be processed. In order to prevent excessive pulverization, the peripheral speed of the mill is preferably set to a slightly low range of 2.5 m / sec to 5.5 m / sec. Depending on the batch of treatment, the slurry viscosity may rise due to some factor even under the same conditions. In this case, the amount of the dispersant is appropriately added within the above range, and the slurry viscosity is always 2200 mPa · s or less. Therefore, it is necessary to obtain stable powder properties.
上記の条件を踏まえ、ミル内への粉砕パス回数を２０回以下に抑えることにより、本発明の複合酸化物焼結体を得るために必要な混合粉末を得ることができる。
Based on the above conditions, the mixed powder necessary to obtain the composite oxide sintered body of the present invention can be obtained by suppressing the number of grinding passes into the mill to 20 or less.
湿式混合処理を行った後のスラリーは、鋳込み成形等の湿式成形方法では、スラリーをそのまま用いることが可能であるが、乾式で成形する場合には、粉末の流動性が高く成形体密度が均一となる乾燥造粒粉末を用いるのが望ましい。造粒方法については限定しないが、噴霧造粒、流動層造粒、転動造粒、撹拌造粒などが使用できる。特に、操作が容易で、多量に処理できる噴霧造粒を用いることが望ましい。
The slurry after the wet mixing treatment can be used as it is in a wet molding method such as cast molding, but in the case of dry molding, the powder fluidity is high and the compact density is uniform. It is desirable to use a dry granulated powder. Although it does not limit about the granulation method, spray granulation, fluidized bed granulation, rolling granulation, stirring granulation, etc. can be used. In particular, it is desirable to use spray granulation which is easy to operate and can be processed in large quantities.
（２）成形工程
成形方法は、原料粉末を目的とした形状に成形できる成形方法を適宜選択することが可能であり、特に限定されるものではない。プレス成形法、鋳込み成形法、射出成形法等が例示できる。 (2) Molding process The molding method is not particularly limited, and a molding method capable of molding the raw material powder into a desired shape can be appropriately selected. Examples thereof include a press molding method, a casting molding method, and an injection molding method.
成形方法は、原料粉末を目的とした形状に成形できる成形方法を適宜選択することが可能であり、特に限定されるものではない。プレス成形法、鋳込み成形法、射出成形法等が例示できる。 (2) Molding process The molding method is not particularly limited, and a molding method capable of molding the raw material powder into a desired shape can be appropriately selected. Examples thereof include a press molding method, a casting molding method, and an injection molding method.
成形圧力は成形体にクラック等の発生がなく、取り扱いが可能な成形体であれば特に限定されるものではないが、成形密度は可能な限り高めた方が好ましい。そのために冷間静水圧プレス（ＣＩＰ）成形等の方法を用いることも可能である。ＣＩＰ圧力は充分な圧密効果を得るため１ｔｏｎ／ｃｍ２以上が好ましく、さらに好ましくは２ｔｏｎ／ｃｍ２以上、とりわけ好ましくは２～３ｔｏｎ／ｃｍ２である。
The molding pressure is not particularly limited as long as it does not cause cracks in the molded body and can be handled, but it is preferable to increase the molding density as much as possible. Therefore, it is also possible to use a method such as cold isostatic pressing (CIP) molding. CIP pressure is preferably for 1 ton / cm 2 or more to obtain a sufficient consolidation effect, more preferably 2 ton / cm 2 or more, especially preferably 2 ~ 3ton / cm 2.
（３）焼成工程
次に得られた成形体を焼成する。焼成方法は、一般的な抵抗加熱式の電気炉を使用すればよい。焼成雰囲気は、酸化性雰囲気である大気雰囲気または酸素雰囲気いずれも可能である。特別な雰囲気制御を必要とせず、大気雰囲気中での焼成が可能となることから、酸化物焼結体の酸素欠損量は、ホットプレスや非酸化性雰囲気で焼成した焼結体に存在する酸素欠損量と比べて少なくなる。 (3) Firing step Next, the obtained molded body is fired. As a firing method, a general resistance heating type electric furnace may be used. The firing atmosphere can be either an air atmosphere or an oxygen atmosphere which is an oxidizing atmosphere. Oxygen deficiency of the oxide sintered body is the oxygen present in the sintered body fired in a hot press or non-oxidizing atmosphere because it can be fired in the air atmosphere without requiring special atmosphere control. Less than the amount of deficiency.
次に得られた成形体を焼成する。焼成方法は、一般的な抵抗加熱式の電気炉を使用すればよい。焼成雰囲気は、酸化性雰囲気である大気雰囲気または酸素雰囲気いずれも可能である。特別な雰囲気制御を必要とせず、大気雰囲気中での焼成が可能となることから、酸化物焼結体の酸素欠損量は、ホットプレスや非酸化性雰囲気で焼成した焼結体に存在する酸素欠損量と比べて少なくなる。 (3) Firing step Next, the obtained molded body is fired. As a firing method, a general resistance heating type electric furnace may be used. The firing atmosphere can be either an air atmosphere or an oxygen atmosphere which is an oxidizing atmosphere. Oxygen deficiency of the oxide sintered body is the oxygen present in the sintered body fired in a hot press or non-oxidizing atmosphere because it can be fired in the air atmosphere without requiring special atmosphere control. Less than the amount of deficiency.
酸素欠損量の制御は、特に高温域での昇温速度および降温速度、保持時間および保持温度と密接に関係するため、１１５０℃以上１３００℃以下の温度にて０．５～５時間焼成保持することが必要である。本発明では、９５０℃から１０５０℃までの昇温速度を２００～３５０℃／ｈ、焼成保持温度から９００℃までの冷却速度を３５０℃／ｈ以上とすることが好ましい。
The control of oxygen deficiency is closely related to the rate of temperature rise and fall, the holding time, and the holding temperature particularly in a high temperature range, and is thus fired and held at a temperature of 1150 ° C. to 1300 ° C. for 0.5 to 5 hours. It is necessary. In the present invention, it is preferable that the temperature increase rate from 950 ° C. to 1050 ° C. is 200 to 350 ° C./h, and the cooling rate from the firing holding temperature to 900 ° C. is 350 ° C./h or more.
（４）ターゲット化工程
得られた焼結体は、平面研削盤、円筒研削盤、旋盤、切断機、マシニングセンター等の機械加工機を用いて、板状、円状、円筒状等の所望の形状に研削加工する。さらに、必要に応じて無酸素銅やチタン等からなるバッキングプレート、バッキングチューブにインジウム半田等を用いて接合（ボンディング）することにより、本発明の焼結体をターゲット材としたスパッタリングターゲットを得ることができる。 (4) Targeting process The obtained sintered body is formed into a desired shape such as a plate shape, a circular shape, or a cylindrical shape by using a machining machine such as a surface grinder, a cylindrical grinder, a lathe, a cutting machine, or a machining center. To grind. Furthermore, a sputtering target using the sintered body of the present invention as a target material is obtained by bonding (bonding) a backing plate made of oxygen-free copper, titanium, or the like to the backing tube or backing tube using indium solder or the like as necessary. Can do.
得られた焼結体は、平面研削盤、円筒研削盤、旋盤、切断機、マシニングセンター等の機械加工機を用いて、板状、円状、円筒状等の所望の形状に研削加工する。さらに、必要に応じて無酸素銅やチタン等からなるバッキングプレート、バッキングチューブにインジウム半田等を用いて接合（ボンディング）することにより、本発明の焼結体をターゲット材としたスパッタリングターゲットを得ることができる。 (4) Targeting process The obtained sintered body is formed into a desired shape such as a plate shape, a circular shape, or a cylindrical shape by using a machining machine such as a surface grinder, a cylindrical grinder, a lathe, a cutting machine, or a machining center. To grind. Furthermore, a sputtering target using the sintered body of the present invention as a target material is obtained by bonding (bonding) a backing plate made of oxygen-free copper, titanium, or the like to the backing tube or backing tube using indium solder or the like as necessary. Can do.
焼結体のサイズは、特に限定されないが、本発明による焼結体は強度が高いため大型のターゲットを製造することが可能となる。平板形スパッタリングターゲットの場合、縦３１０ｍｍ×横３１０ｍｍ（ターゲット面の面積９６１ｃｍ２）以上の大型の焼結体を作製することができる。また、円筒形スパッタリングターゲットの場合、外径９１ｍｍΦ×１７０ｍｍ（ターゲット面の面積４８６ｃｍ２）以上の大型の焼結体を作製することができる。なお、ここで言うターゲット面の面積とは、スパッタリングされる側の焼結体表面の面積を言う。なお、複数の焼結体から構成される多分割ターゲットの場合、それぞれの焼結体の中でスパッタリングされる側の焼結体表面の面積が最大のものを多分割ターゲットにおけるターゲット面の面積である。
The size of the sintered body is not particularly limited, but since the sintered body according to the present invention has high strength, a large target can be manufactured. In the case of a flat-plate-type sputtering target, a large-sized sintered body having a length of 310 mm × width of 310 mm (target surface area 961 cm 2 ) or more can be produced. In the case of a cylindrical sputtering target, a large-sized sintered body having an outer diameter of 91 mmΦ × 170 mm (target surface area 486 cm 2 ) or more can be produced. In addition, the area of the target surface said here means the area of the sintered compact surface by the side of sputtering. In the case of a multi-divided target composed of a plurality of sintered bodies, the area of the surface of the sintered body on the side to be sputtered in each sintered body is the largest in the area of the target surface in the multi-divided target. is there.
本発明の酸化物焼結体は、スパッタリングターゲットとして使用した場合、高パワー投入時においても、異常放電（アーキング）の発生やターゲットの割れが少なく、安定したＤＣ放電が可能となる。また、焼結体の強度が高いために加工が容易となり、大型のターゲットを歩留りよく製造することができる。さらに、ターゲット中の酸素量が従来ホットプレス法による場合よりも多いため、スパッタリング時の酸素導入量を低減でき、高い成膜レートを実現できるだけでなく、光透過性の極めて優れた膜を得ることができる。
When the oxide sintered body of the present invention is used as a sputtering target, even when a high power is applied, the occurrence of abnormal discharge (arcing) and cracking of the target are small, and stable DC discharge is possible. Moreover, since the strength of the sintered body is high, processing becomes easy, and a large target can be manufactured with high yield. Furthermore, since the amount of oxygen in the target is higher than that of the conventional hot press method, the amount of oxygen introduced during sputtering can be reduced, and not only can a high film formation rate be realized, but also a film with extremely excellent light transmission can be obtained. Can do.
以下、実施例により本発明を更に具体的に説明するが、本発明はこれに限定されるものではない。なお、本実施例における各測定は以下のように行った。
（１）焼結体の密度
焼結体の相対密度は、ＪＩＳ Ｒ １６３４に準拠して、アルキメデス法によりかさ密度を測定し、真密度で割って相対密度を求めた。焼結体の真密度は、焼結体中のＮｂ２Ｏ５相がすべてＺｎ３Ｎｂ２Ｏ８相として反応したと仮定し計算したときのＺｎＯ相の重量ａ［ｇ］およびＺｎ３Ｎｂ２Ｏ８相の重量ｂ［ｇ］と、それぞれの真密度５．６０６［ｇ／ｃｍ３］、５．７３４［ｇ／ｃｍ３］を用いて、下記式で表される相加平均より算出した。
ｄ＝（ａ＋ｂ）／（（ａ／５．６０６）＋（ｂ／５．７３４）） ・・・（３）式
（２）Ｘ線回折試験
鏡面研磨した焼結体試料の２θ＝２０～７０°の範囲のＸ線回折パターンを測定した。
走査方法 ：ステップスキャン法（ＦＴ法）
Ｘ線源 ：ＣｕＫα
パワー ：４０ｋＶ、４０ｍＡ
ステップ幅：０．０１°
（３）結晶粒径
鏡面研磨し、ＥＰＭＡによる組成分析によりＺｎＯ相とＺｎ３Ｎｂ２Ｏ８相を同定した後、ＳＥＭ像から直径法で結晶粒径を測定した。サンプルは任意の３点以上を観察し、各々３００個以上の粒子の測定を行った。
（ＥＰＭＡ分析条件）
装置 ：波長分散型電子線マイクロアナライザー
加速電圧 ：１５ｋＶ
照射電流 ：３０ｎＡ
（４）抗折強度
ＪＩＳ Ｒ １６０１に準拠して測定した。
（抗折強度の測定条件）
試験方法 ：３点曲げ試験
支点間距離：３０ｍｍ
試料サイズ：３ｍｍ×４ｍｍ×４０ｍｍ
ヘッド速度：０．５ｍｍ／ｍｉｎ
（５）抵抗率の測定
焼成後の焼結体表面より１ｍｍ以上研削した後の任意の部分より切り出した１０サンプルの平均値を測定データとした。
試料サイズ：１０ｍｍ×２０ｍｍ×１ｍｍ
測定方法：４端子法
測定装置：ロレスタＨＰ ＭＣＰ－Ｔ４１０（三菱油化製）
（６）酸素量の分析
焼成後の焼結体表面より１ｍｍ以上研削した後の任意の部分より切り出した５サンプルの分析値の平均値を測定データとした。
（酸素量分析条件）
測定手法 ：インパルス炉溶融－赤外線吸収法
装置 ：ＬＥＣＯ ＴＣ４３６ 酸素・窒素分析装置
（７）スパッタリング評価
得られた焼結体を１０１．６ｍｍΦ×６ｍｍｔに加工した後、無酸素銅製のバッキングプレートにインジウムハンダによりボンディングしてスパッタリングターゲットとした。このターゲットを用いて投入パワーを変化させてスパッタリングを行い、アーキング計測およびＤＣ放電の安定性の評価及び下記の条件で成膜した膜の評価を行なった。
（スパッタリング条件）
ガス ：アルゴン＋酸素（３％）
圧力 ：０．６Ｐａ
電源 ：ＤＣ
投入パワー：４００Ｗ（４．９Ｗ／ｃｍ２）
６００Ｗ（７．４Ｗ／ｃｍ２）
８００Ｗ（９．９Ｗ／ｃｍ２）
放電時間 ：各１２０ｍｉｎ
アーキング計測条件（しきい電圧）：スパッタ電圧－５０［Ｖ］
（成膜条件）
ガス ：アルゴン＋酸素（３％）
圧力 ：０．６Ｐａ
電源 ：ＤＣ
投入パワー：２００Ｗ（２．４Ｗ／ｃｍ２）
膜厚 ：８０ｎｍ
基板 ：無アルカリガラス（コーニング社製ＥＡＧＬＥ ＸＧ、厚み０．７ｍｍ）
基板温度 ：室温。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In addition, each measurement in a present Example was performed as follows.
(1) Density of Sintered Body The relative density of the sintered body was determined by measuring the bulk density by the Archimedes method in accordance with JIS R 1634 and dividing by the true density. The true density of the sintered body was calculated assuming that all the Nb 2 O 5 phases in the sintered body reacted as the Zn 3 Nb 2 O 8 phase, and the weight a [g] of the ZnO phase and Zn 3 Nb 2 Using the weight b [g] of the O 8 phase and each true density 5.606 [g / cm 3 ], 5.734 [g / cm 3 ], the calculation was made from the arithmetic average represented by the following formula. .
d = (a + b) / ((a / 5.606) + (b / 5.734)) (3) Equation (2) X-ray diffraction test 2θ = 20 to 70 of the sintered sample obtained by mirror polishing An X-ray diffraction pattern in the range of ° was measured.
Scanning method: Step scan method (FT method)
X-ray source: CuKα
Power: 40kV, 40mA
Step width: 0.01 °
(3) Crystal grain size After mirror polishing and identifying a ZnO phase and a Zn 3 Nb 2 O 8 phase by composition analysis with EPMA, the crystal grain size was measured by a diameter method from an SEM image. Three or more arbitrary samples were observed, and 300 or more particles were measured for each sample.
(EPMA analysis conditions)
Apparatus: Wavelength dispersive electron beam microanalyzer Accelerating voltage: 15 kV
Irradiation current: 30 nA
(4) Folding strength Measured according to JIS R 1601.
(Measurement conditions of bending strength)
Test method: 3-point bending test fulcrum distance: 30 mm
Sample size: 3mm x 4mm x 40mm
Head speed: 0.5 mm / min
(5) Measurement of resistivity The average value of 10 samples cut out from an arbitrary portion after grinding 1 mm or more from the sintered body surface after firing was used as measurement data.
Sample size: 10 mm x 20 mm x 1 mm
Measuring method: 4-terminal method Measuring device: Loresta HP MCP-T410 (Mitsubishi Yuka)
(6) Analysis of oxygen content The average value of the analytical values of 5 samples cut out from an arbitrary portion after grinding 1 mm or more from the sintered body surface after firing was used as measurement data.
(Oxygen analysis conditions)
Measurement method: Impulse furnace melting-infrared absorption method apparatus: LECO TC436 Oxygen / nitrogen analyzer (7) Sputtering evaluation After processing the obtained sintered body to 101.6 mmΦ × 6 mmt, indium solder on a backing plate made of oxygen-free copper Was bonded to obtain a sputtering target. Sputtering was performed by changing the input power using this target, and the arcing measurement, the evaluation of the stability of the DC discharge, and the film formed under the following conditions were evaluated.
(Sputtering conditions)
Gas: Argon + oxygen (3%)
Pressure: 0.6Pa
Power supply: DC
Input power: 400 W (4.9 W / cm 2 )
600 W (7.4 W / cm 2 )
800W (9.9W / cm 2 )
Discharge time: 120 min each
Arcing measurement conditions (threshold voltage): Sputtering voltage -50 [V]
(Deposition conditions)
Gas: Argon + oxygen (3%)
Pressure: 0.6Pa
Power supply: DC
Input power: 200 W (2.4 W / cm 2 )
Film thickness: 80nm
Substrate: Alkali-free glass (Corning EAGLE XG, thickness 0.7 mm)
Substrate temperature: Room temperature.
（１）焼結体の密度
焼結体の相対密度は、ＪＩＳ Ｒ １６３４に準拠して、アルキメデス法によりかさ密度を測定し、真密度で割って相対密度を求めた。焼結体の真密度は、焼結体中のＮｂ２Ｏ５相がすべてＺｎ３Ｎｂ２Ｏ８相として反応したと仮定し計算したときのＺｎＯ相の重量ａ［ｇ］およびＺｎ３Ｎｂ２Ｏ８相の重量ｂ［ｇ］と、それぞれの真密度５．６０６［ｇ／ｃｍ３］、５．７３４［ｇ／ｃｍ３］を用いて、下記式で表される相加平均より算出した。
ｄ＝（ａ＋ｂ）／（（ａ／５．６０６）＋（ｂ／５．７３４）） ・・・（３）式
（２）Ｘ線回折試験
鏡面研磨した焼結体試料の２θ＝２０～７０°の範囲のＸ線回折パターンを測定した。
走査方法 ：ステップスキャン法（ＦＴ法）
Ｘ線源 ：ＣｕＫα
パワー ：４０ｋＶ、４０ｍＡ
ステップ幅：０．０１°
（３）結晶粒径
鏡面研磨し、ＥＰＭＡによる組成分析によりＺｎＯ相とＺｎ３Ｎｂ２Ｏ８相を同定した後、ＳＥＭ像から直径法で結晶粒径を測定した。サンプルは任意の３点以上を観察し、各々３００個以上の粒子の測定を行った。
（ＥＰＭＡ分析条件）
装置 ：波長分散型電子線マイクロアナライザー
加速電圧 ：１５ｋＶ
照射電流 ：３０ｎＡ
（４）抗折強度
ＪＩＳ Ｒ １６０１に準拠して測定した。
（抗折強度の測定条件）
試験方法 ：３点曲げ試験
支点間距離：３０ｍｍ
試料サイズ：３ｍｍ×４ｍｍ×４０ｍｍ
ヘッド速度：０．５ｍｍ／ｍｉｎ
（５）抵抗率の測定
焼成後の焼結体表面より１ｍｍ以上研削した後の任意の部分より切り出した１０サンプルの平均値を測定データとした。
試料サイズ：１０ｍｍ×２０ｍｍ×１ｍｍ
測定方法：４端子法
測定装置：ロレスタＨＰ ＭＣＰ－Ｔ４１０（三菱油化製）
（６）酸素量の分析
焼成後の焼結体表面より１ｍｍ以上研削した後の任意の部分より切り出した５サンプルの分析値の平均値を測定データとした。
（酸素量分析条件）
測定手法 ：インパルス炉溶融－赤外線吸収法
装置 ：ＬＥＣＯ ＴＣ４３６ 酸素・窒素分析装置
（７）スパッタリング評価
得られた焼結体を１０１．６ｍｍΦ×６ｍｍｔに加工した後、無酸素銅製のバッキングプレートにインジウムハンダによりボンディングしてスパッタリングターゲットとした。このターゲットを用いて投入パワーを変化させてスパッタリングを行い、アーキング計測およびＤＣ放電の安定性の評価及び下記の条件で成膜した膜の評価を行なった。
（スパッタリング条件）
ガス ：アルゴン＋酸素（３％）
圧力 ：０．６Ｐａ
電源 ：ＤＣ
投入パワー：４００Ｗ（４．９Ｗ／ｃｍ２）
６００Ｗ（７．４Ｗ／ｃｍ２）
８００Ｗ（９．９Ｗ／ｃｍ２）
放電時間 ：各１２０ｍｉｎ
アーキング計測条件（しきい電圧）：スパッタ電圧－５０［Ｖ］
（成膜条件）
ガス ：アルゴン＋酸素（３％）
圧力 ：０．６Ｐａ
電源 ：ＤＣ
投入パワー：２００Ｗ（２．４Ｗ／ｃｍ２）
膜厚 ：８０ｎｍ
基板 ：無アルカリガラス（コーニング社製ＥＡＧＬＥ ＸＧ、厚み０．７ｍｍ）
基板温度 ：室温。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In addition, each measurement in a present Example was performed as follows.
(1) Density of Sintered Body The relative density of the sintered body was determined by measuring the bulk density by the Archimedes method in accordance with JIS R 1634 and dividing by the true density. The true density of the sintered body was calculated assuming that all the Nb 2 O 5 phases in the sintered body reacted as the Zn 3 Nb 2 O 8 phase, and the weight a [g] of the ZnO phase and Zn 3 Nb 2 Using the weight b [g] of the O 8 phase and each true density 5.606 [g / cm 3 ], 5.734 [g / cm 3 ], the calculation was made from the arithmetic average represented by the following formula. .
d = (a + b) / ((a / 5.606) + (b / 5.734)) (3) Equation (2) X-ray diffraction test 2θ = 20 to 70 of the sintered sample obtained by mirror polishing An X-ray diffraction pattern in the range of ° was measured.
Scanning method: Step scan method (FT method)
X-ray source: CuKα
Power: 40kV, 40mA
Step width: 0.01 °
(3) Crystal grain size After mirror polishing and identifying a ZnO phase and a Zn 3 Nb 2 O 8 phase by composition analysis with EPMA, the crystal grain size was measured by a diameter method from an SEM image. Three or more arbitrary samples were observed, and 300 or more particles were measured for each sample.
(EPMA analysis conditions)
Apparatus: Wavelength dispersive electron beam microanalyzer Accelerating voltage: 15 kV
Irradiation current: 30 nA
(4) Folding strength Measured according to JIS R 1601.
(Measurement conditions of bending strength)
Test method: 3-point bending test fulcrum distance: 30 mm
Sample size: 3mm x 4mm x 40mm
Head speed: 0.5 mm / min
(5) Measurement of resistivity The average value of 10 samples cut out from an arbitrary portion after grinding 1 mm or more from the sintered body surface after firing was used as measurement data.
Sample size: 10 mm x 20 mm x 1 mm
Measuring method: 4-terminal method Measuring device: Loresta HP MCP-T410 (Mitsubishi Yuka)
(6) Analysis of oxygen content The average value of the analytical values of 5 samples cut out from an arbitrary portion after grinding 1 mm or more from the sintered body surface after firing was used as measurement data.
(Oxygen analysis conditions)
Measurement method: Impulse furnace melting-infrared absorption method apparatus: LECO TC436 Oxygen / nitrogen analyzer (7) Sputtering evaluation After processing the obtained sintered body to 101.6 mmΦ × 6 mmt, indium solder on a backing plate made of oxygen-free copper Was bonded to obtain a sputtering target. Sputtering was performed by changing the input power using this target, and the arcing measurement, the evaluation of the stability of the DC discharge, and the film formed under the following conditions were evaluated.
(Sputtering conditions)
Gas: Argon + oxygen (3%)
Pressure: 0.6Pa
Power supply: DC
Input power: 400 W (4.9 W / cm 2 )
600 W (7.4 W / cm 2 )
800W (9.9W / cm 2 )
Discharge time: 120 min each
Arcing measurement conditions (threshold voltage): Sputtering voltage -50 [V]
(Deposition conditions)
Gas: Argon + oxygen (3%)
Pressure: 0.6Pa
Power supply: DC
Input power: 200 W (2.4 W / cm 2 )
Film thickness: 80nm
Substrate: Alkali-free glass (Corning EAGLE XG, thickness 0.7 mm)
Substrate temperature: Room temperature.
（実施例１）
表１に示す粉末物性の酸化亜鉛粉末及び酸化ニオブ粉末（純度９９．９％以上）を、Ｎｂ／（Ｚｎ＋Ｎｂ）で０．２４８の割合となるように秤量した。秤量した粉末を純水１０ｋｇにてスラリー化し、ポリアクリレート系分散剤を全粉末量に対して３ｗｔ％入れ、固形分濃度６０％のスラリーを作成した。内容積２．５Ｌのビーズミル装置にφ０．３ｍｍジルコニアビーズを７５％充填し、ミル周速５．０ｍ／ｓｅｃ、スラリー供給量２．０Ｌ／ｍｉｎにてスラリーをミル内に循環させ、粉砕、混合処理を行った。さらに、スラリー供給タンクの温度を８～９℃、スラリー出口温度を１４～１６℃の範囲内で温度管理を行い、ミル内の循環回数（パス回数）は５回とした。その後、得られたスラリーを噴霧乾燥し、乾燥後の粉末を３００μｍの篩に通し、プレス成形法により３００ｋｇ／ｃｍ２の圧力で１２０ｍｍ×１２０ｍｍ×８ｍｍｔの成形体を作製後、２ｔｏｎ／ｃｍ２の圧力でＣＩＰ処理した。 (Example 1)
The powdered physical properties of zinc oxide powder and niobium oxide powder (purity 99.9% or more) shown in Table 1 were weighed so that the ratio of Nb / (Zn + Nb) was 0.248. The weighed powder was slurried with 10 kg of pure water, and 3 wt% of the polyacrylate dispersant was added to the total powder amount to prepare a slurry with a solid content concentration of 60%. Filled with 75% φ0.3mm zirconia beads in a 2.5L bead mill device, and circulated and pulverized and mixed the slurry in the mill at a mill peripheral speed of 5.0m / sec and a slurry supply rate of 2.0L / min. Processed. Furthermore, the temperature was controlled within the range of the slurry supply tank temperature of 8-9 ° C. and the slurry outlet temperature of 14-16 ° C., and the number of circulations (passes) in the mill was 5. Thereafter, the obtained slurry was spray-dried, the dried powder was passed through a 300 μm sieve, and a 120 mm × 120 mm × 8 mmt molded body was produced at a pressure of 300 kg / cm 2 by a press molding method, and then 2 ton / cm 2 . CIP-treated with pressure.
表１に示す粉末物性の酸化亜鉛粉末及び酸化ニオブ粉末（純度９９．９％以上）を、Ｎｂ／（Ｚｎ＋Ｎｂ）で０．２４８の割合となるように秤量した。秤量した粉末を純水１０ｋｇにてスラリー化し、ポリアクリレート系分散剤を全粉末量に対して３ｗｔ％入れ、固形分濃度６０％のスラリーを作成した。内容積２．５Ｌのビーズミル装置にφ０．３ｍｍジルコニアビーズを７５％充填し、ミル周速５．０ｍ／ｓｅｃ、スラリー供給量２．０Ｌ／ｍｉｎにてスラリーをミル内に循環させ、粉砕、混合処理を行った。さらに、スラリー供給タンクの温度を８～９℃、スラリー出口温度を１４～１６℃の範囲内で温度管理を行い、ミル内の循環回数（パス回数）は５回とした。その後、得られたスラリーを噴霧乾燥し、乾燥後の粉末を３００μｍの篩に通し、プレス成形法により３００ｋｇ／ｃｍ２の圧力で１２０ｍｍ×１２０ｍｍ×８ｍｍｔの成形体を作製後、２ｔｏｎ／ｃｍ２の圧力でＣＩＰ処理した。 (Example 1)
The powdered physical properties of zinc oxide powder and niobium oxide powder (purity 99.9% or more) shown in Table 1 were weighed so that the ratio of Nb / (Zn + Nb) was 0.248. The weighed powder was slurried with 10 kg of pure water, and 3 wt% of the polyacrylate dispersant was added to the total powder amount to prepare a slurry with a solid content concentration of 60%. Filled with 75% φ0.3mm zirconia beads in a 2.5L bead mill device, and circulated and pulverized and mixed the slurry in the mill at a mill peripheral speed of 5.0m / sec and a slurry supply rate of 2.0L / min. Processed. Furthermore, the temperature was controlled within the range of the slurry supply tank temperature of 8-9 ° C. and the slurry outlet temperature of 14-16 ° C., and the number of circulations (passes) in the mill was 5. Thereafter, the obtained slurry was spray-dried, the dried powder was passed through a 300 μm sieve, and a 120 mm × 120 mm × 8 mmt molded body was produced at a pressure of 300 kg / cm 2 by a press molding method, and then 2 ton / cm 2 . CIP-treated with pressure.
次にこの成形体をアルミナ製のセッターの上に設置して、抵抗加熱式の電気炉（炉内容積：２５０ｍｍ×２５０ｍｍ×２５０ｍｍ）にて焼成した。得られた焼結体及びスパッタリングターゲットのスパッタリング評価結果を表２に示す。
（焼成条件）
焼成温度：１２５０℃
保持時間：１時間
昇温速度：９５０℃～１０５０℃ ２５０℃／ｈ
その他の温度域 １００℃／ｈ
雰囲気 ：大気雰囲気
降温速度：９００℃まで ３５０℃／ｈ
９００℃以降 １５０℃／ｈ。 Next, this compact was placed on an alumina setter and fired in a resistance heating type electric furnace (furnace internal volume: 250 mm × 250 mm × 250 mm). Table 2 shows the results of sputtering evaluation of the obtained sintered body and sputtering target.
(Baking conditions)
Firing temperature: 1250 ° C
Holding time: 1 hour Temperature rising rate: 950 ° C. to 1050 ° C. 250 ° C./h
Other temperature range 100 ℃ / h
Atmosphere: Air temperature cooling rate: Up to 900 ° C 350 ° C / h
From 900 ° C to 150 ° C / h.
（焼成条件）
焼成温度：１２５０℃
保持時間：１時間
昇温速度：９５０℃～１０５０℃ ２５０℃／ｈ
その他の温度域 １００℃／ｈ
雰囲気 ：大気雰囲気
降温速度：９００℃まで ３５０℃／ｈ
９００℃以降 １５０℃／ｈ。 Next, this compact was placed on an alumina setter and fired in a resistance heating type electric furnace (furnace internal volume: 250 mm × 250 mm × 250 mm). Table 2 shows the results of sputtering evaluation of the obtained sintered body and sputtering target.
(Baking conditions)
Firing temperature: 1250 ° C
Holding time: 1 hour Temperature rising rate: 950 ° C. to 1050 ° C. 250 ° C./h
Other temperature range 100 ℃ / h
Atmosphere: Air temperature cooling rate: Up to 900 ° C 350 ° C / h
From 900 ° C to 150 ° C / h.
（実施例２～１１、比較例１～１２）
使用した粉末、組成を表２の内容に変更した以外は実施例１と同様の方法（実施例４は成形体サイズを３１０ｍｍ×３１０ｍｍ×６ｍｍｔ、実施例５は形体サイズを内径７７ｍｍ×外径９１ｍｍ×１７０ｍｍＬの円筒形状に変更した）で成形体を作製した。次に成形体をそれぞれ表２の条件にて焼成した。得られた焼結体の評価結果を表２に示す。 (Examples 2 to 11, Comparative Examples 1 to 12)
The same method as in Example 1 except that the powder and composition used were changed to the contents shown in Table 2 (Example 4 has a molded body size of 310 mm × 310 mm × 6 mmt, Example 5 has a body size of 77 mm inner diameter × 91 mm outer diameter) The shape was changed to a cylindrical shape of × 170 mmL). Next, each compact was fired under the conditions shown in Table 2. Table 2 shows the evaluation results of the obtained sintered body.
使用した粉末、組成を表２の内容に変更した以外は実施例１と同様の方法（実施例４は成形体サイズを３１０ｍｍ×３１０ｍｍ×６ｍｍｔ、実施例５は形体サイズを内径７７ｍｍ×外径９１ｍｍ×１７０ｍｍＬの円筒形状に変更した）で成形体を作製した。次に成形体をそれぞれ表２の条件にて焼成した。得られた焼結体の評価結果を表２に示す。 (Examples 2 to 11, Comparative Examples 1 to 12)
The same method as in Example 1 except that the powder and composition used were changed to the contents shown in Table 2 (Example 4 has a molded body size of 310 mm × 310 mm × 6 mmt, Example 5 has a body size of 77 mm inner diameter × 91 mm outer diameter) The shape was changed to a cylindrical shape of × 170 mmL). Next, each compact was fired under the conditions shown in Table 2. Table 2 shows the evaluation results of the obtained sintered body.
（薄膜抵抗率の測定）
実施例１～１１で得られた薄膜の抵抗率の測定をロレスタＨＰ ＭＣＰ－Ｔ４１０（三菱油化製）を用いて４端子法で行った。薄膜抵抗は全て１０５Ω以上の高抵抗膜であった。 (Measurement of thin film resistivity)
The resistivity of the thin film obtained in each of Examples 1 to 11 was measured by a four-terminal method using a Loresta HP MCP-T410 (manufactured by Mitsubishi Yuka). All the thin film resistors were high resistance films of 10 5 Ω or more.
実施例１～１１で得られた薄膜の抵抗率の測定をロレスタＨＰ ＭＣＰ－Ｔ４１０（三菱油化製）を用いて４端子法で行った。薄膜抵抗は全て１０５Ω以上の高抵抗膜であった。 (Measurement of thin film resistivity)
The resistivity of the thin film obtained in each of Examples 1 to 11 was measured by a four-terminal method using a Loresta HP MCP-T410 (manufactured by Mitsubishi Yuka). All the thin film resistors were high resistance films of 10 5 Ω or more.
（比較例１３）
実施例１と同様の方法で成形体を作製し、次に焼成雰囲気を窒素雰囲気とした以外実施例１と同様の方法で焼成した。得られた焼結体の評価結果を表２に示す。また、スパッタリング後のターゲット表面に黒色斑点の発生と、成膜基板上にスプラッシュ状のパーティクルが確認された。 (Comparative Example 13)
A molded body was produced in the same manner as in Example 1, and then fired in the same manner as in Example 1 except that the firing atmosphere was changed to a nitrogen atmosphere. Table 2 shows the evaluation results of the obtained sintered body. Moreover, generation | occurrence | production of the black spot on the target surface after sputtering, and the splash-like particle | grains were confirmed on the film-forming board | substrate.
実施例１と同様の方法で成形体を作製し、次に焼成雰囲気を窒素雰囲気とした以外実施例１と同様の方法で焼成した。得られた焼結体の評価結果を表２に示す。また、スパッタリング後のターゲット表面に黒色斑点の発生と、成膜基板上にスプラッシュ状のパーティクルが確認された。 (Comparative Example 13)
A molded body was produced in the same manner as in Example 1, and then fired in the same manner as in Example 1 except that the firing atmosphere was changed to a nitrogen atmosphere. Table 2 shows the evaluation results of the obtained sintered body. Moreover, generation | occurrence | production of the black spot on the target surface after sputtering, and the splash-like particle | grains were confirmed on the film-forming board | substrate.
（参考例）
実施例１と同じ組成にて、同様の方法で作製した粉末を用い、成形体を作製した。次に成形体を黒鉛性のホットプレス型に充填し、ホットプレス装置中で真空下１０００℃にて１時間保持して焼結した。ホットプレス圧力は１９．６ＭＰａとした。得られた焼結体の密度は５．４８５ｇ／ｃｍ３、相対密度で９５．７％であった。得られた焼結体の評価結果を表３に示す。 (Reference example)
Using the same composition as in Example 1 and a powder produced by the same method, a molded body was produced. Next, the compact was filled in a graphite hot press mold and sintered by holding it at 1000 ° C. for 1 hour under vacuum in a hot press apparatus. The hot press pressure was 19.6 MPa. The density of the obtained sintered body was 5.485 g / cm 3 and the relative density was 95.7%. Table 3 shows the evaluation results of the obtained sintered body.
実施例１と同じ組成にて、同様の方法で作製した粉末を用い、成形体を作製した。次に成形体を黒鉛性のホットプレス型に充填し、ホットプレス装置中で真空下１０００℃にて１時間保持して焼結した。ホットプレス圧力は１９．６ＭＰａとした。得られた焼結体の密度は５．４８５ｇ／ｃｍ３、相対密度で９５．７％であった。得られた焼結体の評価結果を表３に示す。 (Reference example)
Using the same composition as in Example 1 and a powder produced by the same method, a molded body was produced. Next, the compact was filled in a graphite hot press mold and sintered by holding it at 1000 ° C. for 1 hour under vacuum in a hot press apparatus. The hot press pressure was 19.6 MPa. The density of the obtained sintered body was 5.485 g / cm 3 and the relative density was 95.7%. Table 3 shows the evaluation results of the obtained sintered body.
本発明を詳細に、また特定の実施態様を参照して説明したが、本発明の本質と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
なお、２０１４年８月１２日に出願された日本特許出願２０１４－１６４５１７号及び２０１４年１２月２４日に出願された日本特許出願２０１４－２６１１９９の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
The specification, claims, drawings and abstract of Japanese Patent Application No. 2014-164517 filed on August 12, 2014 and Japanese Patent Application No. 2014-261199 filed on December 24, 2014 The entire contents are hereby incorporated by reference as the disclosure of the specification of the present invention.
Claims (9)
- 構成元素として、亜鉛、ニオブ及び酸素を有する酸化物焼結体において、亜鉛、ニオブの含有量をそれぞれＺｎ、Ｎｂとしたときに、原子比でＮｂ／（Ｚｎ＋Ｎｂ）が０．０６４～０．３３４であり、相対密度が９８％を超え、バルク抵抗値が１．０～５０００Ω・ｃｍであることを特徴とする酸化物焼結体。 In an oxide sintered body having zinc, niobium and oxygen as constituent elements, when the zinc and niobium contents are Zn and Nb, respectively, Nb / (Zn + Nb) is 0.064 to 0.334 in atomic ratio. An oxide sintered body having a relative density of over 98% and a bulk resistance value of 1.0 to 5000 Ω · cm.
- 酸化物焼結体中のＺｎＯ結晶相の平均粒径が１．５μｍ以上６μｍ以下であることを特徴とする請求項１に記載の酸化物焼結体。 2. The oxide sintered body according to claim 1, wherein an average particle diameter of a ZnO crystal phase in the oxide sintered body is 1.5 μm or more and 6 μm or less.
- 酸化物焼結体の酸素欠損量が５％以下であることを特徴とする請求項１または２に記載の酸化物焼結体。 The oxide sintered body according to claim 1 or 2, wherein the oxide sintered body has an oxygen deficiency of 5% or less.
- 酸化物焼結体の抵抗率のばらつき幅が７０％以内であることを特徴とする請求項１～３のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 1 to 3, wherein the variation range of resistivity of the oxide sintered body is within 70%.
- Ｘ線回折における入射角（２θ）が、３２．３°～３３．８°の間に存在する回折ピークの最大強度をＩ１、３５．８°～３７．３°の間に存在する回折ピークの最大強度をＩ２とした時の、回折強度比Ｉ２／Ｉ１の値が０．６５以上であることを特徴とする請求項１～４のいずれかに記載の酸化物焼結体。 The maximum intensity of the diffraction peak where the incident angle (2θ) in X-ray diffraction is between 32.3 ° and 33.8 ° is the diffraction peak existing between I 1 and 35.8 ° to 37.3 °. 5. The oxide sintered body according to claim 1 , wherein the value of the diffraction intensity ratio I 2 / I 1 is 0.65 or more when the maximum intensity of I is I 2 .
- ターゲット面の面積が９６１ｃｍ２以上である平板形状であることを特徴とする請求項１～５のいずれかに記載の酸化物焼結体。 6. The oxide sintered body according to claim 1, wherein the oxide sintered body has a flat plate shape with an area of the target surface of 961 cm 2 or more.
- ターゲット面の面積が４８６ｃｍ２以上である円筒形状であることを特徴とする請求項１～５のいずれかに記載の酸化物焼結体。 6. The oxide sintered body according to claim 1, wherein the oxide sintered body has a cylindrical shape with an area of a target surface of 486 cm 2 or more.
- 請求項１～７のいずれかに記載の酸化物焼結体をターゲット材として用いることを特徴とするスパッタリングターゲット。 A sputtering target comprising the oxide sintered body according to any one of claims 1 to 7 as a target material.
- 請求項８に記載のスパッタリングターゲットを用いてスパッタリング法で成膜したことを特徴とする薄膜。 A thin film formed by sputtering using the sputtering target according to claim 8.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2014-164517 | 2014-08-12 | ||
| JP2014164517 | 2014-08-12 | ||
| JP2014-261199 | 2014-12-24 | ||
| JP2014261199 | 2014-12-24 |
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| JP (1) | JP6582698B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017164168A1 (en) * | 2016-03-22 | 2017-09-28 | 三菱マテリアル株式会社 | Sputtering target |
| CN108603284A (en) * | 2016-03-22 | 2018-09-28 | 三菱综合材料株式会社 | Sputtering target |
| KR20190120167A (en) * | 2017-03-01 | 2019-10-23 | 미쓰비시 마테리알 가부시키가이샤 | Method for producing sputtering target and sputtering target |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012106880A (en) * | 2010-11-16 | 2012-06-07 | Sumitomo Chemical Co Ltd | Zinc oxide-based transparent conductive film-forming material, method for manufacturing the same, target using the same, and method for forming zinc oxide-based transparent conductive film |
| WO2013065785A1 (en) * | 2011-11-04 | 2013-05-10 | 株式会社コベルコ科研 | Oxide sintered body, sputtering target, and method for producing same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005317093A (en) * | 2004-04-28 | 2005-11-10 | Sumitomo Metal Mining Co Ltd | Sputtering target for forming protection layer and its manufacturing method |
| JP5003600B2 (en) * | 2008-06-13 | 2012-08-15 | 住友金属鉱山株式会社 | Oxide sintered body, target, transparent conductive film obtained using the same, and conductive laminate |
| JP2010160917A (en) * | 2009-01-06 | 2010-07-22 | Kaneka Corp | Substrate with transparent electrode and its manufacturing method |
| EP2921467B1 (en) * | 2012-11-19 | 2019-02-06 | Tosoh Corporation | Oxide sinter, sputtering target using same, and oxide film |
| JP2015074789A (en) * | 2013-10-07 | 2015-04-20 | 三菱マテリアル株式会社 | Niobium oxide system sputtering target and method for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012106880A (en) * | 2010-11-16 | 2012-06-07 | Sumitomo Chemical Co Ltd | Zinc oxide-based transparent conductive film-forming material, method for manufacturing the same, target using the same, and method for forming zinc oxide-based transparent conductive film |
| WO2013065785A1 (en) * | 2011-11-04 | 2013-05-10 | 株式会社コベルコ科研 | Oxide sintered body, sputtering target, and method for producing same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017164168A1 (en) * | 2016-03-22 | 2017-09-28 | 三菱マテリアル株式会社 | Sputtering target |
| CN108603284A (en) * | 2016-03-22 | 2018-09-28 | 三菱综合材料株式会社 | Sputtering target |
| KR20180125946A (en) * | 2016-03-22 | 2018-11-26 | 미쓰비시 마테리알 가부시키가이샤 | Sputtering target |
| KR102237332B1 (en) | 2016-03-22 | 2021-04-06 | 미쓰비시 마테리알 가부시키가이샤 | Sputtering target |
| KR20190120167A (en) * | 2017-03-01 | 2019-10-23 | 미쓰비시 마테리알 가부시키가이샤 | Method for producing sputtering target and sputtering target |
| KR102302021B1 (en) | 2017-03-01 | 2021-09-13 | 미쓰비시 마테리알 가부시키가이샤 | Sputtering target and manufacturing method of sputtering target |
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| JP6582698B2 (en) | 2019-10-02 |
| TW201605762A (en) | 2016-02-16 |
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