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WO2012005366A1 - Cible cylindrique en oxyde de zinc et procédé de fabrication de cette dernière - Google Patents

Cible cylindrique en oxyde de zinc et procédé de fabrication de cette dernière Download PDF

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Publication number
WO2012005366A1
WO2012005366A1 PCT/JP2011/065728 JP2011065728W WO2012005366A1 WO 2012005366 A1 WO2012005366 A1 WO 2012005366A1 JP 2011065728 W JP2011065728 W JP 2011065728W WO 2012005366 A1 WO2012005366 A1 WO 2012005366A1
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WIPO (PCT)
Prior art keywords
zinc oxide
target
cylindrical target
layer
oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2011/065728
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English (en)
Japanese (ja)
Inventor
徹 津吉
俊祐 八ツ波
高橋　小弥太
仁 益子
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Tosoh Corp
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Tosoh Corp
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Priority claimed from JP2010255847A external-priority patent/JP2012107277A/ja
Priority claimed from JP2010291314A external-priority patent/JP2012031502A/ja
Application filed by Tosoh Corp filed Critical Tosoh Corp
Publication of WO2012005366A1 publication Critical patent/WO2012005366A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth

Definitions

  • the present invention relates to a zinc oxide-based cylindrical target suitable for use in a zinc oxide-based cylindrical sputtering target and the like, and a method for producing the same.
  • ITO Indium Tin Oxide
  • indium which is a raw material of ITO, is a rare metal and has a resource problem. For this reason, low-cost alternative materials have been developed, and zinc oxide added with aluminum oxide or gallium oxide has been proposed (for example, see Patent Documents 1 and 2).
  • a cylindrical target is attracting attention as a method that enables high-output film formation with high target utilization efficiency.
  • a zinc oxide-based cylindrical target a zinc oxide-based powder is molded and then sintered to form a sintered body. After processing this sintered body into a predetermined shape, a cylindrical target substrate (hereinafter referred to as backing) There is a method of bonding to the tube.
  • the above-described method has a problem that the manufacturing process is long, particularly the process of bonding to the backing tube is complicated, and the manufacturing cost is high.
  • a plasma spraying method has been proposed in which a substance having a linear expansion coefficient between the backing tube and the target material is interposed between the backing tube and the target material to prevent cracks. According to this method, it has been realized that the thickness is increased to about several millimeters (for example, see Patent Document 3).
  • An object of the present invention is to provide a long-life zinc oxide-based cylindrical target and a manufacturing method thereof without impairing sputtering productivity.
  • the present inventors have made it necessary to sublimate zinc oxide powder in a high-temperature plasma jet in order to produce a zinc oxide-based cylindrical target having a high density and a large thickness. It has been found that it is necessary to make the zinc oxide-based powder stay as long as possible within the range that can be suppressed. As a result, the present inventors have found a zinc oxide cylindrical target having a high density and a large thickness and a method for producing the same, and have completed the present invention.
  • the present invention provides a zinc oxide-based cylinder having a base material such as a backing tube and a zinc oxide-based target layer comprising a structure in which zinc oxide-based powder is sprayed on the base material and melted and flattened splats are stacked.
  • the target is characterized in that the splat average thickness is 2 to 10 ⁇ m (2 ⁇ m or more and 10 ⁇ m or less), and the relative density of the zinc oxide-based target layer is 87% or more.
  • “zinc oxide-based” in this specification refers to zinc oxide which may contain aluminum oxide and / or gallium oxide.
  • Melting flattening means that molten particles that collide and weld to a base material such as a backing tube are flattened into a disk shape when the substrate collides.
  • the thickness of the zinc oxide-based target layer in the zinc oxide-based cylindrical target of the present invention is preferably 7 mm or more, and the average pore diameter of the zinc oxide-based target layer is preferably 600 nm or less.
  • the volume of pores having a pore diameter of 1 ⁇ m or more in the zinc oxide based target layer is preferably 0.015 mL / g or less.
  • the average crystal grain size of the zinc oxide-based target layer is preferably 1.0 ⁇ m or less.
  • the zinc oxide-based target layer contains at least one component of aluminum oxide and gallium oxide, and the total content of the components is preferably 0 to 5% by weight.
  • the dispersibility of aluminum oxide and / or gallium oxide in the zinc oxide-based target layer is preferably 0 to 30%. Moreover, it is preferable that the heat conductivity of a zinc oxide type
  • the zinc oxide-based cylindrical target of the present invention preferably has an underlayer between the backing tube and the zinc oxide-based target layer.
  • the thickness of the underlayer is preferably 0.3 to 2.0 mm.
  • the underlayer is preferably made of zinc, aluminum, a zinc alloy or an aluminum alloy.
  • a method for producing the above-described zinc oxide based cylindrical target wherein the thermal spray raw material powder having an average particle diameter of 20 to 70 ⁇ m is plasma sprayed onto a base material while being cooled by a target substrate cooling structure, and the oxidation
  • a method for producing a zinc oxide-based cylindrical target which includes a step of forming a zinc-based target layer.
  • the present invention it is preferable to perform plasma spraying while cooling the target with a substrate cooling structure so that the surface temperature of the target during spraying of the thermal spray raw material powder is 200 ° C. or lower.
  • the position where the air jetted from the substrate cooling pipe collides with the target is concentric with the distance from the center of the region where the molten particles collide with the target being 20 to 40 mm. It is preferable to arrange a cooling pipe.
  • the present invention preferably includes a step of cutting the zinc oxide-based target layer by a dry process. Moreover, in the process, it is preferable that the zinc oxide target layer is cut by a dry process while the tip of the diamond tool is cooled with a compressed gas and / or a liquefied gas. Further, it is preferable to dry-cut the zinc oxide target layer while cooling the tip of the diamond tool with powdered dry ice generated by spraying liquefied carbon dioxide gas.
  • FIG. 1 is a schematic diagram which shows an example of the process in which a splat accumulates.
  • FIG. 4 is a reflection electron micrograph of a zinc oxide-based cylindrical target produced in Comparative Example 2. It is a schematic diagram which shows an example of the method of forming a base layer in the zinc oxide type
  • group cylindrical target which is one Embodiment of this invention.
  • FIG. 1 is a schematic view showing an example of a process in which splats accumulate in an embodiment of the method for producing a zinc oxide-based cylindrical target of the present invention.
  • the zinc oxide-based cylindrical target 100 includes a backing tube 1 and a zinc oxide-based target layer 10.
  • the zinc oxide-based target layer 10 is a layer formed of a stacked structure of flat splats 2 of molten particles 3.
  • the splat 2 is a particle that is flattened and solidified by collision of heated particles on the backing tube 1 as a base material.
  • the raw material powder 5 supplied to the plasma jet 4 is melted to become molten particles 3, and the molten particles 3 collide with the backing tube 1, It solidifies in a flat state.
  • the molten particles 3 solidified in a flat state are deposited on the backing tube 1 as splats 2.
  • the average thickness of the splat 2 is 2 to 10 ⁇ m, preferably 4 to 8 ⁇ m.
  • the average thickness of the splat is less than 2 ⁇ m, it is not easy to increase the density or increase the wall thickness because fine submicron zinc oxide particles are sprayed in a state of being wound in the target. If the average thickness exceeds 10 ⁇ m, the melting tends to be insufficient, so that a dense target cannot be obtained.
  • the average thickness of the splat is cut so that a cut surface (hereinafter referred to as “cross section”) obtained by cutting along the thickness direction of the target is obtained, and then the cross section is polished with diamond abrasive grains. Thereafter, the polished cross section is observed with a reflection electron microscope, and the average thickness of the stacked splats can be calculated by the intercept method. Specifically, a straight line is drawn in the thickness direction at an arbitrary position on the cross section, and the average thickness of the splats can be calculated from the number of splat particles existing within the length of the straight line.
  • the number of splats 2 to be measured is preferably 200 or more.
  • the relative density of the zinc oxide-based target layer is 87% or more, and more preferably 89% or more.
  • the relative density of the target is less than 87%, dense splats cannot be deposited, and thus there are many open pores and microcracks.
  • zinc oxide sublimation-solidified powder is entrained in the target, and barnacle-like zinc oxide precipitates and grows on the target, greatly reducing the density and homogeneity of the target. To do.
  • the surface unevenness is severe, not only the target surface temperature rises during the film formation, but arcing occurs and the film characteristics are not stabilized, and the film formation speed is lowered and the sputtering productivity is deteriorated.
  • the relative density was calculated
  • the thickness of the zinc oxide based target layer is preferably 7 mm or more. When the thickness is less than 7 mm, the life of the target tends to be significantly reduced when produced at a high output.
  • the average pore diameter of the particles constituting the zinc oxide-based target layer is preferably 600 nm or less.
  • the relationship between the size and amount of the pore diameter is particularly important, and in order to obtain stable membrane characteristics, the pore volume with a pore diameter of 1 ⁇ m or more is preferably 0.015 mL / g or less. . More preferably, the pore volume with a pore diameter of 1 ⁇ m or more is 0.01 mL / g or less.
  • the particles constituting the target are preferably fine crystals having an average particle size of 1.0 ⁇ m or less, and more preferably 0.4 ⁇ m or more and 1.0 ⁇ m or less.
  • the average crystal grain size is an average crystal grain size calculated by the intercept method after cutting the target into a predetermined size, polishing the cross section and observing the microstructure with a reflection electron microscope.
  • the total content of aluminum oxide and / or gallium oxide in the zinc oxide-based target layer is preferably 0 to 5% by weight, and more preferably 0 to 3% by weight.
  • the transparency of the transparent conductive film is lowered, so that it cannot be used as a film.
  • the dispersibility of the added aluminum oxide and / or gallium oxide in the zinc oxide target is preferably 0% to 30%.
  • the dispersibility exceeds 30%, there are many aggregates of aluminum oxide and / or gallium oxide, and the dispersibility is poor, so that film characteristics such as film resistivity tend to deteriorate.
  • the melting of aluminum oxide and / or gallium oxide is insufficient, the dispersibility tends to deteriorate.
  • the dispersibility was obtained by cutting the target into a predetermined size, polishing the cross section, and then performing elemental mapping of Al or / and Ga on an area of 2.5 mm ⁇ 2.5 mm by the EPMA method. By statistically processing the analysis value of ⁇ 256 (points), the coefficient of variation can be calculated and used as an index of dispersibility.
  • the thermal conductivity of the zinc oxide based target layer is preferably 4.0 W / (m ⁇ K) or more.
  • the thickness is less than 4.0 W / (m ⁇ K)
  • the target surface temperature during sputtering increases with the increase in thickness, and target cracks and film characteristics become unstable.
  • the zinc oxide based cylindrical target may be provided with a base layer made of zinc, aluminum, a zinc alloy and an aluminum alloy having a thickness of 0.3 to 2.0 mm between the backing tube and the zinc oxide based target layer.
  • the material of the underlayer is made of zinc, aluminum, zinc alloy or aluminum alloy.
  • the properties required for the material of the underlayer include not only high adhesion to the backing tube and zinc oxide target, but also flexibility that can be plastically deformed to relieve the stress generated on the zinc oxide target during sputter discharge. It is required to be a material.
  • the surface temperature is about 200 to 300 ° C.
  • the zinc oxide target layer becomes thicker, it is applied to the zinc oxide target layer, the underlayer and the backing tube. Thermal stress is generated.
  • the effect of relaxing the thermal stress can be obtained by plastic deformation of the underlayer.
  • the thickness of the underlayer is preferably 0.3 to 2.0 mm.
  • the thickness of the underlayer is less than 0.3 mm, the adhesion and plastic deformation force of the underlayer are not sufficient, and the target may be peeled off or cracked during sputtering discharge.
  • the thickness of the underlayer exceeds 2.0 mm, the influence of the thermal expansion of the underlayer is increased, and the target may be cracked during sputtering discharge.
  • the zinc oxide based cylindrical target according to the present embodiment It is important for the zinc oxide based cylindrical target according to the present embodiment to provide a substrate cooling structure for cooling the target during spraying of the zinc oxide based powder.
  • a raw material powder is uniformly introduced into a plasma jet into a molten state, and the zinc oxide powder is rapidly welded in a state where the molten state is maintained. Is essential.
  • a method of forming a high temperature thermal plasma by increasing the output of the plasma can be considered.
  • a zinc oxide based cylindrical target having an average splat thickness of 2 to 10 ⁇ m and a relative density of the zinc oxide-based target layer of 87% or more can be manufactured.
  • the substrate cooling structure is not particularly limited as long as the surface temperature of the target at the time of thermal spraying can be lowered, but it is preferable to use a substrate cooling pipe that ejects air. This is because a zinc oxide target layer having a uniform structure can be obtained by blowing off the finely sublimated and solidified zinc oxide powder attached to the target.
  • a substrate cooling structure for cooling the target so that the temperature of the surface of the target other than the area where the zinc oxide-based weld particles collide during spraying is 200 ° C. or less.
  • a backing tube provided with a base layer is fixed to a rotating table, and a spray gun is scanned at a constant speed while rotating the rotating table to spray the zinc oxide-based molten powder.
  • the molten particles are in a high temperature state exceeding 1000 ° C., it is necessary to effectively cool the molten particles by the substrate cooling structure.
  • the average particle size of the powder used for the zinc oxide-based target layer according to this embodiment is 20 to 70 ⁇ m.
  • the average particle diameter is preferably 30 to 50 ⁇ m.
  • the average particle size is less than 20 ⁇ m, the powder is light, so that the introduction into the plasma is not successful, the melting degree of the powder is lowered, and it is difficult to increase the target density.
  • the average particle diameter exceeds 70 ⁇ m, a difference occurs in the degree of melting inside and outside the particle in the plasma, and a dense target cannot be produced.
  • the average particle size exceeds 70 ⁇ m, it is necessary to stay in the high-temperature plasma for a long time in order to improve the melting degree. In that case, it is difficult to produce a dense target because zinc oxide is easily sublimated. .
  • the dispersibility of aluminum and / or gallium in the zinc oxide-based powder containing aluminum oxide and / or gallium oxide is preferably in the range of 0% to 30%. When the dispersibility exceeds 30%, the dispersibility of the aluminum oxide and / or gallium oxide added to the zinc oxide powder is poor, and it becomes difficult to produce a high-quality target.
  • the shape of the zinc oxide-based powder is not particularly limited as long as it is in a molten state by being introduced into plasma, and spherical particles or pulverized powder can be used.
  • the method for producing the zinc oxide powder is not particularly limited, and there may be mentioned a method in which a predetermined amount of zinc oxide and aluminum oxide or / and gallium oxide are weighed, dispersed and mixed in water, pulverized by beads mill, and granulated and dried by spray drying. .
  • the backing tube examples include metals such as SUS and Ti.
  • the zinc oxide-based target layer is thickened, in order to relieve the stress generated in the target due to the difference in thermal expansion during sputtering discharge, it is preferable that the product is made of Ti having a thermal expansion coefficient close to that of the zinc oxide-based cylindrical target.
  • the backing tube surface is preferably blasted and roughened. Although it does not specifically limit as a blast material, Commercially available high purity aluminum oxide is preferable.
  • zinc, aluminum, a zinc alloy or an aluminum alloy may be provided as a base layer.
  • FIG. 2 is a schematic view showing a method for producing a zinc oxide-based cylindrical target by spraying the zinc oxide-based powder according to the present embodiment.
  • plasma gas 6 is supplied to a spray gun 7, and a direct current arc is generated by applying a voltage between a cathode and an anode placed facing the inside of the spray gun 7, thereby generating plasma.
  • Jet 4 is generated.
  • the zinc oxide powder (raw material powder 5) is supplied to the plasma jet 4 along with a gas stream such as air and sprayed onto the backing tube 1.
  • thermal spray gun used in the present embodiment a general high-voltage DC plasma gun can be used. Can be used.
  • the plasma gas flow rate is important in order to secure a residence time for the powder charged in the plasma jet to melt.
  • the plasma gas flow rate is 90 to 130 L / min. It is preferable that Plasma gas flow rate is 130 L / min. If it exceeds 1, the linear velocity becomes high and the staying time becomes short, so the melting degree of the zinc oxide-based powder becomes insufficient. Plasma gas flow rate is 90 L / min. If it is less than this, the melting degree in the plasma jet is improved, but since the linear velocity is slow, the time to reach the target surface from the plasma jet end becomes longer. As a result, cooling solidification of the melted particle surface occurs, and the target density shown in the present embodiment cannot be achieved. Moreover, since the residence time in a plasma jet becomes long, sublimation advances and the yield of a zinc oxide-type cylindrical target falls.
  • the plasma gas composition it is desirable to use nitrogen and hydrogen as gases having high thermal conductivity in order to enhance the meltability of the zinc oxide powder.
  • the gas composition ratio (volume%) of hydrogen in the plasma gas is preferably 5 to 30%.
  • hydrogen is less than 5%, the thermal conductivity of the gas is low, so that the meltability of the powder is lowered and a dense target cannot be formed.
  • the hydrogen concentration exceeds 30%, not only the plasma output becomes unstable but also the consumption of the plasma generating electrode material increases, which is not suitable for actual production.
  • the spraying distance is expressed as the distance from the spray gun exit to the target, and the distance is closely related to the time and temperature until the molten particles ejected from the plasma jet are deposited on the target surface. It is an important parameter for increasing the thickness and increasing the wall thickness.
  • the spray distance in this embodiment is preferably 70 to 100 mm. When the spraying distance exceeds 100 mm, particles flying from the plasma jet are cooled and solidified, so that a dense target cannot be manufactured. When the spraying distance is less than 70 mm, the distance from the plasma jet is short, so the target temperature rises due to the radiant heat of the plasma jet, and cracks are generated during target production or cooling after completion of target production, increasing the wall thickness. Tend to be difficult to do.
  • the relative spray distance which is the ratio of the plasma jet length to the spray distance, is preferably 0.75 to 0.95, and more preferably 0.77 to 0.90.
  • the relative spraying distance is less than 0.75, cooling of the molten particles proceeds and it tends to be difficult to produce a high-density target as described in the present invention.
  • the relative spraying distance exceeds 0.95, cracks are generated due to an increase in the target surface temperature, and it tends to be difficult to increase the thickness.
  • the method for feeding the zinc oxide powder is not particularly limited, but a method of feeding into the plasma gas together with the gas fluid quantitatively by using the pressure of a gas such as air from a hopper for storing the generally-known powder can be mentioned. .
  • a feed method (upper feed method) from the upper part on the spray gun outlet side toward the plasma gas fluid is preferable.
  • the upper feed method it is important whether the powder to be fed can be successfully fed to the high temperature part in the center of the plasma jet. Therefore, the optimum range of the flow rate of carrier gas such as air used for feeding powder varies depending on the powder particle diameter used for feeding, the plasma gas flow rate, and the like.
  • the carrier gas flow rate is 3-12L / min. Is preferably 5 to 9 L / min. More preferably.
  • the carrier gas flow rate is 3 L / min. If it is less than 1, the carrier gas flow rate is small, so that the powder cannot be introduced into the plasma gas stream and not only the density is lowered, but also the yield tends to be lowered and the productivity tends to be lowered.
  • the carrier gas flow rate is 12 L / min. In the case of exceeding 1, the powder penetrating the plasma gas stream is seen and the plasma jet tends to sag under the influence of the carrier gas, so the density and yield tend to decrease.
  • the upper limit of the amount of powder feed in this embodiment is not particularly limited, and is preferably 30 g / min. From the viewpoint of productivity. That's it.
  • the position where the air jetted from the substrate cooling pipe collides with the target is 20 to 40 mm concentric with the center position where the molten particles collide with the target. It is preferable to arrange a substrate cooling pipe.
  • the distance is less than 20 mm, the adhesion of sublimated zinc oxide particles cannot be completely removed and the cooling efficiency is lowered, so that it tends to be difficult to produce a target having a high density and a large thickness. If it exceeds 40 mm, the cooling effect is greatly reduced, and therefore it cannot be thickened.
  • FIG. 3 is a side view schematically showing the arrangement of the substrate cooling pipes in the present embodiment.
  • FIG. 4 is a top view schematically showing the arrangement of the substrate cooling pipes in the present embodiment.
  • the horizontal pressure PT is preferably 0.1 MPa or more. When the pressure is less than 0.1 MPa, the target cannot be sufficiently cooled.
  • the number of substrate cooling pipes has a structure where at least 4 or more are mounted on the outer periphery of the spray gun.
  • the surface temperature of the target varies depending on the position of the zinc oxide-based particles to be welded. Therefore, it is necessary to attach the substrate cooling pipe to the outer periphery of the spray gun so as to be interlocked with the change in the surface temperature of the target. Also, it is better to arrange the pipes in the same circle as much as possible from the center where the molten particles collide with the target. Thereby, the surface temperature distribution is easily uniformed, and cracks due to the asymmetry of the temperature distribution can be prevented. Therefore, it is desirable to arrange four or more pipes.
  • FIG. 7 is a schematic diagram showing an example of a method for forming the underlayer 12 on the zinc oxide-based cylindrical target 110 according to an embodiment of the present invention.
  • plasma gas 6 is supplied to a spray gun 7, and a DC arc is generated by applying a voltage between a cathode and an anode placed facing the inside of the spray gun 7.
  • a plasma jet 4 is generated.
  • the raw material powder 5 of the base layer 12 is supplied to the plasma jet 4 together with a gas stream such as air to spray the base layer 12 on the backing tube 1, and then the raw material powder 5 of the zinc oxide based target layer 10 is Similarly, the zinc oxide based target layer 10 is sprayed on the underlayer 12.
  • the zinc oxide-based target layer 10 when it is desired to make the thickness of the zinc oxide-based target layer 10 uniform, by setting the zinc oxide-based cylindrical target 10 on a lathe and rotating it, applying a bite to the zinc oxide-based cylindrical target 10 and sending it in the longitudinal direction, It is preferable to perform a dry cutting process.
  • any one that can cut the outer peripheral surface of a cylinder such as a normal lathe (general horizontal lathe), a vertical lathe, etc., and corresponds to the length of the backing tube may be used.
  • a dense sintered body of zinc oxide is said to have a Mohs hardness of 4 to 5, but the sprayed zinc oxide target has less adhesion of particles than the sintered body. Therefore, the zinc oxide target is softer than the sintered body, and the cutting tool can be made of cemented carbide obtained by sintering fine powders of tungsten carbide and cobalt if the machining amount is small and the machining is performed in a short time.
  • a diamond cutting tool for cutting and perform cutting while cooling the tip of the diamond cutting tool with compressed gas and / or liquefied gas.
  • the type of diamond bite is not particularly limited, but there are various types such as sintered products, CVD products, single crystal products, and single crystal products are preferred.
  • Compressed gas can be any compressed air or nitrogen, but compressed air is preferred in terms of cost.
  • Liquid nitrogen, liquefied carbon dioxide, etc. can be used as the liquefied gas, but since the temperature of the ejecta is very low, the cooling effect of the tip of the diamond bite is higher than that of the compressed gas, and it does not remain immediately after evaporation. There are features.
  • liquefied carbon dioxide gas is preferable because it becomes powdery dry ice when sprayed, so that the tip of the diamond bite can be cooled and the zinc oxide-based target layer can be washed.
  • Liquefied carbon dioxide gas is blown from the nozzle through the regulator to the atmosphere, and suddenly drops in temperature due to adiabatic expansion, resulting in powdered dry ice.
  • the shape and pressure of the powdered dry ice are precisely measured. Therefore, it is preferable to use a commercially available device such as Magic Blast Powder Shot manufactured by Taiyo Nippon Sanso Corporation. Further, nitrogen gas, dry compressed air, or the like may be used to adjust the ejection pressure of the generated powdery dry ice.
  • Powdered dry ice is as fine as several tens of ⁇ m, and further pulverizes easily by colliding with the zinc oxide target layer, so it has the effect of finely biting into the irregularities on the surface and blowing off the powder on the surface for cleaning. And there is an advantage of not remaining after.
  • the zinc oxide target layer may get wet by cooling with powdered dry ice, but there is no problem if the cooled portion is processed while being dried with hot air or the like.
  • True density of the zinc oxide-based target layer 5.606g / cm 3 of the true density of zinc oxide, 3.97 g / cm 3 the true density of the aluminum oxide, the true density of the gallium oxide and 5.95 g / cm 3, It calculated
  • the relative density of the zinc oxide-based target layer was expressed as a percentage of the bulk density ( ⁇ b ) calculated by the above formula (2) with respect to the zinc oxide-based true density. The relative density was measured according to JIS standard (R1634).
  • the thickness of the cylindrical target layer was measured at 5 points using a caliper (total of 10 points). The thickness change before and after thermal spraying was calculated from these measured values, and the average value of the thickness change was taken as the thickness of the cylindrical target.
  • the cut surface (hereinafter referred to as “cross section”) obtained by cutting along the thickness direction of the cylindrical target layer is polished with diamond abrasive grains, the polished cross section is observed with a reflection electron microscope, and the average of the laminated splats
  • the thickness was calculated by the intercept method.
  • the average splat thickness was calculated by the following method. That is, a plurality of straight lines are drawn in the thickness direction at an arbitrary position in the cross section. At this time, a plurality of straight lines are drawn so that the number of splat particles existing within the length of the straight line is 200 or more. A value obtained by dividing the total value of the lengths of the plurality of straight lines by the number of splat particles existing within the length of the straight lines was calculated as an average thickness of the splats.
  • the target layer was cut into a predetermined size, and the resulting cross section was polished. Elemental mapping of Al and / or Ga in a 2.5 mm ⁇ 2.5 mm area of the polished cross section was performed by the EPMA method. The obtained 256 (points) ⁇ 256 (points) analytical value was statistically processed to calculate the coefficient of variation in terms of oxide. This was used as an indicator of the dispersibility of the target layer.
  • the average crystal grain size was calculated by the intercept method using a reflection electron microscope observation photograph of the cut cross section of the target layer.
  • the thermal conductivity was measured by a steady method obtained by giving heat flow energy as an electrical calorific value and measuring a temperature gradient between two points of the sample.
  • the measuring method was performed in accordance with ASTM E1530-04, and the measuring device used was a steady-state thermal conductivity measuring device (trade name “GH-1” manufactured by ULVAC-RIKO).
  • the target layer was sputtered to form a 150 nm thick film on a glass substrate, and the transmittance of this film was measured using a spectrophotometer (trade name “U-4100” manufactured by HITACHI).
  • the measured transmittance was converted to light transmittance with D65 light using the relative spectral distribution value of daylight (D65) described in JIS (RZ8701).
  • Example 1 A SUS backing tube having a diameter of 3 inches (76.2 mm) was blasted with aluminum oxide (trade name “Fuji Random WA-60” manufactured by Fuji Seisakusho). The backing tube was fixed on a turntable, and the raw material of the zinc oxide target was sprayed by rotating at 150 rpm while cooling the inside of the backing tube with water. As a raw material for the zinc oxide target, zinc oxide having an average particle diameter of 45 ⁇ m and containing 1.5% by weight of aluminum oxide was charged into a powder feeder. As the plasma gas, nitrogen gas containing 10% hydrogen was used at 100 L / min. A thermal plasma having an output of 70 kW (390 A) was used.
  • the conditions for the thermal spraying of the raw material for the zinc oxide target were as follows.
  • the spraying distance was 80 mm, and the relative spraying distance at this time was 0.88.
  • the supply amount of the raw material powder was 60 g / min.
  • the argon gas flow rate for supplying the raw material powder was 6 L / min.
  • a total of eight substrate cooling pipes were mounted.
  • the horizontal pressure with respect to the target axis per pipe was 0.3 MPa.
  • four were arranged concentrically with a distance of 25 mm ⁇ from the plasma center on the target surface, and four were concentrically arranged with 35 mm ⁇ , and thermal spraying was performed.
  • the maximum surface temperature of the target during thermal spraying was 136 ° C.
  • a target having an average splat thickness of 6.5 ⁇ m, a relative density of 90.2%, and a thickness of 14 mm was obtained.
  • This target was free of cracks and cracks.
  • the pore volume of the target was 0.021 mL / g, the average pore diameter was 420 nm, and the volume of pores having a pore diameter of 1 ⁇ m or more was 0.0069 mL / g.
  • the average crystal grain size of the target was 0.8 ⁇ m, the aluminum oxide content was 2.2% by weight, the aluminum oxide dispersibility was 24.7%, and the thermal conductivity was 5.0 W / (m ⁇ K). .
  • Example 2 The plasma gas flow rate is 120 L / min.
  • the target was obtained by spraying in the same manner as in Example 1 except that the spraying distance was 90 mm.
  • the maximum surface temperature of the target during thermal spraying was 128 ° C.
  • a target having an average splat thickness of 5.8 ⁇ m, a relative density of 89.4%, and a thickness of 14 mm was obtained.
  • This target was free of cracks and cracks.
  • the pore volume of the target was 0.021 mL / g, the average pore diameter was 465 nm, and the volume of pores having a pore diameter of 1 ⁇ m or more was 0.0070 mL / g.
  • the average crystal grain size of the target was 0.7 ⁇ m, the aluminum oxide content was 2.1 wt%, the dispersibility of aluminum oxide was 25.5%, and the thermal conductivity was 5.0 W / (m ⁇ K). .
  • Example 2 Using this target, sputter discharge was performed under the same conditions as in Example 1. As a result, the number of arcs generated by the sputter discharge was 138. Further, the transmittance of the formed transparent conductive film having a thickness of 150 nm was 89.0%.
  • Example 3 Example 1 except that the mixed gas of nitrogen and hydrogen containing 15% by volume of hydrogen (H 2 ) is a plasma gas, and the horizontal pressure with respect to the target axis per substrate cooling pipe is 0.2 MPa. Thermal spraying was performed in the same manner to obtain a target. The maximum surface temperature of the target during thermal spraying was 151 ° C.
  • a target having an average splat thickness of 7.2 ⁇ m, a relative density of 90.7%, and a thickness of 9 mm was obtained.
  • This target was free of cracks and cracks.
  • the pore volume of the target was 0.020 mL / g, the average pore diameter was 400 nm, and the volume of pores having a pore diameter of 1 ⁇ m or more was 0.0069 mL / g.
  • the average crystal grain size of the target was 0.6 ⁇ m, the aluminum oxide content was 2.0% by weight, the dispersibility of aluminum oxide was 26.1%, and the thermal conductivity was 5.2 W / (m ⁇ K). .
  • Example 2 Using this target, sputter discharge was performed under the same conditions as in Example 1. As a result, the number of arcs generated by sputtering discharge was as small as 124. Further, the transmittance of the formed transparent conductive film having a thickness of 150 nm was 88.3%.
  • Example 4 A target was obtained by performing thermal spraying in the same manner as in Example 2 except that a zinc oxide-based powder containing 2.0% by weight of gallium oxide and having an average particle diameter of 45 ⁇ m was used as a raw material for the zinc oxide-based target. .
  • a target having an average splat thickness of 5.4 ⁇ m, a relative density of 90.3%, and a thickness of 14 mm was obtained.
  • This target was free of cracks and cracks.
  • the pore volume of the target was 0.020 mL / g, the average pore diameter was 420 nm, and the volume of pores having a pore diameter of 1 ⁇ m or more was 0.0069 mL / g.
  • the average crystal grain size of the target was 0.7 ⁇ m, the gallium oxide content was 3.0 wt%, the dispersibility of gallium oxide was 25.4%, and the thermal conductivity was 5.1 W / (m ⁇ K). .
  • Example 2 Using this target, sputter discharge was performed under the same conditions as in Example 1. As a result, the number of arcs generated by the sputter discharge was 198. Further, the transmittance of the formed transparent conductive film having a thickness of 150 nm was 87.9%.
  • Example 1 A target was obtained in the same manner as in Example 1 except that the substrate was not cooled during the thermal spraying.
  • the maximum surface temperature of the target during thermal spraying was 494 ° C.
  • zinc oxide having barnacle-like protrusions was deposited, and very large irregularities were formed on the surface.
  • the inside of the barnacle-like projection had a yellowish color tone, and the outer periphery of the barnacle-like projection had a greenish white color.
  • the target has a mottled pattern due to the color tone of the protrusions, and cannot be used as a cylindrical target.
  • the barnacle portion was coarsened.
  • the target thickness was 3 mm
  • the target surface was covered with the barnacle portion.
  • the relative density of this target was 76.6% and the average splat thickness was 5.0 ⁇ m.
  • Example 2 A zinc oxide powder containing 1.5% by weight of aluminum oxide having an average particle size of 80 ⁇ m was used as a raw material for the zinc oxide target.
  • Thermal spraying was performed under the conditions of 100% N 2 and a spraying distance of 70 mm.
  • a total of two substrate cooling pipes were mounted.
  • the horizontal pressure with respect to the target axis per pipe was set to 0.05 MPa.
  • Thermal spraying was performed by placing two on a concentric circle with a distance of 45 mm ⁇ from the plasma center on the target surface.
  • the maximum surface temperature of the target during thermal spraying was 327 ° C.
  • the target obtained by spraying the raw material as described above had an average splat thickness of 14.9 ⁇ m, a relative density of 82.3%, and a thickness of 3 mm.
  • This target had cracks.
  • the pore volume of this target was 0.037 mL / g, the average pore diameter was 700 nm, and the volume of pores having a pore diameter of 1 ⁇ m or more was 0.021 mL / g.
  • the average crystal grain size of this target is 1.1 ⁇ m, the aluminum oxide content is 2.2% by weight, the dispersibility of aluminum oxide is 31.9%, and the thermal conductivity is 3.0 W / (m ⁇ K). there were.
  • the average thickness of the obtained target splats was 18.5 ⁇ m, the relative density was 77.8%, and the target thickness was 9 mm.
  • the pore volume of this target was 0.055 mL / g, the average pore diameter was 970 nm, and the volume of pores having a pore diameter of 1 ⁇ m or more was 0.040 mL / g.
  • This target has an average crystal grain size of 1.1 ⁇ m, an aluminum oxide content of 2.1 wt%, an aluminum oxide dispersibility of 32.4%, and a thermal conductivity of 2.8 W / (m ⁇ K). there were.
  • Reference Example 2 Aluminum was sprayed in the same manner as in Reference Example 1 except that the thickness of the aluminum underlayer was 1.0 mm. Next, the same zinc oxide as in Reference Example 1 was sprayed to a thickness of 9 mm. This target was 4.5 kW (32.8 W / cm 2 ), Ar gas flow rate: 40 cm 3 / min. The spatter discharge was performed for 20 hours at a pressure of 0.4 Pa, but no cracks occurred.
  • Reference Example 4 A SUS backing tube blasted in the same manner as in Reference Example 3 was sprayed with zinc to a thickness of 0.5 mm in the same manner as in Reference Example 3 to form an underlayer. Next, on this foundation layer, zinc oxide was sprayed to a thickness of 9 mm in the same manner as in Reference Example 3. Using the target thus obtained, 4.5 kW (32.8 W / cm 2 ), Ar gas flow rate: 40 cm 3 / min. The sputtering discharge was performed for 20 hours under the condition of pressure: 0.4 Pa. As a result, no cracks occurred in the target.
  • the zinc oxide-based cylindrical target of the present invention provides a sputtering cylindrical target that can be used for transparent conductive film applications such as electrodes for display elements of laptop computers and mobile phones, electrodes for solar cells, and electrodes for plasma display panels. it can.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

La présente invention se rapporte à une cible cylindrique en oxyde de zinc qui comprend un matériau de base et une couche de cible en oxyde de zinc qui présente une structure formée en empilant des lattes, chaque latte étant fabriquée par pulvérisation thermique d'une poudre d'oxyde de zinc sur le matériau de base et par fusion et aplatissement de la poudre d'oxyde de zinc pulvérisée thermiquement. La cible cylindrique en oxyde de zinc est caractérisée en ce que les lattes ont une épaisseur moyenne comprise entre 2 et 10 μm et en ce que la couche de cible en oxyde de zinc présente une densité relative supérieure ou égale à 87 %.
PCT/JP2011/065728 2010-07-09 2011-07-08 Cible cylindrique en oxyde de zinc et procédé de fabrication de cette dernière Ceased WO2012005366A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2010156537 2010-07-09
JP2010-156538 2010-07-09
JP2010-156537 2010-07-09
JP2010156538 2010-07-09
JP2010-255847 2010-11-16
JP2010255847A JP2012107277A (ja) 2010-11-16 2010-11-16 酸化亜鉛系円筒ターゲットの製造方法
JP2010-291314 2010-12-27
JP2010291314A JP2012031502A (ja) 2010-07-09 2010-12-27 酸化亜鉛系円筒ターゲットおよびその製造方法

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06346232A (ja) * 1993-06-11 1994-12-20 Asahi Glass Co Ltd スパッタリング用ターゲットおよびその製造方法
JPH0711419A (ja) * 1993-06-29 1995-01-13 Asahi Glass Co Ltd 回転カソードターゲット及びその製造方法
JPH11269638A (ja) * 1998-03-24 1999-10-05 Sumitomo Metal Mining Co Ltd スパッタリングターゲットおよびその製造方法
JP2008001554A (ja) * 2006-06-22 2008-01-10 Idemitsu Kosan Co Ltd 焼結体、膜及び有機エレクトロルミネッセンス素子

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06346232A (ja) * 1993-06-11 1994-12-20 Asahi Glass Co Ltd スパッタリング用ターゲットおよびその製造方法
JPH0711419A (ja) * 1993-06-29 1995-01-13 Asahi Glass Co Ltd 回転カソードターゲット及びその製造方法
JPH11269638A (ja) * 1998-03-24 1999-10-05 Sumitomo Metal Mining Co Ltd スパッタリングターゲットおよびその製造方法
JP2008001554A (ja) * 2006-06-22 2008-01-10 Idemitsu Kosan Co Ltd 焼結体、膜及び有機エレクトロルミネッセンス素子

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