WO2019176552A1 - Oxide thin film, and oxide sintered body for sputtering target for producing oxide thin film - Google Patents

Oxide thin film, and oxide sintered body for sputtering target for producing oxide thin film Download PDF

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WO2019176552A1
WO2019176552A1 PCT/JP2019/007733 JP2019007733W WO2019176552A1 WO 2019176552 A1 WO2019176552 A1 WO 2019176552A1 JP 2019007733 W JP2019007733 W JP 2019007733W WO 2019176552 A1 WO2019176552 A1 WO 2019176552A1
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thin film
oxide thin
oxide
film
sintered body
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PCT/JP2019/007733
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French (fr)
Japanese (ja)
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淳史 奈良
慧 宗安
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Ｊｘ金属株式会社
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Priority to KR1020197027207A priority Critical patent/KR102225493B1/en
Priority to CN201980002388.XA priority patent/CN110637102B/en
Priority to KR1020217004031A priority patent/KR102315765B1/en
Priority to JP2019528772A priority patent/JP6767723B2/en
Publication of WO2019176552A1 publication Critical patent/WO2019176552A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/02—Oxides; Hydroxides
    • 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
    • C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density

Definitions

  • the present invention relates to an oxide thin film having light absorption ability and an oxide sintered body for sputtering target for producing the thin film.
  • a transparent conductive film made of ITO is used as a wiring member for liquid crystal displays, plasma displays, organic EL displays, touch panels, solar cells, and the like.
  • ITO is an excellent material as a wiring member because it has excellent transparency to visible light and has a low resistivity among oxides.
  • the resistance becomes high and the increase in area cannot be accommodated.
  • Patent Document 1 discloses an oxide containing any one of Cu and Fe and any one of Ni and Mn as a film that reduces the metallic luster of a wiring pattern of a touch panel screen. The use of physical films is disclosed.
  • Patent Document 2 discloses forming a blackening layer containing oxygen, copper, nickel and molybdenum together with a wiring layer made of copper foil or the like.
  • Patent Documents 3 to 5 relate to a light absorption layer used for a solar absorption layer for solar heat utilization and a black matrix layer of a liquid crystal display, from two layers in which a metal as an absorption component is dispersed in an oxide matrix.
  • a light absorbing layer is disclosed.
  • the thickness of the entire layer is in a range of 180 to 455 nm, a luminous transmittance of less than 1%, a luminous reflectance of less than 6% in a wavelength region of 380 to 780 nm, and the like. ing.
  • phase shift type photomask is known as an application that requires light transmittance, reflectance, and film thickness.
  • the phase shift photomask is used for the purpose of improving resolution by utilizing interference of light.
  • a phase shift photomask film is required to have a specific film thickness, a specific transmittance (several percent), and a low reflectance depending on the laser wavelength used.
  • Patent Document 6 discloses a black matrix thin film having a Nb content of 1 to 35% by weight and the balance being substantially Mo, and a part or all of the thin film is an oxide or nitride. And any one of carbides or two or more compounds. However, Patent Document 6 does not specifically disclose the content ratio of oxygen or the like, and it is not clarified at all how much reflectance and transmittance can be obtained.
  • the present invention relates to an oxide thin film having a light-absorbing ability having both good workability by etching and weather resistance, suitable for preventing light reflection, and a sputtering target suitable for forming the oxide thin film. It is an object to provide an oxide sintered body for use.
  • the oxide sintered body is made of Nb, Mo, and O (oxygen), and the content ratio (atomic ratio) of Nb and Mo is 0.1 ⁇ Nb / (Nb + Mo) ⁇ 0.8.
  • O and metal (Nb + Mo) content ratio (atomic ratio) is 1.5 ⁇ O / (Nb + Mo) ⁇ 2.1
  • XRD peak intensity I MoO2 and background intensity attributed to the ( ⁇ 111) plane of the MoO 2 phase relationship between I BG satisfies I MoO2 / I BG> 3 has the gist at.
  • the present invention it is possible to obtain an oxide thin film having light absorption ability suitable for preventing light reflection, which has both good workability by etching and weather resistance. Moreover, the oxide sintered compact for sputtering targets suitable for formation of the said oxide thin film can be obtained.
  • a metal film as the light absorption film.
  • the light absorptivity is high and the transmittance can be reduced, but metal reflection peculiar to metal occurs, and it is difficult to reduce the reflectance.
  • an oxide film may be formed on the metal film, the manufacturing process increases and the production efficiency is lowered.
  • NbO 2 and MoO 2 are materials that have a relatively low visible light transmittance and a low reflectance, and are considered useful as light absorbing films.
  • the NbO 2 film alone has a problem that the change over time is small and the weather resistance is excellent, while it is difficult to dissolve in an etching solution other than hydrogen fluoride (HF) and the processing by etching is difficult.
  • the MoO 2 film alone can be processed by etching even with a hydrogen peroxide (H 2 O 2 ) -based etchant used for metal wiring, but has a problem of poor weather resistance.
  • the oxide thin film according to the embodiment of the present invention has good weather resistance, but NbO 2 that is difficult to process by etching, and MoO 2 that can be processed by etching but are difficult to weather.
  • the oxide thin film according to the embodiment of the present invention includes Nb, Mo, and O (oxygen), and the content ratio (atomic ratio) of Nb and Mo is 0.1 ⁇ Nb / (Nb + Mo) ⁇ 0.8, The content ratio (atomic ratio) of O and metal (Nb + Mo) is 1.5 ⁇ O / (Nb + Mo) ⁇ 2.0.
  • the oxide thin film according to the embodiment of the present invention that satisfies the composition range 0.1 ⁇ Nb / (Nb + Mo) ⁇ 0.8 has desired optical characteristics, film resistance, and amorphous properties.
  • Nb / (Nb + Mo) is less than 0.1, desired weather resistance cannot be obtained, and if Nb / (Nb + Mo) exceeds 0.8, workability by desired etching cannot be obtained.
  • the content ratio of Nb and Mo is 0.1 ⁇ Nb / (Nb + Mo) ⁇ 0.5.
  • the composition range is set as described above.
  • the oxide thin film according to the embodiment of the present invention has an average reflectance of 30 in the visible light region (wavelength: 380 to 780 nm) when the thin film having a thickness of 100 ⁇ 10 nm is formed on the glass substrate. % Or less is preferable.
  • the “average” reflectivity is obtained by measuring the reflectivity of the wavelength region every 5 nm and calculating the average value.
  • the reflectance includes the reflectance of light incident from the thin film side (film-side reflectance) and the reflectance of light incident from the glass substrate side as illustrated in FIG. 2 (substrate-side reflection).
  • the reflectance means only the film-side reflectance.
  • the reflected light includes specular reflection light and diffuse reflection light. In the present disclosure, it means a relative total light reflectivity obtained by combining the specular reflection light and the diffuse reflection light.
  • the oxide thin film according to the embodiment of the present invention also has an average transmittance for incident light in the visible light region (wavelength: 380 to 780 nm) when a thin film having a thickness of 100 ⁇ 10 nm is formed on a glass substrate. Is preferably 20% or less.
  • the “average” transmittance is obtained by measuring the transmittance of the wavelength region every 5 nm and calculating the average value. With this level of reflectance and transmittance, light reflected from the metal wiring (copper foil or the like) inside the display or the panel can be sufficiently absorbed, and a reduction in visibility can be suppressed. Furthermore, the low reflectance required for the phase shift type photomask application can be satisfied.
  • the transmittance is related to the thickness of the oxide thin film.
  • the transmittance decreases as the thickness increases.
  • the transmittance is specified when the thickness of the oxide thin film is 100 nm ⁇ 10 nm or more.
  • ⁇ 10 nm means that 100 nm can be accurately formed.
  • the film thickness fluctuates ⁇ 10 nm (that is, 90 to 110 nm)
  • the fluctuation range of the transmittance is theoretically within ⁇ 1.3%.
  • the oxide thin film according to the embodiment of the present invention satisfies the average transmittance of 20% or less even when the fluctuation range of the transmittance is taken into consideration.
  • the oxide thin film according to the embodiment of the present invention preferably has a surface resistivity of 1.0 ⁇ 10 5 ⁇ / sq or less.
  • the oxide thin film that functions as a light absorption film is stacked adjacent to the metal wiring to suppress light reflection by the metal wiring.
  • the surface resistivity of the oxide thin film is preferably within the above range.
  • the oxide thin film according to the embodiment of the present invention has excellent weather resistance, and the average transmittance and average reflectance change rate in the visible light region (wavelength: 380 to 780 nm) before and after the constant temperature and humidity test are 30% or less. It is preferable that Moreover, it is preferable that the change rate of the surface resistivity before and after a constant temperature and humidity test is 30% or less.
  • the oxide thin film sample formed on the substrate is left in the room A (temperature 40 ° C.-humidity 90%) and the room B (temperature 85 ° C.-humidity 85%).
  • the transmittance, reflectance, and surface resistivity after 120 hours, 500 hours, and 1000 hours were measured, and the rate of change was examined in comparison with each measured value immediately after film formation. It is.
  • the thickness of the oxide thin film is preferably 20 to 2000 nm. If the film thickness is less than 20 nm, the light absorption ability may be lowered. On the other hand, if the film thickness exceeds 2000 nm, it takes more time than necessary to form the film. However, since the film thickness is finally determined by the device design, the film thickness is not limited to this film thickness as long as the light absorption ability can be secured.
  • the oxide thin film according to the embodiment of the present invention is preferably amorphous. Since the amorphous film has a smaller film stress than the crystallized film, film peeling and cracking hardly occur at the time of lamination. Therefore, it is particularly suitable for use in flexible devices.
  • the oxide sintered body according to the embodiment of the present invention includes Nb, Mo, and O (oxygen), and the content ratio (atomic ratio) of Nb and Mo is 0.1 ⁇ Nb / (Nb + Mo) ⁇ 0.8, The content ratio (atomic ratio) of O and metal (Nb + Mo) is 1.5 ⁇ O / (Nb + Mo) ⁇ 2.1, the XRD peak intensity I MoO2 belonging to the ( ⁇ 111) plane of the MoO 2 phase, and the background intensity relationship between I BG, characterized in that satisfy I MoO2 / I BG> 3.
  • An oxide sintered body having such characteristics can be used as a sputtering target.
  • the oxide sintered body according to the embodiment of the present invention satisfying the composition range of 0.1 ⁇ Nb / (Nb + Mo) ⁇ 0.8 and 1.5 ⁇ O / (Nb + Mo) ⁇ 2.1 is formed by sputtering.
  • the formed thin film has desired optical characteristics, film resistance, and amorphous properties.
  • the oxide sintered body when the content ratio of O and metal (Nb + Mo) is 1.5 ⁇ O / (Nb + Mo) ⁇ 2.1, the oxide sintered body (sputtering target) is used to form a sputter film.
  • the content ratio of O and metal (Nb + Mo) is in the range of 1.5 ⁇ O / (Nb + Mo) ⁇ 2.0, and the desired film characteristics are obtained. can get.
  • the oxide sintered body according to the embodiment of the present invention the XRD peak intensity I Mo02 attributable to (-111) plane of the MoO 2 phase, the relationship between the background intensity I BG, I MoO2 / I BG > 3 but satisfies the, satisfies the XRD peak intensity ratio I MoO2 / I BG> 3, molybdenum in the sintered body (Mo) is present most part as MoO 2, such oxidation When a sintered product is used, desired optical characteristics can be obtained in a sputtered thin film.
  • the oxide sintered body according to the embodiment of the present invention preferably has a relative density of 80% or more. If the relative density is 80% or more, it can withstand practical use as a sputtering target. More preferably, it is 85% or more.
  • the oxide sintered body according to the embodiment of the present invention preferably has a bulk resistivity of 100 m ⁇ ⁇ cm or less. Due to the decrease in bulk resistivity, film formation by DC sputtering becomes possible. Compared with RF sputtering, DC sputtering has a higher film formation rate and superior sputtering efficiency, and can improve throughput. Note that RF sputtering may be performed depending on manufacturing conditions, but even in that case, the film formation rate is improved.
  • the oxide sintered body according to the embodiment of the present invention can be produced, for example, as follows.
  • the raw material powders of NbO 2 powder and MoO 2 powder are weighed and mixed so as to have a desired composition.
  • the raw material powder preferably has a purity of 99.9% or more and a particle diameter (D50) of 0.5 to 10 ⁇ m.
  • D50 particle diameter
  • As a mixing method it is preferable to use a ball mill or the like for pulverization.
  • As raw powder it is conceivable to use a Nb 2 O 5 powder and Mo powder, and Nb 2 O 5 and Mo since the sintering temperature is significantly different, it is difficult to densify.
  • the oxide sintered compact which consists of Nb, Mo, and O with a relative density of 80% or more can be obtained. Further, the obtained oxide sintered body can be processed into a sputtering target by cutting, polishing, or the like.
  • the oxide thin film according to the embodiment of the present invention can be produced, for example, as follows.
  • An NbO 2 sputtering target and a MoO 2 sputtering target are set in a sputtering apparatus, and simultaneous sputtering is performed to form a mixed film of NbO 2 and MoO 2 on the substrate.
  • the film composition can be changed by changing each sputtering power at the time of sputtering.
  • the sputtering target manufactured by the above-described method is placed in a sputtering apparatus, and sputtering is performed to form a mixed film of NbO 2 and MoO 2 on the substrate.
  • the composition of the sputtering target is not completely the same as the composition of the film, but the composition approximates that. Since the composition of the target and the composition of the film are related, it is possible to grasp the composition of the target that can obtain the desired film composition by setting the conditions. In addition, the amount of oxygen in the film can be adjusted by adjusting the flow rate of oxygen introduced during sputtering.
  • the evaluation method of the oxide thin film and the oxide sintered body according to the embodiment of the present invention is as follows, including examples and comparative examples.
  • Apparatus Spectrophotometer UV-2450 manufactured by SHIMADZU Measurement sample: A sample formed with a film thickness of 100 ⁇ 10 nm on a glass substrate having a thickness of 0.7 mm, and an undeposited glass substrate
  • Measurement sample A sample formed with a film thickness of 100 ⁇ 10 nm on a glass substrate having a thickness of 0.7 mm, and an undeposited glass substrate
  • Measuring method (Reflectance) Relative total light reflectance using an integrating sphere (reference sample; specular mirror).
  • the reflectance of light incident from the thin film side includes not only the reflectance from the thin film surface but also the reflectance from the glass substrate (front surface) at the interface with the thin film, from the back surface of the glass substrate. Includes reflectance.
  • the reflectance of light incident from the glass substrate side is It includes the reflectance from the glass substrate surface and the reflectance from the thin film at the interface with the glass substrate. (Transmittance) Relative transmittance using a glass substrate as a reference sample.
  • Judgment was made by the presence or absence of a diffraction peak by X-ray diffraction of the film formation sample.
  • a diffraction peak due to the film material is not observed in the measurement under the following conditions, it is determined as an amorphous film.
  • a case where I max / I BG ⁇ 5 is satisfied is indicated by ⁇ , and a case where it is not satisfied is indicated by ⁇ .
  • Device Rigaku Smart Lab Tube: Cu-K ⁇ line Tube voltage: 40 kV Current: 30mA Measuring method: 2 ⁇ - ⁇ reflection method Scanning speed: 20 ° / min Sampling interval: 0.02 ° Measurement range: 10 ° -60 ° Measurement sample: film formation sample on glass substrate (EagleXG) (film thickness of 100 nm or more)
  • Stylus type step meter Veeco Dektak8 Method The film thickness is measured from the level difference between the film-formed surface and the non-film-formed surface of the formed glass substrate.
  • etching solution a hydrogen peroxide (H 2 O 2 ) -based chemical solution was used.
  • H 2 O 2 hydrogen peroxide
  • I MoO2 I MoO2' / I MoO2 -BG I MoO2 ′ : XRD peak intensity in the range of 25.5 ° ⁇ 2 ⁇ ⁇ 26.5 °
  • I MoO2 -BG XRD average intensity in the range of 19.5 ° ⁇ 2 ⁇ ⁇ 20.5 °.
  • Examples 1-1 to 1-6, Comparative Examples 1-1 to 1-2 NbO 2 target ( ⁇ 6 inch) and MoO 2 target ( ⁇ 6 inch) are installed in a sputtering device (ANELVA SPL-500), and a mixed film of NbO 2 and MoO 2 is formed on a glass substrate (EagleXG, ⁇ 4 inch) by simultaneous sputtering. did.
  • the film formation conditions were as described above, and as shown in Table 1, the power of each target at the time of sputtering was changed to produce films having the compositions shown in Table 1.
  • the MoO 2 film was formed by sputtering only the MoO 2 target.
  • the NbO 2 film was formed by sputtering only the NbO 2 target. It is a film. Thereafter, the transmittance, surface reflectance / back reflectance, and surface resistivity immediately after film formation (room temperature) were measured for each oxide thin film with each composition changed, and etching properties were further investigated. The results are shown in Table 1.
  • each oxide thin film formed on the substrate under the respective conditions was subjected to room A (temperature 40 ° C.-humidity 90%) and room B (temperature 85 ° C.-humidity 85%). Then, after 12 hours, 500 hours, and 1000 hours, changes in transmittance, surface reflectance / back reflectance, and surface resistance were examined. The results are shown in Table 2.
  • the oxide thin films (Examples 1-2 to 1-5) all have 30% or less of change over time in the transmittance, reflectance, and surface resistance (change rate), and are weather resistant. It was an excellent film.
  • the oxide thin film containing only Mo (Comparative Example 1-1) was inferior in weather resistance, and the transmittance and the like increased remarkably with the passage of time.
  • the oxide thin film containing only Nb (Comparative Example 1-3) was hardly dissolved in the etching solution.
  • Example 2-1 to 2-4 Comparative Example 2-1
  • NbO 2 powder and MoO 2 powder having a purity of 99.9% or more and a particle size of 0.5 to 10 ⁇ m were prepared, and these powders were weighed so as to have the predetermined ratios shown in Table 3, The mixing and pulverization were carried out. Next, the obtained mixed powder was hot press sintered in an argon atmosphere at a sintering temperature of 1200 ° C. and a surface pressure of 250 kgf / cm 2 to prepare an oxide sintered body. Note that mixing, pulverization, and sintering were performed under the same conditions except that only the weighing ratio was adjusted. Table 3 shows the evaluation results of the obtained oxide sintered body.
  • the relationship between the XRD peak intensity I Mo02 and background intensity I BG attributable to (-111) plane of the MoO 2 phase satisfies the I MoO2 / I BG> 3 either embodiment,
  • the relative density was 80% or more, and the bulk resistivity was 100 m ⁇ cm or less.
  • Comparative Example 2-1 the XRD peak intensity ratio of the MoO 2 phase was 1.7, and MoO 2 disappeared.
  • the oxide sintered bodies obtained in Examples and Comparative Examples were processed into a sputtering target, and sputtering film formation was performed using the target.
  • Table 3 shows the optical characteristics of the obtained sputtered film.
  • the films formed by sputtering using the oxide sintered body obtained in the examples all had low average transmittance and average reflectance, and exhibited excellent light absorption ability.
  • the oxide thin film according to the embodiment of the present invention has low transmittance and reflectance, has excellent light absorption ability, and can be processed by etching, has high weather resistance, and hardly changes over time. It has excellent characteristics. Moreover, since the oxide sintered body according to the embodiment of the present invention has a high density, it can be used as a sputtering target.
  • An oxide thin film according to an embodiment of the present invention is used as a light absorption film for preventing reflection of light by a metal wiring used in a liquid crystal display, a plasma display, an organic EL display, a touch panel, a solar cell, and the like, and a photomask. It is very useful for materials and decoration.

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Abstract

Provided is an oxide thin film composed of Nb, Mo, and O, wherein the content ratio (atomic ratio) between Nb and Mo satisfies 0.1≤Nb/(Nb+Mo)≤0.8, and the content ratio (atomic ratio) between O and metallic (Nb+Mo) satisfies 1.5<O/(Nb+Mo)<2.0. Also provided is an oxide sintered body composed of Nb, Mo, and O, wherein the content ratio (atomic ratio) between Nb and Mo satisfies 0.1≤Nb/(Nb+Mo)≤0.8, the content ratio (atomic ratio) between O and metallic (Nb+Mo) satisfies 1.5<O/(Nb+Mo)<2.1, and the relationship between the intensity IMoO2 of the XRD peak associated with the (-111) plane of an MoO2 phase and the background intensity IBG satisfies IMoO2/IBG > 3. The present invention addresses the problem of providing: an oxide thin film which has low reflectance and transmittance and excellent light absorption efficiency, is soluble in an etching solution and thus easily processed, and has excellent weather resistance and excellent stability over time; and an oxide sintered body for a sputtering target suitable for forming the thin film.

Description

酸化物薄膜及び該薄膜を製造するためのスパッタリングターゲット用酸化物焼結体Oxide thin film and oxide sintered body for sputtering target for producing the thin film
　本発明は、光吸収能を有する酸化物薄膜及び該薄膜を製造するためのスパッタリングターゲット用酸化物焼結体に関する。 The present invention relates to an oxide thin film having light absorption ability and an oxide sintered body for sputtering target for producing the thin film.
 液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイや、タッチパネル、太陽電池等には、配線部材として、ＩＴＯ（酸化インジウム・スズ）からなる透明導電膜が使用されている。ＩＴＯは、可視光に対して優れた透過性を有し、酸化物の中では抵抗率が低いため、配線部材として優れた材料である。しかし、ディスプレイやパネルを大面積化した場合、抵抗が高くなって、大面積化に対応できないという問題が生じていた。 A transparent conductive film made of ITO (indium tin oxide) is used as a wiring member for liquid crystal displays, plasma displays, organic EL displays, touch panels, solar cells, and the like. ITO is an excellent material as a wiring member because it has excellent transparency to visible light and has a low resistivity among oxides. However, when the area of the display or panel is increased, there is a problem that the resistance becomes high and the increase in area cannot be accommodated.
 このようなことから、ＩＴＯ膜に替えて、抵抗率の低い金属薄膜を配線部材として使用することが検討されている。しかし、配線部材として使用した場合、金属薄膜が可視光を反射して、ディスプレイやパネルの視認性を低下させるという問題が生じていた。これに対して、金属薄膜の近傍に反射光を吸収できる膜を形成して、当該金属薄膜による光の反射を抑制し、視認性の向上を図ることが検討されている。 For this reason, it has been studied to use a metal thin film having a low resistivity as the wiring member instead of the ITO film. However, when used as a wiring member, there has been a problem that the metal thin film reflects visible light and lowers the visibility of a display or a panel. On the other hand, it is studied to form a film capable of absorbing reflected light in the vicinity of the metal thin film to suppress the reflection of light by the metal thin film and improve the visibility.
 光の反射を低減する膜に関し、例えば、特許文献１には、タッチパネル画面の配線パターンの金属光沢を低減する膜として、Ｃｕ及びＦｅのいずれか一種、Ｎｉ及びＭｎのいずれか一種を含有する酸化物膜を用いることが開示されている。また、特許文献２には、銅箔等から構成される配線層と共に、酸素、銅、ニッケル及びモリブデンを含有する黒化層を形成することが開示されている。 Regarding a film that reduces light reflection, for example, Patent Document 1 discloses an oxide containing any one of Cu and Fe and any one of Ni and Mn as a film that reduces the metallic luster of a wiring pattern of a touch panel screen. The use of physical films is disclosed. Patent Document 2 discloses forming a blackening layer containing oxygen, copper, nickel and molybdenum together with a wiring layer made of copper foil or the like.
 特許文献３～５には、太陽熱利用のための太陽光吸収層や液晶ディスプレイのブラックマトリックス層に使用される光吸収層に関して、酸化物マトリックス中に吸収成分である金属が分散した、２層からなる光吸収層が開示されている。また、層全体の厚みが１８０～４５５ｎｍの範囲内にあること、３８０～７８０ｎｍの波長領域において、１％未満の視感透過率、６％未満の視感反射率を有すること、等が記載されている。 Patent Documents 3 to 5 relate to a light absorption layer used for a solar absorption layer for solar heat utilization and a black matrix layer of a liquid crystal display, from two layers in which a metal as an absorption component is dispersed in an oxide matrix. A light absorbing layer is disclosed. In addition, it is described that the thickness of the entire layer is in a range of 180 to 455 nm, a luminous transmittance of less than 1%, a luminous reflectance of less than 6% in a wavelength region of 380 to 780 nm, and the like. ing.
 また他にも、光の透過率や反射率、膜厚が求められる用途として、位相シフト型フォトマスクが知られている。位相シフト型フォトマスクは、光の干渉を利用して、解像度を向上させる目的で使用される。位相シフト型フォトマスク膜には、使用するレーザー波長に応じて、特定の膜厚、特定の透過率（数％程度）、低反射率が求められている。さらに、装飾用途でも、光の反射を低減する膜の需要がある。 In addition, a phase shift type photomask is known as an application that requires light transmittance, reflectance, and film thickness. The phase shift photomask is used for the purpose of improving resolution by utilizing interference of light. A phase shift photomask film is required to have a specific film thickness, a specific transmittance (several percent), and a low reflectance depending on the laser wavelength used. In addition, there is a need for a film that reduces light reflection even in decorative applications.
 なお、特許文献６には、Ｎｂの含有量が１～３５重量％であり、残部が実質的にＭｏであるブラックマトリックス用薄膜であって、その薄膜の一部又は全部が酸化物、窒化物、炭化物のいずれか１種もしくは２種以上の化合物として存在することが記載されている。しかし、特許文献６には、酸素等の含有比率については具体的な開示がなく、どの程度の反射率や透過率が得られるのか、全く明らかにされていない。 Patent Document 6 discloses a black matrix thin film having a Nb content of 1 to 35% by weight and the balance being substantially Mo, and a part or all of the thin film is an oxide or nitride. And any one of carbides or two or more compounds. However, Patent Document 6 does not specifically disclose the content ratio of oxygen or the like, and it is not clarified at all how much reflectance and transmittance can be obtained.
特開２０１６－１６０４４８号公報Japanese Unexamined Patent Publication No. 2016-160448 特開２０１７－４１１１５号公報JP 2017-41115 A 特表２０１６－５０４４８４号公報Special table 2016-504484 特表２０１６－５０２５９２号公報Special table 2016-502592 gazette 特表２０１６－５２２３１７号公報Special table 2016-522317 特開２０００－２１４３０８号公報JP 2000-214308 A
　本発明は、光の反射を防止するのに適した、良好なエッチングによる加工性と耐候性を兼ね備えた光吸収能を有する酸化物薄膜、前記酸化物薄膜を成膜するのに適したスパッタリングターゲット用酸化物焼結体を提供することを課題とする。 The present invention relates to an oxide thin film having a light-absorbing ability having both good workability by etching and weather resistance, suitable for preventing light reflection, and a sputtering target suitable for forming the oxide thin film. It is an object to provide an oxide sintered body for use.
 本発明の実施形態に係る酸化物薄膜は、Ｎｂ、Ｍｏ、Ｏ（酸素）からなる酸化物薄膜であって、ＮｂとＭｏの含有比率（原子比）が０．１≦Ｎｂ／（Ｎｂ＋Ｍｏ）≦０．８、Ｏとメタル（Ｎｂ＋Ｍｏ）の含有比率（原子比）が１.５＜Ｏ／（Ｎｂ＋Ｍｏ）＜２．０、であるところに要旨を有する。
 また、本発明の実施形態に酸化物焼結体は、Ｎｂ、Ｍｏ、Ｏ（酸素）からなり、ＮｂとＭｏの含有比率（原子比）が０．１≦Ｎｂ／（Ｎｂ＋Ｍｏ）≦０．８、Ｏとメタル（Ｎｂ＋Ｍｏ）の含有比率（原子比）が１．５＜Ｏ／（Ｎｂ＋Ｍｏ）＜２．１、ＭｏＯ２相の（－１１１）面に帰属するＸＲＤピーク強度ＩＭｏＯ２とバックグラウンド強度ＩＢＧとの関係がＩＭｏＯ２／ＩＢＧ＞３を満たす、ところに要旨を有する。 The oxide thin film which concerns on embodiment of this invention is an oxide thin film which consists of Nb, Mo, and O (oxygen), Comprising: Content ratio (atomic ratio) of Nb and Mo is 0.1 <= Nb / (Nb + Mo) <= There is a gist where 0.8 and the content ratio (atomic ratio) of O to metal (Nb + Mo) is 1.5 <O / (Nb + Mo) <2.0.
In the embodiment of the present invention, the oxide sintered body is made of Nb, Mo, and O (oxygen), and the content ratio (atomic ratio) of Nb and Mo is 0.1 ≦ Nb / (Nb + Mo) ≦ 0.8. , O and metal (Nb + Mo) content ratio (atomic ratio) is 1.5 <O / (Nb + Mo) <2.1, XRD peak intensity I MoO2 and background intensity attributed to the (−111) plane of the MoO 2 phase relationship between I BG satisfies I MoO2 / I BG> 3, has the gist at.
 本発明によれば、良好なエッチングによる加工性と耐候性を兼ね備えた、光の反射を防止するのに適した光吸収能を有する酸化物薄膜を得ることができる。また、前記酸化物薄膜の形成に適したスパッタリングターゲット用酸化物焼結体を得ることができる。 According to the present invention, it is possible to obtain an oxide thin film having light absorption ability suitable for preventing light reflection, which has both good workability by etching and weather resistance. Moreover, the oxide sintered compact for sputtering targets suitable for formation of the said oxide thin film can be obtained.
薄膜側から入射した光の反射率（膜側反射率）の説明図である。It is explanatory drawing of the reflectance (film | membrane side reflectance) of the light which injected from the thin film side. ガラス基板側から入射した光の反射率（基板側反射率）の説明図である。It is explanatory drawing of the reflectance (substrate side reflectance) of the light which injected from the glass substrate side.
　光吸収膜として金属膜を用いることも考えられる。しかし、この場合、光の吸収性が高く、透過率の低減が可能であるが、金属特有の金属反射が生じてしまい、反射率の低減が難しい。また、金属膜上に酸化膜を成膜することも考えられるが、製造プロセスが増加して、生産効率を低下させることになる。一方、光吸収膜として酸化物膜を用いることが考えられる。この場合、金属反射は生じないため表面反射は抑えられるが、金属膜に比べて光吸収性が低いため、透過率が増加して、下部メタル電極などからの反射光が目立ち、視認性を悪化させることがある。 It is also possible to use a metal film as the light absorption film. However, in this case, the light absorptivity is high and the transmittance can be reduced, but metal reflection peculiar to metal occurs, and it is difficult to reduce the reflectance. In addition, although an oxide film may be formed on the metal film, the manufacturing process increases and the production efficiency is lowered. On the other hand, it is conceivable to use an oxide film as the light absorption film. In this case, metal reflection does not occur, so surface reflection can be suppressed, but light absorption is lower than that of metal film, so that the transmittance increases, reflected light from the lower metal electrode, etc. is noticeable and visibility is deteriorated. There are things to do.
 この点、酸化物の中でもＮｂＯ２やＭｏＯ２は、比較的、可視光の透過率が低く、また、反射率も低い材料であり、光吸収膜として有用と考えられる。しかしながら、ＮｂＯ２膜単独の場合、経時変化が小さく耐候性に優れている一方、フッ化水素（ＨＦ）以外のエッチング液には溶け難く、エッチングによる加工が難しいという問題がある。一方、ＭｏＯ２膜単独の場合には、金属配線に使用される過酸化水素（Ｈ２Ｏ２）系のエッチング液でもエッチングによる加工が可能であるが、耐候性に劣るという問題がある。 In this respect, among oxides, NbO 2 and MoO 2 are materials that have a relatively low visible light transmittance and a low reflectance, and are considered useful as light absorbing films. However, the NbO 2 film alone has a problem that the change over time is small and the weather resistance is excellent, while it is difficult to dissolve in an etching solution other than hydrogen fluoride (HF) and the processing by etching is difficult. On the other hand, the MoO 2 film alone can be processed by etching even with a hydrogen peroxide (H 2 O 2 ) -based etchant used for metal wiring, but has a problem of poor weather resistance.
 このようなことから、本発明の実施形態に係る酸化物薄膜は、耐候性が良好であるが、エッチングによる加工が難しいＮｂＯ２と、エッチングによる加工が可能だが、耐候性に難のあるＭｏＯ２を特定の比率で含有するものである。すなわち、本発明の実施形態に係る酸化物薄膜は、Ｎｂ、Ｍｏ、Ｏ（酸素）からなり、ＮｂとＭｏの含有比率（原子比）が０．１≦Ｎｂ／（Ｎｂ＋Ｍｏ）≦０．８、Ｏとメタル（Ｎｂ＋Ｍｏ）の含有比率（原子比）が１.５＜Ｏ／（Ｎｂ＋Ｍｏ）＜２．０、であることを特徴とする。 For this reason, the oxide thin film according to the embodiment of the present invention has good weather resistance, but NbO 2 that is difficult to process by etching, and MoO 2 that can be processed by etching but are difficult to weather. In a specific ratio. That is, the oxide thin film according to the embodiment of the present invention includes Nb, Mo, and O (oxygen), and the content ratio (atomic ratio) of Nb and Mo is 0.1 ≦ Nb / (Nb + Mo) ≦ 0.8, The content ratio (atomic ratio) of O and metal (Nb + Mo) is 1.5 <O / (Nb + Mo) <2.0.
 上記組成範囲０．１≦Ｎｂ／（Ｎｂ＋Ｍｏ）≦０．８を満たす本発明の実施形態に係る酸化物薄膜は、所望の光学特性、膜抵抗、アモルファス性を有する。一方、Ｎｂ／（Ｎｂ＋Ｍｏ）が０．１未満であると、所望の耐候性が得られず、Ｎｂ／（Ｎｂ＋Ｍｏ）が０．８超であると、所望のエッチングによる加工性が得られない。好ましくは、ＮｂとＭｏとの含有比率が０．１＜Ｎｂ／（Ｎｂ＋Ｍｏ）＜０．５である。また、Ｏとメタル（Ｎｂ＋Ｍｏ）の含有比率Ｏ／（Ｎｂ＋Ｍｏ）が１．５以下であると反射率が大きくなり、２．０以上であると透過率が大きくなって、所望の光学特性が得られない。したがって、上記の組成範囲とする。 The oxide thin film according to the embodiment of the present invention that satisfies the composition range 0.1 ≦ Nb / (Nb + Mo) ≦ 0.8 has desired optical characteristics, film resistance, and amorphous properties. On the other hand, if Nb / (Nb + Mo) is less than 0.1, desired weather resistance cannot be obtained, and if Nb / (Nb + Mo) exceeds 0.8, workability by desired etching cannot be obtained. Preferably, the content ratio of Nb and Mo is 0.1 <Nb / (Nb + Mo) <0.5. Further, when the content ratio O / (Nb + Mo) of O and metal (Nb + Mo) is 1.5 or less, the reflectance increases, and when it is 2.0 or more, the transmittance increases and desired optical characteristics are obtained. I can't. Therefore, the composition range is set as described above.
 また、本発明の実施形態に係る酸化物薄膜は、ガラス基板上に膜厚１００±１０ｎｍの薄膜を形成したときの、可視光域（波長：３８０～７８０ｎｍ）の入射光に対する平均反射率が３０％以下であることが好ましい。ここで「平均」反射率とは、前記の波長領域を５ｎｍごとに反射率を測定し、その平均値を算出したものである。
 反射率には、図１に示すような、薄膜側から入射した光の反射率（膜側反射率）と、図２に示すような、ガラス基板側から入射した光の反射率（基板側反射率）とがあるが、本開示では、反射率は、膜側反射率のみを意味する。また、反射光には、鏡面反射光と拡散反射光とがあるが、本開示では、鏡面反射光と拡散反射光とを合わせた相対全光線反射率を意味する。 In addition, the oxide thin film according to the embodiment of the present invention has an average reflectance of 30 in the visible light region (wavelength: 380 to 780 nm) when the thin film having a thickness of 100 ± 10 nm is formed on the glass substrate. % Or less is preferable. Here, the “average” reflectivity is obtained by measuring the reflectivity of the wavelength region every 5 nm and calculating the average value.
As shown in FIG. 1, the reflectance includes the reflectance of light incident from the thin film side (film-side reflectance) and the reflectance of light incident from the glass substrate side as illustrated in FIG. 2 (substrate-side reflection). In the present disclosure, the reflectance means only the film-side reflectance. Further, the reflected light includes specular reflection light and diffuse reflection light. In the present disclosure, it means a relative total light reflectivity obtained by combining the specular reflection light and the diffuse reflection light.
 また、本発明の実施形態に係る酸化物薄膜は、また、ガラス基板上に膜厚１００±１０ｎｍの薄膜を形成したときの、可視光域（波長：３８０～７８０ｎｍ）の入射光に対する平均透過率は２０％以下であることが好ましい。ここで「平均」透過率とは、前記波長領域を５ｎｍごとに透過率を測定し、その平均値を算出したものである。
 このレベルの反射率及び透過率であれば、ディスプレイやパネル内部における金属配線（銅箔等）から反射された光を十分に吸収することができ、視認性の低下を抑制することができる。さらには、位相シフト型フォトマスク用途として求められる低い反射率を満たすことができる。 In addition, the oxide thin film according to the embodiment of the present invention also has an average transmittance for incident light in the visible light region (wavelength: 380 to 780 nm) when a thin film having a thickness of 100 ± 10 nm is formed on a glass substrate. Is preferably 20% or less. Here, the “average” transmittance is obtained by measuring the transmittance of the wavelength region every 5 nm and calculating the average value.
With this level of reflectance and transmittance, light reflected from the metal wiring (copper foil or the like) inside the display or the panel can be sufficiently absorbed, and a reduction in visibility can be suppressed. Furthermore, the low reflectance required for the phase shift type photomask application can be satisfied.
 ところで、上記透過率は、酸化物薄膜の膜厚と関係があり、通常、膜厚が厚くなるにつれて、透過率は減少する。上記の通り、本発明の実施形態では、酸化物薄膜の膜厚が１００ｎｍ±１０ｎｍ以上のときの透過率について規定しているが、±１０ｎｍとしているのは、１００ｎｍを正確に成膜することが現実的に困難であることを考慮したものであり、膜厚が±１０ｎｍ変動しても（つまり、９０～１１０ｎｍ）、理論上、透過率の変動幅は、±１．３％以内程度である。本発明の実施形態に係る酸化物薄膜は、この透過率の変動幅を考慮しても、平均透過率が２０％以下を満たすものである。 By the way, the transmittance is related to the thickness of the oxide thin film. Usually, the transmittance decreases as the thickness increases. As described above, in the embodiment of the present invention, the transmittance is specified when the thickness of the oxide thin film is 100 nm ± 10 nm or more. However, ± 10 nm means that 100 nm can be accurately formed. Considering that it is practically difficult, even if the film thickness fluctuates ± 10 nm (that is, 90 to 110 nm), the fluctuation range of the transmittance is theoretically within ± 1.3%. . The oxide thin film according to the embodiment of the present invention satisfies the average transmittance of 20% or less even when the fluctuation range of the transmittance is taken into consideration.
 また、本発明の実施形態に係る酸化物薄膜は、表面抵抗率が１．０×１０５Ω／ｓｑ以下であることが好ましい。光吸収膜として機能する酸化物薄膜は、金属配線による光反射を抑制するために金属配線に隣接して積層されるが、酸化物薄膜の抵抗率が高い場合、十分な電流が金属配線に流れない。したがって、酸化物薄膜の表面抵抗率は、上記の範囲内とすることが好ましい。 In addition, the oxide thin film according to the embodiment of the present invention preferably has a surface resistivity of 1.0 × 10 5 Ω / sq or less. The oxide thin film that functions as a light absorption film is stacked adjacent to the metal wiring to suppress light reflection by the metal wiring. However, when the resistivity of the oxide thin film is high, sufficient current flows through the metal wiring. Absent. Therefore, the surface resistivity of the oxide thin film is preferably within the above range.
 また、本発明の実施形態に係る酸化物薄膜は、耐候性に優れ、恒温恒湿試験前後の可視光域（波長：３８０～７８０ｎｍ）の平均透過率及び平均反射率の変化率が３０％以下であることが好ましい。また、恒温恒湿試験前後の表面抵抗率の変化率が３０％以下であることが好ましい。
 ここで、本開示における恒温恒湿試験は、基板上に成膜した酸化物薄膜サンプルを、室内Ａ（温度４０℃－湿度９０％）、室内Ｂ（温度８５℃－湿度８５％）に放置して、１２０時間経過後、５００時間経過後及び１０００時間経過後の、透過率、反射率及び表面抵抗率を測定し、成膜直後の各測定値と対比して、その変化率を調べたものである。 The oxide thin film according to the embodiment of the present invention has excellent weather resistance, and the average transmittance and average reflectance change rate in the visible light region (wavelength: 380 to 780 nm) before and after the constant temperature and humidity test are 30% or less. It is preferable that Moreover, it is preferable that the change rate of the surface resistivity before and after a constant temperature and humidity test is 30% or less.
Here, in the constant temperature and humidity test in the present disclosure, the oxide thin film sample formed on the substrate is left in the room A (temperature 40 ° C.-humidity 90%) and the room B (temperature 85 ° C.-humidity 85%). The transmittance, reflectance, and surface resistivity after 120 hours, 500 hours, and 1000 hours were measured, and the rate of change was examined in comparison with each measured value immediately after film formation. It is.
 また、本発明の実施形態において、酸化物薄膜の膜厚は、２０～２０００ｎｍであることが好ましい。膜厚２０ｎｍ未満であると、光吸収能が低下することがあり、一方、膜厚が２０００ｎｍを超えると、成膜に必要以上の時間が掛かるため好ましくない。但し、膜厚は、最終的に、デバイス設計によって決められるため、光吸収能が確保できていれば、この膜厚に限定されることはない。 In the embodiment of the present invention, the thickness of the oxide thin film is preferably 20 to 2000 nm. If the film thickness is less than 20 nm, the light absorption ability may be lowered. On the other hand, if the film thickness exceeds 2000 nm, it takes more time than necessary to form the film. However, since the film thickness is finally determined by the device design, the film thickness is not limited to this film thickness as long as the light absorption ability can be secured.
 また、本発明の実施形態に係る酸化物薄膜は、非晶質（アモルファス）であることが好ましい。アモルファス膜は、結晶化膜に比べて膜応力が小さいため、積層時の膜剥離やクラックが起こりにくい。そのため、特に、フレキシブルデバイスへの使用に適している。 In addition, the oxide thin film according to the embodiment of the present invention is preferably amorphous. Since the amorphous film has a smaller film stress than the crystallized film, film peeling and cracking hardly occur at the time of lamination. Therefore, it is particularly suitable for use in flexible devices.
 次に、本発明の実施形態に係る酸化物焼結体について、詳細に説明する。
 本発明の実施形態に係る酸化物焼結体は、Ｎｂ、Ｍｏ、Ｏ（酸素）からなり、ＮｂとＭｏの含有比率（原子比）が０．１≦Ｎｂ／（Ｎｂ＋Ｍｏ）≦０．８、Ｏとメタル（Ｎｂ＋Ｍｏ）の含有比率（原子比）が１．５＜Ｏ／（Ｎｂ＋Ｍｏ）＜２．１、ＭｏＯ２相の（－１１１）面に帰属するＸＲＤピーク強度ＩＭｏＯ２と、バックグラウンド強度ＩＢＧとの関係が、ＩＭｏＯ２／ＩＢＧ＞３を満たすことを特徴とする。このような特性を備えた酸化物焼結体は、スパッタリングターゲットとして使用することができる。 Next, the oxide sintered body according to the embodiment of the present invention will be described in detail.
The oxide sintered body according to the embodiment of the present invention includes Nb, Mo, and O (oxygen), and the content ratio (atomic ratio) of Nb and Mo is 0.1 ≦ Nb / (Nb + Mo) ≦ 0.8, The content ratio (atomic ratio) of O and metal (Nb + Mo) is 1.5 <O / (Nb + Mo) <2.1, the XRD peak intensity I MoO2 belonging to the (−111) plane of the MoO 2 phase, and the background intensity relationship between I BG, characterized in that satisfy I MoO2 / I BG> 3. An oxide sintered body having such characteristics can be used as a sputtering target.
 上記組成範囲０．１≦Ｎｂ／（Ｎｂ＋Ｍｏ）≦０．８、及び、１．５＜Ｏ／（Ｎｂ＋Ｍｏ）＜２．１を満たす本発明の実施形態に係る酸化物焼結体は、スパッタ成膜した薄膜において、所望の光学特性、膜抵抗、アモルファス性を有する。前記酸化物焼結体において、Ｏとメタル（Ｎｂ＋Ｍｏ）の含有比率が１．５＜Ｏ／（Ｎｂ＋Ｍｏ）＜２．１の場合、当該酸化物焼結体（スパッタリングターゲット）を用いてスパッタ成膜した薄膜では、スパッタ時における酸素導入を行わない場合であっても、Ｏとメタル（Ｎｂ＋Ｍｏ）の含有比率が１．５＜Ｏ／（Ｎｂ＋Ｍｏ）＜２．０の範囲となり、所望の膜特性が得られる。 The oxide sintered body according to the embodiment of the present invention satisfying the composition range of 0.1 ≦ Nb / (Nb + Mo) ≦ 0.8 and 1.5 <O / (Nb + Mo) <2.1 is formed by sputtering. The formed thin film has desired optical characteristics, film resistance, and amorphous properties. In the oxide sintered body, when the content ratio of O and metal (Nb + Mo) is 1.5 <O / (Nb + Mo) <2.1, the oxide sintered body (sputtering target) is used to form a sputter film. In the thin film, even when oxygen is not introduced during sputtering, the content ratio of O and metal (Nb + Mo) is in the range of 1.5 <O / (Nb + Mo) <2.0, and the desired film characteristics are obtained. can get.
 本発明の実施形態に係る酸化物焼結体は、ＭｏＯ２相の（－１１１）面に帰属するＸＲＤピーク強度ＩＭｏＯ２と、バックグラウンド強度ＩＢＧとの関係が、ＩＭｏＯ２／ＩＢＧ＞３を満たすものであるが、前記ＸＲＤピーク強度比ＩＭｏＯ２／ＩＢＧ＞３を満たせば、焼結体中のモリブデン（Ｍｏ）は、その大部分がＭｏＯ２として存在しており、そのような酸化物焼結体を用いた場合は、スパッタ成膜した薄膜において、所望の光学特性が得られる。 The oxide sintered body according to the embodiment of the present invention, the XRD peak intensity I Mo02 attributable to (-111) plane of the MoO 2 phase, the relationship between the background intensity I BG, I MoO2 / I BG > 3 but satisfies the, satisfies the XRD peak intensity ratio I MoO2 / I BG> 3, molybdenum in the sintered body (Mo) is present most part as MoO 2, such oxidation When a sintered product is used, desired optical characteristics can be obtained in a sputtered thin film.
 また、本発明の実施形態に係る酸化物焼結体は、相対密度が８０％以上であることが好ましい。相対密度が８０％以上であれば、スパッタリングターゲットとして実用的な使用に耐えることができる。より好ましくは、８５％以上である。
 また、本発明の実施形態に係る酸化物焼結体は、バルク抵抗率が１００ｍΩ・ｃｍ以下であることが好ましい。バルク抵抗率の低下により、ＤＣスパッタによる成膜が可能となる。ＤＣスパッタリングはＲＦスパッタリングに比べて、成膜速度が速く、スパッタ効率が優れており、スループットを向上できる。なお、製造条件によってはＲＦスパッタリングを行うことも場合もあるが、その場合でも、成膜速度の向上がある。 In addition, the oxide sintered body according to the embodiment of the present invention preferably has a relative density of 80% or more. If the relative density is 80% or more, it can withstand practical use as a sputtering target. More preferably, it is 85% or more.
The oxide sintered body according to the embodiment of the present invention preferably has a bulk resistivity of 100 mΩ · cm or less. Due to the decrease in bulk resistivity, film formation by DC sputtering becomes possible. Compared with RF sputtering, DC sputtering has a higher film formation rate and superior sputtering efficiency, and can improve throughput. Note that RF sputtering may be performed depending on manufacturing conditions, but even in that case, the film formation rate is improved.
 本発明の実施形態に係る酸化物焼結体は、例えば、以下のようにして、作製することができる。
 ＮｂＯ２粉末、ＭｏＯ２粉末の原料粉末を所望の組成となるように、秤量、混合する。原料粉末は純度が９９．９％以上、粒子径（Ｄ５０）が０．５～１０μｍのものを使用することが好ましい。混合方法としては、ボールミルなどを用いて粉砕を兼ねて、混合することが好ましい。原料粉として、Ｎｂ２Ｏ５粉末とＭｏ粉末を使用することも考えられるが、Ｎｂ２Ｏ５とＭｏとは焼結温度が大きく異なることから、高密度化が困難である。
 次に、混合粉末をＡｒ雰囲気中、１１００℃以上１２００℃以下、加圧力２５０ＭＰａ以上、５～１０時間、ホットプレス（一軸加圧焼結）を行う。これにより、相対密度８０％以上のＮｂ、Ｍｏ、Ｏからなる酸化物焼結体を得ることができる。また、得られた酸化物焼結体を切削、研磨などして、スパッタリングターゲットに加工することができる。 The oxide sintered body according to the embodiment of the present invention can be produced, for example, as follows.
The raw material powders of NbO 2 powder and MoO 2 powder are weighed and mixed so as to have a desired composition. The raw material powder preferably has a purity of 99.9% or more and a particle diameter (D50) of 0.5 to 10 μm. As a mixing method, it is preferable to use a ball mill or the like for pulverization. As raw powder, it is conceivable to use a Nb 2 O 5 powder and Mo powder, and Nb 2 O 5 and Mo since the sintering temperature is significantly different, it is difficult to densify.
Next, hot pressing (uniaxial pressure sintering) is performed on the mixed powder in an Ar atmosphere at 1100 ° C. or more and 1200 ° C. or less and a pressing force of 250 MPa or more for 5 to 10 hours. Thereby, the oxide sintered compact which consists of Nb, Mo, and O with a relative density of 80% or more can be obtained. Further, the obtained oxide sintered body can be processed into a sputtering target by cutting, polishing, or the like.
 本発明の実施形態に係る酸化物薄膜は、例えば、以下のようにして、作製することができる。
 ＮｂＯ２スパッタリングターゲット、ＭｏＯ２スパッタリングターゲットをスパッタ装置に設置し、同時スパッタを行って、基板上にＮｂＯ２とＭｏＯ２の混合膜を成膜する。このとき、スパッタ時のそれぞれのスパッタパワーを変化させることで、膜組成を変えることができる。
　又は、上述した方法によって作製されたスパッタリングターゲットをスパッタ装置に設置し、スパッタを実施して、基板上にＮｂＯ２とＭｏＯ２の混合膜を成膜する。このとき、スパッタリングターゲットの組成は、膜の組成と完全に同一となることはないが、それに近似した組成となる。ターゲットの組成と膜の組成とは関係性があるので、条件出しを行って所望の膜組成を得ることができるターゲットの組成を把握することが可能となる。また、スパッタ時に導入する酸素流量を調整することで、膜中の酸素量を調整することもできる。
　　 ＜成膜条件＞
　　　　スパッタ装置：ＡＮＥＬＶＡ　ＳＰＬ－５００
　　　　 基板温度：室温（基板無加熱）
　　　　 成膜雰囲気：Ａｒ またはＡｒ＋Ｏ２
　　　　 ガス圧：０．２～２．０Ｐａ
　　　　 ガス流量：５０～１００ｓｃｃｍ
　　　　 パワー：１００～１０００Ｗ（ＤＣ、ＲＦ）
　　　　 基板：コーニング製　ＥａｇｌｅＸＧ（φ４ｍｍ×０．７ｍｍ） The oxide thin film according to the embodiment of the present invention can be produced, for example, as follows.
An NbO 2 sputtering target and a MoO 2 sputtering target are set in a sputtering apparatus, and simultaneous sputtering is performed to form a mixed film of NbO 2 and MoO 2 on the substrate. At this time, the film composition can be changed by changing each sputtering power at the time of sputtering.
Alternatively, the sputtering target manufactured by the above-described method is placed in a sputtering apparatus, and sputtering is performed to form a mixed film of NbO 2 and MoO 2 on the substrate. At this time, the composition of the sputtering target is not completely the same as the composition of the film, but the composition approximates that. Since the composition of the target and the composition of the film are related, it is possible to grasp the composition of the target that can obtain the desired film composition by setting the conditions. In addition, the amount of oxygen in the film can be adjusted by adjusting the flow rate of oxygen introduced during sputtering.
<Film formation conditions>
Sputtering equipment: ANELVA SPL-500
Substrate temperature: Room temperature (no substrate heating)
Deposition atmosphere: Ar or Ar + O 2
Gas pressure: 0.2-2.0Pa
Gas flow rate: 50-100sccm
Power: 100-1000W (DC, RF)
Substrate: Corning EagleXG (φ4mm × 0.7mm)
 本発明の実施形態に係る酸化物薄膜及び酸化物焼結体の評価方法等は、実施例、及び比較例を含め、以下の通りである。
（透過率、反射率について）
　 装置：ＳＨＩＭＡＤＺＵ社製　分光光度計　ＵＶ－２４５０
　　測定サンプル：
　　 厚さ０．７ｍｍのガラス基板上に、膜厚１００±１０ｎｍで成膜したサンプル、及び、未成膜ガラス基板
　　測定方法：
（反射率）積分球（基準サンプル；鏡面ミラー）を用いた相対全光線反射率。
　　　　　　　薄膜側から入射した光の反射率（膜側反射率）には、薄膜面からの反射率だけでなく、薄膜との界面にあるガラス基板（表面）からの反射率、ガラス基板の裏面からの反射率を含む。
　　　　　　 ガラス基板側から入射した光の反射率（基板側反射率）には、
　　　　　　 ガラス基板面からの反射率とガラス基板との界面にある薄膜からの反射
　　　　　　 率を含む。
（透過率）基準サンプルにガラス基板を使用した、相対透過率。 The evaluation method of the oxide thin film and the oxide sintered body according to the embodiment of the present invention is as follows, including examples and comparative examples.
(About transmittance and reflectance)
Apparatus: Spectrophotometer UV-2450 manufactured by SHIMADZU
Measurement sample:
A sample formed with a film thickness of 100 ± 10 nm on a glass substrate having a thickness of 0.7 mm, and an undeposited glass substrate Measuring method:
(Reflectance) Relative total light reflectance using an integrating sphere (reference sample; specular mirror).
The reflectance of light incident from the thin film side (film side reflectance) includes not only the reflectance from the thin film surface but also the reflectance from the glass substrate (front surface) at the interface with the thin film, from the back surface of the glass substrate. Includes reflectance.
The reflectance of light incident from the glass substrate side (substrate side reflectance) is
It includes the reflectance from the glass substrate surface and the reflectance from the thin film at the interface with the glass substrate.
(Transmittance) Relative transmittance using a glass substrate as a reference sample.
（膜の成分組成について）
　 装置：ＪＥＯＬ製ＪＸＡ－８５００Ｆ
　 方法：ＥＰＭＡ(電子線マイクロアナライザー)
　　　 加速電圧：５～１０ｋｅＶ
　　　 照射電流：１．０×１０－８～１．０～１０－９Ａ
　　　　　プローブ径１０μｍで、５点、ゴミの付着がなく、基板面がみえていない、平滑な成膜部分を選択し、点分析を行い、それらの平均組成を算出した。 (About the component composition of the film)
Equipment: JEOL JXA-8500F
Method: EPMA (Electron Beam Microanalyzer)
Acceleration voltage: 5 to 10 keV
Irradiation current: 1.0 × 10 −8 to 1.0 to 10 −9 A
A smooth film forming portion having a probe diameter of 10 μm, 5 points, no dust adhesion and no substrate surface was selected, point analysis was performed, and an average composition thereof was calculated.
（膜の表面抵抗について）
　 装置：ＮＰＳ社製　抵抗率測定器　Σ－５＋
　 方法：直流４探針法 (About surface resistance of membrane)
Device: NPS Resistivity measuring instrument Σ-5 +
Method: DC 4 probe method
（膜のアモルファス性について）
 成膜サンプルのＸ線回折による回折ピークの有無で判断した。下記条件での測定にて膜材料に起因する回折ピークが見られない場合、アモルファス膜と判断する。ここで、回折ピークが存在しないとは、２θ＝１０°～６０°における最大ピーク強度をＩｍａｘ、２θ＝２０°～２５°の平均ピーク強度をＩＢＧとしたときに、Ｉｍａｘ／ＩＢＧ ＜ ５ である場合を意味する。また、表において、アモルファス性の判定基準として、Ｉｍａｘ／ＩＢＧ ＜ ５を満たす場合を○、満たさない場合を×とした。
　　　 装置：リガク社製　Smart Lab
　　　 管球：Ｃｕ－Ｋα線
　　　 管電圧：４０ｋＶ
　　　 電流：３０ｍＡ
　　　 測定方法：２θ－θ反射法
　　　 スキャン速度：２０°／ｍｉｎ
　　　 サンプリング間隔：０．０２°
　　　 測定範囲：１０°～６０°
　　　　測定サンプル：ガラス基板（ＥａｇｌｅＸＧ）上の成膜サンプル（膜厚１００ｎｍ以上） (About the amorphous nature of the film)
Judgment was made by the presence or absence of a diffraction peak by X-ray diffraction of the film formation sample. When a diffraction peak due to the film material is not observed in the measurement under the following conditions, it is determined as an amorphous film. Here, the absence of a diffraction peak means that the maximum peak intensity at 2θ = 10 ° to 60 ° is I max , and the average peak intensity at 2θ = 20 ° to 25 ° is I BG , I max / I BG <5 means the case. Further, in the table, as a criterion for determining amorphousness, a case where I max / I BG <5 is satisfied is indicated by ◯, and a case where it is not satisfied is indicated by ×.
Device: Rigaku Smart Lab
Tube: Cu-Kα line Tube voltage: 40 kV
Current: 30mA
Measuring method: 2θ-θ reflection method Scanning speed: 20 ° / min
Sampling interval: 0.02 °
Measurement range: 10 ° -60 °
Measurement sample: film formation sample on glass substrate (EagleXG) (film thickness of 100 nm or more)
 （膜厚測定について）
　 触針式段差計　Ｖｅｅｃｏ製　Ｄｅｋｔａｋ８
 方法；成膜されたガラス基板の成膜面と未成膜面の段差から膜厚を測定。 (About film thickness measurement)
Stylus type step meter Veeco Dektak8
Method: The film thickness is measured from the level difference between the film-formed surface and the non-film-formed surface of the formed glass substrate.
 （膜のエッチングによる加工性について）
　 エッチング液は過酸化水素（Ｈ２Ｏ２）系の薬液を用いた。エッチング判定は、エッチングレートが速い場合を○、遅い場合を△、ほとんど溶けない場合を×とした。 (Processability by film etching)
As the etching solution, a hydrogen peroxide (H 2 O 2 ) -based chemical solution was used. In the etching judgment, the case where the etching rate was fast was evaluated as ◯, the case where the etching rate was slow as Δ, and the case where the etching rate hardly melted as X.
（焼結体の成分組成について）
 装置：ＳＩＩ社製ＳＰＳ３５００ＤＤ
 方法：ＩＣＰ-ＯＥＳ（高周波誘導結合プラズマ発光分析法） (About component composition of sintered body)
Device: SPS3500DD manufactured by SII
Method: ICP-OES (High Frequency Inductively Coupled Plasma Atomic Emission Analysis)
（焼結体の相対密度について）
 焼結体の寸法（ノギスを使用）と重量を測定して寸法密度を算出し、その寸法密度と焼結体の理論密度から、相対密度（％）＝寸法密度／理論密度×１００を算出する。
 理論密度は、各酸化物の配合比とそれぞれの理論密度から計算する。
 ＮｂＯ２重量をａ（ｗｔ％）、ＭｏＯ２重量をｂ（ｗｔ％）としたとき、
　 理論密度＝１００／（ａ／５．９０＋ｂ／６．４４）
 ＮｂＯ２の理論密度：５．９０ｇ／ｃｍ３、ＭｏＯ２の理論密度：６．４４ｇ／ｃｍ３ (Relative density of sintered body)
Dimension density is calculated by measuring the dimensions (using calipers) and weight of the sintered body, and calculating relative density (%) = dimensional density / theoretical density × 100 from the dimensional density and the theoretical density of the sintered body. .
The theoretical density is calculated from the compounding ratio of each oxide and the respective theoretical density.
When NbO 2 weight is a (wt%) and MoO 2 weight is b (wt%),
Theoretical density = 100 / (a / 5.90 + b / 6.44)
Theoretical density of NbO 2 : 5.90 g / cm 3 , Theoretical density of MoO 2 : 6.44 g / cm 3
（焼結体のＸＲＤ分析について）
　　　　装置：リガク社製　Smart Lab
　　　 管球：Ｃｕ－Ｋα線
　　　 管電圧：４０ｋＶ
　　　 電流：３０ｍＡ
　　　 測定方法：２θ－θ反射法
　　　 スキャン速度：２０°／ｍｉｎ
　　　 サンプリング間隔：０．０２°
　　　 測定範囲：１０°～６０°
　　　 サンプル測定箇所：スパッタ面
　なおＭｏＯ２相の（－１ １ １）面に帰属するＸＲＤピークＩＭｏＯ２を以下に定義する。
　　 ＩＭｏＯ２＝ＩＭｏＯ２´／ＩＭｏＯ２－ＢＧ
　　 ＩＭｏＯ２´：２５．５°≦２θ≦２６．５°の範囲におけるＸＲＤピーク強度
　　　ＩＭｏＯ２－ＢＧ：１９．５°≦２θ＜２０．５°の範囲におけるＸＲＤ平均強度。 (XRD analysis of sintered body)
Device: Rigaku Smart Lab
Tube: Cu-Kα line Tube voltage: 40 kV
Current: 30mA
Measuring method: 2θ-θ reflection method Scanning speed: 20 ° / min
Sampling interval: 0.02 °
Measurement range: 10 ° -60 °
Sample measurement location: Sputtered surface The XRD peak I MoO2 belonging to the (-1 1 1) surface of the MoO 2 phase is defined below.
I MoO2 = I MoO2' / I MoO2 -BG
I MoO2 ′ : XRD peak intensity in the range of 25.5 ° ≦ 2θ ≦ 26.5 ° I MoO2 -BG : XRD average intensity in the range of 19.5 ° ≦ 2θ <20.5 °.
 （焼結体のバルク抵抗率について）
　 装置：ＮＰＳ社製　抵抗率測定器　Σ－５＋
　 方法：直流４探針法 (Bulk resistivity of sintered body)
Device: NPS Resistivity measuring instrument Σ-5 +
Method: DC 4 probe method
　以下、実施例および比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例によって何ら制限されるものではない。すなわち、本発明は特許請求の範囲によってのみ制限されるものであり、本発明に含まれる実施例以外の種々の変形を包含するものである。 Hereinafter, description will be made based on examples and comparative examples. In addition, a present Example is an example to the last, and is not restrict | limited at all by this example. In other words, the present invention is limited only by the scope of the claims, and includes various modifications other than the examples included in the present invention.
（実施例１－１～１－６、比較例１－１～１－２）
　ＮｂＯ２ターゲット（φ６ｉｎｃｈ）とＭｏＯ２ターゲット（φ６ｉｎｃｈ）をスパッタ装置（ＡＮＥＬＶＡ　ＳＰＬ－５００）に設置して、同時スパッタによって、ガラス基板（ＥａｇｌｅＸＧ，φ４ｉｎｃｈ）上にＮｂＯ２とＭｏＯ２の混合膜を形成した。成膜条件は上述の通りとし、表１の通り、スパッタ時のそれぞれのターゲットのパワーを変化させて、表１記載の組成の膜を作製した。なお、比較例１－１は、ＭｏＯ２ターゲットのみをスパッタして、ＭｏＯ２膜を成膜したものであり、比較例１－２は、ＮｂＯ２ターゲットのみをスパッタして、ＮｂＯ２膜を成膜したものである。その後、組成をそれぞれ変化させた各酸化物薄膜について、成膜直後（室温）における透過率、表反射率・裏反射率、及び表面抵抗率を測定し、さらにエッチング性について調べた。その結果を表１に示す。 (Examples 1-1 to 1-6, Comparative Examples 1-1 to 1-2)
NbO 2 target (φ6 inch) and MoO 2 target (φ6 inch) are installed in a sputtering device (ANELVA SPL-500), and a mixed film of NbO 2 and MoO 2 is formed on a glass substrate (EagleXG, φ4 inch) by simultaneous sputtering. did. The film formation conditions were as described above, and as shown in Table 1, the power of each target at the time of sputtering was changed to produce films having the compositions shown in Table 1. In Comparative Example 1-1, the MoO 2 film was formed by sputtering only the MoO 2 target. In Comparative Example 1-2, the NbO 2 film was formed by sputtering only the NbO 2 target. It is a film. Thereafter, the transmittance, surface reflectance / back reflectance, and surface resistivity immediately after film formation (room temperature) were measured for each oxide thin film with each composition changed, and etching properties were further investigated. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 表１に示す通り、ＮｂとＭｏの含有比率（原子比）が０．１≦Ｎｂ／（Ｎｂ＋Ｍｏ）≦０．８を満たす酸化物薄膜（実施例１－１～１－６）は、いずれも平均透過率及び平均反射率が低く、優れた光吸収能を示し、また、膜抵抗が低く、エッチング加工性にも優れ、アモルファス性を有した。実施例１－１～１－５は、特に速いエッチングレートを有した。 As shown in Table 1, all of the oxide thin films (Examples 1-1 to 1-6) in which the content ratio (atomic ratio) of Nb and Mo satisfies 0.1 ≦ Nb / (Nb + Mo) ≦ 0.8 The average transmittance and the average reflectance were low, excellent light absorption ability was exhibited, the film resistance was low, the etching processability was excellent, and the film was amorphous. Examples 1-1 to 1-5 had particularly fast etching rates.
 次に、耐候性を調査するために、それぞれの条件で基板上に成膜した各酸化物薄膜を、室内Ａ（温度４０℃－湿度９０％）、室内Ｂ（温度８５℃－湿度８５％）に放置して、１２時間、５００時間及び１０００時間経過後の、透過率、表反射率・裏反射率、表面抵抗、の変化について調べた。その結果を表２に示す。 Next, in order to investigate the weather resistance, each oxide thin film formed on the substrate under the respective conditions was subjected to room A (temperature 40 ° C.-humidity 90%) and room B (temperature 85 ° C.-humidity 85%). Then, after 12 hours, 500 hours, and 1000 hours, changes in transmittance, surface reflectance / back reflectance, and surface resistance were examined. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 表２に示す通り、当該酸化物薄膜（実施例１－２～１－５）は、透過率、反射率及び表面抵抗の経時変化（変化率）は、いずれも３０％以下であり、耐候性に優れた膜であった。
 一方、Ｍｏのみを含有する酸化物薄膜（比較例１－１）は、耐候性が劣るものであり、時間の経過に伴い、透過率等が著しく上昇した。また、Ｎｂのみを含有する酸化物薄膜（比較例１－３）は、エッチング液にほとんど溶けなかった。 As shown in Table 2, the oxide thin films (Examples 1-2 to 1-5) all have 30% or less of change over time in the transmittance, reflectance, and surface resistance (change rate), and are weather resistant. It was an excellent film.
On the other hand, the oxide thin film containing only Mo (Comparative Example 1-1) was inferior in weather resistance, and the transmittance and the like increased remarkably with the passage of time. In addition, the oxide thin film containing only Nb (Comparative Example 1-3) was hardly dissolved in the etching solution.
（実施例２－１～２－４、比較例２－１）
 原料粉末として、純度９９．９％以上、粒径０．５～１０μｍのＮｂＯ２粉とＭｏＯ２粉を準備し、これらの粉末を表３に記載する所定の比率となるように秤量し、ボールミルによる混合・粉砕を実施した。次に、得られた混合粉末をアルゴン雰囲気中、焼結温度１２００℃、面圧２５０ｋｇｆ/ｃｍ２にてホットプレス焼結して、酸化物焼結体を作製した。なお、秤量比のみを調整した以外、いずれも同様の条件で混合・粉砕、焼結を実施した。　得られた酸化物焼結体の評価結果を表３に示す。表３に示されるように、いずれの実施例もＭｏＯ２相の（－１１１）面に帰属するＸＲＤピーク強度ＩＭｏＯ２とバックグラウンド強度ＩＢＧとの関係がＩＭｏＯ２／ＩＢＧ＞３を満たし、また、相対密度が８０％以上であり、バルク抵抗率は１００ｍΩｃｍ以下であった。一方、比較例２－１については、ＭｏＯ２相のＸＲＤピーク強度比が１．７であり、ＭｏＯ２が消失していた。
 次に、実施例、比較例で得られた酸化物焼結体をスパッタリングターゲットに加工し、該ターゲットを用いてスパッタ成膜した。得られたスパッタ膜の光学特性を表３に示す。実施例で得られた酸化物焼結体を用いてスパッタ成膜した膜は、いずれも平均透過率及び平均反射率が低く、優れた光吸収能を示した。 (Examples 2-1 to 2-4, Comparative Example 2-1)
As raw material powders, NbO 2 powder and MoO 2 powder having a purity of 99.9% or more and a particle size of 0.5 to 10 μm were prepared, and these powders were weighed so as to have the predetermined ratios shown in Table 3, The mixing and pulverization were carried out. Next, the obtained mixed powder was hot press sintered in an argon atmosphere at a sintering temperature of 1200 ° C. and a surface pressure of 250 kgf / cm 2 to prepare an oxide sintered body. Note that mixing, pulverization, and sintering were performed under the same conditions except that only the weighing ratio was adjusted. Table 3 shows the evaluation results of the obtained oxide sintered body. As shown in Table 3, the relationship between the XRD peak intensity I Mo02 and background intensity I BG attributable to (-111) plane of the MoO 2 phase satisfies the I MoO2 / I BG> 3 either embodiment, The relative density was 80% or more, and the bulk resistivity was 100 mΩcm or less. On the other hand, in Comparative Example 2-1, the XRD peak intensity ratio of the MoO 2 phase was 1.7, and MoO 2 disappeared.
Next, the oxide sintered bodies obtained in Examples and Comparative Examples were processed into a sputtering target, and sputtering film formation was performed using the target. Table 3 shows the optical characteristics of the obtained sputtered film. The films formed by sputtering using the oxide sintered body obtained in the examples all had low average transmittance and average reflectance, and exhibited excellent light absorption ability.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 本発明の実施形態に係る酸化物薄膜は、透過率及び反射率が低く、優れた光吸収能を有し、さらには、エッチングによる加工が可能であり、耐候性が高く、経時変化が起こり難いという優れた特性を有する。また、本発明の実施形態に係る酸化物焼結体は、高密度なため、スパッタリングターゲットとして使用することができる。本発明の実施形態に係る酸化物薄膜は、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイや、タッチパネル、太陽電池等、に使用される金属配線による光の反射を防止する光吸収膜として、またフォトマスク材料、装飾用途として非常に有用である。 The oxide thin film according to the embodiment of the present invention has low transmittance and reflectance, has excellent light absorption ability, and can be processed by etching, has high weather resistance, and hardly changes over time. It has excellent characteristics. Moreover, since the oxide sintered body according to the embodiment of the present invention has a high density, it can be used as a sputtering target. An oxide thin film according to an embodiment of the present invention is used as a light absorption film for preventing reflection of light by a metal wiring used in a liquid crystal display, a plasma display, an organic EL display, a touch panel, a solar cell, and the like, and a photomask. It is very useful for materials and decoration.

Claims (12)

  1.  Ｎｂ、Ｍｏ、Ｏからなる酸化物薄膜であって、ＮｂとＭｏの含有比率（原子比）が０．１≦Ｎｂ／(Ｎｂ＋Ｍｏ)≦０．８、Ｏとメタル（Ｍｂ＋Ｍｏ）の含有比率（原子比）が１．５＜Ｏ／（Ｎｂ＋Ｍｏ）＜２．０であることを特徴とする酸化物薄膜。 An oxide thin film composed of Nb, Mo, and O, wherein the content ratio (atomic ratio) of Nb and Mo is 0.1 ≦ Nb / (Nb + Mo) ≦ 0.8, and the content ratio of O and metal (Mb + Mo) (atomic Ratio) is 1.5 <O / (Nb + Mo) <2.0.
  2.  可視光域（波長：３８０～７８０ｎｍ）における平均反射率が３０％以下であることを特徴とする請求項１記載の酸化物薄膜。 The oxide thin film according to claim 1, wherein the average reflectance in the visible light region (wavelength: 380 to 780 nm) is 30% or less.
  3.  可視光域（波長：３８０～７８０ｎｍ）における平均透過率が２０％以下であることを特徴とする請求項１又は２記載の酸化物薄膜。 3. The oxide thin film according to claim 1 or 2, wherein the average transmittance in the visible light region (wavelength: 380 to 780 nm) is 20% or less.
  4.  表面抵抗率が１．０×１０５Ω／ｓｑ以下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物薄膜。 The oxide thin film according to any one of claims 1 to 3, wherein the surface resistivity is 1.0 × 10 5 Ω / sq or less.
  5.  恒温恒湿試験前後の可視光域（波長：３８０～７８０ｎｍ）における平均反射率の変化率が３０％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物薄膜。 5. The oxide thin film according to claim 1, wherein a change rate of an average reflectance in a visible light region (wavelength: 380 to 780 nm) before and after the constant temperature and humidity test is 30% or less. .
  6.  恒温恒湿試験前後の可視光域（波長：３８０～７８０ｎｍ）における平均透過率の変化率が３０％以下であることを特徴とする請求項１～５のいずれか一項に記載の酸化物薄膜。 6. The oxide thin film according to claim 1, wherein a change rate of an average transmittance in a visible light region (wavelength: 380 to 780 nm) before and after the constant temperature and humidity test is 30% or less. .
  7.  恒温恒湿試験前後の表面抵抗率の変化率が３０％以下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物薄膜。 The oxide thin film according to any one of claims 1 to 6, wherein the rate of change in surface resistivity before and after the constant temperature and humidity test is 30% or less.
  8.  膜厚が２０～２０００ｎｍであることを特徴とする請求項１～７のいずれか一項に記載の酸化物薄膜。 The oxide thin film according to any one of claims 1 to 7, wherein the film thickness is 20 to 2000 nm.
  9.  アモルファスであることを特徴とする請求項１～８のいずれか一項に記載の酸化物薄膜。 9. The oxide thin film according to claim 1, wherein the oxide thin film is amorphous.
  10.  Ｎｂ、Ｍｏ、Ｏからなる酸化物焼結体であって、ＮｂとＭｏの含有比率（原子比）が０．１≦Ｎｂ／(Ｎｂ＋Ｍｏ)≦０．８、Ｏとメタル（Ｍｂ＋Ｍｏ）の含有比率（原子比）が１．５＜Ｏ／（Ｎｂ＋Ｍｏ）＜２．１、ＭｏＯ２相の（－１１１）面に帰属するＸＲＤピーク強度ＩＭｏＯ２とバックグラウンド強度ＩＢＧとの関係がＩＭｏＯ２／ＩＢＧ＞３を満たすことを特徴とする酸化物焼結体。 An oxide sintered body composed of Nb, Mo, and O, wherein the content ratio (atomic ratio) of Nb and Mo is 0.1 ≦ Nb / (Nb + Mo) ≦ 0.8, and the content ratio of O and metal (Mb + Mo) (atomic ratio) is 1.5 <O / (Nb + Mo ) <2.1, the relationship between the XRD peak intensity I Mo02 and background intensity I BG attributable to (-111) plane of the MoO 2 phase I Mo02 / I An oxide sintered body satisfying BG > 3.
  11.  相対密度が８０％以上であることを特徴とする請求項１０記載の酸化物焼結体。 The oxide sintered body according to claim 10, wherein the relative density of the soot is 80% or more.
  12.  バルク抵抗率が１００ｍΩ・ｃｍ以下であることを特徴とする請求項１０又は１１に記載の酸化物焼結体。 The bulk oxide resistivity is 100 mΩ · cm or less, and the oxide sintered body according to claim 10 or 11.
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JPWO2021125113A1 (en) * 2019-12-18 2021-06-24
WO2021125113A1 (en) * 2019-12-18 2021-06-24 Ａｇｃ株式会社 Transparent substrate provided with multilayer film
JP7156556B2 (en) 2019-12-18 2022-10-19 Ａｇｃ株式会社 Transparent substrate with multilayer film
CN115925414A (en) * 2021-10-06 2023-04-07 Lt金属株式会社 Molybdenum oxide-based sintered body, thin film using the sintered body, thin film transistor including the thin film, and display device
CN115925414B (en) * 2021-10-06 2024-04-23 Lt金属株式会社 Molybdenum oxide-based sintered body, thin film using the sintered body, thin film transistor including the thin film, and display device
WO2024202444A1 (en) * 2023-03-29 2024-10-03 Ｊｘ金属株式会社 Oxide sputtering target and oxide film

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KR102315765B1 (en) 2021-10-22
KR20190120272A (en) 2019-10-23

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