JP7662000B2 - Composite tungsten oxide film, film-forming substrate having said film, and article - Google Patents
Composite tungsten oxide film, film-forming substrate having said film, and article Download PDFInfo
- Publication number
- JP7662000B2 JP7662000B2 JP2023131500A JP2023131500A JP7662000B2 JP 7662000 B2 JP7662000 B2 JP 7662000B2 JP 2023131500 A JP2023131500 A JP 2023131500A JP 2023131500 A JP2023131500 A JP 2023131500A JP 7662000 B2 JP7662000 B2 JP 7662000B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- tungsten oxide
- composite tungsten
- oxide film
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/006—Compounds containing tungsten, with or without oxygen or hydrogen, and containing two or more other elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
-
- 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
-
- 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
- C23C14/58—After-treatment
-
- 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
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
- Physical Vapour Deposition (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、複合タングステン酸化物膜に関し、更には当該複合タングステン酸化物膜を有する膜形成基材や当該複合タングステン酸化物膜が有する機能を利用した物品に関する。 The present invention relates to a composite tungsten oxide film, and further to a film-forming substrate having the composite tungsten oxide film and an article utilizing the functions of the composite tungsten oxide film.
窓材等に使用される遮光部材として各種材料が提案されている。例えば、特許文献１には、窓材などの遮光部材として、アルミニウムなどの金属を蒸着法により形成した鏡面状態を有する膜の遮光部材が記載されている。また、銀等をスパッタリング法により形成した膜の遮光部材もある。しかしながら、これらの遮光部材を用いた場合、外観がハーフミラー状となることから、屋外で使用するには反射がまぶしく、景観上の問題がある。一方で、反射を用いた遮光部材は一般的には遠赤外線も反射し断熱性も併せ持つという特長を有する。遠赤外線を含む当該遮光部材の光の反射は自由電子の作用によりもたらされる。 Various materials have been proposed as light-shielding materials for use in window materials and the like. For example, Patent Document 1 describes a light-shielding material for window materials and the like, which is a film with a mirror-like surface formed by vapor deposition of metals such as aluminum. There are also light-shielding materials made of films formed by sputtering of silver and the like. However, when these light-shielding materials are used, the appearance becomes half-mirror-like, and the reflection is too dazzling for outdoor use, which creates problems with the scenery. On the other hand, light-shielding materials that use reflection generally have the advantage of reflecting far-infrared rays and also having heat insulation properties. The reflection of light, including far-infrared rays, by the light-shielding material is brought about by the action of free electrons.
これに対し本出願人は特許文献２に記載の複合タングステン酸化物微粒子を有する赤外線遮蔽微粒子分散体を提案した。複合タングステン酸化物微粒子は、太陽光線、特に近赤外線領域の光を効率よく吸収し、加えて可視光に対して高い透明性を有する。特許文献２に係る発明では、複合タングステン酸化物微粒子を、適宜な溶媒中に分散させて分散液とし、得られた分散液に媒体樹脂を添加した後、基材表面にコーティングして薄膜を形成し、非常に高い遮熱性を持つ。当該赤外線遮蔽微粒子分散体は優れた光の吸収特性を有する効果で高い遮熱性を示すが、反射特性を殆ど有さないため、断熱性はあまり期待できない。
In response to this, the present applicant has proposed an infrared shielding microparticle dispersion containing composite tungsten oxide microparticles described in
特許文献３には、複合タングステン酸化物の原料化合物を含む溶液を基板に塗布後、熱処理して製造する複合タングステン酸化物膜が開示されている。ここで開示されている膜の一部は同文献の図２および図３の破線に示されるように波長１４００ｎｍにおいて３０％程度の反射率を有しており、ある程度断熱性も期待される。 Patent Document 3 discloses a composite tungsten oxide film produced by applying a solution containing the raw compound of composite tungsten oxide to a substrate and then heat treating it. As shown by the dashed lines in Figures 2 and 3 of the same document, some of the films disclosed here have a reflectance of about 30% at a wavelength of 1400 nm, and are expected to have a certain degree of thermal insulation.
また、特許文献４には、複合タングステン酸化物の原料化合物を含む溶液を回転する基板に滴下し遠心力で成膜したのち、還元雰囲気で焼成したＮａｘＷＯ３膜が開示されている。当該文献のＦｉｇ．１によれば、当該膜は赤外域の光をほとんど反射しており遮蔽性と断熱性を併せ持つと思われる。 In addition, Patent Document 4 discloses a Na x WO 3 film that is formed by dropping a solution containing a raw material compound of a composite tungsten oxide onto a rotating substrate, forming a film by centrifugal force, and then firing the film in a reducing atmosphere. According to Fig. 1 of the document, the film reflects almost all light in the infrared range, and is considered to have both shielding and heat insulation properties.
一方で、このような複合タングステン酸化物膜は色調の調整、反射防止などを目的に、光学設計がなされることがあるが、このとき積層される膜の膜厚は数ｎｍ～数１００ｎｍときわめて薄い。そのため、複合タングステン酸化物膜の膜厚を１００ｎｍ未満で制御する必要があるが、塗布法で膜厚１００ｎｍ未満の領域を制御するのは難しい。また、積層される複合タングステン酸化物膜の表面粗さは平滑性が求められ、成膜面の表面粗さが大きいと所望の光学設計の効果が得られない。特許文献３や特許文献４に記載の塗布焼成法では溶液から結晶が析出し、粒成長するというプロセス上、表面粗さが大きくなりやすい。特許文献３の記載の方法を再現し、レーザー顕微鏡で表面粗さを測定したところ算術平均高さＳａで６０ｎｍを超えるものであった。 On the other hand, such composite tungsten oxide films are sometimes optically designed for the purpose of adjusting color tone and preventing reflection, but the thickness of the laminated film is extremely thin, ranging from a few nm to a few hundreds of nm. Therefore, it is necessary to control the thickness of the composite tungsten oxide film to less than 100 nm, but it is difficult to control the thickness of the film to less than 100 nm using a coating method. In addition, the surface roughness of the laminated composite tungsten oxide film must be smooth, and if the surface roughness of the film formation surface is large, the desired optical design effect cannot be obtained. In the coating and baking method described in Patent Document 3 and Patent Document 4, the surface roughness is likely to become large due to the process in which crystals precipitate from the solution and grow into grains. When the method described in Patent Document 3 was reproduced and the surface roughness was measured with a laser microscope, the arithmetic average height Sa exceeded 60 nm.
複合タングステン酸化物薄膜を得る別の手段として、特許文献１の例に見られる蒸着法やスパッタリング法などの物理的な方法がある。物理的な成膜法の薄膜は、目的とする組成物以外の元素を除外した膜にすることができる。また、高温の処理に適さない分散剤や媒体樹脂を使用する必要がないため、例えば高温熱処理する強化ガラスの製造工程に供することができる。さらに、物理的な成膜法の薄膜は１００ｎｍ未満の膜厚でも膜厚をコントロールすることが容易であり、また、算術平均粗さで数ｎｍ以下の非常に平滑な表面を作成できるため、積層構造も容易に可能である。 As another means for obtaining a composite tungsten oxide thin film, there are physical methods such as vapor deposition and sputtering, as seen in the example of Patent Document 1. Thin films formed by physical film formation methods can be made into films that exclude elements other than the target composition. In addition, since there is no need to use dispersants or medium resins that are not suitable for high-temperature treatment, they can be used in the manufacturing process of tempered glass that undergoes high-temperature heat treatment, for example. Furthermore, thin films formed by physical film formation methods are easy to control the film thickness even at a thickness of less than 100 nm, and a very smooth surface with an arithmetic mean roughness of several nm or less can be created, making it easy to form a layered structure.
特許文献５には車両用窓ガラスとその製造方法が提案され、車両用窓等の大面積の基板への処理が可能な大型インライン方式のスパッタリング装置が用いられている。このような製造設備が使用可能であれば、容易に膜厚が均一で高品質で安定した膜を得られ、かつ、生産性も高い。また、物理的な成膜法の成膜源（例えば、スパッタリング法ではターゲット材料）は単一の化合物でなくても、例えば単体元素の組成物組合せや複数の化合物等から成る混合物でも構わず、組成選択の自由度が極めて広い。 Patent Document 5 proposes a vehicle window glass and a manufacturing method thereof, in which a large in-line sputtering device capable of processing large-area substrates such as vehicle windows is used. If such manufacturing equipment is available, it is easy to obtain a high-quality, stable film with a uniform thickness, and the productivity is also high. Furthermore, the film source in a physical film formation method (for example, the target material in a sputtering method) does not have to be a single compound, and can be, for example, a composition combination of single elements or a mixture of multiple compounds, etc., allowing for an extremely wide degree of freedom in composition selection.
特許文献６には、スパッタリング法により作製した複合タングステン酸化物膜が提案されている。ガラス基板上に、タングステンと周期律表のＩＶａ族、ＩＩＩａ族、ＶＩＩｂ族、ＶＩｂ族及びＶｂ族から成る群から選ばれた少なくとも１種の元素からなる複合タングステン酸化物膜を形成している。しかしながら、この組成の酸化物膜は赤外線透過率が４０％以上と熱線遮蔽性能は十分でなく、他の透明誘電体膜との多層膜にしなければ機能を発揮できないという問題があった。 Patent Document 6 proposes a composite tungsten oxide film produced by a sputtering method. A composite tungsten oxide film consisting of tungsten and at least one element selected from the group consisting of Groups IVa, IIIa, VIIb, VIb, and Vb of the periodic table is formed on a glass substrate. However, the oxide film of this composition has an infrared transmittance of 40% or more, and does not have sufficient heat ray shielding performance, so there is a problem that it cannot function unless it is made into a multilayer film with another transparent dielectric film.
上述の通り、物理的な成膜法による複合タングステン酸化物膜の熱線遮蔽性能は、まだ十分であるとは言えない状況である。一方で、塗布法により形成された膜は光を吸収して熱線を遮蔽する機能は高いが、断熱性はあまり期待できない。加えて膜の平滑性が劣る問題がある。 As mentioned above, the heat ray shielding performance of composite tungsten oxide films formed by physical film formation methods is still not sufficient. On the other hand, films formed by coating methods have a high function of absorbing light and shielding heat rays, but their thermal insulation properties cannot be expected to be very good. In addition, there is a problem with the film's poor smoothness.
そこで、本発明は、このような状況を解決するためになされたものであり、可視光域における透明性を保持しつつ、赤外光を反射して遮蔽する機能、すなわち断熱による熱線遮蔽機能に加え、膜の平滑性が高い複合タングステン膜を提供し、更にはこれら機能を利用した膜形成基材又は物品を提供する。 The present invention was made to solve this problem by providing a composite tungsten film that retains transparency in the visible light range while reflecting and blocking infrared light, i.e., has a heat ray shielding function through insulation, and also has a high film smoothness, and further provides a film-formed substrate or article that utilizes these functions.
本発明者らは、上述した課題に対して、複合タングステン酸化物膜について鋭意研究し、物理的な成膜法によれば、成膜時の条件を最適化することで優れた可視光透過性を保持しつつ、赤外線を反射して断熱する機能を発揮し、加えて極めて平滑な膜を有する複合タングステン膜を得るに至った。 In response to the above-mentioned problems, the inventors have conducted extensive research into composite tungsten oxide films, and by optimizing the conditions during film formation using a physical film formation method, have been able to obtain a composite tungsten film that retains excellent visible light transmittance while reflecting infrared rays and providing thermal insulation, and that also has an extremely smooth film.
すなわち、本発明の一態様は、一般式ＭｘＷｙＯｚ（ただし、Ｍは、アルカリ金属、アルカリ土類金属、Ｆｅ、Ｉｎ、Ｔｌ、Ｓｎの内から選択される１種以上の元素、Ｗはタングステン、Ｏは酸素）で表される組成を主成分とする層のみからなる複合タングステン酸化物膜であって、０．００１≦ｘ／ｙ≦１、２．２≦ｚ／ｙ≦３．０であり、有機物成分を実質的に含まず、波長５５０ｎｍにおける透過率が５０％以上、波長１４００ｎｍにおける透過率が３０％以下、かつ、波長１４００ｎｍにおける反射率が３５％以上であり、六方晶の結晶構造を含む連続膜である。 That is, one aspect of the present invention is a composite tungsten oxide film consisting only of a layer whose main component is a composition represented by the general formula MxWyOz (wherein M is one or more elements selected from among alkali metals, alkaline earth metals, Fe, In, Tl and Sn, W is tungsten, and O is oxygen), in which 0.001≦x/y≦1, 2.2≦z/y≦3.0, the film is substantially free of organic components, has a transmittance of 50% or more at a wavelength of 550 nm, a transmittance of 30% or less at a wavelength of 1400 nm, and a reflectance of 35% or more at a wavelength of 1400 nm , and is a continuous film containing a hexagonal crystal structure .
本発明の一態様によれば、可視光域における透明性を保持しつつ、赤外光を反射して遮蔽する機能、すなわち断熱による熱線遮蔽機能を有する複合タングステン酸化物膜となる。また、スパッタリング成膜由来とすることで、組成選択の自由度が極めて広く、安定に成膜できる複合タングステン酸化物膜とすることができる。また、スパッタリング成膜により、極めて平滑な膜が得られるため、光学設計された積層構造の効果を高めることができる。また、六方晶相は赤外域の反射がより大きいため、効率良く反射することができる。 According to one embodiment of the present invention, a composite tungsten oxide film is obtained that has a function of reflecting and shielding infrared light while maintaining transparency in the visible light range, that is, a heat ray shielding function by heat insulation. In addition, by using sputtering deposition as the origin, a composite tungsten oxide film can be obtained that has a very wide degree of freedom in composition selection and can be stably deposited. In addition, since a very smooth film can be obtained by sputtering deposition, the effect of an optically designed laminated structure can be enhanced. In addition, since the hexagonal phase has a higher reflection in the infrared range, it can be reflected efficiently.
このとき、本発明の一態様では、表面粗さＳａが２０ｎｍ以下であるとしてもよい。 In this case, in one aspect of the present invention, the surface roughness Sa may be 20 nm or less.
上記条件を満たすことで、膜の平滑性が高い複合タングステン膜となる。 By meeting the above conditions, a composite tungsten film with high film smoothness will be obtained.
また、本発明の一態様では、シート抵抗が１０５Ω/□未満であるとしてもよい。 In addition, in one embodiment of the present invention, the sheet resistance may be less than 10 5 Ω/□.
シート抵抗を上記範囲とすることで、より好ましい断熱性を得ることができる。 By keeping the sheet resistance within the above range, more favorable thermal insulation properties can be obtained.
また、本発明の一態様では、Ｍは、Ｃｓ、Ｒｂ、Ｋ、Ｔｌ、Ｉｎ、Ｂａ、Ｌｉ、Ｎａ、Ｃａ、Ｓｒ、Ｆｅ、およびＳｎの内から選択される１種以上の元素であるとしてもよい。 In one embodiment of the present invention, M may be one or more elements selected from Cs, Rb, K, Tl, In, Ba, Li, Na, Ca, Sr, Fe, and Sn.
Ｍを上記元素から選択することで、より高い赤外線を反射して遮蔽する機能に加え膜の平滑性が高い複合タングステン酸化物膜とすることができる。 By selecting M from the above elements, a composite tungsten oxide film can be produced that not only has the ability to reflect and block more infrared rays, but also has a high film smoothness.
このとき、本発明の一態様は、ＣｕＫα線を使用したＸ線回折による六方晶（００２）面の回折強度Ｉ（００２）と、六方晶（２００）面の回折強度Ｉ（２００）の強度比をＩ（００２）／Ｉ（２００）としたとき、Ｉ（００２）／Ｉ（２００）は０．３０以上０．５０以下であり、ＣｕＫα線を使用したＸ線回折による六方晶のａ軸とｃ軸との比ｃ／ａが１．０１８～１．０２９であるとしてもよい。 In this case, one aspect of the present invention is that when the intensity ratio I(002) of the diffraction intensity I(002) of the hexagonal (002) plane and the diffraction intensity I(200) of the hexagonal (200) plane by X-ray diffraction using CuKα radiation is I(002)/I(200), I(002)/I(200) is 0.30 or more and 0.50 or less, and the ratio c/a of the a-axis to the c-axis of the hexagonal crystal by X-ray diffraction using CuKα radiation is 1.018 to 1.029.
Ｘ線回折分析による上記要件を満たす複合タングステン酸化物膜は、優れた可視光透過性を保持しつつ、赤外線を反射して断熱する機能を発揮する複合タングステン酸化物膜となる。 A composite tungsten oxide film that meets the above requirements based on X-ray diffraction analysis will be a composite tungsten oxide film that retains excellent visible light transmittance while also reflecting infrared rays and providing thermal insulation.
本発明の他の態様は、上述した複合タングステン酸化物膜が被成膜基材の少なくとも一方の面に形成されている膜形成基材である。 Another aspect of the present invention is a film-forming substrate in which the above-mentioned composite tungsten oxide film is formed on at least one surface of the substrate.
上述した複合タングステン酸化物膜が形成された膜形成基材とすることで、機械特性や加工性等の実用に供する形態とすることができる。 By forming the composite tungsten oxide film on the film-forming substrate, it is possible to obtain a form that is suitable for practical use, such as mechanical properties and processability.
このとき、本発明の他の態様では、被成膜基材が４００℃以上の軟化点もしくは熱変形温度を有するようにしてもよい。 In this case, in another aspect of the present invention, the substrate on which the film is formed may have a softening point or heat distortion temperature of 400°C or higher.
このような特性とすることで、成膜後の熱処理で、より優れた機能を付与した膜形成基材とすることができる。 By providing these characteristics, the film-forming substrate can be given superior functionality through heat treatment after film formation.
また、本発明の他の態様では、被成膜基材をガラスとすることができる。 In another aspect of the present invention, the substrate on which the film is formed can be glass.
被成膜基材をガラスとすることで、車両用窓や建築用窓のガラス窓、ガラス繊維、太陽光発電用ガラス、ディスプレイ用ガラス、レンズや鏡用ガラス、半導体やＭＥＭＳ等で用いられているガラス基板等、幅広い分野で使用されるガラスを用いた機材に赤外線遮蔽機能を付与することができる。 By using glass as the substrate on which the film is formed, it is possible to impart infrared shielding properties to glass-based materials used in a wide range of fields, such as glass windows for vehicles and buildings, glass fibers, glass for solar power generation, glass for displays, glass for lenses and mirrors, and glass substrates used in semiconductors and MEMS.
また、本発明の他の態様は、上述した複合タングステン酸化物膜及び／又は膜形成基材を１又は複数有することを特徴とする物品である。 Another aspect of the present invention is an article having one or more of the above-mentioned composite tungsten oxide films and/or film-forming substrates.
本発明の他の態様によれば、エネルギー削減や製造時の環境負荷の小さい物品を大量に安価で様々な用途で提供することができる。 According to another aspect of the present invention, it is possible to provide products that reduce energy consumption and have a small environmental impact during production at low cost in large quantities for a variety of uses.
本発明によれば、可視光域における透明性を有し、赤外光域における反射性を併せ持った赤外線反射膜としての複合タングステン酸化物膜を得ることができる。また、本発明によれば、このような複合タングステン酸化物膜を工業的に広く利用され、成膜時に比較的無害な方法で、さらに使用原料が長期保存に優れ、危険物保管や輸送時の制限を受けない、物理的な製造方法で提供することができる。 According to the present invention, a composite tungsten oxide film can be obtained as an infrared reflective film that has transparency in the visible light range and reflectivity in the infrared light range. Furthermore, according to the present invention, such a composite tungsten oxide film can be provided by a physical manufacturing method that is widely used industrially, is relatively harmless during film formation, and further, the raw materials used have excellent long-term storage properties and are not subject to restrictions on storage or transportation of hazardous materials.
以下、本発明に係る複合タングステン酸化物膜とその製造方法について以下の順序で説明する。なお、本発明は以下の例に限定されるものではなく、本発明の要旨を逸脱しない範囲で、任意に変更可能である。
１．複合タングステン酸化物膜
２．複合タングステン酸化物膜の製造方法
２－１．成膜工程
２－２．熱処理工程
３．膜形成基材
４．物品
The composite tungsten oxide film and the method for producing the same according to the present invention will be described below in the following order. Note that the present invention is not limited to the following examples, and can be modified as desired without departing from the gist of the present invention.
1. Composite
＜１．複合タングステン酸化物膜＞
本発明の一実施形態に係る複合タングステン酸化物膜について説明する。本発明の一実施形態に係る複合タングステン酸化物膜は、一般式ＭｘＷｙＯｚ（ただし、Ｍは、アルカリ金属、アルカリ土類金属、Ｆｅ、Ｉｎ、Ｔｌ、Ｓｎの内から選択される１種以上の元素、Ｗはタングステン、Ｏは酸素）で表される組成を主成分とする膜であり、ｘとｙの比が０．００１≦ｘ／ｙ≦１、ｚとｙの比が２．２≦ｚ／ｙ≦３．０の範囲の構成である。
<1. Composite tungsten oxide film>
A composite tungsten oxide film according to one embodiment of the present invention will be described. The composite tungsten oxide film according to one embodiment of the present invention is a film mainly composed of a composition represented by the general formula MxWyOz (wherein M is one or more elements selected from alkali metals, alkaline earth metals, Fe, In , Tl, and Sn, W is tungsten, and O is oxygen), and has a configuration in which the ratio of x to y is in the range of 0.001≦x/y≦1 and the ratio of z to y is in the range of 2.2≦z/y≦3.0.
組成範囲の詳細については、本出願人による特許文献２に詳細が示されており、この組成範囲の複合タングステン酸化物を主成分とすることが、高い透明性と赤外光吸収性を有する膜とするためには必要である。複合タングステン酸化物膜が有する基本的な光学特性は、理論的に算出された、元素Ｍと、タングステンＷおよび酸素Ｏの原子配置に由来する。一方で、本発明の一実施形態は、特許文献２に記載の赤外線遮蔽体とは異なる特性を有する複合タングステン酸化物膜であり、以下、特許文献２に係る発明と適宜対比しながら詳細に説明する。
Details of the composition range are given in
本発明の一実施形態に係る複合タングステン酸化物膜の元素Ｍは、アルカリ金属、アルカリ土類金属、Ｆｅ、Ｉｎ、Ｔｌ、Ｓｎの内から選択される１種以上の元素であり、より好ましくは、Ｃｓ、Ｒｂ、Ｋ、Ｔｌ、Ｉｎ、Ｂａ、Ｌｉ、Ｎａ、Ｃａ、Ｓｒ、Ｆｅ、およびＳｎの内から選択される１種以上の元素である。これは、特許文献２に記載の構成元素よりも狭い範囲としているが、これは実施例に依り効果が確認できた元素を示すに過ぎず、本発明に含まれない特許文献２に記載の元素でも少なからず同様の機能を有する可能性はある。
The element M of the composite tungsten oxide film according to one embodiment of the present invention is one or more elements selected from alkali metals, alkaline earth metals, Fe, In, Tl, and Sn, and more preferably one or more elements selected from Cs, Rb, K, Tl, In, Ba, Li, Na, Ca, Sr, Fe, and Sn. This is a narrower range than the constituent elements described in
本発明の一実施形態に係る複合タングステン酸化物膜の元素Ｍは、Ｃｓ、Ｒｂ、Ｋ、Ｔｌ、Ｂａから選択される１種類以上の元素であることがさらに好ましい。元素Ｍを上記に選定することで複合タングステン膜は、後述するような六方晶を含む結晶構造となり得る。なお、上記元素Ｍは、ｘ／ｙの比率によっては六方晶以外の結晶構造となることもある。例えば、Ｋはｘ／ｙの比率が０．５以上で正方晶となる。六方晶相を含む構造は赤外域の反射がより大きいため、効率良く反射することができる。 More preferably, element M of the composite tungsten oxide film according to one embodiment of the present invention is one or more elements selected from Cs, Rb, K, Tl, and Ba. By selecting element M as above, the composite tungsten film can have a crystal structure including a hexagonal crystal, as described below. Note that element M may have a crystal structure other than a hexagonal crystal depending on the ratio of x/y. For example, K becomes a tetragonal crystal when the ratio of x/y is 0.5 or more. A structure including a hexagonal phase has a higher reflection in the infrared range, and can therefore reflect light efficiently.
本発明の一実施形態に係る複合タングステン酸化物膜は、一般式ＭｘＷｙＯｚにおいて、元素ＭとＷ（タングステン）の原子数比ｘ／ｙが０．００１≦ｘ／ｙ≦１であり、Ｏ（酸素）とＷ（タングステン）の原子数比ｚ／ｙが２．２≦ｚ／ｙ≦３．０である。ｘ／ｙが０．００１未満であると十分な量の自由電子が生成されず赤外線遮蔽効果を得ることができない。また、ｘ／ｙが１を超えると複合タングステン酸化物膜中に不純物相が形成されてしまう。ｚ／ｙが２．２未満であると、複合タングステン酸化物膜中に目的以外であるＷＯ２の結晶相が現れてしまう。また、ｚ／ｙが３．０を超えると赤外線遮蔽効果を得るための自由電子が生成されなくなってしまう。 In the composite tungsten oxide film according to one embodiment of the present invention, the atomic ratio x / y of element M and W (tungsten) is 0.001≦x/y≦1, and the atomic ratio z/ y of O (oxygen) and W (tungsten) is 2.2≦z/y≦3.0 in the general formula M x W y O z. If x/y is less than 0.001, a sufficient amount of free electrons is not generated, and the infrared shielding effect cannot be obtained. If x/y exceeds 1, an impurity phase is formed in the composite tungsten oxide film. If z/y is less than 2.2, a crystal phase of WO 2 other than the intended one appears in the composite tungsten oxide film. If z/y exceeds 3.0, free electrons for obtaining the infrared shielding effect are not generated.
本発明の一実施形態に係る複合タングステン酸化物膜は、有機物成分を実質的に含まない。後述するように、本発明の一実施形態に係る複合タングステン酸化物膜は、物理的な成膜法により形成されるため、特許文献２や特許文献３に係る発明のように分散剤や媒体樹脂、あるいは界面活性剤や溶媒を使用する必要がない。ここで、有機物成分を実質的に含まないとは、膜の製造過程において、例えば高分子分散剤等、意図的に添加される有機物成分を含んでいないことを指す。
The composite tungsten oxide film according to one embodiment of the present invention is substantially free of organic components. As described below, the composite tungsten oxide film according to one embodiment of the present invention is formed by a physical film formation method, and therefore does not require the use of a dispersant, a medium resin, or a surfactant or a solvent as in the inventions of
特許文献３には段落００６０に複合タングステン酸化物を用いた透明導電膜の製造方法が記されている。これによれば、特許文献３の透明導電膜は複合タングステン化合物を含む溶液を出発タングステン原料溶液として基材に塗布後に不活性ガス、不活性ガスと還元性ガス、還元性ガスのいずれかの雰囲気中で熱処理して得られることが示されている。この方法によれば、メタタングステン酸アンモニウム水溶液とＭ元素の塩化物水溶液に有機成分を含有するポリシロキサン骨格を有する界面活性剤を添加して溶液としている。 Patent Document 3, paragraph 0060, describes a method for producing a transparent conductive film using a composite tungsten oxide. It shows that the transparent conductive film of Patent Document 3 is obtained by applying a solution containing a composite tungsten compound as a starting tungsten raw material solution to a substrate, and then heat treating the substrate in an atmosphere of either an inert gas, an inert gas and a reducing gas, or a reducing gas. According to this method, a surfactant having a polysiloxane skeleton containing an organic component is added to an aqueous solution of ammonium metatungstate and an aqueous solution of a chloride of the M element to form a solution.
特許文献３の記載の方法を再現し、レーザー顕微鏡で表面粗さを測定したところ算術平均高さＳａで６０ｎｍを超えるものであった。一方で、本発明の一実施形態に係る複合タングステン酸化物膜は後述するように、スパッタリング法などの物理的な成膜法により形成されるため、表面粗さＳａを２０ｎｍ以下とすることができる。このように、本発明の一実施形態に係る複合タングステン酸化物膜は、特許文献３の透明導電膜とは平滑性が異なる。 When the method described in Patent Document 3 was reproduced and the surface roughness was measured with a laser microscope, the arithmetic mean height Sa exceeded 60 nm. On the other hand, the composite tungsten oxide film according to one embodiment of the present invention is formed by a physical film formation method such as a sputtering method, as described below, and therefore the surface roughness Sa can be made 20 nm or less. In this way, the composite tungsten oxide film according to one embodiment of the present invention differs in smoothness from the transparent conductive film of Patent Document 3.
また、特許文献２の複合タングステン酸化物微粒子を含有する微粒子分散体から成る膜（微粒子分散膜）は、特許文献２の段落００５０や段落００５３に記載のように、光を吸収、特に近赤外線領域における吸収が優れた熱線遮蔽膜として機能することが示されている。
In addition, as described in paragraphs 0050 and 0053 of
図１、図２は、本発明の複合タングステン酸化物膜と、特許文献２に記載の赤外線遮蔽材料微粒子分散体との光学特性の違いを示す図であり、図１は透過率について、図２は反射率について示した図である。図１、図２に示すように、本発明の一実施形態に係る複合タングステン酸化物膜は、特許文献２に係る微粒子分散体から成る膜（微粒子分散膜）とは異なる光学特性を示す。特に、本発明に係る複合タングステン酸化物膜は図２に示すように、１４００ｎｍ以降の赤外領域の光を大きく反射する。この理由についても後述のように微粒子分散膜と連続膜の違いであると推測されるがその詳細は未だ判っていない。
Figures 1 and 2 are diagrams showing the difference in optical properties between the composite tungsten oxide film of the present invention and the infrared shielding material microparticle dispersion described in
本発明の一実施形態に係る複合タングステン酸化物膜は、波長５５０ｎｍにおける透過率が５０％以上かつ波長１４００ｎｍにおける透過率が３０％以下、波長１４００ｎｍにおける反射率が３５％以上の膜である。 The composite tungsten oxide film according to one embodiment of the present invention has a transmittance of 50% or more at a wavelength of 550 nm, a transmittance of 30% or less at a wavelength of 1400 nm, and a reflectance of 35% or more at a wavelength of 1400 nm.
透明性の指標とした、波長５５０ｎｍにおける透過率が５０％より低くても用途によっては使用することができる。例えば、車用のウィンドフィルムでは、後席ウィンドはプライバシー保護の観点から黒色やダークグレーが好まれ、熱線遮蔽材料と同時に顔料などを意図的に使用することがある。 Even if the transmittance at a wavelength of 550 nm, which is an index of transparency, is less than 50%, it can still be used depending on the application. For example, in the case of car window films, black or dark gray is preferred for rear window seats from the standpoint of privacy protection, and pigments may be intentionally used at the same time as the heat shielding material.
本発明の透明性の指標は、前記のような意図的な顔料などを含まない状態での膜特性を指すものである。透明性の指標が前記値より低いと採光が悪くなり、例えば屋内が暗くなる、外部の景色が見づらくなるなどに繋がる。 The transparency index of the present invention refers to the film properties in a state in which the above-mentioned intentional pigments are not included. If the transparency index is lower than the above-mentioned value, the lighting will be poor, leading to, for example, a dark interior and difficulty in seeing the outside scenery.
同様に、光の遮蔽性能と反射性能の指標とした、波長１４００ｎｍにおける透過率および、波長１４００ｎｍにおける反射率が前記値を満たさない構成とすることもできるが、これらの場合は、赤外光の透過が高くなり、遮熱では皮膚のジリジリ感や室温の上昇、光熱変換では発生する熱量の低下などに繋がる。 Similarly, the transmittance at a wavelength of 1400 nm and the reflectance at a wavelength of 1400 nm, which are indicators of light blocking and reflecting performance, can be configured not to satisfy the above values, but in such cases, the transmittance of infrared light will be high, which in the case of heat blocking will lead to a tingling sensation on the skin and an increase in room temperature, and in the case of photothermal conversion, a decrease in the amount of heat generated.
また、本発明の反射は自由電子による反射であるため、プラズマ周波数以下の光を反射する。言い換えればプラズマ周波数に相当する波長以上の波長の光を反射する。つまり、波長１４００ｎｍの反射率が低いと、より波長の長い遠赤外線の反射率も低く、断熱性が低くなり、室内の暖房などの熱を閉じ込める効果が低い。有効な断熱性を得るには波長１４００ｎｍの反射率が３５％以上あることが必要である。 In addition, since the reflection of the present invention is due to free electrons, it reflects light below the plasma frequency. In other words, it reflects light with a wavelength equal to or greater than the wavelength corresponding to the plasma frequency. In other words, if the reflectance at a wavelength of 1400 nm is low, the reflectance of far-infrared rays with longer wavelengths will also be low, resulting in low insulation and a low effect of trapping heat from indoor heating, etc. To obtain effective insulation, it is necessary for the reflectance at a wavelength of 1400 nm to be 35% or more.
本発明の一実施形態に係る複合酸化タングステン膜の表面粗さＳａは２０ｎｍ以下である。光学薄膜設計（膜を積層する場合）では、干渉を利用して特定の波長の反射を強めたり弱めたりすることで急峻な透過プロファイルにしたり（膜の色味の調整）、可視光域の反射防止に利用できる。表面粗さによる影響は、上記光学薄膜設計（膜を積層する場合）で、表面粗さが小さいので光路長の乱れが少なく安定した積層膜を可能とする。本発明の一実施形態に係る複合酸化タングステン膜は、後述するように、スパッタリング法等による成膜で得られる物理的な方法による膜であるため、膜の表面粗さＳａを２０ｎｍ以下とすることができる。２０ｎｍ以下であれば、光学薄膜設計上の問題が生じる可能性が低い。表面粗さが２０ｎｍを超えてくると、均一な積層状態にならず、光学薄膜設計（積層）の効果が得られ難い。 The surface roughness Sa of the composite tungsten oxide film according to one embodiment of the present invention is 20 nm or less. In optical thin film design (when laminating films), interference can be used to strengthen or weaken the reflection of a specific wavelength, resulting in a steep transmission profile (adjusting the color of the film) or to prevent reflection in the visible light range. The effect of surface roughness is that in the above optical thin film design (when laminating films), the surface roughness is small, making it possible to form a stable laminated film with little disturbance in the optical path length. As described below, the composite tungsten oxide film according to one embodiment of the present invention is a film obtained by a physical method such as sputtering, so the surface roughness Sa of the film can be 20 nm or less. If it is 20 nm or less, there is a low possibility of problems occurring in the optical thin film design. If the surface roughness exceeds 20 nm, the laminated state is not uniform, and it is difficult to obtain the effect of the optical thin film design (lamination).
また、本発明の一実施形態に係る複合タングステン酸化物膜は、２０ｎｍを超える膜厚で形成されることが好ましい。本発明の一実施形態に係る複合タングステン酸化物膜は、後述するように、スパッタリング法等による成膜で得られる物理的な方法による膜で、例えば、特許文献３に記載の溶液を塗布後に熱処理して成膜した膜では、成膜に不可欠と成る溶媒や樹脂等の成分を揮発させて形成されるため、膜にはこれに伴う残留応力が生じる。加えて、揮発成分の残留やボイド等の欠陥が内在することがある。本発明の一実施形態に係る複合タングステン酸化物膜は揮発成分を含むことなく成膜されるため、成膜に伴う膜の残留応力を小さくすることができるとともに、揮発成分の残留やボイド等の欠陥が生じない。このため、クラックや剥離のない膜を形成することができる。 In addition, the composite tungsten oxide film according to one embodiment of the present invention is preferably formed with a film thickness of more than 20 nm. As described later, the composite tungsten oxide film according to one embodiment of the present invention is a film obtained by a physical method obtained by film formation by a sputtering method or the like. For example, in a film formed by applying the solution described in Patent Document 3 and then heat treating it, the film is formed by volatilizing components such as solvents and resins that are essential for film formation, and therefore residual stress occurs in the film. In addition, defects such as residual volatile components and voids may be present. Since the composite tungsten oxide film according to one embodiment of the present invention is formed without containing volatile components, the residual stress of the film due to film formation can be reduced, and defects such as residual volatile components and voids do not occur. Therefore, a film without cracks or peeling can be formed.
しかしながら、膜厚が２０ｎｍ以下の場合は、赤外域での十分な反射性能が得られず、１４００ｎｍにおける赤外線透過率が３０％を超えてしまう。本発明は前記膜厚を超える厚さであれば特に制限はない。しかし、膜厚が厚くなると、波長５５０ｎｍにおける可視光域の透過率が５０％を下回り、可視光透過性が悪くなることや、成膜時の残留応力の影響で膜の剥離が生じることがある。膜の透過率は分光光度計を用いて測定することができる。 However, if the film thickness is 20 nm or less, sufficient reflective performance in the infrared range is not obtained, and the infrared transmittance at 1400 nm exceeds 30%. There are no particular limitations to the present invention as long as the thickness exceeds the above film thickness. However, if the film thickness is large, the transmittance in the visible light range at a wavelength of 550 nm falls below 50%, which may result in poor visible light transmittance or peeling of the film due to residual stress during film formation. The transmittance of the film can be measured using a spectrophotometer.
本発明の一実施形態に係る複合タングステン酸化物膜は、シート抵抗が１．０×１０５Ω／□（オーム・パー・スクエアと読む）未満、より好ましくは１．０×１０3Ω／□未満である。膜のシート抵抗が前記値よりも高いと、自由電子による反射が弱まり、より長波長域の遠赤外線を反射できなくなるため断熱性を得られない。シート抵抗は後述の成膜条件や熱処理条件で調整することができる。シート抵抗は、例えば、抵抗率計を用いて測定することができる。 The composite tungsten oxide film according to one embodiment of the present invention has a sheet resistance of less than 1.0×10 5 Ω/□ (read as ohms per square), more preferably less than 1.0×10 3 Ω/□. If the sheet resistance of the film is higher than the above value, the reflection by free electrons is weakened, and far infrared rays in the longer wavelength range cannot be reflected, so that heat insulation cannot be obtained. The sheet resistance can be adjusted by the film formation conditions and heat treatment conditions described later. The sheet resistance can be measured, for example, using a resistivity meter.
また、本発明の一実施形態に係る複合タングステン酸化物膜は、通常は連続膜として形成されるが、パターンニングを行って反射の制御を付与した形態、凹凸を設けてレンズ機能を付与した形態など膜の形状や凹凸などの形態であっても、本発明の特長を有するものであればいかなる形態でも構わない。 The composite tungsten oxide film according to one embodiment of the present invention is usually formed as a continuous film, but it may be in any form, such as a form in which reflection control is provided by patterning, or a form in which irregularities are provided to provide a lens function, or the shape or irregularities of the film, as long as it has the characteristics of the present invention.
本発明の一実施形態に係る複合タングステン酸化物は、六方晶の結晶構造を含むことが好ましい。六方晶の結晶構造を含むことは膜をＸ線回折分析することで知ることができる。複合タングステン酸化物は六方晶、立方晶、正方晶、斜方晶などの結晶構造、及び非晶質構造が知られているが、本発明の一実施形態に係る複合タングステン酸化物膜は六方晶の結晶構造を有し、六方晶以外の立方晶、正方晶、斜方晶などの結晶構造、及び非晶質構造を含んでいても構わない。複合タングステン酸化物膜に六方晶の結晶構造を含むことで、六方晶相は赤外域の反射がより大きいため、効率良く反射することができる。 The composite tungsten oxide according to one embodiment of the present invention preferably includes a hexagonal crystal structure. The inclusion of a hexagonal crystal structure can be confirmed by X-ray diffraction analysis of the film. Composite tungsten oxides are known to have crystal structures such as hexagonal, cubic, tetragonal, and orthorhombic, as well as amorphous structures, but the composite tungsten oxide film according to one embodiment of the present invention has a hexagonal crystal structure and may include crystal structures other than hexagonal, such as cubic, tetragonal, and orthorhombic, as well as amorphous structures. By including a hexagonal crystal structure in the composite tungsten oxide film, the hexagonal phase has a higher reflection in the infrared range, allowing for efficient reflection.
また、本発明の一実施形態に係る複合タングステン酸化物膜では、ＣｕＫα線を使用したＸ線回折による六方晶のａ軸長さとｃ軸長さの比ｃ／ａは１．０１８～１．０２９となることが好ましい。結晶構造データベースのＩＣＤＤリファレンスコード０１－０８１－１２４４によるとｃ／ａは１．０２８である。標準の六方晶構造よりも原子が過剰または不足になると、ａ軸長さやｃ軸長さが変化すると考えられる。 In addition, in the composite tungsten oxide film according to one embodiment of the present invention, the ratio c/a of the a-axis length to the c-axis length of the hexagonal crystals as determined by X-ray diffraction using CuKα radiation is preferably 1.018 to 1.029. According to the crystal structure database ICDD reference code 01-081-1244, c/a is 1.028. It is believed that if there is an excess or shortage of atoms compared to the standard hexagonal crystal structure, the a-axis length and c-axis length will change.
また、本発明の一実施形態に係る複合タングステン酸化物膜では、ＣｕＫα線を使用したＸ線回折による六方晶（００２）面の回折強度Ｉ（００２）と、六方晶（２００）面の回折強度Ｉ（２００）の強度比をＩ（００２）／Ｉ（２００）としたとき、Ｉ（００２）／Ｉ（２００）は０．３０以上０．５０以下となることが好ましい。前述のＩＣＤＤリファレンスコード０１－０８１－１２４４には、（２００）面に対する（００２）面の相対強度は２６．２％と記載されているから、標準の強度比Ｉ（００２）／Ｉ（２００）は０．２６である。塗布焼成法で作製した複合タングステン酸化物膜の強度比はこの標準値であるが、本発明の強度比は０．３０以上０．５０以下である。標準の強度比よりも大きいので、六方晶のａ、ｂ面の成長が抑制されｃ面配向の傾向があると考えられる。前述のｃ／ａが１．０１８～１．０２９を外れ、強度比Ｉ（００２）／Ｉ（２００）が０．３０以上０．５０以下を外れると熱線反射機能が低下する。 In addition, in the composite tungsten oxide film according to one embodiment of the present invention, when the intensity ratio of the diffraction intensity I(002) of the hexagonal (002) plane and the diffraction intensity I(200) of the hexagonal (200) plane by X-ray diffraction using CuKα rays is I(002)/I(200), it is preferable that I(002)/I(200) is 0.30 or more and 0.50 or less. The above-mentioned ICDD reference code 01-081-1244 states that the relative intensity of the (002) plane to the (200) plane is 26.2%, so the standard intensity ratio I(002)/I(200) is 0.26. The intensity ratio of the composite tungsten oxide film produced by the coating and baking method is this standard value, but the intensity ratio of the present invention is 0.30 or more and 0.50 or less. Since it is larger than the standard intensity ratio, it is considered that the growth of the a and b planes of the hexagonal crystal is suppressed and there is a tendency for the c-plane orientation. If the aforementioned c/a is outside the range of 1.018 to 1.029, and the intensity ratio I(002)/I(200) is outside the range of 0.30 to 0.50, the heat ray reflection function will decrease.
なお、元素ＭがＳｎの場合、結晶構造は三方晶であり、上記Ｘ線回折では、六方晶のａ軸長さとｃ軸長さの比ｃ／ａは三方晶のａ軸長さとｃ軸長さの比２ｃ／ａで算出する。 When element M is Sn, the crystal structure is trigonal, and in the above X-ray diffraction, the ratio c/a of the a-axis length to the c-axis length of the hexagonal crystal is calculated as the ratio 2c/a of the a-axis length to the c-axis length of the trigonal crystal.
このような標準と異なる結晶状態と熱線反射機能の関係は、スパッタリング法や真空蒸着法に特有と考えられる。非平衡な非晶質膜が形成された後に、熱処理により結晶構造を形成す過程に起因すると考えられるが、そのメカニズムの詳細は不明である。 This relationship between the non-standard crystal state and the heat ray reflection function is thought to be unique to the sputtering and vacuum deposition methods. It is thought to result from the process in which a crystal structure is formed by heat treatment after a non-equilibrium amorphous film is formed, but the details of this mechanism are unknown.
以上より、本発明の一実施形態に係る複合タングステン酸化物膜によれば、特許文献２や特許文献３に記載の複合タングステン酸化物膜とは異なる特性を有し、可視光域における透明性を有し、赤外光域における反射性を併せ持った赤外線反射膜としての複合タングステン酸化物膜とすることができる。
As described above, the composite tungsten oxide film according to one embodiment of the present invention has properties different from those of the composite tungsten oxide films described in
＜２．複合タングステン酸化物膜の製造方法＞
次に、複合タングステン酸化物膜の製造方法について説明する。図３は、本発明の一実施形態に係る複合タングステン酸化物膜の製造方法の概略を示す工程図である。本発明の一実施形態は、元素ＭとタングステンＷと酸素Ｏを主成分とする複合タングステン酸化物膜の製造方法であって、物理的な成膜法を用いて膜を形成する成膜工程Ｓ１と、膜を熱処理する熱処理工程Ｓ２とを有する。以下、各工程について詳細に説明する。
2. Method for producing composite tungsten oxide film
Next, the method for producing a composite tungsten oxide film will be described. Fig. 3 is a process diagram showing an outline of the method for producing a composite tungsten oxide film according to one embodiment of the present invention. One embodiment of the present invention is a method for producing a composite tungsten oxide film mainly composed of element M, tungsten W, and oxygen O, and includes a film formation step S1 for forming a film using a physical film formation method, and a heat treatment step S2 for heat treating the film. Each step will be described in detail below.
＜２－１．成膜工程＞
成膜工程Ｓ１では、物理的な成膜法を用いて膜を形成する。本発明の一実施形態に係る複合タングステン酸化物膜の物理的な成膜方法としては、真空蒸着法、スパッタリング法、イオンプレーティング法、イオンビーム法などがある。この中でも、スパッタリング法は、成膜粒子のエネルギーが大きく付着力が強い、成膜が緻密で膜質が強い、成膜プロセスが安定していて膜質、膜厚の制御が高い精度で可能である。さらに、スパッタリング法は、高融点金属・合金・化合物の成膜が可能、反応性ガスの導入で酸化物や窒化物などの成膜が可能であり、組成の調整が比較的容易などの特長を持ち、液晶表示素子やハードディスク等の電子機器、ウィンドフィルムやミラー等の汎用品など幅広い分野で多く利用され、製造装置も多いことから好ましい。
<2-1. Film forming process>
In the film forming step S1, a film is formed using a physical film forming method. The physical film forming method of the composite tungsten oxide film according to one embodiment of the present invention includes vacuum deposition, sputtering, ion plating, ion beam, etc. Among these, the sputtering method has high energy of film forming particles and strong adhesion, dense film formation and strong film quality, stable film formation process, and high precision control of film quality and film thickness. Furthermore, the sputtering method has features such as film formation of high melting point metals, alloys, and compounds, film formation of oxides and nitrides by introducing reactive gas, and relatively easy composition adjustment, and is widely used in a wide range of fields such as electronic devices such as liquid crystal display elements and hard disks, and general-purpose products such as window films and mirrors, and is preferred because there are many manufacturing devices.
一般式ＭｘＷｙＯｚで表した複合タングステン酸化物膜を形成するためのスパッタリングターゲットは、例えば、元素Ｍと、元素Ｗからなるスパッタリングターゲット、元素Ｍと、元素Ｗと元素Ｏの化合物から成るスパッタリングターゲット、元素Ｍと元素Ｏの化合物と、元素Ｗから成るスパッタリングターゲットおよび元素Ｍと元素Ｗと元素Ｏの化合物から成るスパッタリングターゲット等、種々の構成から選択することができる。好ましくは、予め化合物相として形成したスパッタリングターゲットを用いることが良い。スパッタリングターゲットを予め化合物相として構成すると各元素の蒸気圧の差による膜組成の依存を軽減することができ、安定した成膜が可能となる。 The sputtering target for forming the composite tungsten oxide film represented by the general formula MxWyOz can be selected from various configurations, such as a sputtering target consisting of element M and element W, a sputtering target consisting of a compound of element M, element W, and element O, a sputtering target consisting of a compound of element M, element O, and element W, and a sputtering target consisting of a compound of element M, element W, and element O. It is preferable to use a sputtering target formed in advance as a compound phase. If the sputtering target is formed in advance as a compound phase, the dependency of the film composition due to the difference in vapor pressure of each element can be reduced, and stable film formation can be achieved.
スパッタリングターゲットは、例えば前記スパッタリングターゲット組成物の粒子からなる粉を圧粉して形成した圧粉体や、前記スパッタリングターゲット組成物を焼結させて形成した焼結体の形態で用いれば良い。 The sputtering target may be used in the form of, for example, a compact formed by compressing a powder consisting of particles of the sputtering target composition, or a sintered body formed by sintering the sputtering target composition.
また、スパッタリングターゲットは、前記の通り圧粉体や焼結体で形成されるため、有機物成分を実質的に含まず、当該ターゲットを用いて形成された膜も有機物成分を実質的に含んでいない。ここで、実質的に含まないとは、例えば高分子分散剤等、意図的に添加される成分を含んでいないことを指す。 As described above, the sputtering target is formed from a pressed powder or sintered body, and therefore does not substantially contain organic components, and the film formed using the target also does not substantially contain organic components. Here, "substantially free" means that it does not contain any intentionally added components, such as polymer dispersants.
スパッタリングターゲットが、例えば比抵抗１Ω・ｃｍ以下の導電体であると生産性が高いＤＣスパッタリング装置を使用することができる。また、スパッタリングターゲットが、例えば相対密度７０％以上の焼結体であると輸送時の振動による割れが少なくなり、装置への取付け時等のハンドリングで極端な注意をする必要がなくなるなど、より工業的な製造に適した形態となる。 If the sputtering target is, for example, a conductor with a resistivity of 1 Ω·cm or less, a highly productive DC sputtering device can be used. Also, if the sputtering target is, for example, a sintered body with a relative density of 70% or more, it is less likely to crack due to vibration during transportation, and there is no need to be extremely careful when handling it when installing it in the device, making it more suitable for industrial production.
成膜工程の雰囲気は、種々選択されるが、不活性ガス雰囲気中が良い。不活性ガスとしては、例えば、ヘリウムガスやアルゴンガスなどの希ガス、窒素ガスなどを用いれば良いが、窒素ガスの場合は、選択元素Ｍによっては窒化物を形成することがあり、一般的に使用され入手が容易なアルゴンガスがより好ましい。用いるガスの純度は９９％以上が好ましく、酸素など酸化性ガスの混合は１％未満であることが好ましい。詳細は不明な点もあるが、不活性雰囲気中で成膜し、のちに述べる条件で熱処理すると、反射率の高い複合タングステン酸化物膜が得られる。一方で酸化性ガスの割合が１%を超えると熱処理後の複合タングステン酸化物膜の反射率が低下する。 The atmosphere for the film formation process may be selected from a variety of options, but an inert gas atmosphere is preferred. Examples of inert gases that may be used include rare gases such as helium gas and argon gas, and nitrogen gas. However, in the case of nitrogen gas, nitrides may be formed depending on the selected element M, and argon gas, which is commonly used and easily available, is more preferred. The purity of the gas used is preferably 99% or more, and the mixture of oxidizing gases such as oxygen is preferably less than 1%. Although some details are unclear, a composite tungsten oxide film with high reflectivity can be obtained by forming the film in an inert atmosphere and heat-treating it under the conditions described below. On the other hand, if the proportion of oxidizing gas exceeds 1%, the reflectivity of the composite tungsten oxide film after heat treatment decreases.
成膜後の膜は、通常は非晶質であるが、Ｘ線回折分析した際に結晶に基づく回折ピークが出現していても構わない。 The film after deposition is usually amorphous, but it is acceptable if diffraction peaks due to crystals appear during X-ray diffraction analysis.
＜２－２．熱処理工程＞
次に、熱処理工程Ｓ２では、成膜工程Ｓ１で得られた膜を熱処理する。本発明の一実施形態に係る複合タングステン酸化物膜の膜特性を得るには熱処理工程Ｓ２を不活性または還元雰囲気中で行う。
<2-2. Heat treatment process>
Next, in the heat treatment step S2, the film obtained in the film formation step S1 is heat treated. In order to obtain the film characteristics of the composite tungsten oxide film according to one embodiment of the present invention, the heat treatment step S2 is performed in an inert or reducing atmosphere.
熱処理工程Ｓ２では、熱処理温度は４００～７００℃が良い。熱処理温度が４００℃よりも低いと膜は非晶質のままで結晶化しないか、または結晶化してもＸ線回折における六方晶の回折ピークが極めて微弱となり、赤外域の遮熱特性が低い。また、熱処理温度が７００℃よりも高いとしても本発明の膜の特徴を得ることができるが、膜と基材が反応する、膜が基材から剥離する、表面粗さが増大するなど実用上の不具合が生じる。 In the heat treatment step S2, the heat treatment temperature is preferably 400 to 700°C. If the heat treatment temperature is lower than 400°C, the film will remain amorphous and will not crystallize, or even if it does crystallize, the hexagonal diffraction peak in X-ray diffraction will be extremely weak, and the heat shielding properties in the infrared range will be poor. Even if the heat treatment temperature is higher than 700°C, the characteristics of the film of the present invention can be obtained, but practical problems will arise, such as the film reacting with the substrate, the film peeling off from the substrate, and increased surface roughness.
前記いずれの熱処理温度においても、熱処理時間は、複合タングステン酸化物の結晶化が完了する程度の時間を確保すればよく基材の熱伝導と生産性との兼ね合いにも依るが、５分～６０分程度で適宜調整するとよい。 At any of the above heat treatment temperatures, the heat treatment time should be long enough to complete the crystallization of the composite tungsten oxide, and may be adjusted appropriately to about 5 to 60 minutes, depending on the balance between the thermal conductivity of the substrate and productivity.
前記の通り熱処理雰囲気は不活性雰囲気または還元雰囲気中で行う。不活性雰囲気としてはたとえば窒素やアルゴン、還元雰囲気としては窒素と水素の混合ガス、アルゴンと水素の混合ガスがあげられる。 As mentioned above, the heat treatment is carried out in an inert atmosphere or a reducing atmosphere. Examples of inert atmospheres include nitrogen and argon, and examples of reducing atmospheres include a mixture of nitrogen and hydrogen gas, and a mixture of argon and hydrogen gas.
以上より、本発明の一実施形態に係る複合タングステン酸化物膜の製造方法によれば、上述した特性を有する複合タングステン酸化物膜を、工業的に広く利用され、成膜時に比較的無害な方法で、更に使用原料の長期保存に優れ、輸送時の制限がない、物理的な製造方法で提供することができる。 As described above, according to the method for producing a composite tungsten oxide film according to one embodiment of the present invention, a composite tungsten oxide film having the above-mentioned characteristics can be provided by a physical production method that is widely used industrially, is relatively harmless when formed, has excellent long-term storage properties for the raw materials used, and has no restrictions on transportation.
＜３．膜形成基材＞
本発明の一実施形態に係る膜形成基材は、上述した複合タングステン酸化物膜が被成膜基材の少なくとも一方の面に形成されたものである。被成膜基材は、本発明の一実施形態に係る複合タングステン酸化物膜の形成が可能であれば特に限定されるものではない。
<3. Film-forming substrate>
The film-forming substrate according to one embodiment of the present invention is a substrate on which the above-mentioned composite tungsten oxide film is formed on at least one surface. The substrate on which the film is formed is not particularly limited as long as the composite tungsten oxide film according to one embodiment of the present invention can be formed.
成膜後の膜の熱処理温度が４００℃以上であるため、被成膜基材は４００℃以上の軟化点もしくは熱変形温度を有する基材が好ましい。軟化点もしくは熱変形温度が４００℃未満の基材を用いた場合、前記熱処理の際に膜が被成膜基材から剥離する、膜にクラックが発生するなどの問題が生じる。好ましくは、被成膜基材の熱膨張係数が膜の熱膨張係数に近いほうが良い。しかしながら、基材から膜を剥離して使用する場合は必ずしも前記条件である必要はなく、例えば、４００℃以下で溶解する基材でも良い。 Because the heat treatment temperature of the film after deposition is 400°C or higher, it is preferable that the substrate on which the film is deposited has a softening point or heat distortion temperature of 400°C or higher. If a substrate with a softening point or heat distortion temperature of less than 400°C is used, problems such as the film peeling off from the substrate on which the film is deposited during the heat treatment or cracks occurring in the film will occur. It is preferable that the thermal expansion coefficient of the substrate on which the film is deposited is close to that of the film. However, when the film is to be peeled off from the substrate for use, the above conditions are not necessarily required; for example, a substrate that melts at 400°C or lower may also be used.
４００℃以上の軟化点もしくは熱変形温度を有する被成膜基材には、ガラス、セラミックス、単結晶等がある。被成膜基材は、必ずしも透明である必要はないが、本発明の複合タングステン酸化物膜を基材と共に用いる場合には透明な基材が求められる。透明基材には、例えば、ガラス、ＹＡＧやＹ２Ｏ３などの透明セラミックス、サファイヤなどの単結晶がある。なかでも、入手しやすく、安価で、耐候性、耐薬品性などの観点から、４００℃以上の軟化点のガラスを被成膜基材に用いるのが好ましい。 The substrate on which the film is to be formed has a softening point or heat distortion temperature of 400°C or more, and includes glass, ceramics, single crystals, etc. The substrate on which the film is to be formed does not necessarily have to be transparent, but when the composite tungsten oxide film of the present invention is used together with a substrate, a transparent substrate is required. The transparent substrate includes, for example, glass, transparent ceramics such as YAG and Y2O3 , and single crystals such as sapphire. Among them, it is preferable to use glass with a softening point of 400°C or more as the substrate on which the film is to be formed, from the viewpoints of easy availability, low cost, weather resistance, chemical resistance, etc.
基材は、平面でなく曲面や凹凸面を有するものでも本発明の特長を損なうものでなく、種々選択すれば良い。 The substrate may be selected from a variety of types, including curved and uneven surfaces rather than flat surfaces, without impairing the features of the present invention.
以上より、本発明の一実施形態に係る膜形成基材によれば、可視光域における透明性を有し、赤外光域における反射性を併せ持った赤外線反射膜を有する膜形成基材とすることができる。 As described above, the film-forming substrate according to one embodiment of the present invention can be made into a film-forming substrate having an infrared reflective film that has transparency in the visible light range and reflectivity in the infrared light range.
＜４．物品＞
本発明の一実施形態に係る物品は、上述した複合タングステン酸化物膜及び／又は膜形成基材を１又は複数有する。本発明の一実施形態に係る物品は、複合タングステン酸化物膜が光を反射する機能を有する物品であればどのような物品でも構わない。
＜4. Articles＞
An article according to an embodiment of the present invention has one or more of the above-mentioned composite tungsten oxide films and/or film-forming substrates. The article according to an embodiment of the present invention may be any article as long as the composite tungsten oxide film has the function of reflecting light.
加えて、本発明の複合タングステン酸化物膜及び／又は膜形成基材が、例えば他の機能を有する膜や粒子等と共に使用されていても、本発明に記載の機能を利用した物品に含まれる。 In addition, even if the composite tungsten oxide film and/or film-forming substrate of the present invention are used together with, for example, films or particles having other functions, they are still included in the articles utilizing the functions described in the present invention.
本発明の複合タングステン酸化物膜は、赤外光域における反射性を有する赤外線反射膜であるが、光を反射して遮蔽する機能を有する物品には、例えば遮熱断熱ガラスがある。
遮熱断熱ガラスは、透明でありながら熱を遮蔽断熱する特長があり、夏場の太陽光による室内温度の上昇や車内温度の上昇などを軽減する。また、冬場の暖房の熱を反射し室内にとどめることもできる。
The composite tungsten oxide film of the present invention is an infrared reflective film having reflectivity in the infrared light region, and examples of articles having the function of reflecting and blocking light include heat insulating glass.
Heat-insulating glass is transparent yet has the characteristic of blocking and insulating heat, reducing the rise in indoor temperature caused by sunlight in the summer and the rise in temperature inside a car. It can also reflect the heat from heating in the winter and keep it inside the room.
以上より、本発明の一実施形態に係る膜形成基材によれば、可視光域における透明性を有し、赤外光域における反射性を併せ持った複合タングステン酸化物膜やそのような膜形成基材を備える物品とすることができる。 As described above, the film-forming substrate according to one embodiment of the present invention can produce a composite tungsten oxide film that has transparency in the visible light range and reflectivity in the infrared light range, or an article that includes such a film-forming substrate.
以下、本発明について、実施例を用いてさらに具体的に説明するが、本発明は、以下の実施例に何ら限定されるものではない。 The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples.
（実施例１）
実施例１では、Ｃｓ／Ｗ原子比が０．３３のセシウムタングステン酸化物粉末（住友金属鉱山株式会社製ＹＭ－０１）をホットプレス装置に投入し、真空雰囲気、温度９５０℃、押し圧２５０ｋｇｆ／ｃｍ２の条件で焼結し、セシウムタングステン酸化物焼結体を作製した。焼結体組成を化学分析した結果、Ｃｓ／Ｗは０．３３であった。この酸化物焼結体を直径１５３ｍｍ、厚み５ｍｍに機械加工で研削し、ステンレス製バッキングプレートに金属インジウム蝋材を用いて接合して、セシウムタングステン酸化物スパッタリングターゲットを作製した。
Example 1
In Example 1, cesium tungsten oxide powder (YM-01 manufactured by Sumitomo Metal Mining Co., Ltd.) with a Cs/W atomic ratio of 0.33 was put into a hot press device and sintered under conditions of a vacuum atmosphere, a temperature of 950°C, and a pressure of 250 kgf/ cm2 to produce a cesium tungsten oxide sintered body. As a result of chemical analysis of the sintered body composition, Cs/W was 0.33. This oxide sintered body was ground by machining to a diameter of 153 mm and a thickness of 5 mm, and joined to a stainless steel backing plate using a metal indium brazing material to produce a cesium tungsten oxide sputtering target.
次に、このスパッタリングターゲットをＤＣスパッタリング装置（アルバック社製ＳＢＨ２３０６）に取り付け、到達真空度５×１０－３Ｐａ以下、成膜時の雰囲気は、アルゴンガス雰囲気とし、ガス圧は０．６Ｐａ、投入電力は直流６００Ｗの条件で、ガラス基板（コーニング社製ＥＸＧ、厚み０．７ｍｍ）の上にセシウムタングステン酸化物膜を成膜した。成膜後の膜厚は１００ｎｍであった（成膜工程Ｓ１）。成膜後の膜の構造をＸ線回折装置（X’Pert-PRO（PANalytical社製））を用いて調べた。成膜後膜は、結晶構造に由来する回折ピークは認められない非晶質の構造であった。 Next, this sputtering target was attached to a DC sputtering device (SBH2306 manufactured by ULVAC), and a cesium tungsten oxide film was formed on a glass substrate (EXG manufactured by Corning, thickness 0.7 mm) under the conditions of an ultimate vacuum of 5 ×10 −3 Pa or less, an argon gas atmosphere during film formation, a gas pressure of 0.6 Pa, and a DC power of 600 W. The film thickness after film formation was 100 nm (film formation step S1). The structure of the film after film formation was examined using an X-ray diffraction device (X'Pert-PRO (manufactured by PANalytical)). The film after film formation had an amorphous structure in which no diffraction peaks derived from a crystalline structure were observed.
成膜後の膜を、ランプ加熱炉（株式会社米倉製作所製ＨＰ－２－９）に投入し、窒素雰囲気中、５００℃の温度で３０分間熱処理した（熱処理工程Ｓ２）。この熱処理後の膜を化学分析した結果、Ｃｓ／Ｗ原子比ｘ／ｙは０．３３であった。 The film after deposition was placed in a lamp heating furnace (HP-2-9 manufactured by Yonekura Seisakusho Co., Ltd.) and heat-treated in a nitrogen atmosphere at a temperature of 500°C for 30 minutes (heat treatment step S2). Chemical analysis of the film after this heat treatment revealed that the Cs/W atomic ratio x/y was 0.33.
熱処理後の膜の構造をＸ線回折装置（X’Pert-PRO（PANalytical社製））を用いて結晶構造、Ｘ線回折強度比、ａ軸とｃ軸の比ｃ／ａを調べた。また、分光光度計（日立製、型番Ｖ－６７０）を用いて、透過率と反射率を測定した。 The structure of the film after heat treatment was examined using an X-ray diffraction device (X'Pert-PRO (PANalytical)) to determine the crystal structure, X-ray diffraction intensity ratio, and a-axis to c-axis ratio c/a. In addition, the transmittance and reflectance were measured using a spectrophotometer (Hitachi, model number V-670).
熱処理後の膜の、結晶構造は六方晶を含む構造であった。Ｘ線回折強度比は０．４０１、ａ軸とｃ軸の比ｃ／ａは１．０２８であった。また、波長５５０ｎｍの透過率は７１．３％、波長１４００ｎｍの透過率は１１．３％、波長１４００ｎｍの反射率は４４．５％であった。 The crystal structure of the film after heat treatment contained hexagonal crystals. The X-ray diffraction intensity ratio was 0.401, and the ratio of the a-axis to the c-axis, c/a, was 1.028. In addition, the transmittance at a wavelength of 550 nm was 71.3%, the transmittance at a wavelength of 1400 nm was 11.3%, and the reflectance at a wavelength of 1400 nm was 44.5%.
熱処理後の膜のシート抵抗は、抵抗率計（三菱化学社製、ロレスタ）を用いた測定の結果、３．０×１０３Ω／□であり、熱処理後の膜は導電性が高い低抵抗の膜であった（抵抗の測定は抵抗率に応じて三菱化学製ロレスタまたはハイレスタを使用した）。 The sheet resistance of the film after the heat treatment was measured using a resistivity meter (Loresta, manufactured by Mitsubishi Chemical Corporation) to be 3.0 × 10 Ω/□, and the film after the heat treatment was a film with high conductivity and low resistance (resistance was measured using Loresta or Hiresta, manufactured by Mitsubishi Chemical Corporation, depending on the resistivity).
また、熱処理後の膜の表面粗さを、レーザー顕微鏡（オリンパス製、OLS4100）を用いて測定したところ算術平均高さ（表面粗さ）Ｓａは８ｎｍであった。 The surface roughness of the film after heat treatment was measured using a laser microscope (OLS4100, manufactured by Olympus), and the arithmetic mean height (surface roughness) Sa was 8 nm.
（実施例２～１７および比較例１～１３）
実施例１と同様に同じ装置を用い、表１及び表２に記載されているように元素Ｍ、組成比、膜厚、成膜雰囲気、熱処理雰囲気、温度および時間を変えて複合タングステン酸化物膜の作成を行い、膜の特性を調べた。表１及び表２に実施例の結果を、比較例の結果と併せて示す。
(Examples 2 to 17 and Comparative Examples 1 to 13)
Using the same apparatus as in Example 1, composite tungsten oxide films were produced and the properties of the films were examined by changing the element M, composition ratio, film thickness, film formation atmosphere, heat treatment atmosphere, temperature and time as shown in Tables 1 and 2. Tables 1 and 2 show the results of the examples and the comparative examples.
表１及び表２より、本発明に係る複合タングステン酸化物膜の製造方法に含まれる実施例１～１７では、波長５５０ｎｍにおける透過率が５０％以上、波長１４００ｎｍにおける透過率が３０％以下かつ波長１４００ｎｍにおける反射率が３５％以上という特性を有する膜となることが確認できた。また、このような、本発明に含まれる実施例１～１７は、シート抵抗が１．０×１０５Ω／□未満であり、表面粗さＳａが２０ｎｍ以下であった。一方で、本発明に係る複合タングステン酸化物膜の製造方法に含まれない比較例１～１３では、光学特性が前記要件を満たしておらず、またシート抵抗が１．０×１０５Ω／□以上となった。 From Tables 1 and 2, it was confirmed that in Examples 1 to 17 included in the manufacturing method of a composite tungsten oxide film according to the present invention, a film having the characteristics of a transmittance of 50% or more at a wavelength of 550 nm, a transmittance of 30% or less at a wavelength of 1400 nm, and a reflectance of 35% or more at a wavelength of 1400 nm was obtained. Moreover, in such Examples 1 to 17 included in the present invention, the sheet resistance was less than 1.0×10 5 Ω/□ and the surface roughness Sa was 20 nm or less. On the other hand, in Comparative Examples 1 to 13 not included in the manufacturing method of a composite tungsten oxide film according to the present invention, the optical characteristics did not satisfy the above requirements, and the sheet resistance was 1.0×10 5 Ω/□ or more.
なお、上記のように本発明の一実施形態及び各実施例について詳細に説明したが、本発明の新規事項及び効果から実体的に逸脱しない多くの変形が可能であることは、当業者には、容易に理解できるであろう。従って、このような変形例は、全て本発明の範囲に含まれるものとする。 Although one embodiment of the present invention and each example have been described in detail above, it will be readily apparent to those skilled in the art that many modifications are possible that do not substantially deviate from the novel features and effects of the present invention. Therefore, all such modifications are intended to be included within the scope of the present invention.
例えば、明細書又は図面において、少なくとも一度、より広義又は同義な異なる用語と共に記載された用語は、明細書又は図面のいかなる箇所においても、その異なる用語に置き換えることができる。また、複合タングステン酸化物膜とその製造方法の構成も本発明の一実施形態及び各実施例で説明したものに限定されず、種々の変形実施が可能である。 For example, a term described at least once in the specification or drawings together with a different term having a broader or similar meaning may be replaced with that different term anywhere in the specification or drawings. Furthermore, the configuration of the composite tungsten oxide film and its manufacturing method are not limited to those described in the embodiment and examples of the present invention, and various modifications are possible.
本発明に係る複合タングステン酸化物膜は、可視光域の高い透明性と赤外域の優れた光反射性と高い膜平滑性を備えているため、光を反射する機能を利用した幅広い用途に利用できる可能性を有している。 The composite tungsten oxide film of the present invention has high transparency in the visible light range, excellent light reflectivity in the infrared range, and high film smoothness, making it potentially useful for a wide range of applications that utilize its light-reflecting properties.
Claims (9)
０．００１≦ｘ／ｙ≦１、２．２≦ｚ／ｙ≦３．０であり、
有機物成分を実質的に含まず、
波長５５０ｎｍにおける透過率が５０％以上、波長１４００ｎｍにおける透過率が３０％以下、かつ、波長１４００ｎｍにおける反射率が３５％以上であり、六方晶の結晶構造を含む連続膜であることを特徴とする複合タングステン酸化物膜。 A composite tungsten oxide film consisting only of a layer mainly composed of a composition represented by the general formula MxWyOz (wherein M is one or more elements selected from alkali metals, alkaline earth metals, Fe, In , Tl, and Sn, W is tungsten, and O is oxygen),
0.001≦x/y≦1, 2.2≦z/y≦3.0,
Substantially free of organic components
A composite tungsten oxide film, characterized in that it has a transmittance of 50% or more at a wavelength of 550 nm, a transmittance of 30% or less at a wavelength of 1400 nm, and a reflectance of 35% or more at a wavelength of 1400 nm, and is a continuous film containing a hexagonal crystal structure .
ＣｕＫα線を使用したＸ線回折による六方晶のａ軸とｃ軸との比ｃ／ａが１．０１８～１．０２９である請求項１に記載の複合タングステン酸化物膜。 When the intensity ratio of the diffraction intensity I(002) of the hexagonal (002) plane to the diffraction intensity I(200) of the hexagonal (200) plane by X-ray diffraction using CuKα radiation is defined as I(002)/I(200), I(002)/I(200) is 0.30 or more and 0.50 or less,
2. The composite tungsten oxide film according to claim 1 , wherein the ratio c/a of the a-axis to the c-axis of the hexagonal crystal, as determined by X-ray diffraction using CuKα radiation, is 1.018 to 1.029.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018117340 | 2018-06-20 | ||
| JP2018117340 | 2018-06-20 | ||
| JP2019024926A JP7395826B2 (en) | 2018-06-20 | 2019-02-14 | Composite tungsten oxide film, method for producing the same, and film-forming substrate and article having the film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019024926A Division JP7395826B2 (en) | 2018-06-20 | 2019-02-14 | Composite tungsten oxide film, method for producing the same, and film-forming substrate and article having the film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2023155281A JP2023155281A (en) | 2023-10-20 |
| JP7662000B2 true JP7662000B2 (en) | 2025-04-15 |
Family
ID=68983958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2023131500A Active JP7662000B2 (en) | 2018-06-20 | 2023-08-10 | Composite tungsten oxide film, film-forming substrate having said film, and article |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7662000B2 (en) |
| CN (1) | CN117326592A (en) |
| WO (1) | WO2019244650A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024095983A1 (en) * | 2022-10-31 | 2024-05-10 | 住友金属鉱山株式会社 | Crystal alignment film, structure, and method for manufacturing crystal alignment film |
| JP2025028570A (en) * | 2023-08-18 | 2025-03-03 | 住友金属鉱山株式会社 | Glass film with near-infrared shielding film, near-infrared shielding film laminate, and method for manufacturing glass film with near-infrared shielding film and method for manufacturing near-infrared shielding film laminate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006347807A (en) | 2005-06-15 | 2006-12-28 | Sumitomo Metal Mining Co Ltd | Oxide sintered body, oxide transparent conductive film, and production method thereof |
| JP2010180449A (en) | 2009-02-04 | 2010-08-19 | Sumitomo Metal Mining Co Ltd | Target material of composite tungsten oxide, and method for manufacturing the same |
| WO2017159790A1 (en) | 2016-03-16 | 2017-09-21 | 住友金属鉱山株式会社 | Near-infrared shielding material microparticles, production method thereof, and near-infrared shielding material microparticle dispersion |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3505108A (en) | 1964-06-26 | 1970-04-07 | Corning Glass Works | Tungsten bronze films |
| JPH05113085A (en) | 1991-10-21 | 1993-05-07 | Dainippon Printing Co Ltd | Lightproof film |
| JPH0812378A (en) | 1994-06-30 | 1996-01-16 | Nissan Motor Co Ltd | Heat-shield glass and method for manufacturing the same |
| US6040939A (en) * | 1998-06-16 | 2000-03-21 | Turkiye Sise Ve Cam Fabrikalari A.S. | Anti-solar and low emissivity functioning multi-layer coatings on transparent substrates |
| JP2002020142A (en) | 2000-06-29 | 2002-01-23 | Nippon Sheet Glass Co Ltd | Windshield for vehicle and method for manufacturing the same |
| WO2005037932A1 (en) | 2003-10-20 | 2005-04-28 | Sumitomo Metal Mining Co., Ltd. | Infrared shielding material microparticle dispersion, infrared shield, process for producing infrared shielding material microparticle, and infrared shielding material microparticle |
| CN101023498B (en) * | 2004-08-31 | 2012-02-29 | 住友金属矿山株式会社 | Conductive particle, visible light transmissive particle dispersed conductor, method for producing same, transparent conductive thin film, method for producing same, transparent conductive article using same, infrared shield article |
| JP5234237B2 (en) | 2004-08-31 | 2013-07-10 | 住友金属鉱山株式会社 | Transparent conductive film and method for producing the same, transparent electrode, infrared absorption reflection film, antifogging film, and electromagnetic shielding film |
| JP5585046B2 (en) * | 2009-10-27 | 2014-09-10 | 東ソー株式会社 | Composite oxide sintered body, target and oxide transparent conductive film |
| JP6328100B2 (en) * | 2013-03-15 | 2018-05-23 | 株式会社東芝 | Battery electrode material and battery substrate, storage battery, dye-sensitized solar cell, capacitor, Li ion secondary battery using the same |
| KR20150088551A (en) * | 2014-01-24 | 2015-08-03 | (주)석경에이티 | Tungsten Oxide Complex Doped with Alkalimetal Oxide, Transparent Conducting Composition, Coating Film, Optical Device Comprising The Same |
| US10764263B2 (en) | 2016-11-28 | 2020-09-01 | Ssh Communications Security Oyj | Authentication of users in a computer network |
| JP6934769B2 (en) | 2017-07-28 | 2021-09-15 | キヤノン株式会社 | Radiation imaging device and radiation imaging method |
| WO2019058737A1 (en) * | 2017-09-22 | 2019-03-28 | 住友金属鉱山株式会社 | Cesium tungsten oxide film and method for manufacturing same |
-
2019
- 2019-06-06 WO PCT/JP2019/022481 patent/WO2019244650A1/en not_active Ceased
- 2019-06-06 CN CN202311298716.XA patent/CN117326592A/en active Pending
-
2023
- 2023-08-10 JP JP2023131500A patent/JP7662000B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006347807A (en) | 2005-06-15 | 2006-12-28 | Sumitomo Metal Mining Co Ltd | Oxide sintered body, oxide transparent conductive film, and production method thereof |
| JP2010180449A (en) | 2009-02-04 | 2010-08-19 | Sumitomo Metal Mining Co Ltd | Target material of composite tungsten oxide, and method for manufacturing the same |
| WO2017159790A1 (en) | 2016-03-16 | 2017-09-21 | 住友金属鉱山株式会社 | Near-infrared shielding material microparticles, production method thereof, and near-infrared shielding material microparticle dispersion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117326592A (en) | 2024-01-02 |
| WO2019244650A1 (en) | 2019-12-26 |
| JP2023155281A (en) | 2023-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI807020B (en) | Composite tungsten oxide film, manufacturing method thereof, and film-forming substrate and article having the same | |
| JP7081183B2 (en) | Cesium Tungsten Oxide Film and Its Manufacturing Method | |
| JP7662000B2 (en) | Composite tungsten oxide film, film-forming substrate having said film, and article | |
| Wang et al. | Effect of substrate temperature on transparent conducting Al and F co-doped ZnO thin films prepared by rf magnetron sputtering | |
| CN112313359B (en) | Composite tungsten oxide film, method for producing same, and film-forming substrate and article each having the film | |
| WO2019058737A1 (en) | Cesium tungsten oxide film and method for manufacturing same | |
| JPWO2000051139A1 (en) | Transparent conductive laminate, method for producing the same, and display element using the same | |
| KR20010042939A (en) | Transparent conductive laminate, its manufacturing method, and display comprising transparent conductive laminate | |
| JP2007314892A (en) | Sputtering target and method for the preparation thereof | |
| JP2000067657A (en) | Transparent conductive film excellent in infrared transmission and its manufacture | |
| CN101785071A (en) | Manufacturing method of conductor layer | |
| Dang et al. | Preparation and optical properties of W-doped VO2/AZO bilayer composite film | |
| WO2016183691A1 (en) | Transparent metallo-dielectric coatings, structures, and devices, and methods of fabrication thereof | |
| JP4145810B2 (en) | Transparent substrate for LCD panel | |
| JP2011190528A (en) | Method of depositing electrically conductive transparent zinc oxide-based film, electrically conductive transparent zinc oxide-based film and transparent conductive substrate | |
| JP7737696B2 (en) | Light-controlling glass, its manufacturing method, and vanadium dioxide thin film with porous moth-eye structure that constitutes the light-controlling glass | |
| Niaz et al. | Fabrication and characterization of multilayer HfO2/Ag/HfO2 films | |
| Hossain et al. | Production of angular-selective films by interdiffusion for novel spectral responses | |
| JP2012132089A (en) | Method for forming electrically conductive transparent zinc oxide-based film, electrically conductive transparent zinc oxide-based film and electrically conductive transparent substrate | |
| JPS63175801A (en) | Magnesium fluoride-based translucent composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230816 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20241022 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20241115 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20250304 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20250317 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7662000 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |