WO2012077512A1 - 酸化亜鉛焼結体、スパッタリングターゲット及び酸化亜鉛薄膜 - Google Patents
酸化亜鉛焼結体、スパッタリングターゲット及び酸化亜鉛薄膜 Download PDFInfo
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- WO2012077512A1 WO2012077512A1 PCT/JP2011/077232 JP2011077232W WO2012077512A1 WO 2012077512 A1 WO2012077512 A1 WO 2012077512A1 JP 2011077232 W JP2011077232 W JP 2011077232W WO 2012077512 A1 WO2012077512 A1 WO 2012077512A1
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- zinc oxide
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Definitions
- the present invention relates to a zinc oxide sintered body used as a raw material when a zinc oxide thin film is produced by a sputtering method, a sputtering target composed of the zinc oxide sintered body, and a zinc oxide thin film. Specifically, it is possible to produce a high-resistance zinc oxide thin film by a sputtering method, a zinc oxide sintered body having high strength and low resistance, a sputtering target composed of the zinc oxide sintered body, and a zinc oxide thin film About.
- Zinc oxide is a white powder having a hexagonal crystal structure, and has recently been used in various forms in the form of a thin film.
- a method of forming this zinc oxide thin film there are a physical vapor deposition method such as a vacuum vapor deposition method and a sputtering method, and a chemical vapor deposition method such as CVD.
- a sputtering method is widely used because it can be stably formed even with a material having a low vapor pressure and is easy to operate.
- the sputtering method In the sputtering method, positive ions such as argon ions are physically collided with the target placed on the cathode, and the material constituting the target is released by the collision energy, and the target material is almost the same composition as the target material.
- a method for depositing a film As the sputtering method, there are a direct current sputtering method (DC sputtering method) and a high frequency sputtering method (RF sputtering method).
- the direct current sputtering method is a method in which a direct current voltage is applied to a cathode target using a direct current power source, and has an advantage that the film forming speed is high and the productivity is high.
- the direct current sputtering method has a restriction that the resistivity of the target to be used must be 10 5 ⁇ ⁇ cm or less. This is because when a target having a resistivity of 10 5 ⁇ ⁇ cm or more is used, the discharge generated during sputtering is not stable.
- the high frequency sputtering method uses a high frequency power supply instead of a DC power supply.
- the target to be used may not be a conductive material, the productivity tends to be low because the deposition rate of the film is slower than the direct current sputtering method.
- the power supply and the device are complicated and expensive, the equipment cost tends to increase. For this reason, the target which can be used for direct current
- a typical application of the zinc oxide thin film is a transparent conductive film.
- a zinc oxide thin film to which zirconium of 0.1 atomic% (corresponding to 1120 weight ppm) or more is added is used for applications such as a transparent conductive film for solar cells by adding an additive to make it conductive.
- has been proposed for example, Patent Document 1).
- the electrical conductivity of the thin film is 0.0003 ⁇ ⁇ cm, and cannot be used as a thin film for high resistance.
- a zinc oxide thin film having high resistance can be mentioned.
- a zinc oxide thin film having a high resistance value of 1.0 ⁇ ⁇ cm or more as a buffer layer of a CIGS thin film solar cell or the like (for example, Patent Document 2).
- Patent Document 2 the higher the resistivity of the zinc oxide thin film, the better.
- Patent Document 3 As the zinc oxide target used when producing such a zinc oxide thin film by a sputtering method, a high-purity target containing as little additive and impurities as possible is used (for example, Patent Document 3). The reason is that if impurities exist in the film, carrier electrons are generated from the impurities and the resistivity of the film is lowered, so that a thin film having high resistance cannot be obtained (Patent Document 2).
- the first problem is that the zinc oxide target used for forming such a thin film is not suitable for DC sputtering because of its low conductivity.
- a high-purity zinc oxide target has a resistivity of 10 7 ⁇ ⁇ cm or more because it generates less carriers due to impurities. For this reason, it is not suitable for DC sputtering. Therefore, it is necessary to use a high-frequency sputtering method with a low deposition rate and high equipment cost.
- a reactive sputtering method As a method for overcoming this problem, a reactive sputtering method is known.
- argon gas is introduced together with a reactive gas, the target material released by the collision of argon ions is reacted with the reactive gas, and is deposited on the substrate as an insulating film.
- This method has a feature that an insulating film can be formed by a direct current sputtering method using a conductive target.
- an insulating zinc oxide thin film can be deposited by using a conductive metal zinc target and adding oxygen gas to argon gas and performing direct current sputtering. Can do.
- the quality of the zinc oxide thin film greatly varies depending on the amount of reactive gas to be added and the temporal change in the deposition rate of zinc. For this reason, it is difficult to control the reaction and it is difficult to obtain a film having a stable resistivity.
- Patent Document 5 As another method of forming a zinc oxide thin film having high resistance, a method of mixing metallic zinc in zinc oxide powder and firing it at a temperature lower than the melting temperature of zinc has been proposed (Patent Document 5). In this method, since the target contains metallic zinc, the resistance can be lowered. However, since the firing temperature is around the melting point of zinc (419.5 ° C.), the densification of zinc oxide does not proceed sufficiently. For this reason, the target becomes extremely brittle, and the target is easily cracked during sputtering.
- the second problem when forming a zinc oxide thin film having high resistance by the sputtering method is that the strength of the target is low.
- the strength here is the physical strength of the target, and the measured value is represented by the bending strength.
- sintering inhibition due to impurities hardly occurs.
- the strength of the sintered body becomes extremely low.
- the outside is sintered earlier than the inside of the sintered body and densification proceeds, bubbles remain inside, and the density of the sintered body tends to be low.
- the interaction at the grain boundary is weak, and cracks, chips, baldness, etc. at the grain boundary part are very likely to occur.
- a cylindrical sputtering target has a greater stress generated inside during sputtering than a conventional flat target. For this reason, higher strength is required. For these reasons, cylindrical targets that have been conventionally formed of a metal material have been widely used.
- a target made of a ceramic material with low strength and brittleness is likely to crack during sputtering and manufacturing. For this reason, the present condition is that the target which consists of ceramic materials is hardly used other than the target by a thermal spraying method.
- a ceramic target obtained by a thermal spraying method is a low-density target having a relative density of 90% or less because bubbles tend to remain in the target. Therefore, there is a problem that cracking of the target and abnormal discharge are likely to occur during sputtering.
- Rotating cathode sputtering equipment using a cylindrical target is not suitable for high frequency sputtering.
- the cylindrical zinc oxide target is required to have high density and high strength, and to have conductivity in order to enable formation by a direct current sputtering method.
- This invention is made
- Objective. Moreover, it aims at providing the zinc oxide thin film which combines a high resistivity and a high transmittance
- the present invention is as follows.
- a sputtering target comprising the zinc oxide sintered body according to any one of (1) to (3) above.
- the strength of the sintered body can be increased (for example, 40 MPa or more) by containing 10 to 1000 ppm of zirconium in the zinc oxide sintered body.
- This makes it possible to prevent cracking and chipping during firing, processing of the sintered body, and bonding at the time of target preparation, which have occurred due to insufficient strength, and improve productivity. it can.
- it becomes possible to stably produce a zinc oxide thin film that sufficiently suppresses cracking of the target during sputtering and has both high resistivity and high transmittance.
- the resistivity of the zinc oxide sintered body is set to 10 5 ⁇ ⁇ cm or less, a sputtering target that can be used for film formation by a direct current sputtering method is obtained.
- the zinc oxide sintered body has high strength, complicated processing such as cylindrical shape can be performed. This makes it possible to manufacture a target for a rotary cathode sputtering apparatus. Further, it becomes possible to sufficiently suppress the cracking of the cylindrical zinc oxide target in the sputtering, and it becomes possible to stably produce a zinc oxide thin film having both high resistivity and high transmittance.
- a zinc oxide thin film containing 10 to 2000 ppm of zirconium and having a high resistivity of 10 ⁇ ⁇ cm or more can be suitably used for an insulating film for a semiconductor or a buffer layer of a solar cell.
- the ppm of zirconium indicates the content (wt ppm) of zirconium based on the weight of the entire weight.
- FIG. 1 is a perspective view of the zinc oxide sintered body of the present embodiment.
- the zinc oxide sintered body 10 of the present embodiment is a sintered body containing zinc oxide as a main component, and contains 10 to 1000 ppm of zirconium in addition to zinc oxide.
- the zinc oxide sintered body (sometimes referred to as “sintered body”) 10 contains zirconium in an amount of 10 ppm or more, so that zirconium can be uniformly present in the grains of the zinc oxide sintered body 10 or in grain boundaries. . Thereby, the strength of the zinc oxide sintered body 10 can be dramatically improved. If the zirconium content is less than 10 ppm, it will be difficult to uniformly disperse zirconium in the zinc oxide sintered body, and it will be difficult to improve the strength of the zinc oxide sintered body 10.
- the strength of the zinc oxide sintered body 10 tends to increase as the zirconium content increases. However, when the zirconium content exceeds 1000 ppm, the resistivity of the zinc oxide thin film formed using the sputtering target made of the sintered body decreases. For this reason, the effect that the zinc oxide thin film which has high resistance can be manufactured will be impaired. Therefore, the zirconium content in the zinc oxide sintered body 10 of the present embodiment is 10 to 1000 ppm.
- the strength of the zinc oxide sintered body 10 can be increased, and a zinc oxide thin film having high resistance when used as a target can be produced.
- the zirconium content is preferably 30 to 1000 ppm.
- the zinc oxide sintered body 10 of the present embodiment has high strength. For this reason, it can be set as a cylindrical zinc oxide type target. Moreover, it can be used conveniently as a sputtering target.
- the resistivity of the zinc oxide sintered body 10 of the present embodiment is preferably 10 5 ⁇ ⁇ cm or less.
- the resistivity of the zinc oxide sintered compact 10 is low, it can be used as a sputtering target of a direct current sputtering method.
- the method of setting the resistivity to 10 5 ⁇ ⁇ cm or less There is no particular limitation on the method of setting the resistivity to 10 5 ⁇ ⁇ cm or less.
- the content of zirconium in the zinc oxide sintered body 10 may be 500 ppm or more, or oxygen defects may be generated in the zinc oxide to reduce the bulk resistance value. When oxygen defects are present in zinc oxide, carriers are generated and the resistivity of the zinc oxide sintered body 10 is reduced.
- the method for producing oxygen defects is not particularly limited.
- the oxygen partial pressure in the atmosphere may be reduced when the zinc oxide sintered body 10 is fired.
- the resistivity of the zinc oxide sintered body 10 can be reduced to about 1/100 that of firing in air.
- the shortage of oxygen may be compensated by adding a small amount of oxygen gas.
- Zinc oxide sintered body 10 containing zirconium can be manufactured, for example, as follows. That is, the manufacturing method described here includes a blending step for preparing a powder containing zinc oxide and a zirconium source, a molding step for molding the powder to produce a molded body, and a firing step for firing the molded body. Have Hereinafter, details of each process will be described.
- Zirconium sources to be added are particularly limited as long as they contain zirconium, such as various zirconium salts such as metal zirconium and zirconium chloride, zirconium complexes, zirconium oxide (zirconia), partially stabilized zirconia, stabilized zirconia, and alumina-added zirconia. Not.
- zirconium oxide partially stabilized zirconia, stabilized zirconia or alumina-added zirconia, which is the same oxide as zinc oxide, is preferable.
- the nature of the additive is not particularly limited.
- the powder is preferably fine in order to improve dispersibility.
- the mixing method for mixing the zinc oxide powder and the zirconium source is not particularly limited. It is preferable to mix the zinc oxide powder and the zirconium source so as to be as uniform as possible. Examples of the mixing method include dry ball mill mixing, wet bead mill mixing, and stirring mixing. Further, a method of further mixing a zinc oxide powder in which a predetermined amount of a zirconium source is mixed with the zinc oxide powder and diluting to a predetermined concentration is also effective as a uniform mixing method.
- zirconium oxide As another method of adding and mixing a zirconium source, there is a method of using zirconium oxide as a medium of a pulverizing, mixing or dispersing apparatus. That is, in this method, a small amount of zirconium is mixed with zinc oxide powder by pulverizing, mixing, and dispersing zinc oxide using a container lined with zirconia beads and / or zirconia as a grinding, mixing, and dispersing device. Is the method.
- This method has the advantage that the media of the grinding, mixing and dispersing apparatus are prevented from becoming a source of contamination and the media is a source of zirconium.
- slurry of zinc oxide is slurried and dispersed in a zirconia lining container together with zirconia beads.
- zirconium and zinc oxide can be mixed uniformly.
- the addition amount can be adjusted by the mixing time, and the zirconium content of the finally obtained zinc oxide sintered body 10 can be controlled to 10 to 1000 ppm.
- the pulverizing, mixing, and dispersing apparatus may be either dry or wet, but is preferably wet from the viewpoint of making the dispersed state of zirconium more uniform.
- the final powder state is not particularly limited.
- a granulated powder in which the powder has high fluidity and has a uniform compact density.
- the granulation method is not particularly limited, and spray granulation, fluidized bed granulation, rolling granulation, stirring granulation and the like can be used.
- spray granulation which is easy to operate and can be processed in large quantities.
- the physical properties of the powder are not particularly limited.
- the BET specific surface area of the powder is preferably 2 to 20 m 2 / g, more preferably 4 to 10 m 2 / g.
- the BET specific surface area is lower than 2 m 2 / g, densification of the sintered body becomes difficult to proceed, and as a result, the density becomes low and the strength of the sintered body tends to decrease.
- the BET specific surface area is higher than 20 m 2 / g, the powder tends to aggregate and it becomes difficult to form.
- the sinterability is good, grain growth proceeds during sintering, and there is a tendency to form coarse particles and reduce the strength of the sintered body.
- the average secondary particle diameter of the powder is preferably 1.5 ⁇ m or less, more preferably 0.1 to 1.5 ⁇ m in consideration of the moldability and sinterability of the powder.
- the secondary particle size here is the particle size of particles in a state where primary particles are aggregated as observed by TEM or the like. The secondary particle size can be measured with a wet particle size distribution meter after the powder is suspended.
- the bulk density of the powder is preferably 0.5 to 1.8 g / cm 3 .
- a powder having a bulk density in the above range is excellent in handleability and has a high molding yield.
- the density of the obtained zinc oxide sintered body can be increased.
- the angle of repose of the powder is preferably 45 ° or less. If the value is higher than this, the fluidity of the powder tends to be impaired, and it tends to be difficult to uniformly fill the powder.
- the angle of repose of the powder is more preferably 35 ° or less from the viewpoint of further improving the fluidity of the powder.
- the method for producing the molded body is not particularly limited, and for example, a die press molding method, a cold isostatic press molding method, or a cast molding method can be used.
- the powder or slurry used as a raw material may contain an organic or inorganic binder.
- the said method can be used for preparation of the molded object of various shapes, such as flat plate shape and cylindrical shape.
- the obtained molded body is sintered at a high temperature to obtain a sintered body.
- the manufacturing apparatus used for manufacturing the sintered body is not particularly limited, and for example, an electric furnace, a gas furnace, a hot press, or the like can be used. Among these, an electric furnace is preferable because of productivity, temperature distribution in the furnace, and relatively inexpensive equipment.
- a dense sintered body having a relative density of 95% or more can be obtained by mixing 10 ppm or more of zirconium with zinc oxide.
- the reason is as follows. That is, zirconium inhibits the firing of zinc oxide during firing. As a result, the shrinkage rate at the time of sintering decreases, so that the particle size of the sintered body particles becomes smaller than when zirconium is not included. In addition, the shrinkage difference due to the firing between the outside and the inside is reduced, and bubbles are hardly left inside the sintered body. Thereby, a high-density sintered body is obtained. Further, by adding zirconium, the interaction force between the grain boundaries can be increased, and the generation of cracks, chips, baldness and the like at the grain boundaries can be suppressed.
- the rate of temperature rise is preferably 10 to 400 ° C./hour.
- the firing temperature is preferably 900 ° C. to 1200 ° C.
- the firing temperature is preferably 950 ° C. to 1150 ° C.
- the temperature lowering rate is preferably 10 to 400 ° C./hour from the viewpoint of preventing cracking.
- the temperature at which the sintered body is taken out of the furnace is preferably around room temperature.
- the relative density is preferably 95% or more, more preferably 97% or more.
- the finer the particle size of the particles constituting the zinc oxide sintered body the higher the strength.
- the average particle size of the particles of the zinc oxide sintered body is preferably 1 to 15 ⁇ m, more preferably 1 to 10 ⁇ m.
- the hardness of the sintered body is preferably 120 HV10 or more, more preferably 150 HV10 or more in terms of Vickers hardness.
- Such a sintered body has high strength.
- the target In order to prevent cracking of the target during sputtering, the target needs to have a strength higher than the thermal stress generated in the target during sputtering. This thermal stress varies depending on the sputtering conditions and the sputtering apparatus, but is generally about 40 MPa. For this reason, in order to prevent the target from cracking during sputtering, the target needs to have a higher strength, that is, a bending strength.
- the bending strength of the target can be 40 MPa or more.
- substrate resulting from the abnormal discharge produced by the crack of the target in the case of sputtering can be suppressed. Thereby, it becomes possible to form a film stably, and a zinc oxide thin film can be manufactured with a high yield.
- zirconium generates carrier electrons and lowers the resistivity of the sintered body. For this reason, it has a resistivity of 10 5 ⁇ ⁇ cm or less by firing at a high temperature. Therefore, it can be suitably used as a target for DC sputtering. However, in order to stably perform DC sputtering, it is preferable to further reduce the resistivity of the zinc oxide sintered body 10.
- the zinc oxide molded body 10 is fired in a state in which an inert gas or nitrogen gas is introduced into the firing furnace to reduce the oxygen partial pressure of the firing atmosphere.
- the oxygen partial pressure in the firing atmosphere depends on the amount of the zinc oxide molded body to be fired.
- the gas flow rate to be introduced is defined as A (L / min)
- the charged amount of the molded body to be fired is defined as B (kg)
- the ratio is defined by the following equation as a gas flow rate parameter.
- Gas flow parameter B / A
- the gas flow rate parameter By setting the gas flow rate parameter to 2.0 or less, if the zirconium content in the zinc oxide sintered body 10 is 10 ppm or more, the resistivity of the sintered body is 10 even if the sintering temperature is 1100 ° C. or less. 5 ⁇ ⁇ cm or less.
- the zinc oxide sintered body 10 of the present embodiment can be used as a sputtering target. In that case, you may process the zinc oxide sintered compact 10 to a predetermined dimension.
- the processing method is not particularly limited, and for example, a surface grinding method, a rotary grinding method, a cylindrical grinding method, or the like can be used. Since the zinc oxide sintered body 10 of this embodiment contains a predetermined amount of zirconium, the grain size of the sintered body is small and the strength of the grain boundary is improved. At the same time, the sintered body becomes dense and the hardness of the sintered body is improved. For this reason, cracking and chipping hardly occur when the sintered body is ground to a predetermined target size. As a result, the yield when manufacturing the sputtering target is improved.
- the zinc oxide sintered body 10 of the present embodiment and the zinc oxide sintered body 20 described later may be fixed (bonded) to a flat plate or cylindrical support with an adhesive such as a solder material, if necessary.
- the material of the support is not particularly limited as long as it has a high thermal conductivity and can support the sintered body.
- the material of the support is preferably a metal such as Cu (copper), SUS (stainless steel) or Ti (titanium) because of its high thermal conductivity and high strength, and Ti ( Titanium) is more preferable.
- FIG. 2 is a perspective view showing another embodiment of the zinc oxide sintered body of the present invention.
- the zinc oxide sintered body 20 may have a flat plate shape as shown in FIG.
- As the shape of the support a cylindrical support is used when the zinc oxide sintered body has a cylindrical shape as shown in FIG.
- a flat plate-shaped support is used.
- the adhesive (bonding material) for bonding the sintered body and the support is not particularly limited as long as it has sufficient adhesive strength to support it.
- a conductive resin e.g., a conductive resin, a tin-based solder material, or an indium-based solder. Material can be used.
- indium solder is preferable because it has high conductivity and thermal conductivity, is soft and easily deforms. The reason is that the heat of the target surface can be efficiently cooled, and the stress between the sintered body and the support generated by thermal expansion can be absorbed to prevent the sintered body from cracking.
- the sputtering target expands by heat generated by sputtering regardless of the shape. For this reason, in the case of a flat target as shown in FIG. 2, the distance between the target and the support does not change. On the other hand, in the case of a cylindrical target as shown in FIG. 1, the distance between the target and the support increases due to thermal expansion of the target. For this reason, a force perpendicular to the interface between the sintered body and the adhesive is applied, and in a target having a low adhesion rate, peeling is increased from the bubble portion and heat conduction is reduced. Therefore, a cylindrical target having a low adhesion rate tends to generate cracks more easily than a flat target.
- the adhesion rate is preferably 90% or more from the viewpoint of preventing cracks.
- the adhesion rate is preferably 95% or more and more preferably 97% or more from the same viewpoint.
- the zinc oxide sintered bodies 10 and 20 have higher strength than a normal high purity zinc oxide sputtering target. For this reason, when bonding the cylindrical sintered compact 10, it can fully endure the stress between the sintered compact 10 and a support which arises by thermal expansion. Therefore, it becomes possible to manufacture a sputtering target with a high yield.
- the sputtering target of this embodiment (sometimes referred to as “target”) is composed of the above-described zinc oxide sintered body, and the zinc oxide sintered body can be used for sputtering as it is or after being processed. Therefore, the sputtering target of this embodiment may have a cylindrical shape or a flat plate shape as shown in FIG. 1 or FIG. Moreover, the sputtering target of this embodiment has the same composition as the above-mentioned zinc oxide sintered body.
- the sputtering target of the present embodiment is made of the above-described zinc oxide sintered body, the density is high and the grain boundary strength is also high. Therefore, cracking of the target is difficult to occur during sputtering, and the generation of particles is small. Moreover, generation
- the zinc oxide thin film of this embodiment (sometimes referred to as “thin film”) is obtained using the above-described sputtering target. Therefore, the zinc oxide thin film has the same composition as the above-described sputtering target (zinc oxide sintered body). That is, by forming a film using a sputtering target made of a zinc oxide sintered body containing zinc oxide as a main component and having a zirconium content of 10 to 1000 ppm, the zirconium content is almost equal to that of the sputtering target. A certain zinc oxide thin film is obtained.
- the zinc oxide thin film of this embodiment has a zirconium content of 10 to 2000 ppm and a high resistivity of 10 ⁇ ⁇ cm or more.
- the method for producing the zinc oxide thin film according to the present embodiment is not particularly limited, and examples thereof include a chemical vapor deposition method using CVD, a coating method by suspending or dissolving in a solvent, and a film forming method using a sputtering method. It is done. Of these, sputtering is preferred.
- a sputtering target used for sputtering a zinc oxide sintered body produced so as to contain a predetermined concentration of zirconium can be used.
- a zinc oxide thin film can also be formed by sputtering using a zinc oxide target with chip-on of zirconium.
- a zinc oxide thin film having a zirconium content of 10 to 1000 ppm can also be obtained by sputtering the above-described sputtering target.
- the zinc oxide thin film of this embodiment has a high resistivity by containing 10 ppm or more of zirconium. And it shows a high resistivity up to about 1000 ppm of zirconium concentration. On the other hand, when it exceeds about 1000 ppm, the resistivity rapidly decreases. Nevertheless, the high resistivity of 10 ⁇ ⁇ cm or more required when used as a high resistance film layer of a solar cell such as CIGS is maintained until it exceeds 2000 ppm. Therefore, the zinc oxide thin film of this embodiment needs to suppress a zirconium content to 2000 ppm or less. As shown in FIG. 5, in order to obtain a zinc oxide thin film having a sufficiently high resistance value, the upper limit is 1000 ppm, which is a region where the resistance value starts to decrease, and the zirconium content is 10 to 1000 ppm.
- the reason why the resistance value increases at about 10 ppm or more and starts to decrease at about 1000 ppm or more is not necessarily clear.
- the position of zirconium changes with the zirconium content, and it is estimated that the conductivity of the thin film is inhibited or improved, and the threshold of the change is estimated to be around 10 ppm and 1000 ppm. .
- the zirconium content is close to 1000 ppm, the change in resistivity of the thin film due to sputtering conditions is not so large.
- the zirconium content is 1200 ppm or more, there is a risk that the resistivity of the thin film is lowered by sputtering with only argon gas. For this reason, by introducing a small amount of oxygen gas at the time of sputtering, the generation of carriers can be suppressed and the resistance value of the thin film can be improved. Even when the zirconium content is 10 to 1000 ppm, oxygen gas may be introduced during sputtering.
- the amount of oxygen gas introduced is 0.2 vol% or more with respect to the amount of argon gas introduced, the above-described effects can be obtained. From the viewpoint of obtaining a thin film having higher resistance, the amount of oxygen gas introduced is preferably 0.4 vol% or more.
- the zinc oxide thin film of this embodiment has a high transmittance because the generation of carriers due to zirconium is sufficiently suppressed.
- the film thickness is 100 nm, it is possible to achieve a very high transmittance of 75% or more over a wide range of 400 to 1200 nm as well as a wavelength of 500 nm. For this reason, it can use suitably for the buffer layer etc. of a thin film type solar cell.
- the present invention is not limited to the above embodiment.
- the shape of the zinc oxide sintered body is not limited to that shown in FIGS. 1 and 2 and may be other shapes.
- BET specific surface area of powder The BET specific surface area of the powder was measured by the BET one-point method using MONOSORB (trade name, manufactured by QUANTACHROME, USA).
- MONOSORB trade name, manufactured by QUANTACHROME, USA.
- Powder bulk density The bulk density of the powder was measured based on the measurement of light bulk density in JIS R9301-2-3.
- the powder was suspended in water and subjected to ultrasonic dispersion for 2 minutes, and then the particle size distribution was measured using COULTER LS (trade name, manufactured by Beckman Coulter, Inc.). The median diameter was determined from the measurement results, and this was taken as the average secondary particle diameter.
- the angle of repose which is a parameter of the fluidity of the powder, was measured by using a device powder tester PT-N type manufactured by Hosokawa Micron.
- the Vickers hardness of the sintered body was measured at HV10 according to JIS R-1610.
- the bending strength of the sintered body was measured according to the standard of JIS R-1601.
- the density of the sintered body was measured by the Archimedes method. The relative density was determined from the measured density and the true density of the sintered body.
- the true density of the sintered body was 5.68 g / cm 3 , which is the density of zinc oxide.
- zirconium content in powder, sintered body and thin film The content of zirconium was measured by ICP analysis after dissolving each object.
- Example 1 Commercially available zinc oxide powder and zirconium oxide powder satisfying JIS type 1 standard were dry-mixed in a 10 L nylon pot for 16 hours by a rotating ball mill using a resin ball with a core of 15 mm in diameter. As a result, 2000 g of mixed powder having a zirconium content of 45 ppm was obtained. Next, the particle size of the mixed powder was adjusted using a 500 ⁇ m sieve, and finally about 1990 g of the mixed powder was obtained. Table 1 shows the physical properties of the powder after particle size adjustment.
- the molded body was heated to 500 ° C. at 50 ° C./h, and heated from 500 ° C. to 1100 ° C. at a heating rate of 20 ° C./h. After maintaining at a firing temperature of 1100 ° C. for 3 hours, it was cooled at a temperature lowering rate of 100 ° C./h. Firing was performed in an air atmosphere. Table 2 shows the firing conditions. Table 2 shows the success rate until firing and target production. The “succes rate” here refers to the ratio of the sintered body and the target that can be produced without cracking or chipping.
- Table 3 shows the relative density, bending strength, Vickers hardness, average particle diameter, resistivity, and zirconium content of the obtained sintered body.
- the values shown in Table 3 are average values of the three sintered bodies. All three molded bodies could be fired without cracking (success rate: 100%).
- the three sintered bodies were each processed into a disk shape having a diameter of 101.6 mm ⁇ and a thickness of 5 mm.
- This disk-shaped sintered body was bonded onto a copper backing plate to produce three zinc oxide targets (sputtering targets).
- In (indium) solder was used as a bonding material.
- Discharge method RF sputtering Film forming device: ULVAC CS2000 (trade name, magnetron sputtering device) Deposition pressure: 0.4 Pa Addition gas: Argon gas + oxygen gas Oxygen concentration: 0.4 vol% Distance between target and substrate: 90mm Discharge power: 450W Zinc oxide thin film thickness: about 100nm Substrate temperature: room temperature (about 25 ° C)
- the resistivity of the zinc oxide thin film obtained by sputtering showed a high value of 5.5 ⁇ 10 6 ⁇ ⁇ cm.
- the transmittance of the zinc oxide thin film was 86% at a film thickness of 100 nm and a wavelength of transmitted light of 500 nm.
- the zirconium content in the zinc oxide thin film is as shown in Table 4, and 40 ppm of zirconium was contained. Thus, it was confirmed that a zinc oxide-based high resistance thin film can be produced using a high-strength zinc oxide-based sputtering target.
- Example 2 A molded body was produced in the same manner as in Example 1 except that the mixing ratio of the zinc oxide powder and the zirconium oxide powder was changed so that the zirconium content was 20 ppm, 45 ppm and 1000 ppm. Three types of molded products (numbers 2, 3, and 4 in Table 1) having different zirconium contents were prepared. Table 1 shows the physical properties of the mixed powder after the particle size adjustment.
- Example 2 Thereafter, bonding was performed in the same manner as in Example 1 to obtain a zinc oxide target. As shown in Table 2, the success rate until target fabrication was 100%.
- Discharge method DC sputtering method
- Film forming device ULVAC CS2000 (trade name, magnetron sputtering device)
- Deposition pressure 0.4 Pa
- Additive gas Argon gas + oxygen gas
- Oxygen concentration 0.8%
- Distance between target and substrate 90mm
- Discharge power 300W
- Zinc oxide thin film thickness about 100 nm
- Substrate temperature room temperature (about 25 ° C)
- the physical properties of the zinc oxide thin film obtained by sputtering were as shown in Table 4. As shown in Table 4, a zinc oxide thin film having a high resistance value and a high transmittance could be obtained. From these results, it was confirmed that a sputtering target containing 18 to 990 ppm of zirconium having both high strength and low resistivity can be produced with high yield. That is, it was confirmed that a zinc oxide-based thin film having a high resistivity can be produced by a direct current sputtering method.
- Example 3 15 kg of commercially available zinc oxide powder satisfying JIS type 1 standard and pure water were mixed to form a slurry. Dispersion treatment was performed with a wet bead mill apparatus in a state where the concentration of the zinc oxide powder in the slurry was 50 wt%.
- the container of the apparatus was made of zirconia, and the beads used were also 0.3 mm zirconia beads.
- the slurry treated with the wet bead mill apparatus was collected and spray granulated. Since the addition amount of zirconium can be increased by lengthening the pulverization time in the wet bead mill apparatus, three types of powders having different zirconium contents were prepared by changing the pulverization time.
- the zirconium content in the prepared powder was 15 ppm, 33 ppm and 120 ppm, respectively.
- Each physical property of each powder is as shown in Table 1, and a powder with high fluidity was obtained.
- Example 2 Thereafter, using the obtained zinc oxide sintered body, bonding was performed in the same manner as in Example 1 to obtain a zinc oxide target. As shown in Table 2, the success rate until firing was 100%.
- Example 2 Using the obtained zinc oxide target, a film was formed under the same conditions as in Example 2 to form a zinc oxide thin film and evaluated.
- the resistivity and transmittance of the zinc oxide thin film obtained by sputtering are as shown in Table 4, and a high resistance zinc oxide thin film having high transmittance could be produced.
- Example 4 A powder identical to the powder prepared in No. 6 in Example 3 was prepared. This powder was filled in a cylindrical rubber mold and CIP-molded at 2000 kgf / cm 2 (196.133 MPa). Thereafter, CIP treatment was performed at 3000 kgf / cm 2 (294.2 MPa) for higher density. In this way, two cylindrical shaped bodies were produced. These molded bodies were not cracked.
- the two molded bodies could be fired without cracking.
- a cylindrical sintered body having a high relative density, a high bending strength, a high hardness, and a low resistivity could be produced with a high yield.
- the sintered body is processed into a cylindrical shape having an inner diameter of 77.5 mm ⁇ , an outer diameter of 91.5 mm ⁇ , and a thickness of 350 mm, and bonded to a titanium backing tube to form a cylindrical zinc oxide target free from cracks and chips.
- Got. In solder was used as the bonding material.
- Discharge method DC sputtering method
- Film forming apparatus cylindrical cathode type Film forming pressure: 0.25 Pa
- Addition gas Argon gas + oxygen gas
- Oxygen concentration 10 vol%
- Distance between target and substrate 90mm
- Discharge power 500W Zinc oxide thin film thickness: about 100 nm
- Substrate temperature room temperature
- the resistance of the zinc oxide thin film obtained by sputtering was as high as 5.0 ⁇ 10 5 ⁇ ⁇ cm.
- the transmittance was 86% at a film thickness of 100 nm and a wavelength of 500 nm. From these results, it was confirmed that a cylindrical sputtering target used for producing a high-resistance zinc oxide thin film, which has been difficult to produce so far, can be produced.
- Example 5 A powder containing zirconium was prepared in the same manner as in Example 3, and a compact was produced in the same manner as in Example 3. In the same manner as in Example 3, three molded articles (numbers 9, 10, and 11 in Table 1) each having three types of compositions were produced.
- Example 2 Thereafter, using the obtained zinc oxide sintered body, bonding was performed in the same manner as in Example 1 to obtain a zinc oxide target. As shown in Table 2, the success rate until firing was 100%.
- Example 2 Using the obtained zinc oxide target, a film was formed under the same conditions as in Example 2 to form a zinc oxide thin film, and the thin film was evaluated.
- the evaluation results are as shown in Table 4.
- the resistivity of the zinc oxide thin film obtained by sputtering was as high as 3.0 ⁇ 10 5 ⁇ ⁇ cm.
- the transmittance was as high as 86% at a film thickness of 100 nm and a wavelength of 500 nm.
- the zirconium content was 65 ppm.
- Example 1 A powder was prepared in the same manner as in Example 1 except that zirconium was not added to a commercially available zinc oxide powder satisfying the JIS type 1 standard.
- the physical properties of the powder were as shown in Table 1. 600 g of the prepared powder was put into a mold having a diameter of 150 mm ⁇ and subjected to pressure molding at 300 kgf / cm 2 (29.42 MPa) to produce three compacts each having numbers 12 to 15 in Table 1. . After pressure molding, CIP treatment was performed at 3000 kgf / cm 2 (294.2 MPa) to increase the density of the molded body.
- the obtained molded body was heated to 500 ° C. at 50 ° C./h, from 500 ° C. to the firing temperature at a rate of 20 ° C./h, and the firing temperature was set to 950 ° C., 1000 ° C., 1100 ° C., or 1200 ° C. Hold for 3 hours. Then, it cooled at the temperature fall rate of 100 degrees C / h, and obtained the sintered compact. Firing was performed in air. Table 2 shows the firing conditions. When three compacts were fired at each firing temperature to produce a zinc oxide sintered body, as shown in Table 2, “Success rate until firing”, the samples 14 and 15 were cracked during firing. There was something. This is considered to be because the strength is lowered as can be seen from the bending strength shown in Table 3.
- Example 2 Using the obtained zinc oxide sintered body, bonding was performed in the same manner as in Example 1 to obtain a zinc oxide target. At this time, cracking occurred during processing, and as shown in Table 2, the success rate until the zinc oxide target was produced decreased.
- the resistivity of the zinc oxide thin film obtained by sputtering was a value between 1.0 ⁇ 10 5 and 1.2 ⁇ 10 6 ⁇ ⁇ cm.
- the transmittance was 86% to 87% at a film thickness of 100 nm and a wavelength of 500 nm.
- Comparative Example 2 Powders were produced in the same manner as in Comparative Example 1, and were molded to produce 3 molded bodies.
- the molded body was heated to 500 ° C. at a rate of 50 ° C./h and from 500 ° C. to 1170 ° C. at a rate of 10 ° C./h, and held at a firing temperature of 1170 ° C. for 3 hours. Then, it cooled at the temperature-fall rate of 100 degrees C / h, and obtained the zinc oxide sintered compact.
- Example 2 Thereafter, using the obtained zinc oxide sintered body, bonding was performed in the same manner as in Example 1 to obtain a zinc oxide target. At that time, cracks were generated during processing, and as shown in Table 2, the success rate until the target production was low.
- Example 2 Using the obtained zinc oxide target, a film was formed under the same conditions as in Example 2 to form a zinc oxide thin film for evaluation.
- the evaluation results are as shown in Table 4.
- the resistivity of the zinc oxide thin film obtained by sputtering was 1.2 ⁇ 10 5 ⁇ ⁇ cm.
- the transmittance was 86% at a film thickness of 100 nm and a wavelength of 500 nm.
- Comparative Example 3 A powder was prepared in the same manner as in Comparative Example 1 except that the amount of the prepared powder was 15 kg.
- the powder was filled in a rubber mold of cylindrical shape, after the CIP molded at 2000kgf / cm 2 (196.133MPa), CIP treatment at 3000kgf / cm 2 (294.2MPa) to densify To produce two cylindrical shaped bodies.
- the obtained sintered body was processed into a cylindrical shape having an inner diameter of 77.5 mm ⁇ , an outer diameter of 91.5 mm ⁇ , and a thickness of 350 mm, and an attempt was made to perform bonding. I could't.
- Example 4 As shown in Table 1, molding was carried out in the same manner as in Example 1 except that the mixing ratio of the zinc oxide powder and the zirconium oxide powder was changed so that the zirconium content in the mixed powder was 5 ppm, 1100 ppm, 3000 ppm, or 8000 ppm. The body was made. Three each of the four types of molded bodies indicated by numbers 18 to 21 in Table 1 were produced. Each powder physical property is as shown in Table 1.
- the success rate until firing is as shown in Table 2.
- the physical properties of the sintered body are as shown in Table 3. When the content of zirconium was small, the strength of the zinc oxide sintered body was low, and cracking occurred during firing.
- Example 2 Thereafter, using the obtained zinc oxide sintered body, bonding was performed in the same manner as in Example 1 to obtain a zinc oxide target. Using the obtained zinc oxide target, a film was formed under the same conditions as in Example 2 to form a zinc oxide thin film, and the thin film was evaluated.
- the physical properties of the zinc oxide thin film obtained by sputtering were as shown in Table 4. When the zirconium content is high, the resistivity is low, and a zinc oxide film having a high resistance value cannot be produced.
- FIG. 3 shows the relationship between the zirconium content of the zinc oxide sintered bodies of Example 2, Example 3, Example 4, and Comparative Example 4 fired in a nitrogen gas atmosphere and the bending strength of the sintered bodies. It is a graph which shows. From this graph, it can be seen that the strength of the sintered body increases as the zirconium content increases. In addition, when the zirconium content is low (less than about 10 ppm), the strength rapidly decreases. As can be seen from the graph, the strength of the sintered body increases from about 10 ppm. That is, by containing 10 ppm or more of zirconium, a zinc oxide sintered body with improved strength can be obtained.
- FIG. 4 shows the zirconium content and the resistivity of the zinc oxide thin film in the zinc oxide sintered bodies of Example 2, Example 3, Comparative Example 2, and Comparative Example 4 formed by direct current sputtering. It is a graph which shows the relationship. As is apparent from this graph, when the zirconium content exceeds about 1000 ppm, the resistivity of the thin film is greatly reduced. Therefore, the resistivity of the zinc oxide thin film can be maintained high by setting the zirconium content to 1000 ppm or less.
- FIG. 5 shows the relationship between the zirconium content in the zinc oxide thin films of Examples 2, 3 and 2, and 4 and the resistivity of the zinc oxide thin film formed by DC sputtering. It is a graph which shows. As is apparent from this graph, when the zirconium content exceeds about 1000 ppm, the resistivity of the zinc oxide thin film is greatly reduced. A high resistivity of 10 ⁇ ⁇ cm or more is exhibited up to at least 2000 ppm, but the resistivity rapidly decreases when the resistivity is exceeded.
- FIG. 6 is a graph showing the relationship between the resistivity and the bending strength of the sintered bodies of Example 2 and Comparative Example 1.
- Example 2 contains zirconium, and Comparative Example 1 does not contain zirconium.
- Comparative Example 1 when no zirconium is contained, the bending strength is lowered when the resistivity of the sintered body is lowered. That is, the bending strength cannot be improved while reducing the resistance of the sintered body.
- Example 2 by containing an appropriate amount of zirconium, both a low resistance of 10 5 ⁇ ⁇ cm or less and a high bending strength of 40 MPa or more can be achieved. That is, by containing an appropriate amount of zirconium, a sputtering target having a higher bending strength and a lower resistivity than a conventional thin film sputtering target having a high resistivity can be produced.
- FIG. 7 is a graph showing the relationship between the resistance of the sintered bodies of Example 2 and Comparative Example 1 and the average particle diameter of the sintered body particles.
- Comparative Example 1 in the conventional sintered body, the average particle diameter of the particles of the sintered body increases as the resistance value of the sintered body decreases.
- Example 2 by containing an appropriate amount of zirconium, it is possible to suppress the particles of the sintered body from becoming large even if the resistance value of the sintered body is reduced.
- These relationships are also related to the relationship of FIG. 6, and the smaller the particles of the sintered body, the better the bending strength of the sintered body. Therefore, by containing zirconium, growth of the sintered body particles can be suppressed, and the resistivity of the sintered body can be reduced by imparting appropriate conductivity to the zirconium.
- FIG. 8 is a graph showing the transmittance of the zinc oxide thin film of No. 6 in Example 3.
- the horizontal axis shows the wavelength of light, and the vertical axis shows the transmittance at that time. It can be seen that high transmittance is exhibited in a wide wavelength range.
- the present invention it becomes possible to prevent cracking and chipping during firing, processing of a sintered body, and bonding at the time of target production, and the productivity of the sputtering target can be improved. Further, it becomes possible to stably produce a zinc oxide thin film that sufficiently suppresses cracking of the target during sputtering and has both high resistivity and high transmittance. Moreover, the zinc oxide thin film which has high resistivity used suitably for the insulating film for semiconductors and the buffer layer of a solar cell is provided.
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Abstract
Description
(2)抵抗率が105Ω・cm以下である、(1)に記載の酸化亜鉛焼結体。
(3)円筒形状である(1)または(2)に記載の酸化亜鉛焼結体。
(4)上述の(1)~(3)いずれか一つに記載の酸化亜鉛焼結体からなるスパッタリングターゲット。
(5)ジルコニウムの含有量が10~2000ppmであり、抵抗率が10Ω・cm以上である酸化亜鉛薄膜。
(6)ジルコニウムの含有量が10~1000ppmである(5)に記載の酸化亜鉛薄膜。
(7)膜厚100nmのとき、波長500nmの透過率が75%以上である、(5)または(6)に記載の酸化亜鉛薄膜。
図1は、本実施形態の酸化亜鉛焼結体の斜視図である。本実施形態の酸化亜鉛焼結体10は、主成分として酸化亜鉛を含有する焼結体であり、酸化亜鉛の他にジルコニウムを10~1000ppm含有する。酸化亜鉛焼結体(場合により「焼結体」という。)10は、ジルコニウムを10ppm以上含有することにより、ジルコニウムを酸化亜鉛焼結体10の粒内や粒界に均一に存在させることができる。これによって、酸化亜鉛焼結体10の強度を飛躍的に向上させることができる。ジルコニウムの含有量が10ppm未満となると、ジルコニウムを均一に酸化亜鉛焼結体中に分散させることが難しくなり、酸化亜鉛焼結体10の強度を向上することが困難になる。
原料である酸化亜鉛粉末は、酸化亜鉛薄膜の抵抗率の低下を抑制するために、不純物を極力含まないものを用いることが好ましい。添加するジルコニウム源としては、金属ジルコニウム、塩化ジルコニウムなどの各種ジルコニウム塩、ジルコニウム錯体、酸化ジルコニウム(ジルコニア)、部分安定化ジルコニア、安定化ジルコニア、及びアルミナ添加ジルコニアなど、ジルコニウムを含むものならば特に限定されない。
成形体の製造方法は特に限定されず、例えば、金型プレス成形法、冷間静水圧プレス成形法または鋳込み成形法を用いることができる。原料として用いる粉末やスラリーは、有機又は無機バインダーを含んでいてもよい。上記方法は、平板形状及び円筒形状等の様々な形状の成形体の作製に用いることができる。
得られた成形体は高温で焼結することによって焼結体とする。焼結体の製造に用いられる製造装置は特に限定されず、例えば、電気炉、ガス炉、ホットプレスなどが使用できる。これらの中でも生産性、炉内の温度分布、装置が比較的安価であることから電気炉が好ましい。
ガス流量パラメータ=B/A
接着率=(接着すべき面積-ボイド面積)/接着すべき面積×100
本実施形態のスパッタリングターゲット(場合により「ターゲット」という。)は、上述の酸化亜鉛焼結体からなり、酸化亜鉛焼結体をそのまま又は加工してスパッタリングに用いることができる。したがって、本実施形態のスパッタリングターゲットは、図1又は図2に示すような円筒形状又は平板形状を有していてもよい。また、本実施形態のスパッタリングターゲットは、上述の酸化亜鉛焼結体と同一の組成を有する。
本実施形態の酸化亜鉛薄膜(場合により「薄膜」という。)は、上述のスパッタリングターゲットを用いて得られる。したがって、酸化亜鉛薄膜は、上述のスパッタリングターゲット(酸化亜鉛焼結体)と同じ組成となる。つまり、主成分として酸化亜鉛を含有し、ジルコニウムの含有量が10~1000ppmである酸化亜鉛焼結体からなるスパッタリングターゲットを用いて成膜することによって、ジルコニウムの含有量がスパッタリングターゲットとほぼ同等である酸化亜鉛薄膜が得られる。
粉末のBET比表面積は、MONOSORB(商品名、米国のQUANTACHROME社製)を用いて、BET式1点法により測定した。
(粉末のかさ密度)
粉末のかさ密度は、JIS R9301-2-3中の軽装かさ密度の測定に準拠して測定した。
粉末を水に懸濁し、超音波分散を2分間行なった後に、COULTER LS(商品名、ベックマン・コールター株式会社製)を用いて粒度分布を測定した。測定結果からメディアン径を求め、これを平均二次粒径とした。
粉末の流動性のパラメータである安息角はホソカワミクロン製の装置パウダーテスターPT-N型を用いることで測定を行なった。
焼結体を研磨後、酢酸にてエッチングを行い、そのエッチング面をSEM(走査型電子顕微鏡)を用いて倍率100~10000倍にて撮影し、粒子の平均粒径をコード法を用いて測定した。
焼結体のビッカース硬度は、JIS R-1610に従ってHV10にて測定した。
(焼結体の抗折強度)
焼結体の抗折強度は、JIS R-1601の基準に従って測定した。
(焼結体の密度)
焼結体の密度はアルキメデス法にて測定を行った。測定した密度と焼結体の真密度とから相対密度を求めた。焼結体の真密度は、酸化亜鉛の密度である5.68g/cm3とした。
ジルコニウムの含有量は各対象物を溶解し、ICP分析によって測定した。
測定装置ハイレスタMCP-HT450(商品名、三菱化学株式会社製)を用い、10~1000Vの電圧を1分間印加したときの電流値を検出し、表面抵抗を求めた。ハイレスタにて測定できないサンプルについては、ローレスタHP MCP-T410(商品名、三菱化学株式会社)を用い、1mA~100mAの定電流を印加して4探針法にて測定した。
(薄膜の透過率)
基板と薄膜との一体物の光透過率を、分光光度計U-4100(商品名、(株)日立製作所製)を用いて波長240nmから2600nmの範囲で測定した。
JIS 1種規格を満足する市販の酸化亜鉛粉末と酸化ジルコニウム粉末とを、10Lのナイロン製ポット中において、直径15mmの鉄心入り樹脂製ボールを用いて回転ボールミルにより16時間乾式混合した。これによって、ジルコニウムの含有量が45ppmである2000gの混合粉末を得た。次いで、500μmの篩を用いて、この混合粉末の粒度の調整を行い、最終的に約1990gの混合粉末を得た。粒度調整後の粉末の物性を表1に示す。
成膜装置:ULVAC CS2000(商品名、マグネトロンスパッタ装置)
成膜圧力:0.4Pa
添加ガス:アルゴンガス+酸素ガス
酸素濃度:0.4vol%
ターゲットと基板との間の距離:90mm
放電パワー:450W
酸化亜鉛薄膜の膜厚:約100nm
基板温度:室温(約25℃)
酸化亜鉛粉末と酸化ジルコニウム粉末の混合比を変えて、ジルコニウムの含有量を20ppm、45ppm及び1000ppmとしたこと以外は、実施例1と同様にして成形体を作製した。ジルコニウムの含有量が異なる3種類の成形体(表1における番号2、3、4)を、それぞれ3枚ずつ作製した。粒度調整後の混合粉末の物性を表1に示す。
放電方式:直流スパッタリング法
成膜装置:ULVAC CS2000(商品名、マグネトロンスパッタ装置)
成膜圧力:0.4Pa
添加ガス:アルゴンガス+酸素ガス
酸素濃度:0.8%
ターゲットと基板の間の距離:90mm
放電パワー:300W
酸化亜鉛薄膜の厚み:約100nm
基板温度:室温(約25℃)
JIS 1種規格を満足する市販の酸化亜鉛粉末15kgと純水とを混合してスラリー化した。スラリー中の酸化亜鉛粉末の濃度を50wt%にした状態で湿式ビーズミル装置にて分散処理を行った。装置の容器はジルコニア製であり、使用したビーズも0.3mmジルコニアビーズを使用した。
実施例3における番号6で調製した粉末と同一の粉末を調製した。この粉末を円筒形状のゴム型に充填し、2000kgf/cm2(196.133MPa)でCIP成形を行った。その後、高密度化のために3000kgf/cm2(294.2MPa)でCIP処理を行った。このようにして、円筒形状の成形体を2本作製した。これらの成形体に、割れは生じていなかった。
成膜装置:円筒カソード式
成膜圧力:0.25Pa
添加ガス:アルゴンガス+酸素ガス
酸素濃度:10vol%
ターゲットと基板との間の距離:90mm
放電パワー:500W
酸化亜鉛薄膜の厚み:約100nm
基板温度:室温
実施例3と同様にしてジルコニウムを含有する粉末を調製し、実施例3と同様にして成形体を作製した。実施例3と同様に、3種類の組成を有する成形体(表1における番号9、10、11)をそれぞれ3枚ずつ作製した。
JIS 1種規格を満足する市販の酸化亜鉛粉末にジルコニウムを添加しなかったこと以外は実施例1と同様の方法で粉末を調製した。粉末の物性は表1に示すとおりであった。調製した粉末のうち600gを直径150mmφの金型に投入し、300kgf/cm2(29.42MPa)にて加圧成形を行い、表1の番号12~15の成形体をそれぞれ3枚ずつ作製した。加圧成形後に、3000kgf/cm2(294.2MPa)にてCIP処理を行い、成形体の密度を高めた。
比較例1と同じ方法で粉末を作製し、成形を行って3枚の成形体を作製した。この成形体を、500℃まで50℃/h、500℃から1170℃まで10℃/hの昇温速度で昇温し、焼成温度1170℃で3時間保持した。その後、降温速度100℃/hで冷却して酸化亜鉛焼結体を得た。焼成条件を表2に示す。焼成は、窒素ガス雰囲気中、ガス流通パラメータ=1.0の条件で行った。
調製する粉末の量を15kgとしたこと以外は、比較例1と同様にして粉末を調製した。この粉末を、円筒形状のゴム型に充填し、2000kgf/cm2(196.133MPa)にてCIP成形を行った後、高密度化するためにさらに3000kgf/cm2(294.2MPa)でCIP処理を行って円筒形状の成形体を2本作製した。
表1に示すとおり、酸化亜鉛粉末と酸化ジルコニウム粉末との混合比を変えて、混合粉末におけるジルコニウムの含有量を5ppm、1100ppm、3000ppm、又は8000ppmとしたこと以外は実施例1と同様にして成形体を作製した。表1の番号18~21に示す4種類の成形体を、それぞれ3枚ずつ作製した。各粉末物性は表1に示すとおりである。
Claims (7)
- ジルコニウムの含有量が10~1000ppmである酸化亜鉛焼結体。
- 抵抗率が105Ω・cm以下である、請求項1に記載の酸化亜鉛焼結体。
- 円筒形状である請求項1又は2に記載の酸化亜鉛焼結体。
- 請求項1~3いずれか一項に記載の酸化亜鉛焼結体からなるスパッタリングターゲット。
- ジルコニウムの含有量が10~2000ppmであり、抵抗率が10Ω・cm以上である酸化亜鉛薄膜。
- ジルコニウムの含有量が10~1000ppmである、請求項5に記載の酸化亜鉛薄膜。
- 膜厚100nmのとき、波長500nmの透過率が75%以上である、請求項5又は6に記載の酸化亜鉛薄膜。
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EP11846891.7A EP2650271B1 (en) | 2010-12-06 | 2011-11-25 | Zinc oxide sintered compact, sputtering target, and zinc oxide thin film |
CN201180058840.8A CN103249693B (zh) | 2010-12-06 | 2011-11-25 | 氧化锌烧结体、溅射靶材以及氧化锌薄膜 |
US13/879,506 US9396830B2 (en) | 2010-12-06 | 2011-11-25 | Zinc oxide sintered compact, sputtering target, and zinc oxide thin film |
KR1020137011769A KR20140000688A (ko) | 2010-12-06 | 2011-11-25 | 산화아연 소결체, 스퍼터링 타겟 및 산화아연 박막 |
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WO2014077395A1 (ja) * | 2012-11-19 | 2014-05-22 | 東ソー株式会社 | 酸化物焼結体、それを用いたスパッタリングターゲット及び酸化物膜 |
WO2014148189A1 (ja) * | 2013-03-19 | 2014-09-25 | 住友金属鉱山株式会社 | 酸化亜鉛系焼結体とその製造方法およびスパッタリングターゲットと透明導電膜 |
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KR101935755B1 (ko) | 2010-12-20 | 2019-01-04 | 토소가부시키가이샤 | 금속 갈륨 침투 질화갈륨 성형물 및 이의 제조방법 |
JP5892016B2 (ja) * | 2012-09-19 | 2016-03-23 | 住友金属鉱山株式会社 | 酸化亜鉛スパッタリングターゲットとその製造方法 |
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KR20170113075A (ko) * | 2016-03-28 | 2017-10-12 | 제이엑스금속주식회사 | 원통형 스퍼터링 타겟 및 그 제조 방법 |
JP6144858B1 (ja) * | 2016-04-13 | 2017-06-07 | 株式会社コベルコ科研 | 酸化物焼結体およびスパッタリングターゲット、並びにそれらの製造方法 |
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JP2012136417A (ja) | 2012-07-19 |
EP2650271B1 (en) | 2020-09-09 |
CN103249693B (zh) | 2017-12-08 |
CN103249693A (zh) | 2013-08-14 |
TW201237193A (en) | 2012-09-16 |
US20130214215A1 (en) | 2013-08-22 |
TWI540214B (zh) | 2016-07-01 |
US9396830B2 (en) | 2016-07-19 |
EP2650271A4 (en) | 2014-07-23 |
EP2650271A1 (en) | 2013-10-16 |
JP5887819B2 (ja) | 2016-03-16 |
KR20140000688A (ko) | 2014-01-03 |
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