WO2019054489A1 - Cible de pulvérisation - Google Patents

Cible de pulvérisation Download PDF

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Publication number
WO2019054489A1
WO2019054489A1 PCT/JP2018/034211 JP2018034211W WO2019054489A1 WO 2019054489 A1 WO2019054489 A1 WO 2019054489A1 JP 2018034211 W JP2018034211 W JP 2018034211W WO 2019054489 A1 WO2019054489 A1 WO 2019054489A1
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Prior art keywords
metal
phase
tin
sputtering target
oxide
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PCT/JP2018/034211
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English (en)
Japanese (ja)
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香歩 木内
雄也 陸田
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三菱マテリアル株式会社
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Priority to KR1020207003567A priority Critical patent/KR20200053469A/ko
Publication of WO2019054489A1 publication Critical patent/WO2019054489A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • C04B35/457—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 based on tin oxides or stannates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • 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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof

Definitions

  • the present invention relates to a sputtering target used when forming an oxide film containing Zn, Sn and O as main components.
  • a sputtering target used when forming an oxide film containing Zn, Sn and O as main components.
  • the oxide film mainly composed of Zn, Sn, and O described above is excellent in the transmittance in the visible light region and excellent in the infrared reflection characteristic, so a heat shielding film such as window glass, an infrared filter, etc.
  • a heat shielding film such as window glass, an infrared filter, etc.
  • the above-described oxide film is formed, for example, by performing sputtering using a sputtering target made of an oxide, as shown in the following Patent Documents 1-5.
  • a sputtering target made of an oxide, as shown in the following Patent Documents 1-5.
  • sputtering target what makes flat form or cylindrical shape, for example is provided.
  • Patent Document 1 proposes a sputtering target consisting of an oxide sintered body mainly composed of a tin-zinc complex oxide phase and a metal tin phase. Moreover, the sputtering target which consists of an oxide sinter of Zn and Sn is proposed by patent documents 2 and 3.
  • FIG. Further, Patent Document 4 proposes a sputtering target which is an oxide sintered body substantially consisting of tin, zinc and oxygen, and is mainly composed of a tin-zinc complex oxide phase and a tin oxide phase.
  • Patent Document 5 proposes a sputtering target in which a metal oxide of at least one of zinc oxide and tin oxide and a metal powder are sintered.
  • Japan JP 2013-177260 A JP JP 2010-037161 A
  • Japan JP 2010-031364 Japanese Patent Application Laid-Open No. 2007-314364
  • Japanese Patent Application Laid-Open No. 2014-167162 A
  • stannous oxide (SnO) is used as a raw material, and a metallic tin phase is formed by reducing the stannous oxide (SnO).
  • the relative density is about 91.1 to 93.6%, and a sufficiently high density has not been obtained.
  • the tin-zinc complex oxide phase and the metal tin phase are the main phases, and in the target sputtering surface, the specific resistance value is largely different between the area of the tin-zinc complex oxide phase and the area of the metal tin phase. There was a risk that the number of occurrences of abnormal discharge at the time would increase.
  • the metal phase is constituted by the metal powder used at the time of sintering
  • the size of the metal phase depends on the particle size of the metal powder, so that the fine metal phase is not segregated and It was difficult to disperse uniformly.
  • many voids exist and the metal phase is nonuniformly present, which may increase the number of occurrences of abnormal discharge at the time of sputtering.
  • cracking may occur during sputtering, which may make it impossible to stably perform sputtering.
  • the present invention has been made in view of the above-described circumstances, and it is possible to provide a sputtering target which can suppress the occurrence of abnormal discharge and can stably perform DC sputtering with a sufficiently low specific resistance value. With the goal.
  • a sputtering target of one embodiment of the present invention (hereinafter referred to as “the sputtering target of the present invention”) is mainly composed of Zn, Sn and O and Zn / Sn in atomic ratio Zn / Sn.
  • (Zn + Sn) is contained in a range of 0.1 or more and 0.6 or less, and the tin oxide phase and the tin-zinc complex oxide phase are main phases, and a metal tin phase is included,
  • the amount of Sn present as a metal tin phase is in the range of 1.0 mol% or more and 8.0 mol% or less, the average equivalent circle diameter of the metal tin phase is 1 ⁇ m or less, and the relative density is 95% or more It is characterized by being.
  • the sputtering target of the present invention while having a tin oxide phase and a tin-zinc complex oxide phase as main phases, it has a metal tin phase, and the average equivalent circle diameter of the metal tin phase in the cross section of the sputtering target Since the value is 1 ⁇ m or less, the metal tin phase is uniformly present without segregation, and the occurrence of abnormal discharge at the time of sputtering can be suppressed. In addition, the relative density can be improved by finely depositing the metal Sn so as to fill the particles of the oxide phase that is to be the parent phase.
  • the tin oxide phase and the tin-zinc complex oxide phase are the main phases” means that the respective proportions (mol%) of the tin oxide phase and the tin-zinc complex oxide phase in the phase constituting the sputtering target Means more than the other phases.
  • "being mainly composed of Zn, Sn, and O” means that the atomic ratio (at%) of each of Zn, Sn, and O in the sputtering target composition is 10 at% or more.
  • the sputtering target of the present invention since the relative density is 95% or more, the number of voids is small, and the occurrence of abnormal discharge at the time of sputtering can be suppressed. In addition, the occurrence of cracking at the time of sputtering can be suppressed. Further, in the sputtering target of the present invention, Zn and Sn are contained so that Zn / (Zn + Sn) is in the range of 0.1 or more and 0.6 or less in atomic ratio, so that the transparency and infrared reflection characteristics are obtained. Can form an excellent oxide film.
  • the sputtering target of the present invention since the amount of Sn present as the metal tin phase is 1.0 mol% or more, the specific resistance value is sufficiently low, and an oxide film is stably formed by DC sputtering. It becomes possible to make a film.
  • the amount of Sn present as the metal tin phase is 8.0 mol% or less, the metal tin phase is not present more than necessary, and it is possible to suppress melting of the metal when heated in the manufacturing process, A sputtering target can be manufactured stably. In addition, even when the temperature rises during sputtering, the occurrence of cracks on the surface of the target due to thermal expansion can be suppressed.
  • the sputtering target of the present invention may further contain an oxide of one or two or more metal elements M selected from Cr, V, Si, Ti, Al, and Zr.
  • tin oxide can be reduced by one or more metal elements M selected from Cr, V, Si, Ti, Al, and Zr, and a metal tin phase can be formed in the sputtering target.
  • the specific resistance value is sufficiently lowered, and the oxide film can be stably formed by DC sputtering.
  • the metal element M be contained so that M / (Zn + Sn + M) is in the range of 0.001 or more and 0.05 or less in atomic ratio.
  • tin oxide can be reliably reduced by the metal element M to form a metal tin phase. Accordingly, the specific resistance value is sufficiently lowered, and the oxide film can be stably formed by DC sputtering. Furthermore, various characteristics of the formed oxide film can be maintained.
  • the sputtering target according to this embodiment contains Zn, Sn, and O as main components, and Zn and Sn in an atomic ratio such that Zn / (Zn + Sn) is in the range of 0.1 or more and 0.6 or less. There is.
  • the sputtering target which is this embodiment while having a tin oxide phase and a tin zinc complex oxide phase as a main phase, it has a metal tin phase.
  • the tin oxide phase is a stannic oxide phase (SnO 2 phase) and the tin-zinc complex oxide phase is a Zn 2 SnO 4 phase.
  • the average value of the circle equivalent diameter of the observed metal tin phase is made into 1 micrometer or less, and the above-mentioned metal tin phase does not have segregation, and is uniformly distributed. .
  • the sputtering target which is this embodiment, it is set as the structure which the metal tin phase disperse
  • this metal tin phase is formed by reduction of tin oxide.
  • the amount of Sn present as the above-mentioned metal tin phase is in the range of 1.0 mol% or more and 8.0 mol% or less.
  • relative density is made into 95% or more.
  • the specific resistance value is set to 1 ⁇ ⁇ cm or less.
  • the sputtering target according to the present embodiment may further contain an oxide of one or more metal elements M selected from Cr, V, Si, Ti, Al, and Zr.
  • content of metallic element M is 0.001 / 0.05 or less in atomic ratio M / (Zn + Sn + M). It is preferable to set so as to be within the range. That is, in the sputtering target according to the present embodiment, the composition contains Zn, Sn, O, and as necessary, the metal element M, and the other components are inevitable impurities.
  • the atomic ratio in the sputtering target according to the present embodiment the average value of the equivalent circle diameters of observed metal tin, the amount of Sn contained as a metal tin phase, the relative density, the specific resistance value, and the metal element M , The reasons defined as above will be described.
  • an oxide film to be a heat shielding film is formed, and it is necessary to satisfy the transmittance in the visible light region and the infrared reflection characteristic.
  • an oxide film satisfying the various characteristics described above is formed by containing Zn and Sn in an atomic ratio such that Zn / (Zn + Sn) is in the range of 0.1 or more and 0.6 or less. be able to.
  • the lower limit of the atomic ratio Zn / (Zn + Sn) is preferably 0.2 or more, and more preferably 0.25 or more in order to reliably form an oxide film excellent in various characteristics.
  • the upper limit of the atomic ratio Zn / (Zn + Sn) is preferably 0.5 or less, and more preferably 0.4 or less.
  • the average equivalent circle diameter of the metal tin phase is 1 ⁇ m or less
  • the average equivalent circle diameter of the observed metal tin phase exceeds 1 ⁇ m, the number of occurrences of abnormal discharge increases, and it may not be possible to stably form a sputter film.
  • the equivalent circle diameter of the metal tin phase is large, the precipitated metal tin phase can not fill the particles between the oxide phases, which may lower the relative density.
  • the average value of the observed metal-tin phase equivalent circle diameters is limited to 1 ⁇ m or less.
  • the average equivalent circle diameter of the observed metal tin phase should be 0.65 ⁇ m or less. Is more preferable, and it is more preferable to set it to 0.60 ⁇ m or less.
  • the average of the circle equivalent diameter of the observed metal tin phase is the circle equivalent diameter Is the average value of the circle equivalent diameter of the metal tin phase of 0.1 ⁇ m or more.
  • the above-described oxide film is formed by DC sputtering.
  • the amount of Sn present as a metal tin phase is less than 1.0 mol%, the specific resistance value becomes high, and there is a possibility that DC sputtering can not be stably performed. Moreover, there existed a possibility that density could not be improved enough.
  • the amount of Sn present as a metal tin phase exceeds 8.0 mol%, melting of metal occurs during sintering, which may make it impossible to stably manufacture a sputtering target.
  • a large amount of metal tin phase having a thermal expansion coefficient largely different from that of the matrix phase is present, and when the temperature rises during sputtering, there is a possibility that the surface of the target may be cracked due to thermal expansion.
  • the amount of Sn present as the metal tin phase is set in the range of 1.0 mol% or more and 8.0 mol% or less.
  • the lower limit of the amount of Sn present as a metal tin phase in order to lower the specific resistance value and carry out DC sputtering more stably, it is preferable to set the lower limit of the amount of Sn present as a metal tin phase to 3.0 mol% or more, and 4.5 mol% or more It is further preferred that
  • it is preferable to set the upper limit of the amount of Sn present as a metal tin phase to 7.5 mol% or less; It is more preferable to set it as 0 mol% or less.
  • collected from a sputtering target is crushed and it is set as powder, It measures by powder X-ray-diffraction method using this powder, Rietvelt It can be calculated by analyzing by the method.
  • the relative density is the measured density divided by the theoretical density.
  • the theoretical density is calculated by the following equation, assuming that the amount of Sn present as a metal tin phase is calculated by the Rietveld method, and the remaining Sn and Zn are respectively SnO 2 and ZnO. did.
  • Theoretical density 100 / ⁇ (Wa / Da) + (Wb / Db) + (Wc / Dc) ⁇ Wa: SnO 2 content (mass%) Da: Theoretical density of SnO 2 (6.95 g / cm 3 ) Wb: ZnO content (mass%) Db: theoretical density of ZnO (5.61 g / cm 3 ) Wc: Content of metal Sn (mass%) Dc: Theoretical density of metal Sn (7.30 g / cm 3 )
  • relative density of the sputtering target calculated by the above formula is less than 95%, a large number of voids will be present, and there is a possibility that abnormal discharge may easily occur at the time of sputtering. Moreover, there is a possibility that a crack may occur in the sputtering target after sputtering. So, in this embodiment, relative density is specified as 95% or more.
  • the density of the sputtering target may exceed the theoretical density calculated by the above equation due to the reaction of the raw material powder, etc., in which case the relative density will exceed 100%.
  • the relative density of the sputtering target is preferably 96% or more, more preferably 98% or more.
  • the upper limit of the relative density is not particularly limited, but it is, for example, less than 105% because it is difficult to prepare a sintered body having a relative density of 105% or more.
  • the specific resistance value is preferably 1 ⁇ ⁇ cm or less, and more preferably 0.1 ⁇ ⁇ cm or less.
  • the lower limit of the specific resistance value is not particularly limited, and is, for example, 0.001 ⁇ ⁇ cm or more.
  • Metal element M Since one or two or more metal elements M selected from Cr, V, Si, Ti, Al, and Zr are elements capable of reducing tin oxide to form a metal tin phase, these metal elements M may be contained. Since the metal element M reduces tin oxide as described above at the time of sintering, it is present as an oxide phase (MOX) in the sputtering target.
  • MOX oxide phase
  • tin oxide in the case where the sputtering target according to the present embodiment contains the metal element M, tin oxide can be obtained by setting M / (Zn + Sn + M) at an atomic ratio of 0.001 or more as the content of the metal element M. It can be reduced to form a metal tin phase sufficiently.
  • M / (Zn + Sn + M) at 0.05 or less in atomic ratio, the influence on the characteristics of the film to be formed can be suppressed.
  • M / (Zn + Sn + M) is preferably in the range of 0.001 or more and 0.05 or less in atomic ratio.
  • the lower limit of M / (Zn + Sn + M) is preferably 0.0015 or more, and more preferably 0.002 or more.
  • the upper limit of M / (Zn + Sn + M) is preferably 0.01 or less, and more preferably 0.008 or less.
  • raw material powder containing zinc oxide powder and tin oxide powder is prepared (raw material powder preparation step S01).
  • stannic oxide (SnO 2 ) powder is used as the tin oxide powder.
  • metal zinc powder or powder of metal element M is included to reduce tin oxide to form a metal tin phase.
  • raw material powder (1) zinc oxide powder + tin oxide powder + metallic zinc powder, (2) zinc oxide powder + tin oxide powder + powder of metal element M, (3) zinc oxide powder + tin oxide powder + It can be mixed in the pattern of metallic zinc powder + metallic element M powder. Then, the weighed raw material powders are mixed using a ball mill or the like.
  • the mixed raw material powder is filled in a forming die, heated while being pressurized to sinter and obtain a sintered body (sintering step S02).
  • the sintering temperature at this time is within the range of 950 ° C. to 1200 ° C.
  • the holding time at the sintering temperature is within the range of 180 min to 300 min
  • the pressurizing pressure is within the range of 20 MPa to 40 MPa.
  • the atmosphere is preferably a vacuum atmosphere (20 Pa or less).
  • the metallic tin reduces tin oxide, whereby the metallic tin phase is uniformly formed without segregation. That is, in the present embodiment, the metal tin phase is formed by reactive sintering. By reactive sintering in this manner, the average equivalent circle diameter of the observed metal tin phase becomes 1 ⁇ m or less. In addition, the relative density is improved by filling the metal tin phase between the oxide phases.
  • the sintering temperature is set to a temperature exceeding the melting point (419.5 ° C.) of zinc metal. However, zinc metal becomes zinc oxide in the process of sintering, so melting out of zinc metal is suppressed.
  • the sintering temperature is set to a temperature exceeding the melting point (231.9 ° C.) of metal tin, the melting of metal tin is suppressed because the metal tin phase is finely formed in the process of sintering. Be done.
  • the obtained sintered body is machined (machining step S03). Thereby, the sputtering target which is this embodiment is manufactured.
  • the main phase is a tin oxide phase and a tin-zinc complex oxide phase, and the metal tin phase is observed, which is observed. Since the average value of the equivalent circle diameter of the phase is 1 ⁇ m or less, the metal tin phase is uniformly present without segregation, and the occurrence of abnormal discharge at the time of sputtering can be suppressed. In addition, the metal tin phase is sufficiently filled between the oxide phases to be the matrix phase, and the relative density can be improved. Furthermore, even when the temperature rises at the time of sputtering, it is possible to suppress the occurrence of cracking of the target surface due to thermal expansion.
  • the relative density is set to 95% or more, so that the number of voids is small, and the occurrence of abnormal discharge at the time of sputtering can be suppressed. In addition, the occurrence of cracking at the time of sputtering can be suppressed.
  • Zn and Sn are contained so that Zn / (Zn + Sn) in the atomic ratio is in the range of 0.1 or more and 0.6 or less. An oxide film excellent in reflection characteristics can be formed.
  • the sputtering target according to the present embodiment since the amount of Sn present as the metal tin phase is 1.0 mol% or more, the specific resistance value is sufficiently low, and the oxide film is stabilized by DC sputtering. It becomes possible to form a film.
  • the amount of Sn present as the metal tin phase is 8.0 mol% or less, the metal tin phase does not exist more than necessary, and it is possible to suppress melting of the metal when heated in the manufacturing process, which is stable The sputtering target can be manufactured. In addition, even when the temperature rises during sputtering, the occurrence of cracks on the surface of the target due to thermal expansion can be suppressed.
  • the sputtering target according to the present embodiment further includes an oxide of one or more metal elements M selected from Cr, V, Si, Ti, Al, and Zr
  • the metal element M The metal tin phase described above can be formed by reducing tin oxide by Therefore, the specific resistance value is sufficiently low, and the oxide film can be stably formed by DC sputtering.
  • the metal element M is oxidized by the metal element M by containing the metal element M so that M / (Zn + Sn + M) is in the range of 0.001 or more and 0.05 or less.
  • Tin can be reliably reduced to form a metal tin phase, the specific resistance value is sufficiently low, an oxide film can be stably formed by DC sputtering, and the formed oxide is formed. It becomes possible to maintain various characteristics in the object film.
  • the raw material powder zinc oxide powder and tin oxide powder (SnO 2 powder) and / or metal zinc powder or metal element M powder are included, and in the sintering step S02 Since reaction sintering is performed to reduce tin oxide with metal zinc or metal element M to form a metal tin phase, the metal tin phase can be uniformly formed without segregation, and the sintering temperature Even if it is set high, melting of metal can be suppressed.
  • the sintering temperature in the sintering step S02 can be set to a relatively high temperature condition within the range of 950 ° C. or more and 1200 ° C. or less. This makes it possible to obtain a sputtering target with a high relative density.
  • the metal element M when the metal element M further includes one or two or more metal elements selected from Cr, V, Si, Ti, Al, and Zr, the content of the metal element M can be M / A in atomic ratio.
  • (Zn + Sn + M) is described to be in the range of 0.001 or more and 0.05 or less, it is not limited to this, and in the case where the metal tin phase is sufficiently formed by metal zinc, the atomic ratio And M / (Zn + Sn + M) may be contained at a level of less than 0.001.
  • M / (Zn + Sn + M) may exceed 0.05 in atomic ratio depending on the characteristics required for the film formed.
  • metal tin powder purity of 99 mass% or more, average particle diameter 15.0 ⁇ m
  • tin oxide powder purity of 99 mass% or more, average particle diameter 25 ⁇ m
  • composition of sputtering target Composition of sputtering target
  • D8 ADVANCE powder X-ray diffractometer
  • Rietveld method analysis software: TOPAS (version 5) manufactured by Bruker AXS
  • the measurement results are shown in Tables 2 and 3.
  • the measurement conditions were as follows. Source: Cu Tube voltage: 40kV Tube current: 40 mA Scanning range: 15 to 128 deg Step width: 0.01 deg
  • the sputtering target of the present invention since the gray part and the black part occupy the main part, in the sputtering target of the present invention, the tin oxide phase and the tin-zinc complex oxide phase exist as the main phase. I understand that Further, since the minute white parts smaller than the gray part and the black part are scattered and present, the sputtering target of the present invention has a metal tin phase, and the average equivalent circle diameter of the metal tin phase is 1 ⁇ m or less It turns out that it is an extent.
  • the resistivity value of the sputtering target was measured by a resistance measuring device. It measured by the four-point probe method using the low resistivity meter (Loresta-GP) made from Mitsubishi Chemical Co., Ltd. as a resistance measurement apparatus. The temperature at the time of measurement was 23 ⁇ 5 ° C., and the humidity was 50 ⁇ 20%. The measurement results are shown in Table 3.
  • Comparative Example 1 In Comparative Example 1 in which the amount of Sn contained as the metal tin phase was 0.83 mol%, the specific resistance value was high and DC sputtering could not be performed. Also, the relative density was less than 95%. In Comparative Example 2 in which the amount of Sn contained as the metal tin phase was 11.75 mol%, melting of the metal was observed at the time of sintering. For this reason, the sputter test was not performed. Also, the relative density was less than 95%. In Comparative Example 3 containing no tin oxide phase and containing a large amount of metallic zinc phase, dissolution of metal was observed at the time of sintering. For this reason, the sputter test was not performed. Also, the relative density was less than 95%.
  • Comparative Example 4 in which metal tin powder is used as a raw material and the amount of Sn contained as a metal tin phase is set to 10.58 mol%, the average equivalent circle diameter of the metal tin phase exceeds 1.32 ⁇ m and 1 ⁇ m. It was In addition, melting of metal was observed at the time of sintering. For this reason, the sputter test was not performed. Furthermore, the relative density was less than 95%. In Comparative Example 5 in which metal tin powder is used as the raw material and the amount of Sn contained as the metal tin phase is 0.54 mol%, the average equivalent circle diameter of the metal tin phase exceeds 1.29 ⁇ m and 1 ⁇ m. It was In addition, the specific resistance value was high, and DC sputtering could not be performed. Furthermore, the relative density was less than 95%.
  • metal tin powder was not used as a raw material in the invention examples 1-10, a metal tin phase was formed in the structure after sintering. It is presumed that a metal tin phase is formed by reduction of part of tin oxide by the metal zinc powder used as a raw material and the metal powder of element M. For this reason, even if the sintering temperature is set high, melting out of the metal was not confirmed at the time of sintering. Further, in the examples 1-10 of the invention, since the sintering temperature is sufficiently high, the relative density is also as high as 95% or more.
  • the average equivalent circle diameter of metal tin in the target is 1 ⁇ m or less, and the metal tin phase is uniformly dispersed without segregation, and the specific resistance value is Was low enough.
  • the number of occurrences of abnormal discharge at the time of sputtering is also suppressed, and DC sputtering can be stably performed.
  • the relative density also increased to 95% or more.
  • Zr is added as the metal element M, but the average value of the circle equivalent diameter of metal tin in the target is 1 ⁇ m or less, and the metal tin phase is not segregated and It was dispersed uniformly, and the specific resistance value was sufficiently low. Furthermore, the relative density also increased to 95% or more.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Physical Vapour Deposition (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

La présente invention concerne une cible de pulvérisation caractérisée en ce qu'elle est principalement composée de Zn, de Sn et d'O, et contient du Zn et du Sn en quantités telles que le rapport atomique Zn/(Zn + Sn) s'inscrit dans la plage de 0,1 à 0,6 (inclus) ; et en ce qu'elle comprend des phases d'oxyde d'étain et des phases d'oxyde complexe d'étain et de zinc en tant que phases principales, tout en comprenant également des phases métalliques d'étain. Cette cible de pulvérisation est également caractérisée en ce que : la quantité de Sn présent sous forme de phases métalliques d'étain s'inscrit dans la plage de 1,0 % en moles à 8,0 % en moles (inclus) ; la moyenne des diamètres de cercle équivalent des phases métalliques d'étain est inférieure ou égale à 1 µm ; et la densité relative est supérieure ou égale à 95 %.
PCT/JP2018/034211 2017-09-14 2018-09-14 Cible de pulvérisation WO2019054489A1 (fr)

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JP5024226B2 (ja) 2008-08-06 2012-09-12 日立金属株式会社 酸化物焼結体およびその製造方法、スパッタリングターゲット、半導体薄膜
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JP2012066968A (ja) * 2010-09-24 2012-04-05 Kobelco Kaken:Kk 酸化物焼結体およびスパッタリングターゲット
JP2012121791A (ja) * 2010-11-16 2012-06-28 Kobelco Kaken:Kk 酸化物焼結体およびスパッタリングターゲット
JP2013177260A (ja) * 2012-02-28 2013-09-09 Sumitomo Chemical Co Ltd 酸化亜鉛−酸化錫焼結体およびその製造方法
JP2014167163A (ja) * 2013-01-31 2014-09-11 Nitto Denko Corp 赤外線反射フィルムの製造方法
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JP2018053311A (ja) * 2016-09-29 2018-04-05 日立金属株式会社 酸化物ターゲット材

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