WO2011046033A1 - Bi-ge-o sintered sputtering target, manufacturing method therefor, and optical recording medium - Google Patents

Bi-ge-o sintered sputtering target, manufacturing method therefor, and optical recording medium Download PDF

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WO2011046033A1
WO2011046033A1 PCT/JP2010/067338 JP2010067338W WO2011046033A1 WO 2011046033 A1 WO2011046033 A1 WO 2011046033A1 JP 2010067338 W JP2010067338 W JP 2010067338W WO 2011046033 A1 WO2011046033 A1 WO 2011046033A1
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geo
target
powder
optical recording
recording medium
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PCT/JP2010/067338
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French (fr)
Japanese (ja)
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淳史 奈良
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Jx日鉱日石金属株式会社
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Priority to CN201080045590.XA priority Critical patent/CN102575339B/en
Priority to JP2010547893A priority patent/JP5259741B2/en
Publication of WO2011046033A1 publication Critical patent/WO2011046033A1/en

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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
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
    • G11B7/266—Sputtering or spin-coating layers
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3287—Germanium oxides, germanates or oxide forming salts thereof, e.g. copper germanate
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24312—Metals or metalloids group 14 elements (e.g. Si, Ge, Sn)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24314—Metals or metalloids group 15 elements (e.g. Sb, Bi)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24318—Non-metallic elements
    • G11B2007/2432—Oxygen
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/004—Recording, reproducing or erasing methods; Read, write or erase circuits therefor
    • G11B7/0045—Recording
    • G11B7/00451—Recording involving ablation of the recording layer
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/2403—Layers; Shape, structure or physical properties thereof
    • G11B7/24035—Recording layers
    • G11B7/24038—Multiple laminated recording layers

Definitions

  • the present invention relates to a Bi—Ge—O-based sintered sputtering target, a method for producing the target, and an optical recording medium, and in particular, the target is not cracked during sputtering, the generation of particles is small, and the high
  • the present invention relates to a Bi—Ge—O-based sintered sputtering target capable of producing a quality thin film and capable of obtaining an optical recording medium free from recording bit errors, a method for manufacturing the target, and an optical recording medium.
  • a write once read many (WORM) optical recording medium is an optical recording medium capable of high-density recording even with a laser beam in a blue wavelength region (350 to 500 nm), particularly a multilayer recording medium having high recording sensitivity.
  • An optical recording medium having a recording layer In order to meet the demand for higher density optical discs, higher density has been achieved by multilayering. Similarly, optical recording media for high-density recording are being developed for optical discs using blue LDs.
  • a film having a stable composition and structure as well as a film having excellent light transmission characteristics are required. Since it is often an oxide and generally has a high melting point, a sputtering method is often used as a film formation method.
  • a sputtering target suitable for obtaining such a film is required.
  • the form and structure of the compound constituting the target also affect the sputtering characteristics, stable sputtering is performed when the compound constituting the target is suitable for the required film characteristics. Whether it can be done is a problem.
  • the generation of particles may increase depending on the target material, which may reduce the quality.
  • the occurrence of recording bit errors due to particles or the like becomes a serious problem. This causes a problem that the product becomes defective and the yield decreases.
  • Patent Document 1 discloses an optical recording medium in which at least a recording layer is formed on a substrate, the main components of the constituent elements of the recording layer are Bi and O (oxygen), contain B, Ge, An optical recording medium containing at least one element X selected from Li, Sn, Cu, Fe, Pd, Zn, Mg, Nd, Mn, and Ni is described.
  • Patent Document 2 discloses that the recording layer has Bi, M (M is Mg, Al, Cr, Mn, Co, Fe, Cu, Zn, Li, Si, Ge, Zr, Ti, Hf, Sn, Mo, V, Nb, Y, Ta) and oxygen, and the recording mark portion on which the information is recorded is composed of crystals of the elements contained in the recording layer and / or oxides of these elements.
  • M Mg, Al, Cr, Mn, Co, Fe, Cu, Zn, Li, Si, Ge, Zr, Ti, Hf, Sn, Mo, V, Nb, Y, Ta
  • a write-once optical recording medium characterized by containing crystals is described.
  • Patent Documents 3 to 8 have been proposed. Under such circumstances, a combination of optical recording media composed of bismuth (Bi), germanium (Ge), and oxygen (O) is conceivable, and these optical recording media are described as being formed by sputtering of a sintered target. There is also.
  • this Bi-Ge-O-based sintered sputtering target is vulnerable to thermal shock, and often cracks and cracks occur during sputtering with high power, resulting in the generation of particles and improving the quality of the recording film and the like. There was a problem to lose.
  • JP 2008-210492 A JP 2006-116948 A JP 2003-48375 A JP 2005-161831 A JP 2005-108396 A JP 2007-169779 A JP 2008-273167 A Japanese Patent No. 4271063
  • the present invention relates to a Bi—Ge—O-based sintered sputtering target, a method for producing the target, and an optical recording medium, and in particular, the target does not crack during sputtering, and the generation of particles is small and stable and high.
  • a method for manufacturing the target, and an optical recording medium Is an issue.
  • the present inventors have conducted intensive research.
  • the Bi-Ge-O-based sintered body having an appropriate composition is selected to control the crystal phase and suppress the thermal shock of the target.
  • the cracking of the target can be prevented and the generation of particles can be effectively suppressed during sputtering.
  • the present invention is based on this finding, 1) A sintered compact target composed of bismuth (Bi), germanium (Ge), and oxygen (O), and the atomic ratio of Bi and Ge is 0.57 ⁇ (Bi / (Bi + Ge)) ⁇ 0.92.
  • Bi-Ge-O based sintered sputtering target characterized in that it includes three phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 , and GeO 2 as crystal phases.
  • the present invention also provides: 4) Starting from GeO 2 powder 0.03 to 89 mol% and Bi 12 GeO 20 powder 11 to 99.97 mol%, the atomic ratio of Bi and Ge is 0.57 ⁇ (Bi / (Bi + Ge). )) After mixing so that ⁇ 0.92, it is hot-pressed at 600 to 840 ° C. and an applied pressure of 150 to 400 kg / cm 2 to obtain Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 .
  • Bi—Ge—O based sintered sputtering target characterized by producing a sintered body containing a three-phase crystal phase 5) 14.3 mol% of GeO 2 powder and 85.7 mol of Bi 2 O 3 powder after% mixture, the 4) method of manufacturing a Bi-GeO oxide sintered sputtering target according to 6, characterized in that to produce Bi 12 GeO 20 powder by solid-phase reaction) Rights 4.
  • the Bi—Ge—O based sintered sputtering target of the present invention does not cause cracking of the target during sputtering, generates less particles, and can stably produce a high-quality thin film. It is possible to obtain an optical recording medium free from the occurrence of this error.
  • the Bi—Ge—O based sintered sputtering target of the present invention is a sintered target made of bismuth (Bi), germanium (Ge), and oxygen (O), and the atomic ratio of Bi and Ge is 0. .57 ⁇ (Bi / (Bi + Ge)) ⁇ 0.92 and includes three phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 , and GeO 2 as crystal phases.
  • a recording film using this composition is a suitable composition that can achieve high-density recording by multilayering, and can stably perform good sputtering film formation.
  • Bi 12 GeO 20 and Bi 4 Ge 3 O 12 In general, when a powder of bismuth oxide (Bi 2 O 3 ) and germanium oxide (GeO 2 ) is used as a starting material and sintered to produce the composition target, Bi 12 GeO 20 and Bi 4 Ge 3 O 12 The two-phase coexistence composition.
  • Bi 12 GeO 20 and Bi 4 Ge 3 O 12 have a large difference in thermal expansion coefficient, they are extremely vulnerable to thermal shock, and there arises a problem that cracking occurs during sputtering film formation at high power.
  • GeO 2 whose thermal expansion coefficient takes a value between Bi 12 GeO 20 and Bi 4 Ge 3 O 12 is used as an intermediate phase, and this is a structure in which three phases coexist in the sintered body.
  • the GeO 2 phase became a buffer phase, and the thermal shock resistance was greatly improved.
  • the thermal expansion coefficient of Bi 12 GeO 20 is 1.39 ⁇ 10 ⁇ 5
  • the thermal expansion coefficient of Bi 4 Ge 3 O 12 is 6.00 ⁇ 10 ⁇ 6
  • the thermal expansion coefficient of GeO 2 is 7.59 ⁇ 10 ⁇ 6, which is a phase having a thermal expansion coefficient between the former two, so that it can be an effective buffer phase.
  • the thermal shock resistance of the target was improved, which enabled film formation with high power, and a great advantage that production efficiency could be increased was obtained.
  • the generation of particles caused by cracks and cracks is remarkably reduced, making it possible to produce stable high quality thin films, producing no recording bit errors, and producing optical recording media that can achieve high recording density. The effect that it becomes possible was obtained.
  • the Bi—Ge—O based sintered sputtering target of the present invention has an average bending strength decrease rate before and after the thermal shock of 50% when the target is subjected to thermal shock by heating at 200 ° C. for 30 minutes. It became the following. In the case of a target having a two-phase coexisting composition of Bi 12 GeO 20 and Bi 4 Ge 3 O 12 as a conventional product, the average bending strength reduction rate before and after the thermal shock exceeds 80%, which is a significant improvement. There was an effect. This makes it possible to directly evaluate the characteristics of the target in order to suppress cracking of the target due to thermal shock.
  • the ratio of the three phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 of the target can be arbitrarily adjusted within the range of the production conditions of the present invention. Although this depends on the degree of thermal shock that the target receives during sputtering, that is, the film formation rate (production rate) and the structure of the sputtering apparatus, it serves as an index for mitigating thermal shock.
  • An optical recording medium formed by sputtering using the above target is a stable and high-quality thin film, and an optical recording medium free from recording bit errors can be obtained.
  • the Bi—Ge—O based sintered sputtering target powders of bismuth oxide and germanium oxide are used as starting materials, and the atomic ratio of Bi and Ge is 0.57 ⁇ (Bi / ( Bi + Ge)) is mixed so that ⁇ 0.92.
  • the mixed powder is hot-pressed at 600 to 840 ° C. and a pressing force of 150 to 400 kg / cm 2 . This makes it possible to produce a sintered body containing three crystal phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 .
  • This sintering condition is a suitable condition for obtaining a target having a uniform composition.
  • the target can be manufactured under sintering conditions outside the above range, the reproducibility of the target quality is inferior, so that the above range is desirable.
  • the atomic ratio of Bi and Ge in the raw material stage 0.57 ⁇ (Bi / (Bi + Ge)) ⁇ 0.92, is directly reflected on the target, and a target having the same composition ratio can be obtained.
  • Bi—Ge—O based sintered sputtering target 0.03 to 89 mol% of GeO 2 powder and 11 to 99.97 mol% of Bi 12 GeO 20 powder are used as sintering raw materials of bismuth oxide and germanium oxide. Is desirable. This is also a requirement for efficiently obtaining a sintered body including three crystal phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 .
  • germanium oxide (GeO 2 ) powder having an average crystal grain size of 10 to 50 ⁇ m. This is because if the amount is less than the above lower limit value, powder aggregation tends to occur and it is difficult to obtain a uniform sintered body. Further, if the above upper limit is exceeded, coarse particles are generated on the sintered target and segregation is likely to occur, so the above range is desirable. This is a more preferable powder condition, and it is possible to use a powder outside this range by adjusting the sintering conditions.
  • the Bi 12 GeO 20 powder can after mixing the GeO 2 powder 14.3 mol% and Bi 2 O 3 powder 85.7Mol%, by solid phase reaction, to prepare in advance by pulverizing it.
  • the particle size of the Bi 12 GeO 20 powder is not particularly limited, and there is no problem as long as it is about 100 ⁇ m or less. This is because there is no aggregation like GeO 2 under the sintering conditions of the present invention.
  • Example 1 A powder of bismuth oxide and germanium oxide with a purity of 3N (99.9%) is used as a starting material, and GeO 2 powder having an average particle diameter of 12 ⁇ m and Bi 12 GeO 20 powder having an average particle diameter of 20 ⁇ m are prepared in advance. After mixing 83.3 mol% of GeO 2 powder and 16.7 mol% of Bi 12 GeO 20 powder so that the atomic ratio of Bi and Ge would be 0.67, respectively, the mixture was further mixed, and the powder after mixing Was filled in a carbon die and hot pressed under the conditions of a temperature of 700 ° C. and a pressure of 250 kg / cm 2 . In this example, GeO 2 powder and Bi 12 GeO 20 powder are added so as to have the above molar ratio. The total ratio of these additions is GeO 2 50.0 mol%, Bi 2 O 3. The blending ratio was adjusted to be 50.0 mol%.
  • the sintered body after hot pressing was finished to obtain a target.
  • the relative density of the target was 102% (7.44 g / cm 3 at 100% density).
  • This sintered body was confirmed by X-ray diffraction measurement to have a three-phase structure of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 . The results are shown in Table 1.
  • the target was subjected to thermal shock by heating at 200 ° C. for 30 minutes. Thereafter, a bending test according to JIS standard 1601 (from 5 arbitrary points in the target, a test piece having a width of 4 ⁇ 0.1 mm, a height of 3 ⁇ 0.1 mm, and a length of 40 to 50 mm was sampled and measured. The average value of the measurement results of the points was determined), and the average bending strength ratio (strength reduction rate) before and after the thermal shock was measured. Some variation occurred depending on the measurement location, but all were less than 50%, and the rate of decrease in strength was small.
  • the embodiment of the present invention provides an optical recording medium that does not generate cracks, can increase production efficiency, can stably produce a high-quality thin film, and does not generate a recording bit error. It was a good target having an excellent effect of being able to be obtained.
  • Example 2 A powder of bismuth oxide and germanium oxide with a purity of 3N (99.9%) is used as a starting material, and GeO 2 powder having an average particle diameter of 12 ⁇ m and Bi 12 GeO 20 powder having an average particle diameter of 20 ⁇ m are prepared in advance. , respectively, the atomic ratio of Bi and Ge is such that 0.80, after compounding GeO 2 powder 66.7Mol%, a Bi 12 GeO 20 powder 33.3 mol%, mixed and further powder after mixing was filled in a carbon die and hot pressed under the conditions of a temperature of 700 ° C. and a pressure of 250 kg / cm 2 .
  • GeO 2 powder and Bi 12 GeO 20 powder were added so as to have the above molar ratio, but the total ratio of these additions was 33.3 mol% GeO 2 and Bi 2 O 3.
  • the blending ratio was adjusted to be 66.7 mol%.
  • the sintered body after hot pressing was finished to obtain a target.
  • the relative density of the target was 95.9% (7.58 g / cm 3 at 100% density).
  • This sintered body was confirmed by X-ray diffraction measurement to have a three-phase structure of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 . The results are shown in Table 1.
  • the target was subjected to thermal shock by heating at 200 ° C. for 30 minutes. Then, the bending test by JIS standard 1601 was implemented, and the average bending strength ratio (strength reduction rate) before and after the thermal shock was measured. Some variation occurred depending on the measurement location, but all were less than 50%, and the rate of decrease in strength was small.
  • the embodiment of the present invention provides an optical recording medium that does not generate cracks, can increase production efficiency, can stably produce a high-quality thin film, and does not generate a recording bit error. It was a good target having an excellent effect of being able to be obtained.
  • Comparative Example 1 A powder of bismuth oxide and germanium oxide having a purity of 3N (99.9%) is used as a starting material, and these are GeO 2 having an average particle diameter of 5 ⁇ m so that the atomic ratio of Bi and Ge is 0.67, respectively. After preparing 50.0 mol% of powder and 50.0 mol% of Bi 2 O 3 powder having an average particle diameter of 20 ⁇ m, they are mixed, and the mixed powder is filled in a carbon die, and the temperature is 730 ° C. and the pressure is 250 kg / Hot pressing was performed under conditions of cm 2 .
  • the sintered body after hot pressing was finished to obtain a target.
  • the relative density of the target was 103% (7.44 g / cm 3 at 100% density). From the X-ray diffraction measurement of this sintered body, it was confirmed that the crystal phase of the target was a two-phase structure of Bi 12 GeO 20 and Bi 4 Ge 3 O 12 .
  • Comparative Example 2 A powder of bismuth oxide and germanium oxide having a purity of 3N (99.9%) is used as a starting material, and GeO 2 powder having an average particle diameter of 5 ⁇ m and Bi 12 GeO 20 powder having an average particle diameter of 20 ⁇ m are prepared in advance. After mixing 83.3 mol% of GeO 2 powder and 16.7 mol% of Bi 12 GeO 20 powder so that the atomic ratio of Bi and Ge would be 0.67, respectively, the mixture was further mixed, and the powder after mixing Was filled in a carbon die and hot pressed under the conditions of a temperature of 700 ° C. and a pressure of 250 kg / cm 2 . In this example, GeO 2 powder and Bi 12 GeO 20 powder are added so as to have the above molar ratio. The total ratio of these additions is GeO 2 50.0 mol%, Bi 2 O 3. The blending ratio was adjusted to be 50.0 mol%.
  • the sintered body after hot pressing was finished to obtain a target.
  • the relative density of the target was 103% (7.58 g / cm 3 at 100% density).
  • the entire amount of GeO reacted and it was confirmed that the sintered body had a two-phase structure of Bi 12 GeO 20 and Bi 4 Ge 3 O 12 .
  • the target is not cracked during sputtering, the generation of particles is small, and a stable and high-quality thin film is formed.
  • the optical recording medium can be manufactured and can produce an optical recording medium free from recording bit errors. The production efficiency of film formation of the optical recording medium can be increased, and a suitable target for manufacturing the optical recording medium can be provided.

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Abstract

Provided are: a sintered target comprising bismuth (Bi), germanium (Ge), and oxygen (O); a manufacturing method therefor; and an optical recording medium. Said Bi-Ge-O sintered sputtering target is characterized in that the relationship between the number of bismuth atoms and the number of germanium atoms satisfies the relation 0.57 < (Bi/(Bi+Ge)) 12GeO20, Bi4Ge3O12, and GeO2. The provided target does not crack upon sputtering, generates few particulates, allows fabrication of stably high-quality thin films, and makes it possible to obtain an optical recording medium with no errors in recorded bits.

Description

Ｂｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲット及びその製造方法並びに光記録媒体Bi-Ge-O-based sintered sputtering target, manufacturing method thereof, and optical recording medium
　本発明は、Ｂｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲット及び同ターゲットの製造方法並びに光記録媒体に関し、特にスパッタリングの際にターゲットの割れが発生せず、パーティクルの発生が少なく、安定して高品質の薄膜の作製が可能であり、記録ビットのエラー発生のない光記録媒体を得ることができるＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲット及び同ターゲットの製造方法並びに光記録媒体に関する。 The present invention relates to a Bi—Ge—O-based sintered sputtering target, a method for producing the target, and an optical recording medium, and in particular, the target is not cracked during sputtering, the generation of particles is small, and the high The present invention relates to a Bi—Ge—O-based sintered sputtering target capable of producing a quality thin film and capable of obtaining an optical recording medium free from recording bit errors, a method for manufacturing the target, and an optical recording medium.
　追記型（ＷＯＲＭ：Ｗｒｉｔｅ Ｏｎｃｅ Ｒｅａｄ Ｍａｎｙ）光記録媒体は、青色波長領域（３５０～５００ｎｍ）のレーザ光でも高密度の記録を行なうことが可能な光記録媒体、特に、高い記録感度を持つ多層の記録層を持つ光記録媒体である。
　光ディスクは高密度化への要求に対応する為、多層化による高密度化が行われている。青色ＬＤを用いる光ディスクにおいても同様に、高密度記録用の光記録媒体の開発が行われている。 A write once read many (WORM) optical recording medium is an optical recording medium capable of high-density recording even with a laser beam in a blue wavelength region (350 to 500 nm), particularly a multilayer recording medium having high recording sensitivity. An optical recording medium having a recording layer.
In order to meet the demand for higher density optical discs, higher density has been achieved by multilayering. Similarly, optical recording media for high-density recording are being developed for optical discs using blue LDs.
　高密度多層記録が可能な追記型光記録媒体を実現するには、安定した組成、構造を持つ材料であることは勿論、光透過特性に優れた膜が必要であるが、そのような材料は酸化物であることが多く、一般的に融点が高い為、成膜法としてスパッタリング法が用いられることが多い。 In order to realize a write-once type optical recording medium capable of high-density multilayer recording, a film having a stable composition and structure as well as a film having excellent light transmission characteristics are required. Since it is often an oxide and generally has a high melting point, a sputtering method is often used as a film formation method.
　従って、そのような膜を得るのに適したスパッタリングターゲットが必要となる。しかし、ターゲットを構成する化合物の形態、構造などが、スパッタリング特性にも影響するため、ターゲットを構成する化合物を、必要な膜の特性に適したものとした時に、良好なスパッタリングを安定して行うことが出来るか否かが問題となる。 Therefore, a sputtering target suitable for obtaining such a film is required. However, since the form and structure of the compound constituting the target also affect the sputtering characteristics, stable sputtering is performed when the compound constituting the target is suitable for the required film characteristics. Whether it can be done is a problem.
　スパッタリング法を用いて基板への光記録媒体用薄膜を形成する場合、ターゲットの材料によってパーティクルの発生が多くなり、品質を低下させる場合がある。特に高記録密度媒体ではパーティクルなどのよる記録ビットのエラー発生が深刻な問題となる。これが原因で、不良品となって歩留まりが低下するという問題が発生する。 When a thin film for an optical recording medium is formed on a substrate using a sputtering method, the generation of particles may increase depending on the target material, which may reduce the quality. Particularly in a high recording density medium, the occurrence of recording bit errors due to particles or the like becomes a serious problem. This causes a problem that the product becomes defective and the yield decreases.
　従来、提案されている光記録媒体として、多数の材料の提案がなされている。例えば、特許文献１には、基板上に少なくとも記録層を形成した光記録媒体であって、記録層の構成元素の主成分がＢｉ及びＯ（酸素）であり、Ｂを含有し、さらにＧｅ、Ｌｉ、Ｓｎ、Ｃｕ、Ｆｅ、Ｐｄ、Ｚｎ、Ｍｇ、Ｎｄ、Ｍｎ、Ｎｉから選択される少なくとも一種の元素Ｘを含有する光記録媒体が記載されている。 Conventionally, many materials have been proposed as optical recording media that have been proposed. For example, Patent Document 1 discloses an optical recording medium in which at least a recording layer is formed on a substrate, the main components of the constituent elements of the recording layer are Bi and O (oxygen), contain B, Ge, An optical recording medium containing at least one element X selected from Li, Sn, Cu, Fe, Pd, Zn, Mg, Nd, Mn, and Ni is described.
　また、特許文献２には、記録層が、Ｂｉ、Ｍ（ＭはＭｇ、Ａｌ、Ｃｒ、Ｍｎ、Ｃｏ、Ｆｅ、Ｃｕ、Ｚｎ、Ｌｉ、Ｓｉ、Ｇｅ、Ｚｒ、Ｔｉ、Ｈｆ、Ｓｎ、Ｍｏ、Ｖ、Ｎｂ、Ｙ、Ｔａのうち少なくとも一つの元素）及び酸素を含有し、情報が記録された記録マーク部が、該記録層に含有される元素の結晶及び／又はそれらの元素の酸化物の結晶を含むことを特徴とする追記型光記録媒体が記載されている。 Patent Document 2 discloses that the recording layer has Bi, M (M is Mg, Al, Cr, Mn, Co, Fe, Cu, Zn, Li, Si, Ge, Zr, Ti, Hf, Sn, Mo, V, Nb, Y, Ta) and oxygen, and the recording mark portion on which the information is recorded is composed of crystals of the elements contained in the recording layer and / or oxides of these elements. A write-once optical recording medium characterized by containing crystals is described.
　この他にも、特許文献３－特許文献８が提案されている。このような中で、ビスマス（Ｂｉ）、ゲルマニウム（Ｇｅ）、酸素（Ｏ）からなる光記録媒体の組合せが考えられ、またこれらの光記録媒体を、焼結体ターゲットのスパッタリングにより成膜する記載もある。しかし、このＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットというのは、熱衝撃に弱く、高パワーによるスパッタリング時に割れ、亀裂が入ることが多く、これによるパーティクルが発生し、記録膜等の品質を損ねる問題があった。 In addition, Patent Documents 3 to 8 have been proposed. Under such circumstances, a combination of optical recording media composed of bismuth (Bi), germanium (Ge), and oxygen (O) is conceivable, and these optical recording media are described as being formed by sputtering of a sintered target. There is also. However, this Bi-Ge-O-based sintered sputtering target is vulnerable to thermal shock, and often cracks and cracks occur during sputtering with high power, resulting in the generation of particles and improving the quality of the recording film and the like. There was a problem to lose.
特開２００８－２１０４９２号公報JP 2008-210492 A 特開２００６－１１６９４８号公報JP 2006-116948 A 特開２００３－４８３７５号公報JP 2003-48375 A 特開２００５－１６１８３１号公報JP 2005-161831 A 特開２００５－１０８３９６号公報JP 2005-108396 A 特開２００７－１６９７７９号公報JP 2007-169779 A 特開２００８－２７３１６７号公報JP 2008-273167 A 特許第４２７１０６３号公報Japanese Patent No. 4271063
　本発明は、Ｂｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲット及び同ターゲットの製造方法並びに光記録媒体に関し、特にスパッタリングの際にターゲットの割れが発生せず、パーティクルの発生が少なく、安定して高品質の薄膜の作製が可能であり、記録ビットのエラー発生のない光記録媒体を得ることができるＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲット及び同ターゲットの製造方法並びに光記録媒体を提供することを課題とする。 The present invention relates to a Bi—Ge—O-based sintered sputtering target, a method for producing the target, and an optical recording medium, and in particular, the target does not crack during sputtering, and the generation of particles is small and stable and high. To provide a Bi-Ge-O-based sintered sputtering target capable of producing a quality thin film and capable of obtaining an optical recording medium free from recording bit errors, a method for manufacturing the target, and an optical recording medium Is an issue.
　上記の課題を解決するために、本発明者らは鋭意研究を行った結果、適切な組成のＢｉ－Ｇｅ－Ｏ系焼結体を選択して結晶相を制御し、ターゲットの熱衝撃を抑制してターゲットの割れを防止し、スパッタリングの際にパーティクルの発生を効果的に抑制することができるとのとの知見を得た。 In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, the Bi-Ge-O-based sintered body having an appropriate composition is selected to control the crystal phase and suppress the thermal shock of the target. As a result, it was found that the cracking of the target can be prevented and the generation of particles can be effectively suppressed during sputtering.
　本発明は、この知見に基づき、
１）ビスマス（Ｂｉ）、ゲルマニウム（Ｇｅ）、酸素（Ｏ）からなる焼結体ターゲットであって、ＢｉとＧｅの原子数比が、０．５７＜（Ｂｉ／（Ｂｉ＋Ｇｅ））＜０．９２であり、結晶相としてＢｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２、ＧｅＯ２の３相を含むことを特徴とするＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲット
２）ターゲットに２００°Ｃ、３０分の加熱による熱衝撃を与えた場合の、該熱衝撃前後の平均曲げ強度低下率が５０％以下であることを特徴とする上記１）記載の焼結体スパッタリングターゲット
３）上記１）又は２）記載のターゲットを用いてスパッタリングすることにより成膜した光記録媒体、を提供する。 The present invention is based on this finding,
1) A sintered compact target composed of bismuth (Bi), germanium (Ge), and oxygen (O), and the atomic ratio of Bi and Ge is 0.57 <(Bi / (Bi + Ge)) <0.92. Bi-Ge-O based sintered sputtering target characterized in that it includes three phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 , and GeO 2 as crystal phases. The sintered body sputtering target 3) described in 1) above, wherein the average bending strength reduction rate before and after the thermal shock is 50% or less when a thermal shock is applied by heating for 3 minutes. And an optical recording medium formed by sputtering using the described target.
　また、本発明は、
４）ＧｅＯ２粉０．０３～８９ｍｏｌ％、Ｂｉ１２ＧｅＯ２０粉１１～９９．９７ｍｏｌ％を出発原料とし、これらの原料をＢｉとＧｅの原子数比が、０．５７＜（Ｂｉ／（Ｂｉ＋Ｇｅ））＜０．９２となるように混合した後、６００～８４０°Ｃ、加圧力１５０～４００ｋｇ／ｃｍ２でホットプレスすることにより、Ｂｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２及びＧｅＯ２の３相の結晶相を含む焼結体を作製することを特徴とするＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットの製造方法
５）ＧｅＯ２粉１４．３ｍｏｌ％とＢｉ２Ｏ３粉８５．７ｍｏｌ％を混合後、固相反応させてＢｉ１２ＧｅＯ２０粉末を作製することを特徴とする上記４）記載のＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットの製造方法
６）平均結晶粒径が１０～５０μｍである酸化ゲルマニウムの焼結原料粉末を用いて焼結することを特徴とする上記４）又は５）記載のＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットの製造方法、を提供する。 The present invention also provides:
4) Starting from GeO 2 powder 0.03 to 89 mol% and Bi 12 GeO 20 powder 11 to 99.97 mol%, the atomic ratio of Bi and Ge is 0.57 <(Bi / (Bi + Ge). )) After mixing so that <0.92, it is hot-pressed at 600 to 840 ° C. and an applied pressure of 150 to 400 kg / cm 2 to obtain Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 . Manufacturing method of Bi—Ge—O based sintered sputtering target characterized by producing a sintered body containing a three-phase crystal phase 5) 14.3 mol% of GeO 2 powder and 85.7 mol of Bi 2 O 3 powder after% mixture, the 4) method of manufacturing a Bi-GeO oxide sintered sputtering target according to 6, characterized in that to produce Bi 12 GeO 20 powder by solid-phase reaction) Rights 4. A method for producing a Bi—Ge—O-based sintered sputtering target according to 4) or 5) above, wherein sintering is performed using a sintering raw material powder of germanium oxide having a crystal grain size of 10 to 50 μm. I will provide a.
　本発明のＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットは、スパッタリングの際にターゲットの割れが発生せず、パーティクルの発生が少なく、安定して高品質の薄膜の作製が可能であり、記録ビットのエラー発生のない光記録媒体を得ることができるという優れた効果を有する。 The Bi—Ge—O based sintered sputtering target of the present invention does not cause cracking of the target during sputtering, generates less particles, and can stably produce a high-quality thin film. It is possible to obtain an optical recording medium free from the occurrence of this error.
　本発明のＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットは、ビスマス（Ｂｉ）、ゲルマニウム（Ｇｅ）、酸素（Ｏ）からなる焼結体ターゲットであって、ＢｉとＧｅの原子数比が、０．５７＜（Ｂｉ／（Ｂｉ＋Ｇｅ））＜０．９２であり、結晶相としてＢｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２、ＧｅＯ２の３相を含むことを特徴とする。この組成を利用した記録膜は、多層化による高密度記録が達成できる好適な組成であり、良好なスパッタリング成膜を安定的に行うことが可能である。 The Bi—Ge—O based sintered sputtering target of the present invention is a sintered target made of bismuth (Bi), germanium (Ge), and oxygen (O), and the atomic ratio of Bi and Ge is 0. .57 <(Bi / (Bi + Ge)) <0.92 and includes three phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 , and GeO 2 as crystal phases. A recording film using this composition is a suitable composition that can achieve high-density recording by multilayering, and can stably perform good sputtering film formation.
　一般に、酸化ビスマス（Ｂｉ２Ｏ３）と酸化ゲルマニウム（ＧｅＯ２）の粉末を出発原料とし、これを焼結して、当該組成ターゲットを作製した場合、Ｂｉ１２ＧｅＯ２０とＢｉ４Ｇｅ３Ｏ１２の２相共存組成となる。
　ところが、Ｂｉ１２ＧｅＯ２０とＢｉ４Ｇｅ３Ｏ１２は熱膨張係数差が大きいため、熱衝撃に極めて弱くなり、高パワーでのスパッタリング成膜時に割れが発生するという問題が発生する。 In general, when a powder of bismuth oxide (Bi 2 O 3 ) and germanium oxide (GeO 2 ) is used as a starting material and sintered to produce the composition target, Bi 12 GeO 20 and Bi 4 Ge 3 O 12 The two-phase coexistence composition.
However, since Bi 12 GeO 20 and Bi 4 Ge 3 O 12 have a large difference in thermal expansion coefficient, they are extremely vulnerable to thermal shock, and there arises a problem that cracking occurs during sputtering film formation at high power.
　このため、本願発明においては、熱膨張係数がＢｉ１２ＧｅＯ２０とＢｉ４Ｇｅ３Ｏ１２の間の値をとるＧｅＯ２を中間相とし、これを焼結体の中に３相が共存する組織とすることで、ＧｅＯ２相が緩衝相となり、耐熱衝撃性が大きく向上することになった。因みに、Ｂｉ１２ＧｅＯ２０の熱膨張係数は１．３９×１０－５で、Ｂｉ４Ｇｅ３Ｏ１２の熱膨張係数は６．００×１０－６である。他方、ＧｅＯ２の熱膨張係数は７．５９×１０－６であり、前２者の間の熱膨張係数を持つ相なので、有効な緩衝相とすることができる。 Therefore, in the present invention, GeO 2 whose thermal expansion coefficient takes a value between Bi 12 GeO 20 and Bi 4 Ge 3 O 12 is used as an intermediate phase, and this is a structure in which three phases coexist in the sintered body. As a result, the GeO 2 phase became a buffer phase, and the thermal shock resistance was greatly improved. Incidentally, the thermal expansion coefficient of Bi 12 GeO 20 is 1.39 × 10 −5 , and the thermal expansion coefficient of Bi 4 Ge 3 O 12 is 6.00 × 10 −6 . On the other hand, the thermal expansion coefficient of GeO 2 is 7.59 × 10 −6, which is a phase having a thermal expansion coefficient between the former two, so that it can be an effective buffer phase.
　この結果、ターゲットの耐熱衝撃性が向上し、これによって高パワーでの成膜が可能となり、生産効率を上昇させることができる大きな利点が得られた。
　また、割れや亀裂が原因となるパーティクルの発生が著しく減少し、安定した高品質の薄膜の作製が可能となり、記録ビットのエラー発生のない、そして高記録密度が達成できる光記録媒体の製造が可能となるという効果が得られた。 As a result, the thermal shock resistance of the target was improved, which enabled film formation with high power, and a great advantage that production efficiency could be increased was obtained.
In addition, the generation of particles caused by cracks and cracks is remarkably reduced, making it possible to produce stable high quality thin films, producing no recording bit errors, and producing optical recording media that can achieve high recording density. The effect that it becomes possible was obtained.
　スパッタリングの際のパーティクル発生防止には、ターゲットの結晶平均粒度を１００μｍ以下とすることも有効である。
　また、本発明のＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットは、ターゲットに２００°Ｃ、３０分の加熱による熱衝撃を与えた場合の、該熱衝撃前後の平均曲げ強度低下率が５０％以下となった。
　従来品のＢｉ１２ＧｅＯ２０とＢｉ４Ｇｅ３Ｏ１２の２相共存組成のターゲットの場合には、前記熱衝撃前後の平均曲げ強度低下率が８０％を超えているのに対して、大きな改善効果があった。これによって、ターゲットの熱衝撃による割れを抑制する上で、ターゲットの特性を直接的に評価できるものである。 In order to prevent the generation of particles during sputtering, it is also effective to set the average crystal grain size of the target to 100 μm or less.
Further, the Bi—Ge—O based sintered sputtering target of the present invention has an average bending strength decrease rate before and after the thermal shock of 50% when the target is subjected to thermal shock by heating at 200 ° C. for 30 minutes. It became the following.
In the case of a target having a two-phase coexisting composition of Bi 12 GeO 20 and Bi 4 Ge 3 O 12 as a conventional product, the average bending strength reduction rate before and after the thermal shock exceeds 80%, which is a significant improvement. There was an effect. This makes it possible to directly evaluate the characteristics of the target in order to suppress cracking of the target due to thermal shock.
　また、前記ターゲットのＢｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２、ＧｅＯ２の３相の比率は本発明の製造条件の範囲で任意に調整できる。これは、スパッタリング時にターゲットが受ける熱衝撃の程度、すなわち成膜速度（生産速度）やスパッタリング装置の構造にもよるが、熱衝撃を緩和するための指標となるものである。
　上記のターゲットを用いてスパッタリングすることにより成膜した光記録媒体は、安定した高品質の薄膜であり、記録ビットのエラー発生のない光記録媒体を得ることができる Further, the ratio of the three phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 of the target can be arbitrarily adjusted within the range of the production conditions of the present invention. Although this depends on the degree of thermal shock that the target receives during sputtering, that is, the film formation rate (production rate) and the structure of the sputtering apparatus, it serves as an index for mitigating thermal shock.
An optical recording medium formed by sputtering using the above target is a stable and high-quality thin film, and an optical recording medium free from recording bit errors can be obtained.
　Ｂｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットの製造に際しては、酸化ビスマスと酸化ゲルマニウムの粉末を出発原料とし、これらの原料を、ＢｉとＧｅの原子数比が、０．５７＜（Ｂｉ／（Ｂｉ＋Ｇｅ））＜０．９２となるように混合する。そして、この混合粉末を、６００～８４０°Ｃ、加圧力１５０～４００ｋｇ／ｃｍ２でホットプレスする。これによって、Ｂｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２及びＧｅＯ２の３相の結晶相を含む焼結体を作製することが可能となる。 In the production of the Bi—Ge—O based sintered sputtering target, powders of bismuth oxide and germanium oxide are used as starting materials, and the atomic ratio of Bi and Ge is 0.57 <(Bi / ( Bi + Ge)) is mixed so that <0.92. The mixed powder is hot-pressed at 600 to 840 ° C. and a pressing force of 150 to 400 kg / cm 2 . This makes it possible to produce a sintered body containing three crystal phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 .
　この焼結条件は、均一組成のターゲットを得ることができる好適な条件である。上記の範囲を外れる焼結条件でターゲットを製造することも可能であるが、ターゲット品質の再現性が劣るので、上記の範囲とするのが望ましい。また、前記原料段階のＢｉとＧｅの原子数比、０．５７＜（Ｂｉ／（Ｂｉ＋Ｇｅ））＜０．９２は、ターゲットに直接反映され、同組成比のターゲットを得ることができる。 This sintering condition is a suitable condition for obtaining a target having a uniform composition. Although the target can be manufactured under sintering conditions outside the above range, the reproducibility of the target quality is inferior, so that the above range is desirable. Further, the atomic ratio of Bi and Ge in the raw material stage, 0.57 <(Bi / (Bi + Ge)) <0.92, is directly reflected on the target, and a target having the same composition ratio can be obtained.
　Ｂｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットの製造に際して、酸化ビスマスと酸化ゲルマニウムの焼結原料として、ＧｅＯ２粉０．０３～８９ｍｏｌ％、Ｂｉ１２ＧｅＯ２０粉１１～９９．９７ｍｏｌ％を使用するが望ましい。これは、Ｂｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２及びＧｅＯ２の３相の結晶相を含む焼結体を、効率良く得るための要件でもある。 In the production of the Bi—Ge—O based sintered sputtering target, 0.03 to 89 mol% of GeO 2 powder and 11 to 99.97 mol% of Bi 12 GeO 20 powder are used as sintering raw materials of bismuth oxide and germanium oxide. Is desirable. This is also a requirement for efficiently obtaining a sintered body including three crystal phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 .
　また、平均結晶粒径が１０～５０μｍである酸化ゲルマニウム（ＧｅＯ２）粉末を用いて焼結することが望ましい。上記の下限値未満では、粉末の凝集が生じ易くなり、均一な焼結体を得ることが難しくなるからである。また、上記の上限値を超えると、焼結したターゲットに粗大粒子が発生し、偏析し易くなるので、上記の範囲とするのが望ましい。これは、より好ましい粉末の条件であり、焼結条件を調整することにより、この範囲外の粉末を使用することも可能である。 Further, it is desirable to sinter using germanium oxide (GeO 2 ) powder having an average crystal grain size of 10 to 50 μm. This is because if the amount is less than the above lower limit value, powder aggregation tends to occur and it is difficult to obtain a uniform sintered body. Further, if the above upper limit is exceeded, coarse particles are generated on the sintered target and segregation is likely to occur, so the above range is desirable. This is a more preferable powder condition, and it is possible to use a powder outside this range by adjusting the sintering conditions.
　Ｂｉ１２ＧｅＯ２０粉については、ＧｅＯ２粉１４．３ｍｏｌ％とＢｉ２Ｏ３粉８５．７ｍｏｌ％を混合後、固相反応させ、これを粉砕して事前に作製することができる。Ｂｉ１２ＧｅＯ２０粉の粒径については、特に制限はなく、凡そ１００μｍ以下であれば、問題はない。これは、本願発明の焼結条件では、ＧｅＯ２のような凝集がないからである。 The Bi 12 GeO 20 powder can after mixing the GeO 2 powder 14.3 mol% and Bi 2 O 3 powder 85.7Mol%, by solid phase reaction, to prepare in advance by pulverizing it. The particle size of the Bi 12 GeO 20 powder is not particularly limited, and there is no problem as long as it is about 100 μm or less. This is because there is no aggregation like GeO 2 under the sintering conditions of the present invention.
　以下、実施例および比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例によって何ら制限されるものではない。すなわち、本発明は特許請求の範囲によってのみ制限されるものであり、本発明に含まれる実施例以外の種々の変形を包含するものである。 Hereinafter, description will be made based on examples and comparative examples. In addition, a present Example is an example to the last, and is not restrict | limited at all by this example. In other words, the present invention is limited only by the scope of the claims, and includes various modifications other than the examples included in the present invention.
（実施例１）
　純度３Ｎ（９９．９％）の酸化ビスマスと酸化ゲルマニウムの粉末を出発原料とすると共に、予め平均粒径が１２μｍのＧｅＯ２粉と平均粒径が２０μｍのＢｉ１２ＧｅＯ２０粉を準備し、これらをそれぞれ、ＢｉとＧｅの原子数比が、０．６７となるように、ＧｅＯ２粉８３．３ｍｏｌ％、Ｂｉ１２ＧｅＯ２０粉１６．７ｍｏｌ％を調合した後、混合し、さらに混合後の粉末をカーボン製ダイスに充填し、温度７００°Ｃ、圧力２５０ｋｇ／ｃｍ２の条件でホットプレスを行った。
　なお、本実施例において、ＧｅＯ２粉、Ｂｉ１２ＧｅＯ２０粉を上記のモル比となるように添加しているが、これらの添加の総合比は、ＧｅＯ２５０．０ｍｏｌ％、Ｂｉ２Ｏ３５０．０ｍｏｌ％に一致する配合比になるように調整した。 Example 1
A powder of bismuth oxide and germanium oxide with a purity of 3N (99.9%) is used as a starting material, and GeO 2 powder having an average particle diameter of 12 μm and Bi 12 GeO 20 powder having an average particle diameter of 20 μm are prepared in advance. After mixing 83.3 mol% of GeO 2 powder and 16.7 mol% of Bi 12 GeO 20 powder so that the atomic ratio of Bi and Ge would be 0.67, respectively, the mixture was further mixed, and the powder after mixing Was filled in a carbon die and hot pressed under the conditions of a temperature of 700 ° C. and a pressure of 250 kg / cm 2 .
In this example, GeO 2 powder and Bi 12 GeO 20 powder are added so as to have the above molar ratio. The total ratio of these additions is GeO 2 50.0 mol%, Bi 2 O 3. The blending ratio was adjusted to be 50.0 mol%.
　ホットプレス後の焼結体を仕上げ加工してターゲットとした。ターゲットの相対密度は１０２％（１００％密度で７．４４ｇ／ｃｍ３）であった。
　この焼結体の、Ｘ線回折測定により、Ｂｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２、ＧｅＯ２の３相構造であることを確認した。この結果を表１に示す。 The sintered body after hot pressing was finished to obtain a target. The relative density of the target was 102% (7.44 g / cm 3 at 100% density).
This sintered body was confirmed by X-ray diffraction measurement to have a three-phase structure of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 . The results are shown in Table 1.
　次に、このターゲットを２００°Ｃ、３０分の加熱による熱衝撃を与えた。その後、ＪＩＳ規格１６０１による曲げ試験（ターゲット中の任意の箇所５点から、幅４±０．１ｍｍ、高さ３±０．１ｍｍ、長さ４０～５０ｍｍの試験片を採取して測定し、５点の測定結果の平均値を求める）を実施し、該熱衝撃前後の平均曲げ強度比（強度の低下率）を測定した。測定箇所により多少のばらつきが生じたが、いずれも５０％未満となり、強度の低下率が少なかった。 Next, the target was subjected to thermal shock by heating at 200 ° C. for 30 minutes. Thereafter, a bending test according to JIS standard 1601 (from 5 arbitrary points in the target, a test piece having a width of 4 ± 0.1 mm, a height of 3 ± 0.1 mm, and a length of 40 to 50 mm was sampled and measured. The average value of the measurement results of the points was determined), and the average bending strength ratio (strength reduction rate) before and after the thermal shock was measured. Some variation occurred depending on the measurement location, but all were less than 50%, and the rate of decrease in strength was small.
　次に、このターゲットを用いて、２ｋＷのパワーでスパッタリングした。この結果、ターゲットに割れや亀裂の発生はなく、下記の比較例に較べ、パーティクルの発生は著しく少なかった。
　この結果、本願発明の実施例は、割れの発生がなく、生産効率を上げることができ、かつ安定して高品質の薄膜の作製が可能であり、記録ビットのエラー発生のない光記録媒体を得ることができるという優れた効果を有する良好なターゲットであった。 Next, sputtering was performed using this target at a power of 2 kW. As a result, there were no cracks or cracks in the target, and the generation of particles was significantly less than in the following comparative example.
As a result, the embodiment of the present invention provides an optical recording medium that does not generate cracks, can increase production efficiency, can stably produce a high-quality thin film, and does not generate a recording bit error. It was a good target having an excellent effect of being able to be obtained.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（実施例２）
　純度３Ｎ（９９．９％）の酸化ビスマスと酸化ゲルマニウムの粉末を出発原料とすると共に、予め平均粒径が１２μｍのＧｅＯ２粉と平均粒径が２０μｍのＢｉ１２ＧｅＯ２０粉を準備し、これらをそれぞれ、ＢｉとＧｅの原子数比が、０．８０となるように、ＧｅＯ２粉６６．７ｍｏｌ％、Ｂｉ１２ＧｅＯ２０粉３３．３ｍｏｌ％を調合した後、混合し、さらに混合後の粉末をカーボン製ダイスに充填し、温度７００°Ｃ、圧力２５０ｋｇ／ｃｍ２の条件でホットプレスを行った。
　なお、本実施例において、ＧｅＯ２粉、Ｂｉ１２ＧｅＯ２０粉を上記のモル比となるように添加しているが、これらの添加の総合比は、ＧｅＯ２３３．３ｍｏｌ％、Ｂｉ２Ｏ３６６．７ｍｏｌ％に一致する配合比になるように調整した。 (Example 2)
A powder of bismuth oxide and germanium oxide with a purity of 3N (99.9%) is used as a starting material, and GeO 2 powder having an average particle diameter of 12 μm and Bi 12 GeO 20 powder having an average particle diameter of 20 μm are prepared in advance. , respectively, the atomic ratio of Bi and Ge is such that 0.80, after compounding GeO 2 powder 66.7Mol%, a Bi 12 GeO 20 powder 33.3 mol%, mixed and further powder after mixing Was filled in a carbon die and hot pressed under the conditions of a temperature of 700 ° C. and a pressure of 250 kg / cm 2 .
In this example, GeO 2 powder and Bi 12 GeO 20 powder were added so as to have the above molar ratio, but the total ratio of these additions was 33.3 mol% GeO 2 and Bi 2 O 3. The blending ratio was adjusted to be 66.7 mol%.
　ホットプレス後の焼結体を仕上げ加工してターゲットとした。ターゲットの相対密度は９５．９％（１００％密度で７．５８ｇ／ｃｍ３）であった。
　この焼結体の、Ｘ線回折測定により、Ｂｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２、ＧｅＯ２の３相構造であることを確認した。この結果を表１に示す。 The sintered body after hot pressing was finished to obtain a target. The relative density of the target was 95.9% (7.58 g / cm 3 at 100% density).
This sintered body was confirmed by X-ray diffraction measurement to have a three-phase structure of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 . The results are shown in Table 1.
　次に、このターゲットを２００°Ｃ、３０分の加熱による熱衝撃を与えた。その後、ＪＩＳ規格１６０１による曲げ試験を実施し、該熱衝撃前後の平均曲げ強度比（強度の低下率）を測定した。測定箇所により多少のばらつきが生じたが、いずれも５０％未満となり、強度の低下率が少なかった。 Next, the target was subjected to thermal shock by heating at 200 ° C. for 30 minutes. Then, the bending test by JIS standard 1601 was implemented, and the average bending strength ratio (strength reduction rate) before and after the thermal shock was measured. Some variation occurred depending on the measurement location, but all were less than 50%, and the rate of decrease in strength was small.
　次に、このターゲットを用いて、２ｋＷのパワーでスパッタリングした。この結果、ターゲットに割れや亀裂の発生はなく、パーティクルの発生も少なかった。
　この結果、本願発明の実施例は、割れの発生がなく、生産効率を上げることができ、かつ安定して高品質の薄膜の作製が可能であり、記録ビットのエラー発生のない光記録媒体を得ることができるという優れた効果を有する良好なターゲットであった。 Next, sputtering was performed using this target at a power of 2 kW. As a result, there were no cracks or cracks in the target, and there were few particles.
As a result, the embodiment of the present invention provides an optical recording medium that does not generate cracks, can increase production efficiency, can stably produce a high-quality thin film, and does not generate a recording bit error. It was a good target having an excellent effect of being able to be obtained.
（比較例１）
　純度３Ｎ（９９．９％）の酸化ビスマスと酸化ゲルマニウムの粉末を出発原料とし、これらをそれぞれ、ＢｉとＧｅの原子数比が、０．６７となるように、平均粒径が５μｍのＧｅＯ２粉５０．０ｍｏｌ％、平均粒径が２０μｍのＢｉ２Ｏ３粉５０．０ｍｏｌ％を調合した後、混合し、さらに混合後の粉末をカーボン製ダイスに充填し、温度７３０°Ｃ、圧力２５０ｋｇ／ｃｍ２の条件でホットプレスを行った。 (Comparative Example 1)
A powder of bismuth oxide and germanium oxide having a purity of 3N (99.9%) is used as a starting material, and these are GeO 2 having an average particle diameter of 5 μm so that the atomic ratio of Bi and Ge is 0.67, respectively. After preparing 50.0 mol% of powder and 50.0 mol% of Bi 2 O 3 powder having an average particle diameter of 20 μm, they are mixed, and the mixed powder is filled in a carbon die, and the temperature is 730 ° C. and the pressure is 250 kg / Hot pressing was performed under conditions of cm 2 .
　ホットプレス後の焼結体を仕上げ加工してターゲットとした。ターゲットの相対密度は１０３％（１００％密度で７．４４ｇ／ｃｍ３）であった。
　この焼結体のＸ線回折測定により、ターゲットの結晶相がＢｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２の２相構造であることを確認した。 The sintered body after hot pressing was finished to obtain a target. The relative density of the target was 103% (7.44 g / cm 3 at 100% density).
From the X-ray diffraction measurement of this sintered body, it was confirmed that the crystal phase of the target was a two-phase structure of Bi 12 GeO 20 and Bi 4 Ge 3 O 12 .
　次に、このターゲットを２００°Ｃ、３０分の加熱による熱衝撃を加えた。その後、ＪＩＳ１６０１による平均曲げ強度試験を実施した。該熱衝撃前後の平均曲げ強度比（強度の低下率）の測定結果を、同様に表１に示す。
　この結果、平均曲げ強度の低下率が８２％となった。このターゲットを用いて、２ｋＷのパワーでスパッタリングした。その結果、スパッタリング中、ターゲットに割れが発生した。また、実施例に較べて、パーティクルの発生が著しく増加した。これはスパッタリング中のターゲットの割れが原因と考えられる。 Next, a thermal shock was applied to the target by heating at 200 ° C. for 30 minutes. Then, the average bending strength test by JIS1601 was implemented. The measurement results of the average bending strength ratio (strength reduction rate) before and after the thermal shock are also shown in Table 1.
As a result, the reduction rate of the average bending strength was 82%. Using this target, sputtering was performed at a power of 2 kW. As a result, cracks occurred in the target during sputtering. In addition, the generation of particles was remarkably increased compared to the examples. This is thought to be caused by cracks in the target during sputtering.
（比較例２）
　純度３Ｎ（９９．９％）の酸化ビスマスと酸化ゲルマニウムの粉末を出発原料とすると共に、予め平均粒径が５μｍのＧｅＯ２粉と平均粒径が２０μｍのＢｉ１２ＧｅＯ２０粉を準備し、これらをそれぞれ、ＢｉとＧｅの原子数比が、０．６７となるように、ＧｅＯ２粉８３．３ｍｏｌ％、Ｂｉ１２ＧｅＯ２０粉１６．７ｍｏｌ％を調合した後、混合し、さらに混合後の粉末をカーボン製ダイスに充填し、温度７００°Ｃ、圧力２５０ｋｇ／ｃｍ２の条件でホットプレスを行った。
　なお、本実施例において、ＧｅＯ２粉、Ｂｉ１２ＧｅＯ２０粉を上記のモル比となるように添加しているが、これらの添加の総合比は、ＧｅＯ２５０．０ｍｏｌ％、Ｂｉ２Ｏ３５０．０ｍｏｌ％に一致する配合比になるように調整した。 (Comparative Example 2)
A powder of bismuth oxide and germanium oxide having a purity of 3N (99.9%) is used as a starting material, and GeO 2 powder having an average particle diameter of 5 μm and Bi 12 GeO 20 powder having an average particle diameter of 20 μm are prepared in advance. After mixing 83.3 mol% of GeO 2 powder and 16.7 mol% of Bi 12 GeO 20 powder so that the atomic ratio of Bi and Ge would be 0.67, respectively, the mixture was further mixed, and the powder after mixing Was filled in a carbon die and hot pressed under the conditions of a temperature of 700 ° C. and a pressure of 250 kg / cm 2 .
In this example, GeO 2 powder and Bi 12 GeO 20 powder are added so as to have the above molar ratio. The total ratio of these additions is GeO 2 50.0 mol%, Bi 2 O 3. The blending ratio was adjusted to be 50.0 mol%.
　ホットプレス後の焼結体を仕上げ加工してターゲットとした。ターゲットの相対密度は１０３％（１００％密度で７．５８ｇ／ｃｍ３）であった。
　この焼結体の、Ｘ線回折測定により、ＧｅＯは全量が反応し、Ｂｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２の２相構造であることを確認した。 The sintered body after hot pressing was finished to obtain a target. The relative density of the target was 103% (7.58 g / cm 3 at 100% density).
By the X-ray diffraction measurement of this sintered body, the entire amount of GeO reacted and it was confirmed that the sintered body had a two-phase structure of Bi 12 GeO 20 and Bi 4 Ge 3 O 12 .
　次に、このターゲットを２００°Ｃ、３０分の加熱による熱衝撃を加えた。その後、ＪＩＳ１６０１による平均曲げ強度試験を実施した。該熱衝撃前後の平均曲げ強度比（強度の低下率）の測定結果を、同様に表１に示す。
　この結果、平均曲げ強度の低下率が８０％となった。このターゲットを用いて、２ｋＷのパワーでスパッタリングした。その結果、スパッタリング中、ターゲットに割れが発生した。また、実施例に較べて、パーティクルの発生が著しく増加した。これはスパッタリング中のターゲットの割れが原因と考えられる。 Next, a thermal shock was applied to the target by heating at 200 ° C. for 30 minutes. Then, the average bending strength test by JIS1601 was implemented. The measurement results of the average bending strength ratio (strength reduction rate) before and after the thermal shock are also shown in Table 1.
As a result, the reduction rate of the average bending strength was 80%. Using this target, sputtering was performed at a power of 2 kW. As a result, cracks occurred in the target during sputtering. In addition, the generation of particles was remarkably increased compared to the examples. This is thought to be caused by cracks in the target during sputtering.
　本発明のＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲット及びこのターゲットの製造方法によれば、スパッタリングの際にターゲットの割れが発生せず、パーティクルの発生が少なく、安定して高品質の薄膜の作製が可能であり、記録ビットのエラー発生のない光記録媒体を得ることができるという優れた効果を有する。光記録媒体の成膜の生産効率を上げることができ、光記録媒体の製造に好適なターゲットを提供できる。 According to the Bi—Ge—O-based sintered sputtering target of the present invention and the method for producing the target, the target is not cracked during sputtering, the generation of particles is small, and a stable and high-quality thin film is formed. The optical recording medium can be manufactured and can produce an optical recording medium free from recording bit errors. The production efficiency of film formation of the optical recording medium can be increased, and a suitable target for manufacturing the optical recording medium can be provided.

Claims (6)

  1. 　ビスマス（Ｂｉ）、ゲルマニウム（Ｇｅ）、酸素（Ｏ）からなる焼結体ターゲットであって、ＢｉとＧｅの原子数比が、０．５７＜（Ｂｉ／（Ｂｉ＋Ｇｅ））＜０．９２であり、結晶相としてＢｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２、ＧｅＯ２の３相を含むことを特徴とするＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲット。 The sintered compact target is made of bismuth (Bi), germanium (Ge), and oxygen (O), and the atomic ratio of Bi and Ge is 0.57 <(Bi / (Bi + Ge)) <0.92. A Bi—Ge—O-based sintered sputtering target comprising three phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 , and GeO 2 as crystal phases.
  2. 　ターゲットに２００°Ｃ、３０分の加熱による熱衝撃を与えた場合の、該熱衝撃前後の平均曲げ強度低下率が５０％以下であることを特徴とする請求項１記載の焼結体スパッタリングターゲット。 2. The sintered sputtering target according to claim 1, wherein when the target is subjected to thermal shock by heating at 200 ° C. for 30 minutes, the average bending strength reduction rate before and after the thermal shock is 50% or less. .
  3. 　請求項１又は２記載のターゲットを用いてスパッタリングすることにより成膜した光記録媒体。 An optical recording medium formed by sputtering using the target according to claim 1.
  4. 　ＧｅＯ２粉０．０３～８９ｍｏｌ％、Ｂｉ１２ＧｅＯ２０粉１１～９９．９７ｍｏｌ％を出発原料とし、これらの原料をＢｉとＧｅの原子数比が、０．５７＜（Ｂｉ／（Ｂｉ＋Ｇｅ））＜０．９２となるように混合した後、６００～８４０°Ｃ、加圧力１５０～４００ｋｇ／ｃｍ２でホットプレスすることにより、Ｂｉ１２ＧｅＯ２０、Ｂｉ４Ｇｅ３Ｏ１２及びＧｅＯ２の３相の結晶相を含む焼結体を作製することを特徴とするＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットの製造方法。 GeO 2 powder 0.03 to 89 mol% and Bi 12 GeO 20 powder 11 to 99.97 mol% are used as starting materials, and the atomic ratio of Bi and Ge is 0.57 <(Bi / (Bi + Ge)). After mixing so as to be <0.92, three phases of Bi 12 GeO 20 , Bi 4 Ge 3 O 12 and GeO 2 are hot-pressed at 600 to 840 ° C. and a pressing force of 150 to 400 kg / cm 2. A method for producing a Bi—Ge—O-based sintered sputtering target comprising producing a sintered body containing a crystalline phase of
  5. 　ＧｅＯ２粉１４．３ｍｏｌ％とＢｉ２Ｏ３粉８５．７ｍｏｌ％を混合後、固相反応させてＢｉ１２ＧｅＯ２０粉末を作製することを特徴とする請求項４記載のＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットの製造方法。 5. The Bi—Ge—O system according to claim 4, wherein 14.3 mol% of GeO 2 powder and 85.7 mol% of Bi 2 O 3 powder are mixed and then subjected to solid phase reaction to produce Bi 12 GeO 20 powder. Manufacturing method of sintered compact sputtering target.
  6. 　平均結晶粒径が１０～５０μｍである酸化ゲルマニウムの焼結原料粉末を用いて焼結することを特徴とする請求項４又は５記載のＢｉ－Ｇｅ－Ｏ系焼結体スパッタリングターゲットの製造方法。 6. The method for producing a Bi—Ge—O-based sintered sputtering target according to claim 4, wherein sintering is performed using a sintering raw material powder of germanium oxide having an average crystal grain size of 10 to 50 μm.
PCT/JP2010/067338 2009-10-13 2010-10-04 Bi-ge-o sintered sputtering target, manufacturing method therefor, and optical recording medium WO2011046033A1 (en)

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US9566618B2 (en) 2011-11-08 2017-02-14 Tosoh Smd, Inc. Silicon sputtering target with special surface treatment and good particle performance and methods of making the same

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JPS51109300A (en) * 1975-03-20 1976-09-28 Matsushita Electric Ind Co Ltd Gerumaniumusanbisumasuhakumakuno seizohoho
JPS5313200A (en) * 1976-07-21 1978-02-06 Matsushita Electric Ind Co Ltd Production method of piezo-electric thin film
JPS58167429A (en) * 1982-03-26 1983-10-03 Otsuka Chem Co Ltd Amorphous material of bismuth-germanium type oxide and preparation thereof
JP2003277923A (en) * 2002-03-27 2003-10-02 Sumitomo Metal Mining Co Ltd Ge-Bi ALLOY TARGET FOR SPUTTERING AND PRODUCTION METHOD THEREOF

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JPS51109300A (en) * 1975-03-20 1976-09-28 Matsushita Electric Ind Co Ltd Gerumaniumusanbisumasuhakumakuno seizohoho
JPS5313200A (en) * 1976-07-21 1978-02-06 Matsushita Electric Ind Co Ltd Production method of piezo-electric thin film
JPS58167429A (en) * 1982-03-26 1983-10-03 Otsuka Chem Co Ltd Amorphous material of bismuth-germanium type oxide and preparation thereof
JP2003277923A (en) * 2002-03-27 2003-10-02 Sumitomo Metal Mining Co Ltd Ge-Bi ALLOY TARGET FOR SPUTTERING AND PRODUCTION METHOD THEREOF

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9566618B2 (en) 2011-11-08 2017-02-14 Tosoh Smd, Inc. Silicon sputtering target with special surface treatment and good particle performance and methods of making the same

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