WO2010090137A1 - 酸化チタンを主成分とする薄膜及び酸化チタンを主成分とする焼結体スパッタリングターゲット - Google Patents
酸化チタンを主成分とする薄膜及び酸化チタンを主成分とする焼結体スパッタリングターゲット Download PDFInfo
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- WO2010090137A1 WO2010090137A1 PCT/JP2010/051232 JP2010051232W WO2010090137A1 WO 2010090137 A1 WO2010090137 A1 WO 2010090137A1 JP 2010051232 W JP2010051232 W JP 2010051232W WO 2010090137 A1 WO2010090137 A1 WO 2010090137A1
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- Prior art keywords
- titanium oxide
- thin film
- film
- oxygen
- target
- Prior art date
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000010409 thin film Substances 0.000 title claims abstract description 60
- 238000005477 sputtering target Methods 0.000 title claims abstract description 30
- 239000010408 film Substances 0.000 claims abstract description 145
- 230000008033 biological extinction Effects 0.000 claims abstract description 63
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000001301 oxygen Substances 0.000 claims abstract description 62
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 230000003287 optical effect Effects 0.000 claims abstract description 42
- 239000010936 titanium Substances 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 34
- 230000001681 protective effect Effects 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 63
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 34
- 239000010931 gold Substances 0.000 claims description 27
- 229910052697 platinum Inorganic materials 0.000 claims description 25
- 229910052737 gold Inorganic materials 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 229910052763 palladium Inorganic materials 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 16
- 150000002739 metals Chemical class 0.000 claims description 16
- 239000000758 substrate Substances 0.000 abstract description 33
- 239000011521 glass Substances 0.000 abstract description 27
- 230000003247 decreasing effect Effects 0.000 abstract description 10
- 238000002834 transmittance Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 51
- 238000004544 sputter deposition Methods 0.000 description 46
- 239000002245 particle Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 27
- 239000010410 layer Substances 0.000 description 27
- 239000011812 mixed powder Substances 0.000 description 24
- 239000000843 powder Substances 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000004453 electron probe microanalysis Methods 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 12
- 238000007731 hot pressing Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000011241 protective layer Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000005328 architectural glass Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002355 dual-layer Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
- G11B7/2542—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins
- G11B7/2545—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins containing inorganic fillers, e.g. particles or fibres
-
- 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
- C04B35/46—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 titanium oxides or titanates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
Definitions
- the present invention relates to a thin film mainly composed of titanium oxide having a high refractive index and a low extinction coefficient, and a sintered compact sputtering target mainly composed of titanium oxide suitable for manufacturing the thin film.
- CD-RW which appeared in 1977 as a rewritable CD
- the CD-RW is rewritten about 1000 times.
- DVD-RW has been developed and commercialized for DVD use, but the layer structure of this disc is basically the same as or similar to CD-RW.
- the number of rewrites is about 1000 to 10,000. These are used to record, reproduce, and add information by irradiating a light beam to cause optical changes such as transmittance and reflectance of the recording material. is there.
- a phase change optical disk used for CD-RW, DVD-RW, or the like is formed on both sides of a recording thin film layer such as Ag-In-Sb-Te system or Ge-Sb-Te system with a high level of ZnS / SiO 2 or the like. It has a four-layer structure sandwiched between protective layers of melting point dielectrics and further provided with a reflective film of silver, silver alloy or aluminum alloy. In order to increase the number of repetitions, an interface layer is added between the memory layer and the protective layer as necessary.
- the reflective layer and the protective layer are required to have an optical function to increase the difference in reflectance between the amorphous portion and the crystalline portion of the recording layer, and also have a moisture resistance of the recording thin film and a function to prevent deformation due to heat.
- a function called thermal condition control is required (see Non-Patent Document 1).
- Patent Document 1 a single-sided dual-layer optical recording medium has been proposed in order to enable high-capacity and high-density recording.
- this Patent Document 1 there are a first information layer formed on the substrate 1 and a second information layer formed on the substrate 2 from the incident direction of the laser beam, and these are mutually information films via an intermediate layer. They are attached to face each other.
- the first information layer includes a recording layer and a first metal reflective layer
- the second information layer includes a first protective layer, a second protective layer, a recording layer, and a second metal reflective layer.
- layers such as a hard coat layer and a heat diffusion layer for protecting from scratches, dirt and the like may be arbitrarily formed.
- Various materials have been proposed for these protective layers, recording layers, reflective layers, and the like.
- the protective layer made of a high-melting-point dielectric is resistant to repeated thermal stresses caused by heating and cooling, and further prevents these thermal effects from affecting the reflective film and other parts. Thin, low reflectivity and toughness that does not change is required. In this sense, the dielectric protective layer has an important role.
- the recording layer, the reflective layer, the interference film layer, etc. are equally important in the sense that they perform their respective functions in the electronic parts such as CD and DVD described above. Don't hesitate.
- Each thin film of these multilayer structures is usually formed by sputtering.
- a substrate composed of a positive electrode and a negative electrode is opposed to a target, and an electric field is generated by applying a high voltage between the substrate and the target in an inert gas atmosphere. Electrons that have been ionized and an inert gas collide to form a plasma. The cations in the plasma collide with the target (negative electrode) surface and knock out target constituent atoms, and the substrate that the ejected atoms face. This is based on the principle that a film is formed on the surface.
- a target using titanium oxide (TiO x ) has been proposed as a sputtering target for forming a heat ray reflective film and an antireflection film (see Patent Document 2).
- the specific resistance value is set to 0.35 ⁇ cm or less to enable DC sputtering and to obtain a film having a high refractive index.
- measures are taken to further introduce oxygen by setting the oxygen content to 35% by weight or more.
- a metal oxide is added to improve the film formation rate.
- a precision optical member that requires a film having a higher refractive index and less absorption is required.
- JP 2006-79710 A Japanese Patent No. 3836163
- the present invention provides a thin film mainly composed of titanium oxide having a high refractive index and a low extinction coefficient, and a sintered body based on titanium oxide suitable for manufacturing the thin film.
- An object is to obtain a target, and at the same time, an object is to obtain a thin film that is excellent in transmittance and has little decrease in reflectance and is useful as an interference film or a protective film of an optical information recording medium. Further, it can be applied to a glass substrate, that is, used as a heat ray reflective film, an antireflection film, or an interference filter.
- the present inventors have conducted intensive research. As a result, it is extremely effective to add a metal such as copper or platinum to titanium oxide, and the interference film or protection of an optical information recording medium. It was found that a material capable of maintaining the transmittance and preventing the decrease in the reflectance without deteriorating the characteristics as a film can be obtained.
- Titanium, oxygen and copper are contained, Ti is 29.0 at% or more and 34.0 at% or less, Cu is 0.003 at% or more and 7.7 at% or less, and the balance is oxygen and inevitable impurities, and oxygen component
- the ratio O / (2Ti + 0.5Cu) of the metal component is 0.96 or more
- the thin film 2 is mainly composed of titanium oxide, and contains titanium, oxygen and platinum, and Ti is 29.0 at% or more, 34.0 at% or less, Pt is 0.003 at% or more and 5.7 at% or less, the balance is composed of oxygen and inevitable impurities, and the ratio O / (2Ti + Pt) of oxygen component to metal component is 0.95 or more.
- a thin film mainly composed of titanium oxide characterized by the following: 3) including one or more metals M selected from titanium, oxygen and cobalt, nickel, palladium, gold, and Ti of 29.0 at% or more, 34.0a % Or less, M is 0.003 at% or more and 7.7 at% or less, the balance is composed of oxygen and inevitable impurities, and the ratio O / (2Ti + M) of oxygen component to metal component is 0.95 or more.
- Component thin film 5) Thin film mainly composed of titanium oxide according to any one of 1) to 4) above, wherein an extinction coefficient in a wavelength region of 400 to 410 nm is 0.1 or less 6)
- a thin film used for an optical interference film or a protective film It is characterized by being A thin film mainly comprising titanium oxide according to any one of 1) to 6) 8) A thin film used as an optical recording medium, according to any one of 1) to 6) above Thin film mainly composed of titanium oxide as described
- the target is mainly composed of titanium oxide composed of titanium, oxygen and inevitable impurities, and each component is (TiO 2-m ) 1-n Pt n (where 0 ⁇ m ⁇ 0.5, 0 .0001 ⁇ n ⁇ 0.15), and a specific resistance is 100 ⁇ cm or less, and a sintered sputtering target mainly composed of titanium oxide 11) From cobalt, nickel, palladium, gold Selection
- a target comprising, as a main component, titanium oxide composed of at least one selected metal M and the balance
- the present invention is a thin film mainly composed of titanium oxide having a high refractive index and a low extinction coefficient, and a sintered body sputtering target mainly composed of titanium oxide suitable for manufacturing the thin film.
- the thin film obtained by the present invention has a great effect as a film / layer of an optical information recording medium.
- the thin film of the present invention is particularly useful as an interference film or a protective film of an optical information recording medium because it has excellent transmittance and little decrease in reflectance.
- the high-melting-point dielectric protective layer must be resistant to repeated thermal stresses caused by heating and cooling, and the thermal effects of these layers should not affect the reflective film or other parts.
- the thin film mainly composed of titanium oxide of the present invention has characteristics that can be applied to such materials.
- the amount of oxygen during sputtering can be adjusted within a small range, there is also an effect that a decrease in film formation rate can be suppressed.
- the thin film mainly composed of titanium oxide of the present invention contains one or more metals M selected from copper, platinum, cobalt, nickel, palladium, and gold in addition to the components of titanium and O.
- metals M selected from copper, platinum, cobalt, nickel, palladium, and gold in addition to the components of titanium and O.
- Ti is 29.0 at% or more and 34.0 at% or less
- Cu is 0.003 at% or more and 7.7 at% or less
- the balance is composed of oxygen and inevitable impurities.
- the ratio of O / (2Ti + 0.5Cu) is a thin film mainly composed of titanium oxide having a composition ratio of 0.96 or more.
- Ti is 29.0 at% or more and 34.0 at% or less, Pt is 0.003 at% or more and 5.7 at% or less, the balance is oxygen and inevitable impurities, It is a thin film mainly composed of titanium oxide having a composition ratio of metal component ratio O / (2Ti + Pt) of 0.95 or more. Further, when one or more metals M selected from cobalt, nickel, palladium, and gold are included, Ti is 29.0 at% or more and 34.0 at% or less, and M is 0.003 at% or more and 7.7 at% or less.
- the thin film is mainly composed of titanium oxide, the balance of which is composed of oxygen and inevitable impurities, and the ratio O / (2Ti + M) of the oxygen component to the metal component is 0.96 or more.
- the presence of one or more metals M selected from copper, platinum, cobalt, nickel, palladium, and gold has an effect of increasing the refractive index of the thin film. If it is less than 0.003, these addition effects are small, and 7.4 at% (in the case of adding one or more metals M selected from copper or cobalt, nickel, palladium, gold) or 5.7 at% (in the case of adding platinum) ),
- the extinction coefficient of the thin film tends to increase, so the Ag content in the thin film should be 0.03 at% or more and 7.4 at% or less (in the latter case: 5.7 at%). This is desirable.
- one or more metals M selected from copper, platinum, cobalt, nickel, palladium, and gold are fine particles (nanoparticles) in an amorphous titanium oxide film. Etc.).
- some of these additive metals may exist as metal oxides.
- the refraction is similarly caused. An increase in rate is observed.
- the high refractive index material obtained in this way increases the degree of freedom in designing the multilayer optical film and becomes a more suitable material.
- These thin films are amorphous films, and a film having a refractive index of 2.60 or more in a wavelength region of 400 to 410 nm can be obtained. Further, it is possible to obtain a thin film having an extinction coefficient of 0.1 or less and a extinction coefficient of 0.05 or less in the wavelength region of 400 to 410 nm.
- the wavelength region of 400 to 410 nm is the wavelength region of the blue laser, and in this wavelength region, the refractive index is 2.60 or more as described above, but this refractive index is preferably higher.
- the extinction coefficient can be 0.1 or less, and further 0.05 or less, the lower the extinction coefficient, the more suitable for multilayering.
- the thin film mainly composed of titanium oxide is useful as an interference film or a protective film, and particularly useful as an optical recording medium.
- the thin film contains one or more metals M selected from copper or cobalt, nickel, palladium, and gold, and the remainder is a target mainly composed of titanium oxide composed of titanium, oxygen, and inevitable impurities.
- the component has a composition ratio of (TiO 2-m ) 1-n M n (where 0 ⁇ m ⁇ 0.5, 0.0001 ⁇ n ⁇ 0.2), and the specific resistance is 100 ⁇ cm or less.
- each component is (TiO 2-m ) 1-n Pt n (where 0 ⁇ m ⁇ 0.5, 0.0001 ⁇ n ⁇ 0.15), and the main component is titanium oxide having a specific resistance of 100 ⁇ cm or less.
- Sintered body It can be manufactured by using a sputtering target.
- the sintered compact target of the present invention approximates the component composition of the thin film, but is not the same. That is, the basic component of the target is composed of Ti, additive metals (Cu, Pt, Co, Ni, Pd, Au), and O, and each component has the above composition ratio. This target has a specific resistance of 100 ⁇ cm or less.
- n is desirably 0.5 or less.
- n is preferably 0.0001 or more and 0.2 (however, 0.15 in the case of Pt).
- the conductivity of the target is necessary.
- the target of the present invention has this condition, and DC sputtering is possible.
- the average particle size is 20 ⁇ m or less. Is desirable.
- sputtering was performed in an argon gas atmosphere containing 0.1 to 16% oxygen, and Cu, Pt, Co, Ni, Pd, Au and / or these metals were formed on the substrate.
- a titanium oxide thin film containing an oxide can be formed.
- the substrate contains titanium, oxygen and copper, Ti is 29.0 at% or more and 34.0 at% or less, Cu is 0.003 at% or more and 7.7 at% or less, and the balance is oxygen and inevitable.
- a thin film mainly composed of titanium oxide having a ratio O / (2Ti + 0.5Cu) of an oxygen component to a metal component of 0.96 or more or titanium, oxygen and platinum, and Ti is 29.0 at% or more, Oxidation where 34.0 at% or less, Pt is 0.003 at% or more and 5.7 at% or less, the balance is oxygen and inevitable impurities, and the ratio O / (2Ti + Pt) of oxygen component to metal component is 0.95 or more
- a thin film mainly containing titanium or one or more metals M selected from titanium, oxygen, cobalt, nickel, palladium, and gold, and Ti is 29.0 at% or more, 34.0a % Titanium, M is 0.003 at% or more, 7.7 at% or less, the balance is oxygen and inevitable impurities, and the ratio O / (2Ti + M) of oxygen component to metal component is 0.95 or more.
- a thin film as a component can be formed. In this case, it is possible to form a film by direct current
- titanium oxide (TiO 2 ) having a high purity (usually 4N or more) and an average particle size of 10 ⁇ m or less and copper having a high purity (usually 3N or more) and an average particle size of 20 ⁇ m or less are used as raw materials.
- metal M powders selected from platinum or cobalt, nickel, palladium, and gold are mixed so that it may become the composition ratio of this invention.
- mixing is performed using a wet ball mill or a dry blender (mixer) so that these selected added metals are uniformly dispersed in the titanium oxide powder.
- the hot pressing conditions can be varied depending on the composition components, but are usually in the range of 800 to 1100 ° C. and the surface pressure in the range of 100 to 500 kgf / cm 2 . However, this condition shows a typical condition, and the selection is arbitrary and is not particularly limited.
- the sintered body is machined to finish the target shape.
- the basic component of the target is composed of one or more metals M selected from titanium, copper or platinum, cobalt, nickel, palladium, gold, and oxygen, and each component has the above composition ratio, and titanium oxide.
- a target in which one or more metals M selected from copper, platinum, cobalt, nickel, palladium, and gold and / or oxides thereof are dispersed as fine particles can be obtained.
- Example 1 As raw materials, titanium oxide (TiO 2 ) having an average particle diameter of 3 ⁇ m and a purity of 4N (99.99%) and copper powder having an average particle diameter of 15 ⁇ m and a purity of 3N (99.9%) Using. This was prepared and mixed so as to have the target composition shown in Table 1. 1 kg of the mixed powder was mixed using a wet ball mill so that copper was uniformly dispersed in the titanium oxide powder. Next, the mixed powder dried by evaporating water was filled in a carbon die and hot pressed. The hot pressing conditions were 970 ° C. and a surface pressure of 200 kgf / cm 2 . The obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, a target having a density of 97% or more and a specific resistance of 0.01 to 10 ⁇ cm as shown in Table 1 was obtained. There was no abnormal discharge during sputtering. The results are shown in Table 1.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- the sputtering conditions are DC sputtering with Ar gas atmosphere or Ar gas-O 2 (2 to 10%) gas atmosphere, gas pressure: 0.5 Pa, gas flow rate: 50 sccm, sputtering power: 500 to 1000 w. Carried out.
- DC sputtering could be carried out without any problem, and it was confirmed that this target was conductive.
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 1 shows the film formation rate and the film composition analyzed by EPMA (SIMS in the Cu low concentration region). O is a balance display.
- O / (2Ti + 0.5Cu) was 0.96 to 1.00.
- the refractive index and extinction coefficient of this sputtered film were measured.
- the refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm. These results are also shown in Table 1. As a result, the refractive index increased to 2.6 to 2.68, and the extinction coefficient decreased to 0.005 to 0.08. In either case, it was possible to form a suitable interference film or protective film for an optical recording medium.
- Comparative Examples 1 to 5 As raw materials, titanium oxide (TiO 2 ) with an average particle diameter of 3 ⁇ m and purity of 4N (99.99%) and copper powder with an average particle diameter of 15 ⁇ m and purity of 3N (99.9%) are used. It was. This was prepared and mixed so as to have the target composition shown in Table 1.
- the comparative example 1 is a case where copper powder is not added. 1 kg of the mixed powder was mixed using a wet ball mill so that copper was uniformly dispersed in the titanium oxide powder. Next, the mixed powder dried by evaporating water was filled in a carbon die and hot pressed. The hot pressing conditions were 970 ° C. and a surface pressure of 200 kgf / cm 2 .
- the obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, the density was 95 to 98%. As shown in Table 1, the specific resistance of the target was> 100 ⁇ cm to 0.0005 ⁇ cm.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- DC sputtering was performed with Ar gas or Ar gas-O 2 (2 to 10%) gas, gas pressure: 0.5 Pa, gas flow rate: 50 sccm, sputtering power: 500 to 1000 w. .
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 1 shows the film formation rate and the composition of the film analyzed by EPMA (Cu low concentration region SIMS).
- O / (2Ti + 0.5Cu) was 0.76 to 1.00.
- the refractive index and extinction coefficient of this sputtered film were measured.
- the refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm.
- Comparative Example 1 is a titanium oxide target to which no Cu is added. Although the extinction coefficient decreased to 0.004, the refractive index decreased to 2.59. As a result, it was unsuitable as an interference film or protective film for optical recording media.
- Comparative Example 2 the ratio O / (2Ti + 0.5Cu) of the oxygen component to the metal component is 0.95, which does not satisfy the conditions of the present invention. In this case, the refractive index was as high as 2.7, but the extinction coefficient was increased to 0.2. As a result, it was unsuitable as an interference film or protective film for optical recording media.
- Comparative Example 3 the amount of Cu is too large, and the ratio O / (2Ti + 0.5Cu) between the oxygen component and the metal component is 0.92, which is less than the conditions of the present invention.
- the refractive index was as high as 2.7, but the extinction coefficient was increased to 0.2. As a result, it was unsuitable as an interference film or protective film for optical recording media.
- Comparative Example 4 the amount of Cu is as small as 0.002 at%, which does not satisfy the conditions of the present invention. In this case, the extinction coefficient decreased to 0.005, but the refractive index was as low as 2.59. As a result, it was unsuitable as an interference film or protective film for optical recording media.
- Comparative Example 5 the ratio O / (2Ti + 0.5Cu) between the oxygen component and the metal component is as small as 0.76, which does not satisfy the conditions of the present invention. In this case, the refractive index was as low as 2.55, and the extinction coefficient was also increased to 0.5. As a result, it was unsuitable as an interference film or protective film for optical recording media.
- Example 9 to 15 As raw materials, titanium oxide (TiO 2 ) having an average particle diameter of 3 ⁇ m and a purity of 4N (99.99%) and palladium (Pd) having an average particle diameter of 25 ⁇ m and a purity of 3N (99.9%) ) Powder was used. This was mixed and mixed so as to have the target composition shown in Table 2. 1 kg of the mixed powder was mixed using a wet ball mill so that Pd was uniformly dispersed in the titanium oxide powder. Next, the mixed powder dried by evaporating water was filled in a carbon die and hot pressed. The hot pressing conditions were 970 ° C. and a surface pressure of 200 kgf / cm 2 .
- the obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, a target having a density of 95% or more and a specific resistance of 0.01 to 30 ⁇ cm as shown in Table 2 was obtained.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- DC sputtering was performed in Ar gas or Ar gas-O 2 (1 to 10%) gas, gas pressure: 0.5 Pa, gas flow rate: 50 sccm, and sputtering power: 500 to 1000 w. did.
- DC sputtering could be carried out without any problem, and it was confirmed that this target had conductivity.
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 2 shows the film formation rate and the film composition analyzed by EPMA. As shown in Table 2, O / (2Ti + Pd) was 0.95 to 1.00. The refractive index and extinction coefficient of this sputtered film were measured.
- the refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm. These results are also shown in Table 2. As a result, the refractive index increased to 2.60 to 2.68, and the extinction coefficient decreased to 0.008 to 0.1. In either case, it was possible to form a suitable interference film or protective film for an optical recording medium.
- the obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, the density was 95% or more. As shown in Table 2, the specific resistance of the target was 0.001 ⁇ cm to 20 ⁇ cm.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- DC sputtering was performed in an Ar gas atmosphere or Ar gas-O 2 (20%) gas atmosphere at a gas pressure of 0.5 Pa, a gas flow rate of 50 sccm, and a sputtering power of 500 to 1000 w. did.
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 2 shows the film formation rate and the film composition analyzed by EPMA.
- O / (2Ti + Pd) was 0.85 to 0.94.
- the refractive index and extinction coefficient of this sputtered film were measured. The refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm.
- Comparative Example 6 the ratio O / (2Ti + Pd) of the oxygen component to the metal component is 0.94, which does not satisfy the conditions of the present invention.
- the refractive index increased to 2.68, but the extinction coefficient increased to 0.19.
- the amount of Pd is too large, 12.5 at%, and the ratio O / (2Ti + Pd) of the oxygen component to the metal component is 0.85, which does not satisfy the conditions of the present invention.
- the refractive index was as low as 2.54 and the extinction coefficient was increased to 0.3. As a result, it was unsuitable as an interference film or protective film for optical recording media.
- Example 16 to 17 As raw materials, titanium oxide (TiO 2 ) having an average particle diameter of 3 ⁇ m and a purity of 4N (99.99%) and cobalt (Co) having an average particle diameter of 25 ⁇ m and a purity of 3N (99.9%) ) Powder was used. This was prepared and mixed so as to have the target composition shown in Table 3. 1 kg of the mixed powder was mixed using a wet ball mill so that Co was uniformly dispersed in the titanium oxide powder. Next, the mixed powder dried by evaporating water was filled in a carbon die and hot pressed. The hot press conditions were 970 ° C. and a surface pressure of 300 kgf / cm 2 .
- the obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, a target having a density of 95% or more and a specific resistance of 0.06 to 50 ⁇ cm as shown in Table 3 was obtained.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- DC sputtering was performed in an Ar gas atmosphere or an Ar gas-O 2 (10%) gas atmosphere at a gas pressure of 0.5 Pa, a gas flow rate of 50 sccm, and a sputtering power of 500 to 1000 w. did.
- DC sputtering could be carried out without any problem, and it was confirmed that this target had conductivity.
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 3 shows the film formation rate and the composition of the film analyzed by EPMA. As shown in Table 3, O / (2Ti + Co) was 0.95 to 1.00.
- the refractive index and extinction coefficient of this sputtered film were measured.
- the refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm. These results are also shown in Table 3. As a result, the refractive index increased to 2.61 to 2.67, and the extinction coefficient decreased to 0.01 to 0.1. In either case, it was possible to form a suitable interference film or protective film for an optical recording medium.
- the obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, the density was 95% or more. As shown in Table 3, the specific resistance of the target was 0.002 ⁇ cm to 6 ⁇ cm.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- sputtering conditions are as follows: Ar gas atmosphere or Ar gas-O 2 (0.5 to 10%) gas atmosphere, gas pressure: 0.5 Pa, gas flow rate: 50 sccm, sputtering power: 500 to 1000 w DC sputtering was performed.
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 3 shows the film formation rate and the composition of the film analyzed by EPMA. As shown in Table 3, O / (2Ti + Co) was 0.84 to 0.94.
- the refractive index and extinction coefficient of this sputtered film were measured. The refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm.
- the ratio O / (2Ti + Pd) of the oxygen component to the metal component is 0.94, which does not satisfy the conditions of the present invention.
- the refractive index was as low as 2.57, and the extinction coefficient was also increased to 0.11.
- the amount of Co is too large at 12.5 at%, and the ratio O / (2Ti + Pd) of the oxygen component to the metal component is 0.84, which does not satisfy the conditions of the present invention.
- the refractive index was as low as 2.55, and the extinction coefficient was increased to 0.32. As a result, it was unsuitable as an interference film or protective film for optical recording media.
- Example 22 to Example 26 As raw materials, titanium oxide (TiO 2 ) having an average particle diameter of 1 ⁇ m and a purity of 4N (99.99%) and platinum (Pt) having an average particle diameter of 7 ⁇ m and a purity of 3N (99.9%) ) Powder was used. This was prepared and mixed so as to have the target composition shown in Table 4. 1 kg of the mixed powder was mixed using a wet ball mill so that Pt was uniformly dispersed in the titanium oxide powder. Next, the mixed powder dried by evaporating water was filled in a carbon die and hot pressed. The hot pressing conditions were 1000 ° C. and a surface pressure of 250 kgf / cm 2 .
- the obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, a target having a density of 95% or more and a specific resistance of 0.07 to 50 ⁇ cm as shown in Table 4 was obtained.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- the sputtering conditions are DC sputtering with Ar gas atmosphere or Ar gas-O 2 (1 to 10%) gas atmosphere, gas pressure: 0.5 Pa, gas flow rate: 50 sccm, sputtering power: 500 to 1000 w. Carried out. DC sputtering could be carried out without any problem, and it was confirmed that this target had conductivity.
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 4 shows the film formation rate and the film composition analyzed by EPMA. As shown in Table 4, O / (2Ti + Pt) was 0.95 to 1.00.
- the refractive index and extinction coefficient of this sputtered film were measured.
- the refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm. These results are similarly shown in Table 4. As a result, the refractive index increased to 2.62 to 2.74, and the extinction coefficient decreased to 0.008 to 0.1. In either case, it was possible to form a suitable interference film or protective film for an optical recording medium.
- the obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, the density was 95% or more. As shown in Table 4, the specific resistance of the target was 0.005 ⁇ cm to 50 ⁇ cm.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- DC sputtering was performed in an Ar gas atmosphere or Ar gas-O 2 (20%) gas atmosphere at a gas pressure of 0.5 Pa, a gas flow rate of 50 sccm, and a sputtering power of 500 to 1000 w. did.
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 4 shows the film formation rate and the film composition analyzed by EPMA. As shown in Table 4, O / (2Ti + Pt) was 0.89 to 0.92. The refractive index and extinction coefficient of this sputtered film were measured. The refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm. These results are similarly shown in Table 4.
- Comparative Example 10 the ratio O / (2Ti + Pt) of the oxygen component to the metal component is 0.92, which does not satisfy the conditions of the present invention.
- the refractive index increased to 2.69, but the extinction coefficient increased to 0.21.
- the amount of Pt is too large at 7.7 at%, and the ratio O / (2Ti + Pt) of the oxygen component to the metal component is 0.89, which does not satisfy the conditions of the present invention.
- the refractive index increased to 2.65, but the extinction coefficient increased to 0.4.
- Example 27 to Example 32 As raw materials, titanium oxide (TiO 2 ) having an average particle diameter of 1 ⁇ m and a purity of 4N (99.99%) and nickel (Ni of an average particle diameter of 20 ⁇ m and a purity of 3N (99.9%)) ) Powder was used. This was prepared and mixed so as to have the target composition shown in Table 5. 1 kg of the mixed powder was mixed using a wet ball mill so that Ni was uniformly dispersed in the titanium oxide powder. Next, the mixed powder dried by evaporating water was filled in a carbon die and hot pressed. The hot pressing conditions were 1000 ° C. and a surface pressure of 250 kgf / cm 2 .
- the obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, a target having a density of 95% or more and a specific resistance of 0.06 to 37 ⁇ cm as shown in Table 5 was obtained.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- DC sputtering was performed in an Ar gas atmosphere or Ar gas-O 2 (10%) gas atmosphere at a gas pressure of 0.5 Pa, a gas flow rate of 50 sccm, and a sputtering power of 500 to 1000 w. did.
- DC sputtering could be carried out without any problem, and it was confirmed that this target had conductivity.
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 5 shows the film formation rate and the film composition analyzed by EPMA. As shown in Table 5, O / (2Ti + Ni) was 0.96 to 1.00.
- the refractive index and extinction coefficient of this sputtered film were measured.
- the refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm. These results are also shown in Table 5. As a result, the refractive index increased to 2.61 to 2.68, and the extinction coefficient decreased to 0.008 to 0.1. In either case, it was possible to form a suitable interference film or protective film for an optical recording medium.
- the obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, the density was 95% or more. As shown in Table 5, the specific resistance of the target was 0.005 ⁇ cm to 11 ⁇ cm.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- DC sputtering was performed in an Ar gas atmosphere or Ar gas-O 2 (20%) gas atmosphere at a gas pressure of 0.5 Pa, a gas flow rate of 50 sccm, and a sputtering power of 500 to 1000 w. did.
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 5 shows the film formation rate and the film composition analyzed by EPMA.
- O / (2Ti + Pt) was 0.83 to 0.93.
- the refractive index and extinction coefficient of this sputtered film were measured. The refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm. These results are also shown in Table 5.
- the ratio O / (2Ti + Pt) of the oxygen component to the metal component is 0.93, which does not satisfy the conditions of the present invention.
- the refractive index was as low as 2.58, and the extinction coefficient was increased to 0.15.
- the amount of Ni is too large, 12.5 at%, and the ratio O / (2Ti + Ni) of the oxygen component to the metal component is 0.83, which does not satisfy the conditions of the present invention.
- the refractive index was as low as 2.54 and the extinction coefficient was increased to 0.35. As a result, it was unsuitable as an interference film or protective film for optical recording media.
- Example 33 to Example 38 As raw materials, titanium oxide (TiO 2 ) with an average particle diameter of 3 ⁇ m and a purity of 4N (99.99%), and gold (Au with an average particle diameter of 20 ⁇ m and a purity of 3N (99.9%)) ) Powder was used. This was prepared and mixed so as to have the target composition shown in Table 6. 1 kg of this mixed powder was mixed using a wet ball mill so that Au was uniformly dispersed in the titanium oxide powder. Next, the mixed powder dried by evaporating water was filled in a carbon die and hot pressed. The hot pressing conditions were 950 ° C. and surface pressure 350 kgf / cm 2 .
- the obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, a target having a density of 95% or more and a specific resistance of 0.06 to 51 ⁇ cm as shown in Table 6 was obtained.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- DC sputtering was performed in an Ar gas atmosphere or Ar gas-O 2 (10%) gas atmosphere at a gas pressure of 0.5 Pa, a gas flow rate of 50 sccm, and a sputtering power of 500 to 1000 w. did.
- DC sputtering could be carried out without any problem, and it was confirmed that this target had conductivity.
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 6 shows the film formation rate and the composition of the film analyzed by EPMA. As shown in Table 6, O / (2Ti + Au) was 0.96 to 1.00.
- the refractive index and extinction coefficient of this sputtered film were measured.
- the refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm. These results are similarly shown in Table 6. As a result, the refractive index increased to 2.62 to 2.70, and the extinction coefficient decreased to 0.007 to 0.1. In either case, it was possible to form a suitable interference film or protective film for an optical recording medium.
- Table 6 shows the particle diameters of the raw materials, the hot press conditions, the surface pressure, and the particle diameter of the Pd phase in the target of Comparative Examples 14 to 15.
- the obtained sintered body was machined to obtain a target of ⁇ 152 mm and 5 mmt. As a result, the density was 95% or more.
- the specific resistance of the target was 0.01 ⁇ cm to 35 ⁇ cm.
- a sputtered film was formed on the glass substrate using the sputtering target thus produced.
- DC sputtering was performed in an Ar gas atmosphere or Ar gas-O 2 (20%) gas atmosphere at a gas pressure of 0.5 Pa, a gas flow rate of 50 sccm, and a sputtering power of 500 to 1000 w. did.
- a 1 ⁇ m sputtered film was formed on the glass substrate.
- Table 6 shows the film formation rate and the composition of the film analyzed by EPMA.
- O / (2Ti + Au) was 0.83 to 0.92.
- the refractive index and extinction coefficient of this sputtered film were measured. The refractive index and extinction coefficient were measured with an ellipsometer using a light wavelength of 405 nm. These results are similarly shown in Table 6.
- Comparative Example 14 the ratio O / (2Ti + Pt) of the oxygen component to the metal component is 0.92, which does not satisfy the conditions of the present invention.
- the refractive index increased to 2.60, but the extinction coefficient increased to 0.13.
- the Au amount is too large at 12.5 at%, and the ratio O / (2Ti + Ni) of the oxygen component to the metal component is 0.83, which does not satisfy the conditions of the present invention.
- the refractive index was as low as 2.56, and the extinction coefficient was increased to 0.32. As a result, it was unsuitable as an interference film or protective film for optical recording media.
- Example and Comparative Examples About the said Example and comparative example, all in the range of this invention had a high refractive index, and the extinction coefficient became small. Similarly, when each component of the sputtering target is in the conditions of the present invention, the specific resistance of the target was 100 ⁇ cm or less, and an excellent discharge was not observed.
- the present invention is a thin film mainly composed of titanium oxide having a high refractive index and a low extinction coefficient, and a sintered body sputtering target mainly composed of titanium oxide suitable for manufacturing the thin film.
- the thin film obtained by the present invention can be used as a film / layer of an optical information recording medium such as an electronic component such as a CD or a DVD.
- the thin film of the present invention is particularly useful as an interference film or a protective film of an optical information recording medium because it has excellent transmittance and little decrease in reflectance.
- the protective layer of refractory dielectric is resistant to repeated thermal stresses caused by heating and cooling, and further prevents these thermal effects from affecting the reflective film and other parts, and it is also thin.
- the material having such characteristics can be used for architectural glass, automotive glass, CRT, and flat display, that is, a heat ray reflective film, an antireflection film, and an interference filter.
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Abstract
Description
また、DVD用としてDVD-RWが開発され商品化されているが、このディスクの層構造は基本的にCD-RWと同一又は類似するものである。この書き換え回数は1000~10000回程度である。
これらは、光ビームを照射することにより、記録材料の透過率、反射率などの光学的な変化を生じさせて、情報の記録、再生、追記を行うものであり、急速に普及した電子部品である。
反射層と保護層は、記録層のアモルファス部と結晶部との反射率の差を増大させる光学的機能が要求されるほか、記録薄膜の耐湿性や熱による変形の防止機能、さらには記録の際の熱的条件制御という機能が要求される(非特許文献1参照)。
この場合、第一情報層は記録層と第1金属反射層からなり、第二情報層は第1保護層、第2保護層、記録層、第2金属反射層から構成されている。この他に、傷、汚れ等から保護するハードコート層、熱拡散層等の層を任意に形成しても良いとされている。また、これらの保護層、記録層、反射層などに、多様な材料が提案されている。
しかし、膜の透過率が低下するため、酸素含有量を35重量%以上とし、さらに酸素を導入する方策が採られている。また、酸素の導入により成膜速度が低下するため、金属酸化物を添加して、成膜速度の向上を図っているが、より屈折率が高く、吸収の少ない膜が求められる精密光学部材や電子部品としての適用には問題がある。特に、400nm付近の短波長側では問題があると考えられる。
1)チタン、酸素及び銅を含み、Tiが29.0at%以上、34.0at%以下、Cuが0.003at%以上、7.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+0.5Cu)が0.96以上であることを特徴とする酸化チタンを主成分とする薄膜
2)チタン、酸素及び白金を含み、Tiが29.0at%以上、34.0at%以下、Ptが0.003at%以上、5.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+Pt)が0.95以上であることを特徴とする酸化チタンを主成分とする薄膜
3)チタン、酸素及びコバルト、ニッケル、パラジウム、金から選択した一種以上の金属Mを含み、Tiが29.0at%以上、34.0at%以下、Mが0.003at%以上、7.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+M)が0.95以上であることを特徴とする酸化チタンを主成分とする薄膜
4)400~410nmの波長域における屈折率が2.60以上であることを特徴とする上記1)~3)のいずれか一項に記載の酸化チタンを主成分とする薄膜
5)400~410nmの波長域における消衰係数が0.1以下であることを特徴とする上記1)~4)のいずれか一項に記載の酸化チタンを主成分とする薄膜
6)400~410nmの波長域における消衰係数が0.05以下であることを特徴とする上記5)記載の酸化チタンを主成分とする薄膜
7)光干渉膜又は保護膜に使用する薄膜であることを特徴とする上記1)~6)のいずれか一項に記載の酸化チタンを主成分とする薄膜
8)光記録媒体として使用する薄膜であることを特徴とする上記1)~6)のいずれか一項に記載の酸化チタンを主成分とする薄膜
9)銅を含み、残余がチタン、酸素及び不可避的不純物からなる酸化チタンを主成分とするターゲットであって、各成分は(TiO2-m)1-nCun(但し、0≦m≦0.5、0.0001≦n≦0.2)の組成比を有し、比抵抗が100Ωcm以下であることを特徴とする酸化チタンを主成分とする焼結体スパッタリングターゲット
10)白金を含み、残余がチタン、酸素及び不可避的不純物からなる酸化チタンを主成分とするターゲットであって、各成分は(TiO2-m)1-nPtn(但し、0≦m≦0.5、0.0001≦n≦0.15)の組成比を有し、比抵抗が100Ωcm以下であることを特徴とする酸化チタンを主成分とする焼結体スパッタリングターゲット
11)コバルト、ニッケル、パラジウム、金から選択した一種以上の金属Mを含み、残余がチタン、酸素及び不可避的不純物からなる酸化チタンを主成分とするターゲットであって、各成分は(TiO2-m)1-nMn(但し、0≦m≦0.5、0.0001≦n≦0.2)の組成比を有し、比抵抗が100Ωcm以下であることを特徴とする酸化チタンを主成分とする焼結体スパッタリングターゲット
高融点誘電体の保護層は、昇温と冷却による熱の繰返しストレスに対して耐性が必要であり、さらにこれらの熱影響が反射膜や他の箇所に影響を及ぼさないようにし、かつそれ自体も薄く、低反射率でかつ変質しない強靭さが必要であるが、本願発明の酸化チタンを主成分とする薄膜は、このような材料に適用できる特性を備えている。
また、スパッタリング中の酸素量も少ない範囲で調整できるため、成膜速度の低下も抑制できるという効果もある。
銅を含有する場合は、Tiが29.0at%以上、34.0at%以下、Cuが0.003at%以上、7.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+0.5Cu)が0.96以上の組成比を有する酸化チタンを主成分とする薄膜である。
また、白金を含有する場合は、Tiが29.0at%以上、34.0at%以下、Ptが0.003at%以上、5.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+Pt)が0.95以上の組成比を有する酸化チタンを主成分とする薄膜である。
さらに、コバルト、ニッケル、パラジウム、金から選択した一種以上の金属Mを含む場合には、Tiが29.0at%以上、34.0at%以下、Mが0.003at%以上、7.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+M)が0.96以上の組成比を有する酸化チタンを主成分とする薄膜である。
これらの添加金属は、場合によっては、その一部が金属酸化物として存在する場合もあるが、このように一部が酸化物として存在する場合も、特に問題となるものではなく、同様に屈折率向上が認められる。このようにして得られる高屈折率の材料は、多層光学膜設計の自由度が高まり、より好適な材料となる。
上記400~410nmの波長領域は、青色レーザーの波長領域であり、この波長領域において、上記の通り屈折率が2.60以上であるが、この屈折率は高い方が良い。また、消衰係数が0.1以下、さらには0.05以下を達成できるが、この消衰係数が低いほど、多層化により適している。この酸化チタンを主成分とする薄膜は、干渉膜又は保護膜として有用であり、特に光記録媒体として有用である。
本発明の焼結体ターゲットは、薄膜の成分組成に近似するが、同一ではない。すなわち、ターゲットの基本成分はTi、添加金属(Cu、Pt、Co、Ni、Pd、Au)、Oの成分からなるが、各成分は上記の組成比を有する。そして、このターゲットは100Ωcm以下の比抵抗を備えている。
焼結体スパッタリングターゲット中に存在するCu、Pt、Co、Ni、Pd、Au相は微細粒として均一に分散する方が異常放電の防止に効果を発揮出来るので、平均粒径は20μm以下であることが望ましいと言える。
この焼結体スパッタリングターゲットを使用し、0.1~16%の酸素を含有するアルゴンガス雰囲気中でスパッタリングし、基板上にCu、Pt、Co、Ni、Pd、Au及び/又はこれらの金属の酸化物を含有する酸化チタン薄膜を形成することができる。
すなわち、これによって、基板上にチタン、酸素及び銅を含み、Tiが29.0at%以上、34.0at%以下、Cuが0.003at%以上、7.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+0.5Cu)が0.96以上である酸化チタンを主成分とする薄膜若しくはチタン、酸素及び白金を含み、Tiが29.0at%以上、34.0at%以下、Ptが0.003at%以上、5.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+Pt)が0.95以上である酸化チタンを主成分とする薄膜又はチタン、酸素及びコバルト、ニッケル、パラジウム、金から選択した一種以上の金属Mを含み、Tiが29.0at%以上、34.0at%以下、Mが0.003at%以上、7.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+M)が0.95以上である酸化チタンを主成分とする薄膜を形成することが可能となる。この場合、直流スパッタリングで成膜することが可能である。
次に、酸化チタン粉にこれらの選択した添加金属が均一に分散するように、湿式ボールミル又は乾式ブレンダー(混合機)を用いて混合する。
これによって、ターゲットの基本成分はチタン、銅若しくは白金又はコバルト、ニッケル、パラジウム、金から選択した一種以上の金属M、及び酸素の成分からなり、各成分は上記の組成比を有し、酸化チタンのマトリックスの中に、銅若しくは白金又はコバルト、ニッケル、パラジウム、金から選択した一種以上の金属M及び/又はこれらの酸化物が微細粒子として分散したターゲットを得ることができる。
原料として、平均粒径が3μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と、平均粒径が15μmであり、純度が3N(99.9%)の銅粉を用いた。これを、表1に示すターゲット組成となるように調合し、混合した。
この混合粉1kgを、銅が酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、970°C、面圧200kgf/cm2とした。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度97%以上、比抵抗は表1に示すように0.01~10Ωcmのターゲットが得られた。スパッタリング中の異常放電は無かった。この結果を、表1に示す。
この結果、DCスパッタリングが問題なく実施でき、このターゲットに導電性があることが確認できた。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMA(Cu低濃度領域ではSIMS)で分析した膜の組成を、それぞれ表1に示す。Oはバランス表示としている。この表1に示すように、O/(2Ti+0.5Cu)は0.96~1.00であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表1に示す。
以上の結果、屈折率は、2.6~2.68と高くなり、また消衰係数は0.005~0.08となり低下した。いずれも、好適な光記録媒体の干渉膜又は保護膜を形成することが可能であった。
原料として、平均粒径が3μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と平均粒径が15μmであり、純度が3N(99.9%)の銅粉を用いた。これを、表1に示すターゲット組成となるように調合し、混合した。なお、比較例1は銅粉を添加しなかった場合である。
この混合粉1kgを、銅が酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、970°C、面圧200kgf/cm2とした。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度は95~98%となった。表1に示すように、ターゲットの比抵抗は>100Ωcm~0.0005Ωcmとなった。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMA(Cu低濃度領域SIMS)で分析した膜の組成を、それぞれ表1に示す。この表1に示すように、O/(2Ti+0.5Cu)は0.76~1.00であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表1に示す。
比較例2については、酸素成分と金属成分の比O/(2Ti+0.5Cu)が0.95で、本願発明の条件に満たないものである。この場合、屈折率は2.7と高くなったが、逆に消衰係数は0.2と増加した。この結果、光記録媒体の干渉膜又は保護膜としては不適であった。
比較例3については、Cu量が多過ぎ、酸素成分と金属成分の比O/(2Ti+0.5Cu)が0.92で、本願発明の条件に満たないものである。この場合、屈折率は2.7と高くなったが、逆に消衰係数は0.2と増加した。この結果、光記録媒体の干渉膜又は保護膜としては不適であった。
比較例5については、酸素成分と金属成分の比O/(2Ti+0.5Cu)が0.76と少なく、本願発明の条件に満たないものである。この場合、屈折率は2.55と低く、消衰係数も0.5と増加した。この結果、光記録媒体の干渉膜又は保護膜としては不適であった。
原料として、平均粒径が3μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と、平均粒径が25μmであり、純度が3N(99.9%)のパラジウム(Pd)粉を用いた。これを、表2に示すターゲット組成となるように調合し、混合した。
この混合粉1kgを、Pdが酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、970°C、面圧200kgf/cm2とした。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度95%以上、比抵抗は表2に示すように0.01~30Ωcmのターゲットが得られた。
DCスパッタリングが問題なく実施でき、このターゲットに導電性があることが確認できた。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMAで分析した膜の組成を、それぞれ表2に示す。この表2に示すように、O/(2Ti+Pd)は0.95~1.00であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表2に示す。
以上の結果、屈折率は2.60~2.68と高くなり、また消衰係数は0.008~0.1となり低下した。いずれも、好適な光記録媒体の干渉膜又は保護膜を形成することが可能であった。
原料として、平均粒径が3μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と、平均粒径が25μmであり、純度が3N(99.9%)のパラジウム(Pd)粉を用いた。これを、表2に示すターゲット組成となるように調合し、混合した。
この混合粉1kgを、Pdが酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、970°C、面圧200kgf/cm2とした。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度は95%以上となった。表2に示すように、ターゲットの比抵抗は0.001Ωcm~20Ωcmとなった。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMAで分析した膜の組成を、それぞれ表2に示す。この表2に示すように、O/(2Ti+Pd)は0.85~0.94であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表2に示す。
比較例7については、Pd量が12.5at%と多過ぎ、酸素成分と金属成分の比O/(2Ti+Pd)が0.85で、本願発明の条件に満たないものである。この場合、屈折率は2.54と低く、消衰係数は0.3と増加した。この結果、光記録媒体の干渉膜又は保護膜としては不適であった。
原料として、平均粒径が3μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と、平均粒径が25μmであり、純度が3N(99.9%)のコバルト(Co)粉を用いた。これを、表3に示すターゲット組成となるように調合し、混合した。
この混合粉1kgを、Coが酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、970°C、面圧300kgf/cm2とした。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度95%以上、比抵抗は表3に示すように0.06~50Ωcmのターゲットが得られた。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMAで分析した膜の組成を、それぞれ表3に示す。この表3に示すように、O/(2Ti+Co)は0.95~1.00であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表3に示す。
以上の結果、屈折率は2.61~2.67と高くなり、また消衰係数は0.01~0.1となり低下した。いずれも、好適な光記録媒体の干渉膜又は保護膜を形成することが可能であった。
原料として、平均粒径が3μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と、平均粒径が20であり、純度が3N(99.9%)のコバルト(Co)粉を用いた。これを、表3に示すターゲット組成となるように調合し、混合した。
この混合粉1kgを、Coが酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、970°C、面圧300kgf/cm2とした。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度は95%以上となった。表3に示すように、ターゲットの比抵抗は0.002Ωcm~6Ωcmとなった。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMAで分析した膜の組成を、それぞれ表3に示す。この表3に示すように、O/(2Ti+Co)は0.84~0.94であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表3に示す。
比較例9については、Co量が12.5at%と多過ぎ、酸素成分と金属成分の比O/(2Ti+Pd)が0.84で、本願発明の条件に満たないものである。この場合、屈折率は2.55と低く、消衰係数は0.32と増加した。この結果、光記録媒体の干渉膜又は保護膜としては不適であった。
原料として、平均粒径が1μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と、平均粒径が7μmであり、純度が3N(99.9%)の白金(Pt)粉を用いた。これを、表4に示すターゲット組成となるように調合し、混合した。
この混合粉1kgを、Ptが酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、1000°C、面圧250kgf/cm2とした。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度95%以上、比抵抗は表4に示すように0.07~50Ωcmのターゲットが得られた。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMAで分析した膜の組成を、それぞれ表4に示す。この表4に示すように、O/(2Ti+Pt)は0.95~1.00であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表4に示す。
以上の結果、屈折率は2.62~2.74と高くなり、また消衰係数は0.008~0.1となり低下した。いずれも、好適な光記録媒体の干渉膜又は保護膜を形成することが可能であった。
原料として、平均粒径が1μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と、平均粒径が7μmであり、純度が3N(99.9%)の白金(Pt)粉を用いた。これを、表4に示すターゲット組成となるように調合し、混合した。
この混合粉1kgを、Ptが酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、1000°C、面圧250kgf/cm2とした。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度は95%以上となった。表4に示すように、ターゲットの比抵抗は0.005Ωcm~50Ωcmとなった。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMAで分析した膜の組成を、それぞれ表4に示す。この表4に示すように、O/(2Ti+Pt)は0.89~0.92であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表4に示す。
比較例11については、Pt量が7.7at%と多過ぎ、酸素成分と金属成分の比O/(2Ti+Pt)が0.89で、本願発明の条件に満たないものである。この場合、屈折率は2.65と高くなったが、消衰係数は0.4と増加した。この結果、光記録媒体の干渉膜又は保護膜としては不適であった。
原料として、平均粒径が1μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と、平均粒径が20μmであり、純度が3N(99.9%)のニッケル(Ni)粉を用いた。これを、表5に示すターゲット組成となるように調合し、混合した。
この混合粉1kgを、Niが酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、1000°C、面圧250kgf/cm2とした。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度95%以上、比抵抗は表5に示すように0.06~37Ωcmのターゲットが得られた。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMAで分析した膜の組成を、それぞれ表5に示す。この表5に示すように、O/(2Ti+Ni)は0.96~1.00であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表5に示す。
以上の結果、屈折率は2.61~2.68と高くなり、また消衰係数は0.008~0.1となり低下した。いずれも、好適な光記録媒体の干渉膜又は保護膜を形成することが可能であった。
原料として、平均粒径が1μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と、平均粒径が20μmであり、純度が3N(99.9%)のニッケル(Ni)粉を用いた。これを、表5に示すターゲット組成となるように調合し、混合した。
この混合粉1kgを、Niが酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、1000°C、面圧250kgf/cm2とした。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度は95%以上となった。表5に示すように、ターゲットの比抵抗は0.005Ωcm~11Ωcmとなった。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMAで分析した膜の組成を、それぞれ表5に示す。この表5に示すように、O/(2Ti+Pt)は0.83~0.93であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表5に示す。
比較例13については、Ni量が12.5at%と多過ぎ、酸素成分と金属成分の比O/(2Ti+Ni)が0.83で、本願発明の条件に満たないものである。この場合、屈折率は2.54と低く、消衰係数は0.35と増加した。この結果、光記録媒体の干渉膜又は保護膜としては不適であった。
原料として、平均粒径が3μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と、平均粒径が20μmであり、純度が3N(99.9%)の金(Au)粉を用いた。これを、表6に示すターゲット組成となるように調合し、混合した。この混合粉1kgを、Auが酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、950°C、面圧350kgf/cm2とした。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度95%以上、比抵抗は表6に示すように0.06~51Ωcmのターゲットが得られた。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMAで分析した膜の組成を、それぞれ表6に示す。この表6に示すように、O/(2Ti+Au)は0.96~1.00であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表6に示す。
以上の結果、屈折率は2.62~2.70と高くなり、また消衰係数は0.007~0.1となり低下した。いずれも、好適な光記録媒体の干渉膜又は保護膜を形成することが可能であった。
原料として、平均粒径が3μmであり、純度が4N(99.99%)の酸化チタン(TiO2)と、平均粒径が20μmであり、純度が3N(99.9%)の金(Au)粉を用いた。これを、表6に示すターゲット組成となるように調合し、混合した。この混合粉1kgを、Auが酸化チタン粉に均一に分散するように、湿式ボールミルを用いて混合した。
次に、水分を蒸発させて乾燥した混合粉を、カーボン製のダイスに充填し、ホットプレスを行った。ホットプレスの条件は、950°C、面圧350kgf/cm2とした。
比較例14~比較例15の原料の粒径、ホットプレス条件、面圧、ターゲット中のPd相の粒径を、同様に表6に示す。
得られた焼結体を機械加工して、φ152mm、5mmtのターゲットとした。この結果、密度は95%以上となった。表6に示すように、ターゲットの比抵抗は0.01Ωcm~35Ωcmとなった。
ガラス基板上に、1μmのスパッタ膜が形成された。成膜速度、EPMAで分析した膜の組成を、それぞれ表6に示す。この表6に示すように、O/(2Ti+Au)は0.83~0.92であった。このスパッタ膜の屈折率及び消衰係数を測定した。屈折率及び消衰係数は、光波長:405nmを用い、エリプソメーターにより測定した。これらの結果を、同様に表6に示す。
比較例15については、Au量が12.5at%と多過ぎ、酸素成分と金属成分の比O/(2Ti+Ni)が0.83で、本願発明の条件に満たないものである。この場合、屈折率は2.56と低く、消衰係数は0.32と増加した。この結果、光記録媒体の干渉膜又は保護膜としては不適であった。
上記実施例と比較例については、本願発明の範囲にあるものは、いずれも屈折率が高く、消衰係数が小さくなった。同様に、スパッタリングターゲットの各成分が本願発明の条件にあるものは、ターゲットの比抵抗がいずれも100Ωcm以下となり、異常放電が見られないという良好な結果となった。
また、本発明の薄膜は、同時に透過率に優れ、反射率の低下が少なく、光情報記録媒体の干渉膜又は保護膜として、特に有用である。高融点誘電体の保護層は昇温と冷却による熱の繰返しストレスに対して耐性をもち、さらに、これらの熱影響が反射膜や他の箇所に影響を及ぼさないようにし、かつそれ自体も薄く、低反射率でかつ変質しない強靭さが必要である誘電体保護層として有用である。
さらに、このような特性をもつ材料は、建築用ガラス、自動車用ガラス、CRT用、フラットディスプレイ用への適用、すなわち熱線反射膜、反射防止膜、干渉フィルタとして使用することも可能である。
Claims (11)
- チタン、酸素及び銅を含み、Tiが29.0at%以上、34.0at%以下、Cuが0.003at%以上、7.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+0.5Cu)が0.96以上であることを特徴とする酸化チタンを主成分とする薄膜。
- チタン、酸素及び白金を含み、Tiが29.0at%以上、34.0at%以下、Ptが0.003at%以上、5.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+Pt)が0.95以上であることを特徴とする酸化チタンを主成分とする薄膜。
- チタン、酸素及びコバルト、ニッケル、パラジウム、金から選択した一種以上の金属Mを含み、Tiが29.0at%以上、34.0at%以下、Mが0.003at%以上、7.7at%以下、残部が酸素及び不可避的不純物からなり、酸素成分と金属成分の比O/(2Ti+M)が0.95以上であることを特徴とする酸化チタンを主成分とする薄膜。
- 400~410nmの波長域における屈折率が2.60以上であることを特徴とする請求項1~3のいずれか一項に記載の酸化チタンを主成分とする薄膜。
- 400~410nmの波長域における消衰係数が0.1以下であることを特徴とする請求項1~4のいずれか一項に記載の酸化チタンを主成分とする薄膜。
- 400~410nmの波長域における消衰係数が0.05以下であることを特徴とする請求項5記載の酸化チタンを主成分とする薄膜。
- 光干渉膜又は保護膜に使用する薄膜であることを特徴とする請求項1~6のいずれか一項に記載の酸化チタンを主成分とする薄膜。
- 光記録媒体として使用する薄膜であることを特徴とする請求項1~6のいずれか一項に記載の酸化チタンを主成分とする薄膜。
- 銅を含み、残余がチタン、酸素及び不可避的不純物からなる酸化チタンを主成分とするターゲットであって、各成分は(TiO2-m)1-nCun(但し、0≦m≦0.5、0.0001≦n≦0.2)の組成比を有し、比抵抗が100Ωcm以下であることを特徴とする酸化チタンを主成分とする焼結体スパッタリングターゲット。
- 白金を含み、残余がチタン、酸素及び不可避的不純物からなる酸化チタンを主成分とするターゲットであって、各成分は(TiO2-m)1-nPtn(但し、0≦m≦0.5、0.0001≦n≦0.15)の組成比を有し、比抵抗が100Ωcm以下であることを特徴とする酸化チタンを主成分とする焼結体スパッタリングターゲット。
- コバルト、ニッケル、パラジウム、金から選択した一種以上の金属Mを含み、残余がチタン、酸素及び不可避的不純物からなる酸化チタンを主成分とするターゲットであって、各成分は(TiO2-m)1-nMn(但し、0≦m≦0.5、0.0001≦n≦0.2)の組成比を有し、比抵抗が100Ωcm以下であることを特徴とする酸化チタンを主成分とする焼結体スパッタリングターゲット。
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CN2010800068659A CN102325920B (zh) | 2009-02-05 | 2010-01-29 | 以氧化钛为主要成分的薄膜和以氧化钛为主要成分的烧结体溅射靶 |
JP2010549450A JP5214745B2 (ja) | 2009-02-05 | 2010-01-29 | 酸化チタンを主成分とする薄膜及び酸化チタンを主成分とする焼結体スパッタリングターゲット |
EP10738471.1A EP2395124A4 (en) | 2009-02-05 | 2010-01-29 | THIN LAYER COMPRISING TITANIUM OXIDE AS THE MAIN COMPONENT AND SINTERED SPRAY TARGET COMPRISING TITANIUM OXIDE AS THE MAIN COMPONENT |
US13/145,641 US8501052B2 (en) | 2009-02-05 | 2010-01-29 | Thin film comprising titanium oxide as main component and sintered compact sputtering target comprising titanium oxide as main component |
US13/444,943 US20120192763A1 (en) | 2009-02-05 | 2012-04-12 | Thin Film Comprising Titanium Oxide as Main Component and Sintered Compact Sputtering Target Comprising Titanium Oxide as Main Component |
US13/445,984 US20120196076A1 (en) | 2009-02-05 | 2012-04-13 | Thin Film Comprising Titanium Oxide as Main Component and Sintered Compact Sputtering Target Comprising Titanium Oxide as Main Component |
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US13/445,984 Division US20120196076A1 (en) | 2009-02-05 | 2012-04-13 | Thin Film Comprising Titanium Oxide as Main Component and Sintered Compact Sputtering Target Comprising Titanium Oxide as Main Component |
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KR20130029440A (ko) * | 2008-07-07 | 2013-03-22 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | 산화물 소결체, 산화물 소결체로 이루어지는 스퍼터링 타깃, 산화물 소결체의 제조 방법 및 산화물 소결체 스퍼터링 타깃 게이트의 제조 방법 |
WO2010004861A1 (ja) * | 2008-07-07 | 2010-01-14 | 日鉱金属株式会社 | 酸化ランタン基焼結体、同焼結体からなるスパッタリングターゲット、酸化ランタン基焼結体の製造方法及び同製造方法によるスパッタリングターゲットの製造方法 |
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US20120196076A1 (en) | 2012-08-02 |
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US20110278511A1 (en) | 2011-11-17 |
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TW201035346A (en) | 2010-10-01 |
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