WO2013151091A1 - Optical film - Google Patents

Optical film Download PDF

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WO2013151091A1
WO2013151091A1 PCT/JP2013/060204 JP2013060204W WO2013151091A1 WO 2013151091 A1 WO2013151091 A1 WO 2013151091A1 JP 2013060204 W JP2013060204 W JP 2013060204W WO 2013151091 A1 WO2013151091 A1 WO 2013151091A1
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optical film
composite oxide
titanium composite
refractive index
optical
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PCT/JP2013/060204
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French (fr)
Japanese (ja)
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伊村　正明
金井　敏正
仁 高村
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日本電気硝子株式会社
国立大学法人東北大学
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Publication of WO2013151091A1 publication Critical patent/WO2013151091A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—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
    • 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
    • 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
    • C04B35/462—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 based on titanates
    • 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
    • C04B35/462—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 based on titanates
    • C04B35/478—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 based on titanates based on aluminium titanates
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate

Definitions

  • the present invention relates to an optical film.
  • Patent Document 1 discloses a high refractive index dielectric film in which another metal oxide is added to titanium oxide.
  • the main object of the present invention is to provide an optical film having a refractive index higher than that of the titanium oxide film.
  • the optical film according to the present invention is made of a titanium composite oxide containing Al or Ga, and includes a crystal having a rutile structure.
  • the optical film according to the first aspect of the present invention is made of an aluminum titanium composite oxide.
  • the ratio of Al to Ti (Al / Ti) is 17/83 or less in terms of atomic ratio.
  • the aluminum titanium composite oxide includes a rutile crystal.
  • the optical film according to the second aspect of the present invention is made of a gallium titanium composite oxide.
  • the ratio of Ga to Ti (Ga / Ti) is 20/80 or less in terms of atomic ratio.
  • the gallium titanium composite oxide includes a crystal having a rutile structure.
  • the refractive index of the optical film at a wavelength of 400 nm is preferably 2.8 or more.
  • the optical film may include an amorphous region.
  • an optical film having a higher refractive index than that of a titanium oxide film can be provided.
  • FIG. 1 is a graph showing the relationship between the atomic ratio of Al and the refractive index in the optical films of Examples 1 and 2 and Reference Examples 1 to 3.
  • FIG. 2 is an electron diffraction pattern of the optical film of Example 1.
  • FIG. 3 is a graph showing the relationship between the atomic ratio of Ga and the refractive index in the optical films of Examples 3 and 4 and Reference Examples 4 and 5.
  • FIG. 4 is an X-ray diffraction pattern of the optical films of Examples 3 and 4 and Reference Examples 4 and 5.
  • the optical film according to this embodiment is made of an aluminum titanium composite oxide.
  • the ratio of Al to Ti (Al / Ti) contained in the aluminum titanium composite oxide is 17/83 or less in terms of atomic ratio.
  • the optical film includes a rutile structure crystal of an aluminum titanium composite oxide. For this reason, the optical film according to the present embodiment has a high refractive index of, for example, 2.8 or more at a wavelength of 400 nm.
  • the ratio of Al to Ti (Al / Ti) contained in the aluminum-titanium composite oxide is preferably about 2/98 to 17/83 in atomic ratio. More preferably, it is about 95 to 12/88.
  • the optical film may be composed only of a rutile structure crystal of an aluminum-titanium composite oxide, but may contain an amorphous region of an aluminum-titanium composite oxide or an anatase structure crystal of an aluminum-titanium composite oxide. Good. However, from the viewpoint of obtaining a higher refractive index, it is preferable that the proportion of crystals of the rutile structure of the aluminum titanium composite oxide in the optical film is higher.
  • the optical film according to this embodiment is made of a gallium titanium composite oxide.
  • the ratio of Ga to Ti (Ga / Ti) contained in the gallium titanium composite oxide is 20/80 or less in terms of atomic ratio.
  • the optical film includes a rutile crystal of gallium titanium composite oxide. For this reason, the optical film according to the present embodiment has a high refractive index of, for example, 2.8 or more at a wavelength of 400 nm.
  • the ratio of Ga to Ti contained in the gallium titanium composite oxide is preferably about 2/98 to 20/80 in atomic ratio. More preferably, it is about 90 to 18/82.
  • the optical film may be composed only of a rutile structure crystal of gallium titanium composite oxide, but may contain an amorphous region of gallium titanium composite oxide or an anatase structure crystal of gallium titanium composite oxide. Good. However, from the viewpoint of obtaining a higher refractive index, it is preferable that the ratio of the crystals of the rutile structure of the gallium titanium composite oxide in the optical film is higher.
  • the thickness of the optical film is not particularly limited, but can be, for example, about 5 nm to 1000 nm.
  • the optical film is preferably formed on a substrate having a temperature of 420 ° C. or higher, and more preferably formed on a substrate having a temperature of 450 ° C. or higher.
  • a higher refractive index can be obtained by increasing the temperature of the substrate when forming the optical film. Although this reason is not certain, it is thought that it is because the ratio of the crystal of the rutile structure of the aluminum titanium composite oxide or the gallium titanium composite oxide in the optical film is increased.
  • the optical film can be formed by, for example, a physical deposition method.
  • a physical deposition method include a pulse laser deposition method, a sputtering method, and an electron beam evaporation method.
  • the substrate is not particularly limited, and examples thereof include glass, plastic, resin, and film.
  • 10 g of oxide powder was obtained.
  • 10 g of the oxide powder and 30 cc of 2-propanol were placed in a partially stabilized zirconia container and mixed for 1 hour with a planetary ball mill apparatus to form a slurry.
  • the slurry was dried, uniaxially pressed at 64 MPa, then isostatically pressed at a pressure of 250 MPa, and fired at 1150 ° C. for 36 hours in the air to obtain a target.
  • Atmosphere Oxygen Atmospheric pressure / 1.5 ⁇ 10 ⁇ 5 Pa or less Distance between target and substrate / 35 mm Temperature of non-alkali glass substrate during film formation / 500 ° C Laser / KrF excimer laser with a wavelength of 248 nm (laser power / 200 mJ / pulse, laser frequency / 5 Hz) Deposition time / 20 minutes
  • the thickness of the obtained optical film was 39 nm.
  • the composition of the optical film and the composition of the target were measured by EDX (energy dispersive X-ray spectroscopy). As a result, it was confirmed that the composition in the optical film and the target composition were almost the same.
  • the refractive index n of the optical film at a wavelength of 400 nm was measured by molecular ellipsometry.
  • the refractive index of the optical film at a wavelength of 400 nm was 2.98 as shown in FIG.
  • Auto SE manufactured by Horiba Jobin Yvon was used for the evaluation by molecular ellipsometry.
  • the electron beam diffraction pattern of the optical film obtained in Example 1 was measured using an atomic resolution analytical electron microscope (JEM-ARM200F manufactured by JEOL Ltd.). The electron diffraction pattern is shown in FIG. As shown in FIG. 2, it was confirmed that the optical film obtained in Example 1 contained rutile type crystals and anatase type crystals. In addition, an amorphous region was also present in the optical film.
  • Reference Example 1 An optical film was formed in the same manner as in Example 1 except that the target was produced without mixing Al 2 O 3 .
  • the thickness of the optical film was 21 nm.
  • the composition of the optical film was measured and the optical characteristics were evaluated.
  • the refractive index of the optical film was 2.81. Although not shown, it was confirmed that the optical film obtained in Reference Example 1 did not contain rutile crystals and contained anatase crystals.
  • Example 3 [Preparation of target]
  • a target was obtained in the same manner as in Example 1.
  • the thickness of the obtained optical film was 131 nm.
  • the composition of the optical film was measured by EDX.
  • the amount of Ga in the optical film was 15.6%. Therefore, Ga / Ti in the optical film was 15.6 / 84.4. Therefore, in the case of the gallium titanium composite oxide, the Ga amount in the ratio of Ga and Ti in the optical film is increased as compared with the target composition.
  • FIG. 3 shows the relationship between the atomic ratio of Ga and the refractive index in the optical films of Examples 3 and 4 and Reference Examples 4 and 5. As shown in FIG. 3, it can be seen that when Ga is contained and the ratio of Ga to Ti (Ga / Ti) is 20/80 or less, the refractive index is higher than that of the titanium oxide of Reference Example 4.

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Abstract

Provided is an optical film that has a higher refractive index than titanium oxide films. The optical film comprises an aluminum-titanium composite oxide or a gallium-titanium composite oxide. In the aluminum-titanium composite oxide, the ratio of Al to Ti (Al/Ti) is 17/83 or less in atomic ratio. In the gallium-titanium composite oxide, the ratio of Ga to Ti (Ga/Ti) is 20/80 or less in atomic ratio. The aluminum-titanium composite oxide or the gallium-titanium composite oxide comprises crystals of a rutile structure.

Description

光学膜Optical film
　本発明は、光学膜に関する。 The present invention relates to an optical film.
　従来、高い屈折率を有する光学膜としては、酸化チタン膜が用いられている。しかしながら、近年、反射防止膜等の膜数の低減や、高性能化が強く求められるようになってきており、それに伴い、酸化チタンの単体からなる酸化チタン膜（以下、実質的に酸化チタンのみからなる膜を「酸化チタン膜」とする。）よりも高い屈折率を有する光学膜が求められている。例えば、特許文献１には、酸化チタンに他の金属酸化物を添加した高屈折率誘電体膜が開示されている。 Conventionally, a titanium oxide film has been used as an optical film having a high refractive index. However, in recent years, there has been a strong demand for reduction in the number of films such as antireflection films and higher performance, and accordingly, a titanium oxide film made of a single titanium oxide (hereinafter, substantially titanium oxide only). An optical film having a higher refractive index than that of a “titanium oxide film” is demanded. For example, Patent Document 1 discloses a high refractive index dielectric film in which another metal oxide is added to titanium oxide.
特開２００２－２７７６３０号公報JP 2002-277630 A
　特許文献１に記載された高屈折率誘電体膜では、酸化チタン膜と同等の屈折率が実現されているものの、酸化チタン膜よりも高い屈折率を得ることは困難である。 In the high refractive index dielectric film described in Patent Document 1, a refractive index equivalent to that of the titanium oxide film is realized, but it is difficult to obtain a higher refractive index than that of the titanium oxide film.
　本発明は、酸化チタン膜よりも高い屈折率を有する光学膜を提供することを主な目的とする。 The main object of the present invention is to provide an optical film having a refractive index higher than that of the titanium oxide film.
　本発明に係る光学膜は、ＡｌまたはＧａを含有するチタン複合酸化物からなり、ルチル構造の結晶を含む。 The optical film according to the present invention is made of a titanium composite oxide containing Al or Ga, and includes a crystal having a rutile structure.
　本発明の第１の局面に係る光学膜は、アルミニウムチタン複合酸化物からなる。アルミニウムチタン複合酸化物において、ＡｌとＴｉとの比（Ａｌ／Ｔｉ）は、原子比で１７／８３以下である。アルミニウムチタン複合酸化物は、ルチル構造の結晶を含む。 The optical film according to the first aspect of the present invention is made of an aluminum titanium composite oxide. In the aluminum titanium composite oxide, the ratio of Al to Ti (Al / Ti) is 17/83 or less in terms of atomic ratio. The aluminum titanium composite oxide includes a rutile crystal.
　本発明の第２の局面に係る光学膜は、ガリウムチタン複合酸化物からなる。ガリウムチタン複合酸化物において、ＧａとＴｉとの比（Ｇａ／Ｔｉ）は、原子比で２０／８０以下である。ガリウムチタン複合酸化物は、ルチル構造の結晶を含む。 The optical film according to the second aspect of the present invention is made of a gallium titanium composite oxide. In the gallium titanium composite oxide, the ratio of Ga to Ti (Ga / Ti) is 20/80 or less in terms of atomic ratio. The gallium titanium composite oxide includes a crystal having a rutile structure.
　波長４００ｎｍにおける光学膜の屈折率が２．８以上であることが好ましい。 The refractive index of the optical film at a wavelength of 400 nm is preferably 2.8 or more.
　光学膜は、アモルファス領域を含んでいてもよい。 The optical film may include an amorphous region.
　本発明によれば、酸化チタン膜よりも高い屈折率を有する光学膜を提供することができる。 According to the present invention, an optical film having a higher refractive index than that of a titanium oxide film can be provided.
図１は、実施例１，２及び参考例１～３の光学膜におけるＡｌの原子比と屈折率との関係を示すグラフである。FIG. 1 is a graph showing the relationship between the atomic ratio of Al and the refractive index in the optical films of Examples 1 and 2 and Reference Examples 1 to 3. 図２は、実施例１の光学膜の電子線回折パターンである。FIG. 2 is an electron diffraction pattern of the optical film of Example 1. 図３は、実施例３，４及び参考例４，５の光学膜におけるＧａの原子比と屈折率との関係を示すグラフである。FIG. 3 is a graph showing the relationship between the atomic ratio of Ga and the refractive index in the optical films of Examples 3 and 4 and Reference Examples 4 and 5. 図４は、実施例３，４及び参考例４，５の光学膜のＸ線回折パターンである。FIG. 4 is an X-ray diffraction pattern of the optical films of Examples 3 and 4 and Reference Examples 4 and 5.
　以下、本発明を実施した好ましい形態の一例について説明する。但し、以下の実施形態は、単なる一例であり、本発明は、以下の実施形態に何ら限定されない。 Hereinafter, an example of a preferable embodiment in which the present invention is implemented will be described. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments.
　（第１の局面の実施形態）
　本実施形態に係る光学膜は、アルミニウムチタン複合酸化物からなる。アルミニウムチタン複合酸化物に含まれるＡｌとＴｉとの比（Ａｌ／Ｔｉ）は、原子比で１７／８３以下である。光学膜は、アルミニウムチタン複合酸化物のルチル構造の結晶を含む。このため、本実施形態に係る光学膜は、例えば波長４００ｎｍにおいて２．８以上という高い屈折率を有する。 (Embodiment of the first aspect)
The optical film according to this embodiment is made of an aluminum titanium composite oxide. The ratio of Al to Ti (Al / Ti) contained in the aluminum titanium composite oxide is 17/83 or less in terms of atomic ratio. The optical film includes a rutile structure crystal of an aluminum titanium composite oxide. For this reason, the optical film according to the present embodiment has a high refractive index of, for example, 2.8 or more at a wavelength of 400 nm.
　より高い屈折率を得る観点からは、アルミニウムチタン複合酸化物に含まれるＡｌとＴｉとの比（Ａｌ／Ｔｉ）は、原子比で２／９８～１７／８３程度であることが好ましく、５／９５～１２／８８程度であることがより好ましい。 From the viewpoint of obtaining a higher refractive index, the ratio of Al to Ti (Al / Ti) contained in the aluminum-titanium composite oxide is preferably about 2/98 to 17/83 in atomic ratio. More preferably, it is about 95 to 12/88.
　光学膜は、アルミニウムチタン複合酸化物のルチル構造の結晶のみからなるものであってもよいが、アルミニウムチタン複合酸化物のアモルファス領域や、アルミニウムチタン複合酸化物のアナターゼ構造の結晶を含んでいてもよい。但し、より高い屈折率を得る観点からは、光学膜におけるアルミニウムチタン複合酸化物のルチル構造の結晶の占める割合が高い方が好ましい。 The optical film may be composed only of a rutile structure crystal of an aluminum-titanium composite oxide, but may contain an amorphous region of an aluminum-titanium composite oxide or an anatase structure crystal of an aluminum-titanium composite oxide. Good. However, from the viewpoint of obtaining a higher refractive index, it is preferable that the proportion of crystals of the rutile structure of the aluminum titanium composite oxide in the optical film is higher.
　（第２の局面の実施形態）
　本実施形態に係る光学膜は、ガリウムチタン複合酸化物からなる。ガリウムチタン複合酸化物に含まれるＧａとＴｉとの比（Ｇａ／Ｔｉ）は、原子比で２０／８０以下である。光学膜は、ガリウムチタン複合酸化物のルチル構造の結晶を含む。このため、本実施形態に係る光学膜は、例えば波長４００ｎｍにおいて２．８以上という高い屈折率を有する。 (Embodiment of the second aspect)
The optical film according to this embodiment is made of a gallium titanium composite oxide. The ratio of Ga to Ti (Ga / Ti) contained in the gallium titanium composite oxide is 20/80 or less in terms of atomic ratio. The optical film includes a rutile crystal of gallium titanium composite oxide. For this reason, the optical film according to the present embodiment has a high refractive index of, for example, 2.8 or more at a wavelength of 400 nm.
　より高い屈折率を得る観点からは、ガリウムチタン複合酸化物に含まれるＧａとＴｉとの比（Ｇａ／Ｔｉ）は、原子比で２／９８～２０／８０程度であることが好ましく、１０／９０～１８／８２程度であることがより好ましい。 From the viewpoint of obtaining a higher refractive index, the ratio of Ga to Ti contained in the gallium titanium composite oxide (Ga / Ti) is preferably about 2/98 to 20/80 in atomic ratio. More preferably, it is about 90 to 18/82.
　光学膜は、ガリウムチタン複合酸化物のルチル構造の結晶のみからなるものであってもよいが、ガリウムチタン複合酸化物のアモルファス領域や、ガリウムチタン複合酸化物のアナターゼ構造の結晶を含んでいてもよい。但し、より高い屈折率を得る観点からは、光学膜におけるガリウムチタン複合酸化物のルチル構造の結晶の占める割合が高い方が好ましい。 The optical film may be composed only of a rutile structure crystal of gallium titanium composite oxide, but may contain an amorphous region of gallium titanium composite oxide or an anatase structure crystal of gallium titanium composite oxide. Good. However, from the viewpoint of obtaining a higher refractive index, it is preferable that the ratio of the crystals of the rutile structure of the gallium titanium composite oxide in the optical film is higher.
　（第１の局面及び第２の局面に共通の実施形態）
　光学膜の厚みは、特に限定されないが、例えば、５ｎｍ～１０００ｎｍ程度とすることができる。 (Embodiment common to 1st aspect and 2nd aspect)
The thickness of the optical film is not particularly limited, but can be, for example, about 5 nm to 1000 nm.
　光学膜を、４２０℃以上の温度の基板上に成膜することが好ましく、４５０℃以上の温度の基板上に成膜することがより好ましい。光学膜を成膜する際の基板の温度を高めることにより、より高い屈折率を得ることが可能となる。この理由は定かではないが、光学膜に占めるアルミニウムチタン複合酸化物またはガリウムチタン複合酸化物のルチル構造の結晶の割合が高くなるためであると考えられる。 The optical film is preferably formed on a substrate having a temperature of 420 ° C. or higher, and more preferably formed on a substrate having a temperature of 450 ° C. or higher. A higher refractive index can be obtained by increasing the temperature of the substrate when forming the optical film. Although this reason is not certain, it is thought that it is because the ratio of the crystal of the rutile structure of the aluminum titanium composite oxide or the gallium titanium composite oxide in the optical film is increased.
　光学膜は、例えば、物理的堆積法等により成膜することができる。物理的堆積法の具体例としては、パルスレーザー堆積法、スパッタリング法、電子ビーム蒸着法などが挙げられる。 The optical film can be formed by, for example, a physical deposition method. Specific examples of the physical deposition method include a pulse laser deposition method, a sputtering method, and an electron beam evaporation method.
　基板としては、特に限定されず、例えば、ガラス、プラスチック、樹脂、フィルムなどが挙げられる。 The substrate is not particularly limited, and examples thereof include glass, plastic, resin, and film.
　以下、本発明について、具体的な実施例に基づいて、さらに詳細に説明する。本発明は、以下の実施例に何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施することが可能である。 Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples, and can be implemented with appropriate modifications without departing from the scope of the invention.
　＜第１の局面＞
　（実施例１）
　［ターゲットの作製］
　ＴｉＯ２（株式会社高純度化学研究所製、純度９９％）とＡｌ２Ｏ３（株式会社高純度化学研究所製、純度９９％）とを、原子比でＡｌ／Ｔｉ＝１０／９０となるように混合して、酸化物粉末１０ｇを得た。酸化物粉末１０ｇと２－プロパノール３０ｃｃとを部分安定化ジルコニア製の容器に入れ、遊星型ボールミル装置で１時間混合し、スラリーとした。スラリーを乾燥し、６４ＭＰａで一軸プレスした後、２５０ＭＰａの圧力で静水圧プレスし、１１５０℃で、３６時間、大気中で焼成して、ターゲットを得た。 <First aspect>
Example 1
[Preparation of target]
TiO 2 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99%) and Al 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99%) have an atomic ratio of Al / Ti = 10/90. Thus, 10 g of oxide powder was obtained. 10 g of the oxide powder and 30 cc of 2-propanol were placed in a partially stabilized zirconia container and mixed for 1 hour with a planetary ball mill apparatus to form a slurry. The slurry was dried, uniaxially pressed at 64 MPa, then isostatically pressed at a pressure of 250 MPa, and fired at 1150 ° C. for 36 hours in the air to obtain a target.
　［光学膜の成膜］
　次に、上記作製のターゲットを用い、パルスレーザー堆積（ＰＬＤ）法により、以下の条件で、無アルカリガラス基板（日本電気硝子株式会社製のＯＡ－１０Ｇ、１５ｍｍ角、０．７ｍｍ厚）の上に光学膜を成膜した。 [Deposition of optical film]
Next, on the non-alkali glass substrate (OA-10G manufactured by Nippon Electric Glass Co., Ltd., 15 mm square, 0.7 mm thickness) by the pulse laser deposition (PLD) method using the above-mentioned target, under the following conditions An optical film was formed.
　雰囲気：酸素
　雰囲気の圧力／１．５×１０－５Ｐａ以下
　ターゲットと基板との距離／３５ｍｍ
　成膜時の無アルカリガラス基板の温度／５００℃
　レーザー／波長２４８ｎｍのＫｒＦエキシマレーザー（レーザーパワー／２００ｍＪ／パルス、レーザーの周波数／５Ｈｚ）
　成膜時間／２０分 Atmosphere: Oxygen Atmospheric pressure / 1.5 × 10 −5 Pa or less Distance between target and substrate / 35 mm
Temperature of non-alkali glass substrate during film formation / 500 ° C
Laser / KrF excimer laser with a wavelength of 248 nm (laser power / 200 mJ / pulse, laser frequency / 5 Hz)
Deposition time / 20 minutes
　得られた光学膜の厚みは、３９ｎｍであった。光学膜の組成とターゲットの組成を、ＥＤＸ（エネルギー分散型Ｘ線分光法）により測定した。その結果、光学膜における組成とターゲット組成は、ほぼ同一であることが確認された。 The thickness of the obtained optical film was 39 nm. The composition of the optical film and the composition of the target were measured by EDX (energy dispersive X-ray spectroscopy). As a result, it was confirmed that the composition in the optical film and the target composition were almost the same.
　［光学特性評価］
　分子エリプソメトリーにより、波長４００ｎｍにおける光学膜の屈折率ｎを測定した。波長４００ｎｍにおける光学膜の屈折率は、図１に示されるように２．９８であった。なお、分子エリプソメトリーによる評価には、Ｈｏｒｉｂａ　Ｊｏｂｉｎ　Ｙｖｏｎ製のＡｕｔｏ　ＳＥを用いた。 [Optical characteristics evaluation]
The refractive index n of the optical film at a wavelength of 400 nm was measured by molecular ellipsometry. The refractive index of the optical film at a wavelength of 400 nm was 2.98 as shown in FIG. For the evaluation by molecular ellipsometry, Auto SE manufactured by Horiba Jobin Yvon was used.
　［電子線回折パターンの測定］
　原子分解能分析電子顕微鏡（日本電子株式会社製のＪＥＭ－ＡＲＭ２００Ｆ）を用いて、実施例１で得られた光学膜の電子線回折パターンを測定した。電子線回折パターンを図２に示す。図２に示されるように、実施例１で得られた光学膜には、ルチル型の結晶とアナターゼ型の結晶が含まれていることが確認された。また、光学膜には、アモルファス領域も存在していた。 [Measurement of electron diffraction pattern]
The electron beam diffraction pattern of the optical film obtained in Example 1 was measured using an atomic resolution analytical electron microscope (JEM-ARM200F manufactured by JEOL Ltd.). The electron diffraction pattern is shown in FIG. As shown in FIG. 2, it was confirmed that the optical film obtained in Example 1 contained rutile type crystals and anatase type crystals. In addition, an amorphous region was also present in the optical film.
　（実施例２）
　ＴｉＯ２とＡｌ２Ｏ３とを、原子比でＡｌ／Ｔｉ＝５／９５となるように混合してターゲットを作製したこと以外は、実施例１と同様にして光学膜を成膜した。光学膜の厚みは、３７ｎｍであった。次に、実施例１と同様にして、光学膜の組成を測定し、光学特性を評価した。光学膜の屈折率は、２．９２であった。また、図示していないが、実施例１と同様に、実施例２で得られた光学膜には、ルチル型の結晶とアナターゼ型の結晶が含まれていることが確認された。 (Example 2)
An optical film was formed in the same manner as in Example 1 except that a target was prepared by mixing TiO 2 and Al 2 O 3 so that the atomic ratio was Al / Ti = 5/95. The thickness of the optical film was 37 nm. Next, in the same manner as in Example 1, the composition of the optical film was measured and the optical characteristics were evaluated. The refractive index of the optical film was 2.92. Although not shown, it was confirmed that the optical film obtained in Example 2 contained rutile type crystals and anatase type crystals as in Example 1.
　（参考例１）
　Ａｌ２Ｏ３を混合せずにターゲットを作製したこと以外は、実施例１と同様にして光学膜を成膜した。光学膜の厚みは、２１ｎｍであった。次に、実施例１と同様にして、光学膜の組成を測定し、光学特性を評価した。光学膜の屈折率は、２．８１であった。また、図示していないが、参考例１で得られた光学膜には、ルチル型の結晶は含まれておらず、アナターゼ型の結晶が含まれていることが確認された。 (Reference Example 1)
An optical film was formed in the same manner as in Example 1 except that the target was produced without mixing Al 2 O 3 . The thickness of the optical film was 21 nm. Next, in the same manner as in Example 1, the composition of the optical film was measured and the optical characteristics were evaluated. The refractive index of the optical film was 2.81. Although not shown, it was confirmed that the optical film obtained in Reference Example 1 did not contain rutile crystals and contained anatase crystals.
　（参考例２）
　ＴｉＯ２とＡｌ２Ｏ３とを、原子比でＡｌ／Ｔｉ＝２０／８０となるように混合してターゲットを作製したこと以外は、実施例１と同様にして光学膜を成膜した。光学膜の厚みは、３２ｎｍであった。次に、実施例１と同様にして、光学膜の組成を測定し、光学特性を評価した。光学膜の屈折率は、２．６９であった。また、図示していないが、参考例２で得られた光学膜には、ルチル型の結晶もアナターゼ型の結晶も含まれていないことが確認された。 (Reference Example 2)
An optical film was formed in the same manner as in Example 1 except that TiO 2 and Al 2 O 3 were mixed so that the atomic ratio was Al / Ti = 20/80 to prepare a target. The thickness of the optical film was 32 nm. Next, in the same manner as in Example 1, the composition of the optical film was measured and the optical characteristics were evaluated. The refractive index of the optical film was 2.69. Although not shown, it was confirmed that the optical film obtained in Reference Example 2 did not contain rutile crystals or anatase crystals.
　（参考例３）
　ＴｉＯ２とＡｌ２Ｏ３とを、原子比でＡｌ／Ｔｉ＝４０／６０となるように混合してターゲットを作製したこと以外は、実施例１と同様にして光学膜を成膜した。光学膜の厚みは、３１ｎｍであった。次に、実施例１と同様にして、光学膜の組成を測定し、光学膜の屈折率は、２．３９であった。また、図示していないが、参考例３で得られた光学膜には、ルチル型の結晶もアナターゼ型の結晶も含まれていないことが確認された。 (Reference Example 3)
An optical film was formed in the same manner as in Example 1 except that a target was prepared by mixing TiO 2 and Al 2 O 3 so that the atomic ratio was Al / Ti = 40/60. The thickness of the optical film was 31 nm. Next, the composition of the optical film was measured in the same manner as in Example 1, and the refractive index of the optical film was 2.39. Although not shown, it was confirmed that the optical film obtained in Reference Example 3 contains neither rutile-type crystals nor anatase-type crystals.
　＜第２の局面＞
　（実施例３）
　［ターゲットの作製］
　実施例１のターゲットの作製において、Ａｌ２Ｏ３に代えて、Ｇａ２Ｏ３（株式会社高純度化学研究所製、純度９９％）を用い、ＴｉＯ２とＧａ２Ｏ３とを、原子比でＧａ／Ｔｉ＝１０／９０となるように混合して、酸化物粉末を得た。これを用いて、実施例１と同様にしてターゲットを得た。 <Second aspect>
(Example 3)
[Preparation of target]
In the preparation of the target in Example 1, in place of the Al 2 O 3, Ga 2 O 3 ( produced by Kojundo Chemical Laboratory Co., Ltd., purity 99%) was used, and a TiO 2 and Ga 2 O 3, the atomic ratio Were mixed to obtain Ga / Ti = 10/90 to obtain an oxide powder. Using this, a target was obtained in the same manner as in Example 1.
　［光学膜の成膜］
　次に、上記作製のターゲットを用い、パルスレーザー堆積（ＰＬＤ）法により、以下の条件で、無アルカリガラス基板（日本電気硝子株式会社製のＯＡ－１０Ｇ、１５ｍｍ角、０．７ｍｍ厚）の上に光学膜を成膜した。
　雰囲気：酸素
　雰囲気の圧力／１．５×１０－５Ｐａ以下
　ターゲットと基板との距離／５０ｍｍ
　成膜時の無アルカリガラス基板の温度／５００℃
　レーザー／波長２４８ｎｍのＫｒＦエキシマレーザー（レーザーパワー／２００ｍＪ／パルス、レーザーの周波数／５Ｈｚ）
　成膜時間／２０分 [Deposition of optical film]
Next, on the non-alkali glass substrate (OA-10G manufactured by Nippon Electric Glass Co., Ltd., 15 mm square, 0.7 mm thickness) by the pulse laser deposition (PLD) method using the above-described target, under the following conditions: An optical film was formed.
Atmosphere: Oxygen Atmospheric pressure / 1.5 × 10 −5 Pa or less Distance between target and substrate / 50 mm
Temperature of non-alkali glass substrate during film formation / 500 ° C
Laser / KrF excimer laser with a wavelength of 248 nm (laser power / 200 mJ / pulse, laser frequency / 5 Hz)
Deposition time / 20 minutes
　得られた光学膜の厚みは、１３１ｎｍであった。光学膜の組成を、ＥＤＸで測定した。光学膜におけるＧａ量は、１５．６％であった。従って、光学膜におけるＧａ／Ｔｉは、１５．６／８４．４であった。従って、ガリウムチタン複合酸化物の場合、光学膜におけるＧａとＴｉの割合は、ターゲット組成に比較してＧａ量が増加していた。 The thickness of the obtained optical film was 131 nm. The composition of the optical film was measured by EDX. The amount of Ga in the optical film was 15.6%. Therefore, Ga / Ti in the optical film was 15.6 / 84.4. Therefore, in the case of the gallium titanium composite oxide, the Ga amount in the ratio of Ga and Ti in the optical film is increased as compared with the target composition.
　［光学特性の評価］
　実施例１と同様にして、分子エリプソメトリーにより、波長４００ｎｍにおける光学膜の屈折率ｎを測定した。波長４００ｎｍにおける光学膜の屈折率は、２．９８であった。 [Evaluation of optical properties]
In the same manner as in Example 1, the refractive index n of the optical film at a wavelength of 400 nm was measured by molecular ellipsometry. The refractive index of the optical film at a wavelength of 400 nm was 2.98.
　（実施例４）
　Ｇａ２Ｏ３とＴｉＯ２とを、原子比でＧａ／Ｔｉ＝５／９５となるように混合してターゲットを作製したこと以外は、実施例３と同様にして光学膜を成膜した。光学膜の厚みは１５７ｎｍであった。次に、実施例３と同様にして、光学膜の組成を測定した。光学膜の組成は、Ｇａ／Ｔｉが７．３／９２．７であった。また、実施例３と同様にして、光学特性を評価した。光学膜の屈折率は、２．８４であった。 (Example 4)
An optical film was formed in the same manner as in Example 3 except that the target was prepared by mixing Ga 2 O 3 and TiO 2 so that the atomic ratio was Ga / Ti = 5/95. The thickness of the optical film was 157 nm. Next, the composition of the optical film was measured in the same manner as in Example 3. The composition of the optical film was Ga / Ti 7.3 / 92.7. Further, the optical characteristics were evaluated in the same manner as in Example 3. The refractive index of the optical film was 2.84.
　（参考例４）
　Ｇａ２Ｏ３を混合せずにターゲットを作製したこと以外は、実施例３と同様にして光学膜を成膜した。光学膜の厚みは、１４３ｎｍであった。次に、実施例３と同様にして、光学特性を評価した。光学膜の屈折率は、２．８１であった。 (Reference Example 4)
An optical film was formed in the same manner as in Example 3 except that the target was produced without mixing Ga 2 O 3 . The thickness of the optical film was 143 nm. Next, the optical characteristics were evaluated in the same manner as in Example 3. The refractive index of the optical film was 2.81.
　（参考例５）
　Ｇａ２Ｏ３とＴｉＯ２とを、原子比でＧａ／Ｔｉ＝２０／８０となるように混合してターゲットを作製したこと以外は、実施例３と同様にして光学膜を成膜した。光学膜の厚みは、１３９ｎｍであった。次に、実施例３と同様にして光学膜の組成を測定し、光学特性を評価した。光学膜の組成は、Ｇａ／Ｔｉ＝２６．３／７３．７であった。光学膜の屈折率は、２．６３であった。 (Reference Example 5)
An optical film was formed in the same manner as in Example 3, except that Ga 2 O 3 and TiO 2 were mixed so that the atomic ratio was Ga / Ti = 20/80 to prepare a target. The thickness of the optical film was 139 nm. Next, the composition of the optical film was measured in the same manner as in Example 3 to evaluate the optical characteristics. The composition of the optical film was Ga / Ti = 26.3 / 73.7. The refractive index of the optical film was 2.63.
　図３に、実施例３，４及び参考例４，５の光学膜におけるＧａの原子比と屈折率との関係を示す。図３に示すように、Ｇａを含み、かつＧａとＴｉとの比（Ｇａ／Ｔｉ）が２０／８０以下であるときに、参考例４のチタン酸化物より高い屈折率を示すことが分かる。 FIG. 3 shows the relationship between the atomic ratio of Ga and the refractive index in the optical films of Examples 3 and 4 and Reference Examples 4 and 5. As shown in FIG. 3, it can be seen that when Ga is contained and the ratio of Ga to Ti (Ga / Ti) is 20/80 or less, the refractive index is higher than that of the titanium oxide of Reference Example 4.
　［Ｘ線回折パターンの測定］
　実施例３，４及び参考例４，５で得られた光学膜について、Ｘ線回折パターンを測定した。Ｘ線回折パターンを図４に示す。図４に示されるように、実施例３及び４の光学膜は、２７．５度にルチル型結晶のピークが、ショルダーとして観察されている。従って、光学膜にはルチル型結晶が含まれていることが分かる。参考例４及び参考例５においては、このルチル型結晶のピークがほとんど認められなくなっている。 [Measurement of X-ray diffraction pattern]
The X-ray diffraction pattern was measured for the optical films obtained in Examples 3 and 4 and Reference Examples 4 and 5. An X-ray diffraction pattern is shown in FIG. As shown in FIG. 4, in the optical films of Examples 3 and 4, a rutile crystal peak is observed as a shoulder at 27.5 degrees. Therefore, it can be seen that the optical film contains a rutile crystal. In Reference Example 4 and Reference Example 5, the rutile crystal peak is hardly observed.

Claims (5)

  1. 　ＡｌまたはＧａを含有するチタン複合酸化物からなり、ルチル構造の結晶を含む、光学膜。 An optical film made of a titanium composite oxide containing Al or Ga and containing a crystal having a rutile structure.
  2. 　原子比でＡｌ／Ｔｉが１７／８３以下であるアルミニウムチタン複合酸化物からなる、請求項１に記載の光学膜。 The optical film according to claim 1, comprising an aluminum titanium composite oxide having an atomic ratio of Al / Ti of 17/83 or less.
  3. 　原子比でＧａ／Ｔｉが２０／８０以下であるガリウムチタン複合酸化物からなる、請求項１に記載の光学膜。 The optical film according to claim 1, comprising a gallium titanium composite oxide having an atomic ratio of Ga / Ti of 20/80 or less.
  4. 　波長４００ｎｍにおける屈折率が２．８以上である、請求項１～３のいずれか１項に記載の光学膜。 The optical film according to any one of claims 1 to 3, wherein the refractive index at a wavelength of 400 nm is 2.8 or more.
  5. 　アモルファス領域を含む、請求項１～４のいずれか１項に記載の光学膜。 The optical film according to any one of claims 1 to 4, comprising an amorphous region.
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JP2006518809A (en) * 2003-01-28 2006-08-17 コーニンクレッカ　フィリップス　エレクトロニクス　エヌ　ヴィ Titanium oxide transparent film having at least one of aluminum and aluminum oxide and having a rutile structure
JP2008052913A (en) * 2006-08-22 2008-03-06 Sumitomo Chemical Co Ltd Transparent conductive film, and its manufacturing method
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JP2964513B2 (en) * 1988-12-27 1999-10-18 東芝ライテック株式会社 High heat resistant high refractive index composite oxide thin film, composition for forming the same, and incandescent lamp
JPH06219786A (en) * 1993-01-22 1994-08-09 Nippon Sheet Glass Co Ltd Tio2 film, its production, heat ray reflecting film and heat ray reflector
JP2006518809A (en) * 2003-01-28 2006-08-17 コーニンクレッカ　フィリップス　エレクトロニクス　エヌ　ヴィ Titanium oxide transparent film having at least one of aluminum and aluminum oxide and having a rutile structure
JP2005179129A (en) * 2003-12-19 2005-07-07 Kyocera Corp Conductive titanium oxide sintered compact, sputtering target, translucent member, and image display device
JP2008052913A (en) * 2006-08-22 2008-03-06 Sumitomo Chemical Co Ltd Transparent conductive film, and its manufacturing method
JP2008050677A (en) * 2006-08-28 2008-03-06 Kanagawa Acad Of Sci & Technol Metal oxide film

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Publication number Priority date Publication date Assignee Title
JP2017044904A (en) * 2015-08-27 2017-03-02 日本電気硝子株式会社 Optical film and manufacturing method therefor

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