CN1990422A - Oxidate sintered body and method for making same, sputtering target and transparent conductive film - Google Patents
Oxidate sintered body and method for making same, sputtering target and transparent conductive film Download PDFInfo
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- CN1990422A CN1990422A CNA2006101425729A CN200610142572A CN1990422A CN 1990422 A CN1990422 A CN 1990422A CN A2006101425729 A CNA2006101425729 A CN A2006101425729A CN 200610142572 A CN200610142572 A CN 200610142572A CN 1990422 A CN1990422 A CN 1990422A
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- sintered body
- oxidate sintered
- sputtering target
- nesa coating
- oxidate
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- 238000009499 grossing Methods 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 abstract description 19
- 238000007599 discharging Methods 0.000 abstract description 2
- 229910003437 indium oxide Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000012789 electroconductive film Substances 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910001887 tin oxide Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 27
- 239000010408 film Substances 0.000 description 27
- 230000000803 paradoxical effect Effects 0.000 description 19
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 208000037656 Respiratory Sounds Diseases 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 5
- 230000002950 deficient Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000011863 silicon-based powder Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Images
Classifications
-
- 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
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
- C04B35/505—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium oxide
-
- 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
- C23C14/083—Oxides of refractory metals or yttrium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Manufacturing Of Electric Cables (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The invention provides a oxide sintered body, which when used as a sputtering target stable sputtering discharging from early stage to last stage, moreover obtaining small transparent electroconductive films of Ra and Ry which used in organic EL and high fine LCD, preparation process thereof, sputtering targets and transparent electroconductive films are also provided. The oxide sintered body has relative density more than 102% which contains silica, indium oxide and tin oxide according to need.
Description
Technical field
The present invention relates to oxidate sintered body and manufacture method thereof, and the sputtering target that adopts it, in order to form nesa coating, this oxidate sintered body is used for sputtering target or the sputter sheet that sputtering method or ion plating method use; Particularly, those that are used for that the transparency electrode of FPD (flat-panel monitor) such as LCD (liquid-crystal display), OLED display forms.
Background technology
Indium sesquioxide-stannic oxide (In
2O
3-SnO
2Composite oxides, be called ITO below) the visible light permeability height of film, therefore and electroconductibility height is widely used as nesa coating in liquid-crystal display or anti-glass dewfall in heating film, infrared reflection film etc.For example, for the nesa coating that uses in the flat-panel monitor (FPD), select low resistance (resistivity 2 * 10
-4About Ω cm) those.
In this case, the someone proposes: as principal constituent, have high resistance and the good transparency (referring to patent documentation 1) to the nesa coating of doped stannum oxide and silicon oxide or aluminum oxide wherein with Indium sesquioxide.
Yet according to the embodiment of this communique, the sputtering target that forms nesa coating is not sintered compact but press-powder body, and has high resistance, can not use the DC magnetron.
On the other hand, as have can be in the DC magnetic control sputtering device volume resistance, the electrically conducting transparent membrane resistance height and the high sputtering target of light transmission rate of formation of usage degree, the applicant at first develops the high resistance nesa coating that added insulativity oxide compounds such as silicon oxide with sputtering target (referring to patent documentation 2).In addition, disclose with Indium sesquioxide and stannic oxide, contained at least a kind the sputtering target (referring to patent documentation 3) of silicon oxide or titanium oxide as principal constituent.The sputtering target that has also proposed to adopt silicon oxide-containing but do not had the silicon oxide phase of high resistance material is with the film technique (referring to patent documentation 4) that forms low-resistance nesa coating.
Yet,, when continuous long-term sputtering discharge,, be easy to generate paradoxical discharge, the problem that generation can not keep to the final stable sputtering discharge owing to there is the such insulation layer of silicon oxide by research thereafter.
For example, the technology of record in the patent documentation 3, owing to add the insulator oxide silicon that is used to improve resistance, in sintered compact, there is the isolator that constitutes by silicon oxide, and become the reason of the paradoxical discharge that the insulation breakdown that causes because of charging charge produces, so there is the problem that can not get stablizing for a long time sputtering discharge in this technology.In addition, and then also exist because paradoxical discharge causes generating the problem that the productivity of particle, equipment etc. also descends.In addition, the sintered compact of putting down in writing among the embodiment of patent documentation 4 also is a low density, and it is many to contain pin hole, and life-time service also can be easy to generate the problem of paradoxical discharge.
Former in addition, for the interpolation in ITO the target of silicon oxide, it is unbodied carrying out nesa coating that sputter forms with it, the residue by wet etching is than ITO excellence, but still insufficient.
Also have, bad by the nesa coating surface smoothing that the sputtering target before this forms, so the problem that exists is: may produce detrimentally affect to display unit to its most advanced and sophisticated overcurrent.Particularly in surface smoothing, when maximum difference of height Ry is big, become the starting point of overcurrent easily.
The surface smoothing of this nesa coating is important membrane property in organic EL field especially, the membrane property that the LCD that the ITO film that uses among the LCD presents uses, for example, and the surface smoothing of Ra=0.74nm, Ry=11.3nm, it can not satisfy the membrane property that organic EL uses.
In addition, in LCD, the surface smoothing of existing ITO film is fine, but as Ra, when Ry diminishes, and the residue of etching reduces, and then makes the more high-precision wet etching of employing carry out pattern to be processed into possibility.
Therefore, the nesa coating that Ra that uses among organic EL or the high meticulous LCD etc. or Ry are little and be used to realize it and the appearance of the sputtering target that produces is desirable.
[patent documentation 1] spy opens flat 4-206403 communique (measure that is used to deal with problems etc.)
[patent documentation 2] spy opens 2003-105532 communique (measure that is used to deal with problems etc.)
[patent documentation 3] spy opens 2003-277921 communique (scope of claim etc.)
[patent documentation 4] spy opens 2004-123479 communique (working of an invention scheme etc.)
Summary of the invention
In view of the foregoing, the invention provides an oxide sintered body, when using as sputtering target, can obtain stable sputtering discharge from the use initial stage to latter stage, realized the Ra or the little nesa coating of Ry of use among organic EL or the high meticulous LCD etc. in addition, the present invention also provides its manufacture method and sputtering target and nesa coating.
The present invention's first scheme that is used to solve above-mentioned problem relates to an oxide sintered body, it is characterized in that, it is for containing Indium sesquioxide and contain stannic oxide as required, and together contains the oxidate sintered body of silicon oxide, and its relative density is more than 102%.
In this first scheme, be oxidate sintered body more than 102%, for example as sputtering target the time, can obtain stable sputtering discharge, in addition, can obtain the nesa coating of surface smoothing from the use initial stage to latter stage by forming relative density.
Alternative plan of the present invention relates to oxidate sintered body, it is characterized in that, in the oxidate sintered body of putting down in writing in first scheme, the above pinhole number of the intravital expense human relations of this sintering (Off エ レ one) diameter 2 μ m is 50/mm of per unit area
2Below.
In this alternative plan,, for example, as sputtering target the time, be difficult to produce paradoxical discharge because pinhole number is few in the sintered compact.
Third party's case of the present invention relates to an oxide sintered body, it is characterized in that, first or the oxidate sintered body of alternative plan record in, during with the arbitrary cross-section of this sintered compact of microscopic examination, the ratio of precipitated phase is more than 40% by the area ratio.
In this third party's case, because the precipitated phase ratio greatly to more than 40%, for example, as sputtering target the time, can obtain up to the film that uses the stability of characteristics in latter stage.
Cubic case of the present invention relates to the manufacture method of oxidate sintered body, it is characterized in that, contain Indium sesquioxide and contain stannic oxide as required, and together contain in the oxidate sintered body manufacture method of silicon oxide, the median size of raw silicon oxide material powder is 0.2 μ m～0.6 μ m, with after other raw material powder are mixed, carry out sintering more than 1400 ℃ in firing temperature.
In this cubic case, because the raw silicon oxide material powder carries out sintering with the regulation particle diameter, so the sintered density of sintered compact significantly rises, for example, as sputtering target the time, stable sputtering discharge can be obtained, in addition, the oxidate sintered body of the nesa coating of surface smoothing can be obtained to obtain from the use initial stage to latter stage.
The 5th scheme of the present invention relates to the manufacture method of oxidate sintered body, it is characterized in that, in the manufacture method of the oxidate sintered body that cubic case is put down in writing, the relative phase density of resulting oxidate sintered body is more than 102%.
In the 5th scheme, can obtain relative phase density and be the oxidate sintered body more than 102%, for example, as sputtering target the time, can obtain stable sputtering discharge, in addition, can obtain the nesa coating of surface smoothing from the use initial stage to latter stage.
The 6th scheme of the present invention relates to sputtering target, it is characterized in that, the oxidate sintered body that first to the 3rd any one scheme is put down in writing is incorporated into backboard.
In the 6th scheme, as sputtering target the time, can obtain stable sputtering discharge from the use initial stage to latter stage.
The 7th scheme of the present invention relates to sputtering target, it is characterized in that, in the sputtering target of the 6th scheme record, at the surface smoothing of the nesa coating of the thickness 200nm that forms by sputter on the glass substrate be: maximum difference of height Ry is below 6.0nm.
In the 7th scheme, can obtain maximum difference of height Ry is the following nesa coating of 6.0nm, can prevent the generation of overcurrent.
All directions of the present invention case relates to nesa coating, it is characterized in that, it is the nesa coating that adopts sputtering target of the 6th scheme or the record of the 7th scheme to form by sputter, and at the surface smoothing of the nesa coating of the thickness 200nm that forms by sputter on the glass substrate be: maximum difference of height Ry is below 6.0nm.
In this all directions case, forming maximum difference of height Ry is the following nesa coating of 6.0nm, can prevent the generation of overcurrent electricity.
The effect that the present invention produces is: an oxide sintered body is provided, for example as sputtering target the time, it can obtain the stable sputtering discharge from the use initial stage to latter stage, in addition, realized the Ra or the little nesa coating of Ry of use among organic EL or the high meticulous LCD etc. in addition, manufacture method and the sputtering target and the nesa coating of this oxidate sintered body also is provided.
Description of drawings
Fig. 1 is the photo of the SEM image of expression embodiment 1.
Fig. 2 is the photo of the SEM image of expression embodiment 2.
Fig. 3 is the photo of the SEM image of expression comparative example 2.
Fig. 4 is the photo of the SEM image of expression comparative example 5.
Embodiment
The oxidate sintered body that the present invention relates to, be to contain Indium sesquioxide and contain stannic oxide as required, and together contain the oxidate sintered body of silicon oxide, it is characterized in that relative density is more than 102%, for example, when using, can obtain stable sputtering discharge from the use initial stage to latter stage as sputtering target.
Here, so-called stable sputtering discharge means as far as possible paradoxical discharge does not take place, and whereby, does not produce crackle, slight crack or defective that particle does not produce target yet, and over time little from the use initial stage to latter stage of the sputtered film characteristic by sputter formation.
Therefore, relative density is the oxidate sintered body more than 102%, and its physical strength improves, is difficult to crack or defective, can obtain stable sputtering discharge.Additional advantage is that when this oxidate sintered body sputter, resulting sputtered film surface is very level and smooth.
Also have, when relative density when being lower than 102%, crackle or defective take place in physical strength low than more than 102% easily, in addition, the surface smoothing of sputtered film has the tendency of deterioration.
Here so-called level and smooth, the maximum difference of height Ry that means surface smoothing for example is below the 10.0nm, below the preferred 6.0nm.As mentioned above, maximum difference of height Ry below the 10.0nm, more level and smooth below the preferred 6.0nm, then can prevent to enter the overcurrent at the tip of sputtered film, can get rid of by entering the detrimentally affect that most advanced and sophisticated overcurrent produces organic EL display element.In addition, in the meticulous LCD manufacturing step of height, can reduce the residue that wet etching causes.
In addition, so-called relative density means the density of calculating with respect to theoretical density.The calculating one of theoretical density for example down.In as each raw material
2O
3Density be 7.179g/cm
3, SnO
2Density be 6.950g/cm
3, SiO
2Density be 2.200g/cm
3The time, then the density of calculating by weighted mean is theoretical density, and with it as 100%.For example, the In of 85 weight %
2O
3The SnO of-10 weight %
2The SiO of-5 weight %
2Situation under theoretical density be 6.43g/cm
3, the relative density of this composition is that 100% o'clock actual density is 6.43g/cm
3
In addition, the pinhole number of the oxidate sintered body that described relative density is significantly high is little, and paradoxical discharge is difficult to be taken place, and in the preferred case, the above pinhole number of the intravital expense human relations of this sintering diameter 2 μ m is 50/mm of per unit area
2Below.Therefore, the pinhole number more than the intravital expense human relations of this sintering diameter 2 μ m is 50/mm of per unit area
2When following, can suppress paradoxical discharge from use initial stage to the latter stage of target, in addition, resulting sputtered film is very level and smooth.
And, take pinhole number more than the human relations diameter 2 μ m more than 50/mm when sintered compact inside
2The time, use the paradoxical discharge in initial stage to latter stage that multiple tendency is arranged from target, thereby be unfavorable, in addition, the smoothness of resulting sputtered film also has the tendency of decline.
Here, what is called is taken the human relations diameter, means when pin hole is observed as particle, clamps the parallel lines interval of certain certain direction of particle.For example, can observe instrumentation by the SEM image of 100 times of magnifications.Concrete is, the arbitrary cross-section of this sintered compact is ground, make to reach mirror status, carry out 2 values by SEM image and handle, determine pin hole, count the above pinhole number of expense human relations diameter 2 μ m with image processing software (particle is resolved III: エ one ァ イ ソ Off ト society and made) to 100 times of magnifications.
In addition, for oxidate sintered body of the present invention, in the preferred case, the precipitated phase ratio the arbitrary cross-section of this sintered compact during with microscopic examination is more than 40% by the area ratio.Therefore, when precipitated phase is 40% when above, for example, as sputtering target the time, use the stability of characteristics of the sputtered film in initial stage to latter stage from target, in addition, sputtered film has the tendency that becomes more level and smooth.
Also have, press area than for less than 40% the time, when using, use initial stage to latter stage from target as sputtering target when the precipitated phase ratio, the tendency increase that the characteristic variations of sputtered film is big, thereby be unfavorable, in addition, the smoothness of sputtered film presents the tendency of decline.
Here, so-called precipitated phase means those of separating out as crystallization phases in oxidate sintered body inside, can by microscopic examination arbitrarily section detect.For example, can detect by the SEM image observation of observing 5000 times of magnifications.In the present invention, the precipitated phase area ratio in the regulation arbitrary cross-section, it is to be preferred more than 40%.
Specifically, in order to produce arbitrary cross-section, grind section, use in addition etching of acid again, then,, can calculate the area ratio of precipitated phase by observing section (for example amplifying 5000 times SEM image) up to reaching mirror status.Also have, as described below, by the diffraction result of X line, think that this precipitated phase is In
2Si
2O
7Phase.
Oxidate sintered body of the present invention as required can stanniferous (Sn).When stanniferous, its scope is 0.001～0.3 mole, preferred 0.01～0.15 mole, more preferably 0.05～0.1 mole scope to 1 mole of indium.As be in this scope, can suitably control the current-carrying electrons density and the mobility of sputtering target, thereby electroconductibility is remained in the good scope.In addition, when surpassing this scope interpolation, the current-carrying electrons mobility of sputtering target descends, and the tendency that makes the electroconductibility deterioration is arranged simultaneously, is unfavorable.
The manufacture method of oxidate sintered body of the present invention is described as follows.
Starting raw material as constituting oxidate sintered body generally adopts In
2O
3, SnO
2, SiO
2Powder, but these monomer, compound, composite oxides etc. also can be made raw material.When using monomer, compound, make it become oxide compound in advance by certain technology.Also have, importantly the median size of the raw material powder of silicon oxide will be 0.2 μ m～0.6 μ m here.
Promptly, preferable production process for oxidate sintered body of the present invention, containing Indium sesquioxide and containing stannic oxide as required and together contain in the manufacture method of oxidate sintered body of silicon oxide, the median size of the raw material powder of silicon oxide is 0.2 μ m～0.6 μ m, with after other raw material powder are mixed, carry out sintering more than 1400 ℃ at firing temperature.In more detail, at first, contain Indium sesquioxide and containing preferred 5～15 weight % stannic oxide as required, and together contain in the manufacture method of oxidate sintered body of preferred 2～8 weight % silicon oxide, the median size of raw silicon oxide material powder is 0.2 μ m～0.6 μ m, with after other raw material powder is mixed 5～48 hours by dry ball, adds the #1500PVA tackiness agent in the powder mix that obtains, its relative powder mix weight is 3～8 weight %, and mixes by mortar etc.With its with screening such as 20～30 purpose sieves after, evenly be filled in the mould, by cold press process etc., with 500kg/cm
2～5ton/cm
2Pressure is pressed.When being lower than 500kg/cm
2The time, compact density descends, and agglomerating carries out insufficient, and sintered density descends.When greater than 5ton/cm
2The time, equipment volume is huge, thereby is unfavorable.This formed body is carried out more than 1400 ℃ burning till in the atmosphere at firing temperature, about heating up, for room temperature～800 ℃, with 40 ℃～100 ℃ of/hour intensifications, for making uniformity of temperature profile in the sintered body, according to the sintered body size, keep more than 4 hours, in 800 ℃ as required for 800～1300 ℃, with 50～450 ℃ of/hour intensifications, for 1300 ℃～design temperature (for example 1450 ℃),, keep more than 4 hours at design temperature with 50～100 ℃ of/hour intensifications.For cooling, be cooled to room temperature with 50～400 ℃/hour.
Therefore, the median size of the raw material powder of silicon oxide is 0.2 μ m～0.6 μ m, is more than 1400 ℃ by making firing temperature, and the density of oxidate sintered body is significantly improved, and the pin hole of sintered compact inside reduces, and precipitated phase increases.
In addition, when the median size of the raw material powder of silicon oxide less than 0.2 μ m, particularly median size when 0.05 μ m is following, burn till back density and descend, thereby be unfavorable, in addition, when median size during greater than 0.6 μ m, sintered density reduces, and precipitated phase descends, and is not preferred therefore.
Here, the raw material powder particle diameter beyond the raw silicon oxide material is not particularly limited, but can adopt about median size 0.3～1.5 μ m, about preferred 0.4～1.1 μ m those.
When sintering temperature reaches more than 1400 ℃, preferred because relative density improves; In addition, can improve the smoothness of sputtered film, thereby be preferred, but in order further to improve relative density, to reduce because of burning till the sintered compact sinuousness that causes, 1450 ℃～1550 ℃ is preferred.Also have, when being higher than 1550 ℃, particularly when burning till more than 1600 ℃, the raising of effect is not remarkable, and the installation cost of firing furnace and running cost costliness are unfavorable tendencies.On the other hand, when being lower than 1400 ℃, because relative density descends but be unfavorable.
Also have, in the present invention, the desirable cooperation ratio of raw material powder, blending means, forming method are not particularly limited, can adopt known before this various wet methods or dry method.
As dry method, can enumerate cold press process (Cold Press) or pressure sintering (Hot Press) etc.In cold press process, powder mix is filled into makes formed body in the forming mould, burn till sintering in air atmosphere or in the oxygen atmosphere.In pressure sintering, powder mix is direct sintering in forming mould.
As wet method, for example, it is preferred adopting the filtering type method of forming (opening flat 11-286002 communique referring to the spy).For this filtering type method of forming, in order to obtain formed body from the decompression draining of ceramic raw material slurry, and the filtering type forming mould that constitutes by non-water soluble material, it constitutes: the strainer with water-permeable that the moulding with 1 above suction eye is provided with on counterdie with counterdie, in this moulding, by being used to seal the sealing material of this strainer, from the forming mould framework of upper face side clamping; Above-mentioned moulding is assembled respectively with counterdie, forming mould framework, sealing material and strainer approval with decomposing, adopt the filtering type forming mould of only discharging the moisture the slurry from the decompression of this filter plane side, the slurry that preparation is made of powder mix, ion exchanged water and organic additive, this slurry is injected the filtering type forming mould, only thereby moisture is made formed body from this filter plane side decompression discharge slurry, burning till behind the ceramic molding drying defatted that obtains.
In each method, implement mechanical workout behind the sintering, thereby the size of forming process Cheng Suoding is for example made target.
Embodiment
Below by specific embodiment explanation the present invention.
Embodiment 1
The silicon oxide powder of the stannic oxide powder of the indium oxide powder of median size 0.48 μ m and median size 0.91 μ m and median size 0.2 μ m, with 85: 10: 5 mixed of weight ratio.In the resin system of the putting it into crucible, mixed 21 hours by the dry type ball milling.When this dry type ball milling, adopt zirconium white system ball to make medium.By screening,, in the powder mix that obtains, mix behind the PVA tackiness agent of the concentration 4% of interpolation specified amount medium and raw material powder classification.This powder is filled in the mould of 236 * 440 sizes, by cold press process at 800kg/cm
2Forming under the pressure.This formed body following sintering that carries out in air atmosphere., kept 5 hours in 1400 ℃ ℃ with 60 ℃ of/hour intensifications from room temperature～1400, be cooled to 1200 ℃ with 200 ℃/hour, obtain sintered compact.This sintered compact is processed into diameter 6 inches (15.24cm), thick 5mm.With its melts combine to anaerobic copper backboard and obtain sputtering target.Add man-hour, sputter face is carried out plane grinding by No. 170 grinding stones.
Embodiment 2
Except that the firing condition of formed body is changed by following method, adopt with embodiment 1 complete same method and make sintered compact, and obtain sputtering target.
From room temperature～800 ℃ with 50 ℃ of/hour intensifications, in 800 ℃ keep 4 hours after, be warming up to 1300 ℃ with 400 ℃/hour, be warming up to 1450 ℃ with 50 ℃/hour, in 1450 ℃ keep 8 hours after, be cooled to 800 ℃ with 50 ℃/hour.Burn till in air atmosphere and carry out.
Embodiment 3
Except that the median size of oxidation Si powder is the firing condition of 0.6 μ m, formed body changes by following method, adopts with the same fully method of embodiment 1 and make sintered compact, and obtain sputtering target.
From room temperature～800 ℃ with 50 ℃ of/hour intensifications, in 800 ℃ keep 4 hours after, be warming up to 1300 ℃ with 400 ℃/hour, be warming up to 1450 ℃ with 50 ℃/hour, in 1450 ℃ keep 8 hours after, be cooled to 800 ℃ with 50 ℃/hour.Burn till in air atmosphere and carry out.
Comparative example 1
Except that the median size of oxidation Si powder is 0.05 μ m, adopts with the same fully method of embodiment 1 and make sintered compact, and obtain sputtering target.
Comparative example 2
Except that the median size of oxidation Si powder is 0.9 μ m, adopts with the same fully method of embodiment 1 and make sintered compact, and obtain sputtering target.
Comparative example 3
Except that the median size of oxidation Si powder is 1.5 μ m, adopts with the same fully method of embodiment 1 and make sintered compact, and obtain sputtering target.
Comparative example 4
Except that the median size of oxidation Si powder is the firing condition of 1.5 μ m, formed body changes by following method, adopts with the same fully method of embodiment 1 and make sintered compact, obtain sputtering target.
From room temperature～800 ℃ with 50 ℃ of/hour intensifications, in 800 ℃ keep 4 hours after, be warming up to 1300 ℃ with 400 ℃/hour, be warming up to 1450 ℃ with 50 ℃/hour, in 1450 ℃ keep 8 hours after, be cooled to 800 ℃ with 50 ℃/hour.Burn till in air atmosphere and carry out.
Comparative example 5
Except that the firing condition of formed body is changed by following method, adopt with embodiment 1 complete same method and make sintered compact, and obtain sputtering target.
Be warming up to 1100 ℃ with 60 ℃/hour, kept 5 hours in 1100 ℃, be cooled to 1000 ℃ with 200 ℃/hour, obtain sintered compact.Burn till in air atmosphere and carry out.
Comparative example 6
Except that the firing condition of formed body is changed by following method, adopt with embodiment 1 complete same method and make sintered compact, and obtain sputtering target.
Be warming up to 1100 ℃ with 60 ℃/hour, kept 5 hours in 1100 ℃, be cooled to 1000 ℃ with 200 ℃/hour, obtain sintered compact.Burn till in oxygen atmosphere and carry out.
Relative density is estimated
To the sintered compact of embodiment 1～comparative example 6,, calculate relative density by the volume that the weight of measuring with electronic scale and Archimedes's method are measured.At this moment, each raw material In
2O
3Density be 7.179g/cm
3, SnO
2Density be 6.950g/cm
3, SiO
2Density be 2.200g/cm
3, the density of calculating by weighted mean is as 100%.For example, work as In
2O
3Be 85 weight %, SnO
2Be 10 weight %, SiO
2When being the raw material ratio of 5 weight %, 6.430g/cm
3Be relative density 100%.Relative density the results are shown in table 1.
Physical strength is estimated
To the sintered compact of embodiment 1～comparative example 6, carry out the bending strength evaluation according to JIS R1601 with the proof bend test device.Bending strength the results are shown in table 1.
Pin hole is estimated
Sintered compact to embodiment 1～comparative example 6 is pulverized, adopt #2000 sand paper to grind to section by the spin finishing device, reach mirror status, SEM image with 100 times of magnifications carries out 2 value picture processing, adopt image processing software, the above pinhole number of expense human relations diameter 2 μ m that exists in the visual field is counted.The pin hole evaluation result is shown in table 1.
The area of precipitated phase is than estimating
Sintered compact to embodiment 1～comparative example 6 is pulverized, and adopts #2000 sand paper to grind by the spin finishing device to section, reaches mirror status, at the acid (HCl: H that remains in 40 ℃
2O: HNO
3=1: immersed 9 minutes 1: 0.08 weight ratio), etching is carried out on the sintered compact surface after, take the SEM image for 5000 times in magnification.As the example of evaluation result, the SEM image of embodiment 1,2 and comparative example 2,5 is shown in Fig. 1～Fig. 4.Residue by etching has occurred as Fig. 1～precipitated phase shown in Figure 3.
This SEM image is carried out picture processing, carry out 2 value image conversions, calculate with respect to all precipitated phase area ratios by image processing software.The area ratio the results are shown in table 1.In addition, to these sintered compacies, the result by the X-ray diffraction device analysis is except that comparative example 5 and 6, to present In
2O
3Phase and In
2Si
2O
7The peak of phase.And In does not appear in comparative example 5 and 6
2Si
2O
7The peak of phase.Can think that from the result of these SEM and XRD above-mentioned precipitated phase is In
2Si
2O
7Phase.
Paradoxical discharge is estimated
To the target of embodiment 1～comparative example 6, adopt the magnetically controlled DC sputtering device and electric arc (paradoxical discharge) counter of De Bodawu (デ Port ダ ウ Application) mode to come paradoxical discharge is counted.Adopt following sputtering condition, the cumulative number of the paradoxical discharge that takes place in 73 hours continuous sputtering discharge is shown in table 1.But, to the target of comparative example 5, owing to sharply increase from the discharge beginning paradoxical discharge frequency after 38 hours, so end discharge, and be exposed to atmosphere, the result of observation target can confirm the crackle of target, and the vestige of paradoxical discharge is arranged in crack site.For the target beyond the comparative example 5, the target residual thickness after the discharge in 73 hours is measured with the ternary tester, its result can confirm: any all below 0.5mmt, and use latter stage in work-ing life up to target.In addition, the result of the target that detects by an unaided eye is that crackle, slight crack and defective do not take place any target yet.
Sputtering condition
Operating pressure 1 * 10
-4Pa
100 ℃ of Heating temperatures
Import partial pressure of ar gas 0.5Pa
Import oxygen partial pressure 5 * 10
-3Pa
Dc power 300W
73 hours discharge times
Glass substrate コ one ニ Application グ society makes, #1737 (two sides grinding object)
Membrane property over time
In above-mentioned continuous discharge, to through after 10 hours, 40 hours, 70 hours, on glass substrate, form the ITO film of 200nm from discharge beginning.It is measured the thin-film electro resistance with four probe method, estimate over time.The results are shown in table 1.
The surface smoothing of film
To embodiment 1～3 and comparative example 1,2,4,5,, estimate the interior surfaceness of 10 μ m with surface shape measuring device AFM to above-mentioned film through the 200nm that forms after 40 hours.The results are shown in table 1.
Evaluation appts
Electronic scales GP3400IP Sartorius society makes
SEM JSM-6380A JEOL society makes
The image processing software particle is resolved III エ one ァ イ ソ Off ト society and is made
X-ray diffraction device MXP3 MAC Science society makes
The X-ray diffraction condition determination
Gamma ray source: CuK α
1: λ=1.5405
Tube voltage: 40kV
Tube current: 30mA
Measurement range: 20～40 °
Sampling interval: 0.02 °
Sweep velocity: 4 °/minute
Divergent slit: 1 °
Scatter slit: 1 °
Receive slit: 0.3mm
Proof bend test device: オ one ト グ ラ Off island Jin She makes
The electric arc counter: Arc Monitor ラ Application De マ one Network society makes
Ternary tester: GJ1000D Tokyo precision
The sheet resistance tester: MCP-TP06P ダ イ ァ イ Application ス Star Le メ Application ト society makes
Surface shape measuring device: AFM SPI3700 (manufacturing of SII society)
Table 1
| Silicon oxide powder median size (μ m) | Burn till gas neon-temperature | Relative density (%) | Bending strength (kg/mm 2) | Pinhole number is (individual/mm 2) | The precipitated phase area is than (%) | Paradoxical discharge cumulative number (inferior) | Sheet resistance (Ω/) | Surface smoothing | |||||
| 10 hours | 40 hours | 70 hours | Over time | Average surface roughness Ra (nm) | Maximum difference of height Ry (nm) | ||||||||
| Embodiment 1 | ?0.2 | Atmosphere-1400 ℃ | 102.2 | ?18.3 | 24.5 | 44.7 | 69 | 74 | 75.2 | 74.6 | Little | 0.43 | 4.2 |
| Embodiment 2 | ?0.2 | Atmosphere-1450 ℃ | 103.1 | ?19.8 | 5.3 | 43 | 23 | 73.2 | 73.8 | 73.9 | Little | 0.43 | 5.7 |
| Embodiment 3 | ?0.6 | Atmosphere-1450 ℃ | 102.3 | ?18.4 | 12.3 | 41 | 34 | 75.6 | 74.6 | 77.6 | Little | 0.48 | 5.9 |
| Comparative example 1 | ?0.05 | Atmosphere-1400 ℃ | 101.5 | ?16.3 | 149.3 | 38.2 | 259 | 75.3 | 79.6 | 110.8 | Greatly | 0.57 | 9.3 |
| Comparative example 2 | ?0.9 | Atmosphere-1400 ℃ | 97.2 | ?16.5 | 252 | 38.7 | 323 | 76.9 | 85.3 | 135.4 | Greatly | 0.52 | 12.6 |
| Comparative example 3 | ?1.5 | Atmosphere-1400 ℃ | 96.6 | ?15.7 | 324 | 33.3 | 635 | 75.4 | 125.7 | 156.8 | Greatly | - | - |
| Comparative example 4 | ?1.5 | Atmosphere-1450 ℃ | 101.6 | ?16.9 | 156.8 | 33 | 256 | 74.9 | 95.3 | 126.8 | Greatly | 0.48 | 11.3 |
| Comparative example 5 | ?0.2 | Atmosphere-1100 ℃ | 63.9 | ?11.8 | 985.6 | 0 | Crack | 79.3 | - | - | - | 1.21 | 18.6 |
| Comparative example 6 | ?0.2 | Oxygen-1100 ℃ | 64.5 | ?12 | 1114.5 | 0 | 8962 | 78.2 | 2458.2 | 2878.3 | Greatly | - | - |
Test-results
From the result shown in the table 1 as can be known, the median size of raw silicon oxide material powder is 0.2～0.6 μ m, the firing temperature embodiment 1～3 more than 1400 ℃, and sintered density improves, and the pin hole of sintered compact inside reduces simultaneously, and in addition, precipitated phase increases.
Therefore, by improving sintered density, physical strength strengthens, and in the time of can suppressing paradoxical discharge or the crackle or the defective of the sintered compact during thermal shocking, further also confirms to obtain the little smooth film of Ra, Ry by sputter.In addition, reduce by pin hole, paradoxical discharge in the time of can suppressing sputter is further confirmed to obtain the little smooth film of Ra, Ry by sputter.In addition, by the increase of precipitated phase, the characteristic of sputtered film uses the variation in time in initial stage to latter stage to diminish from target, further confirms to obtain the little smooth film of Ra, Ry by sputter.
On the other hand, be that relative density is lower than 102% in the comparative example 1 of 0.05 μ m and the comparative example 2,4 that median size is 0.9 μ m and 1.5 μ m in the median size of raw silicon oxide material powder, in addition, the pinhole number of generation is many, and precipitated phase also is lower than 40%, and the Ry of film is big.In addition, both having made when the median size of raw silicon oxide material powder is 0.2 μ m, is that relative density significantly diminishes under 1100 ℃ the low temperature condition when firing temperature, and pinhole number significantly increases simultaneously, and paradoxical discharge also significantly increases, and forms the big film of Ra, Ry.
Claims (9)
1. oxidate sintered body is characterized in that, it is the oxidate sintered body that contains Indium sesquioxide and stannic oxide as required and together contain silicon oxide, and its relative density is more than 102%.
2. according to the oxidate sintered body described in the claim 1, it is characterized in that the pinhole number more than this sintered compact Nei Feilun diameter 2 μ m is 50/mm of per unit area
2Below.
3. according to the oxidate sintered body described in the claim 1, it is characterized in that during with the arbitrary cross-section of this sintered compact of microscopic examination, the precipitated phase ratio is more than 40% by the area ratio.
4. according to the oxidate sintered body described in the claim 2, it is characterized in that during with the arbitrary cross-section of this sintered compact of microscopic examination, the precipitated phase ratio is more than 40% by the area ratio.
5. the manufacture method of oxidate sintered body, it is the oxidate sintered body manufacture method that contains Indium sesquioxide and stannic oxide as required and together contain silicon oxide, it is characterized in that, the median size of raw silicon oxide material powder is 0.2 μ m～0.6 μ m, with after other raw material powder are mixed, carry out sintering more than 1400 ℃ in firing temperature.
6. according to the manufacture method of the oxidate sintered body described in the claim 5, it is characterized in that the relative density of resulting oxidate sintered body is more than 102%.
7. sputtering target is characterized in that, any one described oxidate sintered body in the claim 1～4 is incorporated into backboard.
8. according to the sputtering target described in the claim 7, it is characterized in that at the surface smoothing of the nesa coating of the thickness 200nm that forms by sputter on the glass substrate be: maximum difference of height Ry is below 6.0nm.
9. nesa coating, it is the nesa coating that adopts the sputtering target described in the claim 7 to form by sputter, it is characterized in that at the surface smoothing of the nesa coating of the thickness 200nm that forms by sputter on the glass substrate be: maximum difference of height Ry is below 6.0nm.
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|---|---|---|---|
| JP2005373456A JP2007176706A (en) | 2005-12-26 | 2005-12-26 | Oxide sintered compact, its production method, sputtering target and transparent electrically conductive film |
| JP2005373456 | 2005-12-26 |
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| CN1990422A true CN1990422A (en) | 2007-07-04 |
| CN100551871C CN100551871C (en) | 2009-10-21 |
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|---|---|
| JP (1) | JP2007176706A (en) |
| KR (1) | KR100814321B1 (en) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967054A (en) * | 2010-09-07 | 2011-02-09 | 昆明理工大学 | Preparation method of In2O3/SnO2 gas sensitive material with porous structure |
| CN103270191A (en) * | 2011-02-10 | 2013-08-28 | 三菱综合材料株式会社 | Sputtering target for forming transparent film for solar cells, and process for production thereof |
| CN110546299A (en) * | 2017-05-15 | 2019-12-06 | 三井金属矿业株式会社 | Sputtering target for transparent conductive film |
| CN110546300A (en) * | 2017-05-15 | 2019-12-06 | 三井金属矿业株式会社 | Sputtering target for transparent conductive film |
Families Citing this family (5)
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| KR20120070597A (en) * | 2009-11-19 | 2012-06-29 | 가부시키가이샤 아루박 | Manufacturing method and device for transparent conductive film, sputtering target and transparent conductive film |
| JP4970633B1 (en) * | 2010-12-15 | 2012-07-11 | Ｊｘ日鉱日石金属株式会社 | Ferromagnetic material sputtering target and manufacturing method thereof |
| KR101240197B1 (en) * | 2011-11-18 | 2013-03-06 | 주식회사 나노신소재 | Transparent conducting film, target for transparent conducting film and method of preparing target for transparent conducting film |
| JP6149804B2 (en) | 2014-05-30 | 2017-06-21 | 住友金属鉱山株式会社 | Oxide sintered body and manufacturing method thereof |
| KR102620041B1 (en) * | 2021-12-28 | 2024-01-02 | 미쓰이금속광업주식회사 | Oxide sintered body, manufacturing method thereof, and sputtering target material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3707622B2 (en) * | 1995-04-11 | 2005-10-19 | 日立金属株式会社 | Metal silicide target material |
| JPH09262813A (en) * | 1996-03-27 | 1997-10-07 | Mitsubishi Materials Corp | Manufacture of ito sintered body |
| JP3386677B2 (en) * | 1996-08-13 | 2003-03-17 | 日立金属株式会社 | Metal silicide target material |
| JP3501614B2 (en) | 1997-02-26 | 2004-03-02 | 株式会社オプトロン | ITO sintered body, method of manufacturing the same, and method of forming ITO film using the ITO sintered body |
| JP2000001772A (en) * | 1998-06-16 | 2000-01-07 | Kobe Steel Ltd | Ito target for low resistance film |
| JP4424889B2 (en) * | 2001-06-26 | 2010-03-03 | 三井金属鉱業株式会社 | Sputtering target for high resistance transparent conductive film and method for producing high resistance transparent conductive film |
| CN1320155C (en) * | 2001-06-26 | 2007-06-06 | 三井金属矿业株式会社 | Sputtering target for high resistance transparent conductive membrane and mfg. method of high resistance transparent conductive membrane |
| JP4028269B2 (en) | 2002-03-19 | 2007-12-26 | 日鉱金属株式会社 | Sputtering target for high resistance transparent conductive film |
| JP4175071B2 (en) * | 2002-10-04 | 2008-11-05 | 住友金属鉱山株式会社 | Oxide sintered body and sputtering target |
| JP2004149883A (en) * | 2002-10-31 | 2004-05-27 | Mitsui Mining & Smelting Co Ltd | Sputtering target for high resistance transparent conductive film, and manufacturing method of high resistance transparent conductive film |
| JP2005135649A (en) * | 2003-10-28 | 2005-05-26 | Mitsui Mining & Smelting Co Ltd | Indium oxide based transparent conductive film and its manufacturing method |
| JP2005268616A (en) * | 2004-03-19 | 2005-09-29 | Tosoh Corp | Transparent conductive film and manufacturing method |
| JP4481239B2 (en) * | 2005-11-21 | 2010-06-16 | 三井金属鉱業株式会社 | Sputtering target for high resistance transparent conductive film, high resistance transparent conductive film and method for producing the same |
-
2005
- 2005-12-26 JP JP2005373456A patent/JP2007176706A/en active Pending
-
2006
- 2006-09-27 TW TW095135713A patent/TWI334857B/en not_active IP Right Cessation
- 2006-10-11 KR KR1020060098901A patent/KR100814321B1/en not_active IP Right Cessation
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967054A (en) * | 2010-09-07 | 2011-02-09 | 昆明理工大学 | Preparation method of In2O3/SnO2 gas sensitive material with porous structure |
| CN101967054B (en) * | 2010-09-07 | 2012-11-21 | 昆明理工大学 | Preparation method of In2O3/SnO2 gas sensitive material with porous structure |
| CN103270191A (en) * | 2011-02-10 | 2013-08-28 | 三菱综合材料株式会社 | Sputtering target for forming transparent film for solar cells, and process for production thereof |
| CN110546299A (en) * | 2017-05-15 | 2019-12-06 | 三井金属矿业株式会社 | Sputtering target for transparent conductive film |
| CN110546300A (en) * | 2017-05-15 | 2019-12-06 | 三井金属矿业株式会社 | Sputtering target for transparent conductive film |
| CN110546299B (en) * | 2017-05-15 | 2022-09-30 | 三井金属矿业株式会社 | Sputtering target for transparent conductive film |
| CN110546300B (en) * | 2017-05-15 | 2022-09-30 | 三井金属矿业株式会社 | Sputtering target for transparent conductive film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20070068251A (en) | 2007-06-29 |
| CN100551871C (en) | 2009-10-21 |
| TWI334857B (en) | 2010-12-21 |
| TW200726732A (en) | 2007-07-16 |
| JP2007176706A (en) | 2007-07-12 |
| KR100814321B1 (en) | 2008-03-18 |
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