WO2013088785A1 - Elément cible de pulvérisation cathodique d'indium et son procédé de production - Google Patents

Elément cible de pulvérisation cathodique d'indium et son procédé de production Download PDF

Info

Publication number
WO2013088785A1
WO2013088785A1 PCT/JP2012/070764 JP2012070764W WO2013088785A1 WO 2013088785 A1 WO2013088785 A1 WO 2013088785A1 JP 2012070764 W JP2012070764 W JP 2012070764W WO 2013088785 A1 WO2013088785 A1 WO 2013088785A1
Authority
WO
WIPO (PCT)
Prior art keywords
indium
target member
sputtering target
grain boundary
member according
Prior art date
Application number
PCT/JP2012/070764
Other languages
English (en)
Japanese (ja)
Inventor
瑶輔 遠藤
坂本　勝
Original Assignee
Jx日鉱日石金属株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to KR1020137011328A priority Critical patent/KR101365284B1/ko
Publication of WO2013088785A1 publication Critical patent/WO2013088785A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • 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
    • C23C14/0623—Sulfides, selenides or tellurides
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an indium sputtering target member and a method for manufacturing the same.
  • Indium is used as a sputtering target member for forming a light absorption layer of a Cu—In—Ga—Se (CIGS) thin film solar cell.
  • CGS Cu—In—Ga—Se
  • Patent Document 1 describes a method in which an indium thin film is formed on a backing plate, and then indium is poured onto the thin film and cast so as to be integrated with the backing plate.
  • Patent Document 2 describes a predetermined amount of indium raw material is charged into a heated mold and dissolved, indium oxide floating on the surface is removed, and cooled to obtain an ingot.
  • the indium target obtained in this way has a problem that the film formation rate is insufficient and the productivity is low.
  • arcing is likely to occur during sputtering, the erosion surface is rough, and particles adhere to the substrate, resulting in a decrease in yield.
  • an object of the present invention is to provide an indium sputtering target that can obtain a high film formation rate and preferably can suppress the occurrence of arcing.
  • the present inventor has intensively studied to solve the above problems, and makes it easy to see the crystal structure by means such as acid etching, electropolishing, and sputtering, and when observed from the surface direction, linear grain boundaries are formed in the crystal grains. It has been discovered that the target having a higher film formation rate than the target having no linear grain boundary. Further, when this linear grain boundary was analyzed by EBSP, it was found that the crystals sandwiching the linear grain boundary had a geometrically consistent relationship, that is, the linear grain boundary was a corresponding grain boundary. It turns out that. And it discovered that this corresponding grain boundary was ⁇ 7.
  • an indium sputtering target member having crystal grains having a linear grain boundary on the surface to be sputtered, and the area ratio of the crystal grains being 65.1% or more. is there.
  • the area ratio of the crystal grains having the linear grain boundary is 88.9% or more.
  • indium sputtering target member in another embodiment, it is formed by heat treatment in the range of 80 to 150 ° C. for 10 minutes or more after plastic working with a total rolling reduction of 65 to 90%.
  • the total rolling reduction of the plastic working is 80% or more.
  • the heat treatment is performed at 120 ° C. or more for 2 hours or more.
  • the following sputtering conditions ⁇ Sputtering gas: Ar ⁇ Sputtering gas pressure: 0.5Pa ⁇ Sputter gas flow rate: 50 SCCM Sputtering temperature: No heating Sputtering power density: 2.0 W / cm 2 ⁇ Substrate: ⁇ 4 inch x 0.7mmt When the sputtering is continuously performed for 1 hour, the number of arcing is 0.
  • the number of voids having a pore diameter of 50 ⁇ m or more is 1 / cm 3 or less.
  • At least a part of the linear grain boundary is a corresponding grain boundary, and the ⁇ value of the corresponding grain boundary is 7.
  • the ratio of the grain boundary length corresponding to ⁇ 7 on the surface to be sputtered to the total grain boundary length is 71.4% or more.
  • the present invention is a sputtering target in which an indium sputtering target member according to the present invention is bonded onto a backing plate.
  • the present invention is a method for producing an indium sputtering target member, which comprises plastically processing an indium ingot under a condition of a total rolling reduction of 65 to 90%.
  • the method includes a step of heat treatment in the range of 80 to 150 ° C. for 10 minutes or longer after the plastic working.
  • the total rolling reduction of the plastic working is 80% or more.
  • the heat treatment is performed at 120 ° C. or more for 2 hours or more.
  • linear grain boundary In the indium sputtering target member according to the present invention, the area ratio of crystal grains having linear grain boundaries and linear grain boundaries on the surface of the target member subjected to sputtering is defined.
  • linear grain boundary means a grain boundary in which the protrusion in the perpendicular direction of a line segment formed when connecting adjacent corners of a grain boundary forming a crystal grain with a straight line is less than 0.1 mm.
  • the straight line means a case where there is a linear region of 50 ⁇ m or more, and when it is less than 50 ⁇ m, it is not included in the straight line.
  • the grain boundary is made easier to see by etching, the grain boundary may be scraped depending on the degree of etching, but the linear shape is not impaired. Therefore, in the present invention, in such a case, the side edge of the cut grain boundary is defined as the grain boundary in the crystal grain to be observed.
  • “a crystal grain having a linear grain boundary” is a crystal grain having a grain boundary satisfying the definition of the linear grain boundary in one or more of the grain boundaries forming the crystal grain.
  • the crystal grain boundary is substantially curved, whereas the indium sputtering target member according to the present invention has many linear grain boundaries.
  • FIG. 1 shows an example of surface photographs of crystal grains of a target member according to the present invention (left side) and a conventional target member (right side) having a linear grain boundary when the surface of the target member after sputtering is photographed with a digital camera. Show.
  • FIG. 1 shows an example of surface photographs of crystal grains of a target member according to the present invention (left side) and a conventional target member (right side) having a linear grain boundary when the surface of the target member after sputtering is photographed with a digital camera. Show.
  • FIG. 1 shows an example of surface photographs of crystal grains of a target member according to the present invention (left side) and a conventional target member (right side) having a linear grain boundary when the surface of the target member after sputtering is photographed with a digital camera. Show.
  • FIG. 1 shows an example of surface photographs of crystal grains of a target member according to the present invention (left side) and a conventional target member (right side) having a linear grain boundary when the surface of the target member after sp
  • FIG. 2 shows a photograph of the surface of crystal grains of a target member according to the present invention (left side) and a conventional target member (right side) having linear grain boundaries when the target member after etching with acid is photographed with a digital microscope.
  • An example is shown.
  • linear grain boundaries can be clearly observed with the product of the present invention, but not with the conventional indium target shown as a comparative example.
  • linear grain boundaries can be observed in the product of the present invention, but not in the comparative example which is a conventional product.
  • the area ratio of crystal grains having a linear grain boundary is defined.
  • the effect of increasing the film formation rate can be obtained by increasing the area ratio of crystal grains having linear grain boundaries. The reason for this is not clear, but it is presumed that grain boundary energy or the like has an effect. If the area ratio is too small, the effect of increasing the film formation rate is small.
  • the area ratio is required to be 10% or more, preferably 15% or more, more preferably 20% or more, Even more preferably 25% or more, even more preferably 30% or more, even more preferably 40% or more, even more preferably 50% or more, and even more preferably 60% or more, Even more preferably, it is 70% or more, for example, 30% to 100%.
  • the area ratio of crystal grains having linear grain boundaries is measured by the following method. Etching the indium target with an acid, electrolytic polishing, or sputtering removes the work-affected layer on the surface and facilitates observation of the structure. Thereafter, the surface is photographed with a digital camera or the like, and the photographed image is subjected to image processing software or the like to obtain the area of the crystal having a linear structure and the photographing field area.
  • the area ratio of crystal grains having a linear grain boundary is represented by ⁇ (area of crystal having a linear structure) / (photographing field area) ⁇ ⁇ 100 (%).
  • photography visual field is measured by the area containing at least 10 or more crystal grains.
  • the corresponding grain boundary length and the ratio of all the grain boundary lengths are also defined.
  • Corresponding grain boundaries are special grain boundaries with high geometrical consistency, and materials with corresponding grain boundaries are compared to materials with only general grain boundaries (random grain boundaries) Often has excellent chemical and mechanical properties.
  • the corresponding grain boundary when one of adjacent crystals sandwiching the crystal grain boundary is rotated around the crystal axis, part of the lattice points periodically coincides with the lattice point of the other crystal grain. It is a grain boundary having such a relationship (this lattice point is called a corresponding lattice point).
  • the ratio between the original unit cell volume and the unit cell volume newly formed by the corresponding lattice point is called a ⁇ value.
  • the corresponding grain boundary is described, for example, in “Physics of Ceramic Materials—Crystals and Interfaces” (Nikkan Kogyo Shimbun, edited by Yuichi Ikuhara, 2003, page 82).
  • the linear grain boundary is a corresponding grain boundary of ⁇ 7.
  • the orientations coincide with each other by rotation of about 85.5 ° (85.5 ° ⁇ 1 °) with the ⁇ 110> axis as a common rotation axis.
  • the ⁇ value of the grain boundary is assumed to be 7.
  • the corresponding grain boundary length for all the grain boundary lengths in the observation field (3.5 mm ⁇ 3.5 mm or more).
  • the ratio is prescribed.
  • the grain boundary length ratio is required to be 15% or more, preferably 25% or more. Yes, more preferably 40% or more, for example 25% or more and 90% or less.
  • the ratio of the ⁇ 7 corresponding grain boundary length is set as the ratio of the above length.
  • the length ratio of the grain boundary corresponding to ⁇ 7 is measured by the following method.
  • the common rotation axis is the ⁇ 110> axis and the rotation angle is about 85 ° (85.5 ° ⁇ 1 °).
  • Other common rotation axes and rotation angles may be used as long as they are equivalent, but in general, when measurement is performed by EBSP, the display is performed with the smallest rotation angle.
  • an EBSP Electron Backscatter Diffraction Pattern
  • FEEPMA Field Emission Electron Probe Micro Analyzer
  • This method is a method of analyzing crystal orientation based on a backscattered electron diffraction pattern (Kikuchi pattern) generated when an electron beam is obliquely applied to a sample surface.
  • analysis is performed in the following procedure. First, the measurement area on the surface of the target material to be measured (observation field of view 3.5 mm ⁇ 3.5 mm) is usually divided into hexagonal areas (pixels), and the Kikuchi pattern obtained for each divided area is known.
  • the step is 20 ⁇ m.
  • the crystal orientation of a measurement point adjacent to the measurement point is obtained, and if the orientation difference between both crystals is 5 ° or more, the interval (side where both hexagons are in contact) is used as the grain boundary and 5 ° If it is less, both are made the same crystal. In this way, the crystal orientation on the sample surface and the distribution of grain boundaries are obtained.
  • the sum total of the grain boundary lengths of the crystal grains included in the observation visual field is calculated using software attached to EBSP.
  • each crystal grain has a corresponding grain boundary ⁇ 7, and among the grain boundaries of the crystal grains included in the observation field of view, the length of the ⁇ 7 corresponding grain boundary is Calculate the total sum.
  • the ratio (%) of the corresponding grain boundary ⁇ 7 is obtained by multiplying (total sum of the lengths of the corresponding grain boundaries ⁇ 7) / (total sum of the lengths of the crystal grain boundaries) by 100.
  • the ratio of the length of the ⁇ 7-corresponding grain boundary to the total grain boundary length is calculated, and the average value in any four observation fields is taken as the measurement value.
  • the common rotation axis is designated as ⁇ 110>
  • the rotation angle is designated as 85.5 °
  • ⁇ 7 Identify the corresponding grain boundaries. Note that the measurement error of the rotation angle is different for each apparatus, but is in the range of 85.5 ° ⁇ 1 °.
  • the number of voids having a pore diameter of 50 ⁇ m or more is 1 / cm 3 or less. It is desirable that the gaps present in the target, particularly large gaps having a hole diameter of 0.5 mm or more, be reduced as much as possible because they cause abnormal discharge during sputtering.
  • the cooling rate is high, voids are formed inside the target, and thus there is a problem that abnormal discharge is likely to occur during sputtering.
  • the voids having a pore diameter of 50 ⁇ m or more are preferably 0.5 pieces / cm 3 or less, more preferably 0.3 pieces / cm 3 or less, still more preferably 0.1 pieces / cm 3 or less, for example, 0 ⁇ 0.3 / cm 3 . It may be 0 / cm 3 .
  • the number of voids having a pore diameter of 50 ⁇ m or more is measured with an electronic scanning ultrasonic flaw detector.
  • Set the target in the flaw detector water tank of the above device measure with a frequency band of 1.5-20MHz, pulse repetition frequency 5KHz, scan speed 60mm / min, and count voids with a hole diameter of 50 ⁇ m or more from the obtained image image.
  • the number ratio of voids is obtained from the volume of the target to be measured.
  • the hole diameter is defined by the diameter of the smallest circle surrounding the hole of the image image.
  • indium which is a raw material is dissolved and poured into a mold.
  • the raw material indium to be used preferably has a high purity because the conversion efficiency of a solar cell produced from the raw material is reduced when impurities are contained. For example, 99.99 mass %, Typically 99.99% to 99.9999% by weight purity of raw materials can be used.
  • it cools to room temperature and forms an indium ingot. Increasing the cooling rate improves production efficiency, but voids are likely to occur.
  • the voids can be reduced by applying a compressive force such as pressing or rolling, so that, for example, 8 ° C./min or more, preferably 10 ° C./min or more, typically 8 to It becomes possible to cool at a rate of 12 ° C./min.
  • a compressive force such as pressing or rolling
  • strain is inserted into the ingot obtained by melt casting by performing plastic working such as pressing or rolling.
  • the ingot after melt casting has few crystal grains having corresponding grain boundaries, but the grain boundaries corresponding to ⁇ 7 increase by inserting strain into indium by rolling or the like.
  • the plastic working may be cold or hot. If the total rolling reduction of plastic processing is too low, the corresponding grain boundaries will not increase sufficiently, while if the total rolling reduction is too high, the ingot thickness before processing will need to be increased, resulting in poor productivity and handling. It is preferable to perform pressing or rolling so that the rolling reduction is 15 to 90%, and it is more preferable to perform pressing or rolling so that the total rolling reduction is 50 to 85%.
  • heat treatment can be applied after plastic working such as pressing or rolling.
  • heat treatment By applying heat treatment, crystal grains having linear grain boundaries are significantly grown, and the ratio of linear grain boundaries and the area ratio of crystal grains having linear grain boundaries can be increased, thereby further increasing the film formation rate. it can.
  • a heat treatment method for example, there is a method in which the material is heated at 80 to 150 ° C. ⁇ 10 to 300 minutes, typically 100 to 140 ° C. ⁇ 60 to 180 minutes. When the heat treatment time is less than 10 minutes, almost no effect is observed, but when the heat treatment time is 10 minutes or more, the above effect is observed.
  • the heating time may be longer than 300 minutes, but it is preferably about 10 to 300 minutes because it causes a decrease in productivity such as occupation of heat treatment equipment.
  • the ratio of the corresponding grain boundary length is about 0% to 20% and the area ratio of the crystal grains having the linear grain boundary is about 0% to about 25%, a dramatic film formation rate increasing effect is seen, Since the effect of increasing the film formation rate becomes moderate in the region beyond that, the heat treatment may be omitted in view of productivity.
  • the thickness of the indium tile after the plastic working is not particularly limited, and may be appropriately set according to the sputtering apparatus to be used, the film formation usage time, etc., but is usually about 3 to 20 mm, typically about 5 to 18 mm. It is.
  • the indium target member thus obtained can be bonded to a sputtering plate with a backing plate and a bonding material.
  • the shape processing of the indium target member may be performed either before or after being bonded to the backing plate. Moreover, you may implement pickling and degreasing
  • the indium sputtering target thus obtained can be suitably used as a sputtering target for preparing a light absorption layer for a CIGS thin film solar cell.
  • Example 1 An indium raw material (purity 4N) dissolved at 170 ° C. was poured into a SUS mold having a length of 250 mm, a width of 160 mm, and a depth of 80 mm (inner dimensions) at 170 ° C., and then allowed to cool to room temperature (about 1 5 ° C./min) to produce an ingot. Subsequently, cold rolling was performed from a thickness of 6.3 mm to a total rolling reduction of 20%, and a tile serving as a target member having a thickness of 5 mm was produced.
  • purity 4N purity 4N
  • This tile was cut into polygonal prisms, bonded to a copper backing plate having a diameter of 250 mm and a thickness of 5 mm, and processed into a disk shape having a diameter of 204 mm ⁇ thickness of 5 mm by a lathe to produce an indium target.
  • Example 2 An indium target was produced in the same manner as in Example 1 except that the thickness of the indium ingot before rolling was adjusted so that the total rolling reduction was 30%.
  • Example 3 An indium target was produced in the same manner as in Example 1 except that the thickness of the indium ingot before rolling was adjusted so that the total rolling reduction was 50%.
  • Example 4 An indium target was produced in the same manner as in Example 1 except that the thickness of the indium ingot before rolling was adjusted so that the total rolling reduction was 65%.
  • Example 5 An indium target was produced in the same manner as in Example 1 except that the thickness of the indium ingot before rolling was adjusted so that the total rolling reduction was 80%.
  • Example 6 An indium target was produced in the same manner as in Example 1 except that the thickness of the indium ingot before rolling was adjusted so that the total rolling reduction was 90%.
  • Example 7 An indium target was produced in the same manner as in Example 5 except that the cooling rate during casting was 10 ° C./min (rapid cooling).
  • Example 9 An indium target was produced in the same manner as in Example 8 except that the thickness of the indium ingot before pressing was adjusted so that the total rolling reduction was 30%.
  • Example 10 An indium target was produced in the same manner as in Example 8 except that the thickness of the indium ingot before pressing was adjusted so that the total rolling reduction was 50%.
  • Example 11 An indium target was produced in the same manner as in Example 8 except that the thickness of the indium ingot before pressing was adjusted so that the total rolling reduction was 65%.
  • Example 17 An indium tile was produced in the same manner as in Example 8, and then an indium target was produced in the same manner as in Example 8, except that heat treatment was performed in air at 120 ° C. for 2 hours.
  • Example 18 An indium target was produced in the same manner as in Example 12 except that an indium tile was produced in the same manner as in Example 12 and then heat treatment was performed in air at 120 ° C. for 2 hours.
  • the area ratio of crystal grains having linear grain boundaries, the ⁇ 7-corresponding grain boundary length ratio, and the number ratio of voids having a pore diameter of 50 ⁇ m or more were measured by the following methods. The results are shown in Table 1.
  • the film-forming rate from the start of sputtering was measured. Specifically, by sputtering under the following conditions, the thickness of the obtained film was measured with a stylus type surface shape measuring instrument (Dektak 8 manufactured by ULVAC), and the film thickness was divided by the film formation time (3 min). The film formation rate was calculated. Furthermore, 1 h continuous sputtering was performed under the following conditions, and the arcing number was measured by a visual method.
  • the sputtering conditions are as follows.
  • Sputtering device Canon Anelva, SPF-313H ⁇ Sputtering gas: Ar ⁇ Sputtering gas pressure: 0.5Pa ⁇ Sputter gas flow rate: 50 SCCM Sputtering temperature: T.A. (No heating) ⁇ Sputtering power density: 2.0 W / cm 2 -Substrate: Corning Eagle 2000, ⁇ 4 inch x 0.7 mmt
  • the number ratio of voids having a pore diameter of 50 ⁇ m or more was measured using an electronic scanning ultrasonic flaw detection system PA-101 manufactured by Nippon Kraut Kramer Co., Ltd. according to the method described above.
  • Comparative Example 1 is a comparative example in which plastic processing was not performed, and the film formation rate is slower than that of the inventive example. In addition, there were many voids and arcing. Comparative Example 2 was an example in which the cooling rate at the time of casting was increased as compared with Comparative Example 1, and the number of voids increased, and accordingly the number of arcing increased.
  • Comparative Examples 3 to 6 are examples in which the total rolling reduction was low, and although the crystal grains having linear grain boundaries and the corresponding grain boundaries could be confirmed, since the ratio was small, the effect of increasing the film formation rate was small. In comparison with this, a slight increase in film formation rate was observed. In addition, compared with Comparative Example 1, there was a slight decrease in voids, and the effect of reducing arcing was small.
  • Example 1 is a reference example. By performing rolling at an appropriate total rolling reduction, the area ratio of crystal grains having linear grain boundaries is 10% or more, and the corresponding grain boundary length ratio is 15% or more. Improved. Moreover, compared with the comparative example, the space
  • Example 2 is a reference example.
  • Example 3 is a reference example.
  • Rolling with a total rolling reduction of 50% results in an area ratio of crystal grains having linear grain boundaries of 35.2% and a corresponding grain boundary length ratio of 40.3%, which is higher than that of the comparative example.
  • the film rate was improved.
  • gap decreased and the reduction of arcing was seen in connection with it.
  • Example 4 is an invention example.
  • Example 5 is an invention example.
  • Rolling with a total rolling reduction of 80% resulted in an area ratio of crystal grains having linear grain boundaries of 87.1% and a corresponding grain boundary length ratio of 69.5%, which is higher than that of the comparative example.
  • the film rate was improved.
  • gap decreased and the reduction of arcing was seen in connection with it.
  • Example 6 is an invention example.
  • Example 7 is an invention example. Because of the rapid cooling during casting, the number of voids is the same as in Comparative Example 2 before rolling. However, by rolling with a total rolling reduction of 80%, the voids are greatly reduced, and arcing is reduced accordingly. It was seen.
  • Example 8 is a reference example. By pressing with a total rolling reduction of 20%, the area ratio of crystal grains having linear grain boundaries was 16.3%, and the corresponding grain boundary length ratio was 19.5%.
  • Example 9 is a reference example. By performing the pressing with the total rolling reduction of 30%, the area ratio of crystal grains having linear grain boundaries was 22.5%, and the corresponding grain boundary length ratio was 20.4%. The film rate was improved. Moreover, compared with the comparative example, the space
  • Example 10 is a reference example. By pressing with a total rolling reduction of 50%, the area ratio of crystal grains having linear grain boundaries was 38.5%, and the corresponding grain boundary length ratio was 38.4%. The film rate was improved.
  • Example 11 is a reference example.
  • the area ratio of crystal grains having linear grain boundaries was 63.1%, and the corresponding grain boundary length ratio was 45.1%, which is compared with the comparative example.
  • the film formation rate was improved.
  • gap decreased and the reduction of arcing was seen in connection with it.
  • Example 12 is an invention example. By carrying out the pressing with the total rolling reduction of 80%, the area ratio of crystal grains having linear grain boundaries was 85.1%, and the corresponding grain boundary length ratio was 70.1%, which was higher than that of the comparative example.
  • Example 13 is an invention example.
  • the area ratio of crystal grains having linear grain boundaries was 96.5%, and the corresponding grain boundary length ratio was 86.4%.
  • the film rate was improved and reached the maximum among all examples.
  • gap decreased and the reduction of arcing was seen with it.
  • Example 14 is an invention example. Because of the rapid cooling during casting, the number of voids was the same as in Comparative Example 2 before pressing, but by pressing with a total rolling reduction of 80%, the voids were greatly reduced, and arcing decreased accordingly.
  • Example 15 is a reference example. After rolling at a total rolling reduction of 20%, heat treatment was performed to increase the area ratio of crystal grains having linear grain boundaries and the corresponding grain boundary length ratio, and the film formation rate also increased.
  • Example 16 is an invention example. After rolling at a total rolling reduction of 80%, heat treatment was applied to increase the area ratio of crystal grains having linear grain boundaries and the corresponding grain boundary length ratio, and the film formation rate also increased.
  • Example 17 is a reference example. After pressing at a total rolling reduction of 20%, heat treatment was applied to increase the area ratio of crystal grains having linear grain boundaries and the corresponding grain boundary length ratio, and the film formation rate also increased.
  • Example 18 is an invention example. After pressing at a total rolling reduction of 80%, heat treatment was applied to increase the area ratio of crystal grains having linear grain boundaries and the corresponding grain boundary length ratio, and the film formation rate also increased.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne une cible de pulvérisation cathodique d'indium qui obtient un taux de formation de film élevé. Un élément cible de pulvérisation cathodique d'indium comprend des grains cristallins qui possèdent des joints de grains linéaires sur la surface pulvérisée cathodiquement, et la fraction de surface des grains cristallins est d'au moins 65,1 %.
PCT/JP2012/070764 2011-12-12 2012-08-15 Elément cible de pulvérisation cathodique d'indium et son procédé de production WO2013088785A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020137011328A KR101365284B1 (ko) 2011-12-12 2012-08-15 인듐제 스퍼터링 타겟 부재 및 그 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011271334 2011-12-12
JP2011-271334 2011-12-12

Publications (1)

Publication Number Publication Date
WO2013088785A1 true WO2013088785A1 (fr) 2013-06-20

Family

ID=48612245

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/070764 WO2013088785A1 (fr) 2011-12-12 2012-08-15 Elément cible de pulvérisation cathodique d'indium et son procédé de production

Country Status (3)

Country Link
KR (1) KR101365284B1 (fr)
TW (1) TWI468537B (fr)
WO (1) WO2013088785A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6344820B2 (fr) * 1981-05-07 1988-09-07 Mitsui Mining & Smelting Co
JP2007113033A (ja) * 2005-10-18 2007-05-10 Hitachi Metals Ltd Ｍｏターゲット材の製造方法およびＭｏターゲット材
WO2009107763A1 (fr) * 2008-02-29 2009-09-03 新日鉄マテリアルズ株式会社 Matériau métallique cible de pulvérisation cathodique
JP2010024474A (ja) * 2008-07-16 2010-02-04 Sumitomo Metal Mining Co Ltd インジウムターゲットの製造方法
JP2011179054A (ja) * 2010-02-26 2011-09-15 Kobe Steel Ltd Ａｌ基合金スパッタリングターゲット
JP2011236445A (ja) * 2010-04-30 2011-11-24 Jx Nippon Mining & Metals Corp インジウムメタルターゲット及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6344820B2 (fr) * 1981-05-07 1988-09-07 Mitsui Mining & Smelting Co
JP2007113033A (ja) * 2005-10-18 2007-05-10 Hitachi Metals Ltd Ｍｏターゲット材の製造方法およびＭｏターゲット材
WO2009107763A1 (fr) * 2008-02-29 2009-09-03 新日鉄マテリアルズ株式会社 Matériau métallique cible de pulvérisation cathodique
JP2010024474A (ja) * 2008-07-16 2010-02-04 Sumitomo Metal Mining Co Ltd インジウムターゲットの製造方法
JP2011179054A (ja) * 2010-02-26 2011-09-15 Kobe Steel Ltd Ａｌ基合金スパッタリングターゲット
JP2011236445A (ja) * 2010-04-30 2011-11-24 Jx Nippon Mining & Metals Corp インジウムメタルターゲット及びその製造方法

Also Published As

Publication number Publication date
TW201323639A (zh) 2013-06-16
KR101365284B1 (ko) 2014-02-19
KR20130087022A (ko) 2013-08-05
TWI468537B (zh) 2015-01-11

Similar Documents

Publication Publication Date Title
TWI518197B (zh) 熱軋銅板
TWI460298B (zh) 濺鍍靶之製造方法及濺鍍靶
TWI390067B (zh) Indium target and its manufacturing method
JP4948634B2 (ja) インジウムターゲット及びその製造方法
JP5254290B2 (ja) インジウムターゲット及びその製造方法
TW201408399A (zh) 銦製圓筒型濺鍍靶及其製造方法
TWI398409B (zh) Indium target and its manufacturing method
WO2019187311A1 (fr) Élément cible de pulvérisation et son procédé de production
WO2012029364A1 (fr) Cible d'indium et son procédé de production
WO2012029355A1 (fr) Cible d'indium et son procédé de production
JP5291754B2 (ja) 太陽電池用スパッタリングターゲット
JP6027823B2 (ja) 熱延銅板、及び、熱延銅板の形状調整方法
JP5183818B1 (ja) インジウム製スパッタリングターゲット部材及びその製造方法
US20170169998A1 (en) In-Cu Alloy Sputtering Target And Method For Producing The Same
WO2013088785A1 (fr) Elément cible de pulvérisation cathodique d'indium et son procédé de production
JP7198750B2 (ja) スパッタリングターゲット材、スパッタリングターゲット、スパッタリングターゲット用アルミニウム板及びその製造方法
TW202245018A (zh) 熱軋銅合金板及濺鍍靶
KR20230007314A (ko) 이트륨 잉곳 및 그것을 사용한 스퍼터링 타깃
JP2016141876A (ja) Ｃｕ−Ｇａ合金スパッタリングターゲット、及び、Ｃｕ−Ｇａ合金鋳塊

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 20137011328

Country of ref document: KR

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12858415

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12858415

Country of ref document: EP

Kind code of ref document: A1