WO2010103914A1 - Tantalum oxide thin film and thin film laminate - Google Patents

Tantalum oxide thin film and thin film laminate Download PDF

Info

Publication number
WO2010103914A1
WO2010103914A1 PCT/JP2010/052706 JP2010052706W WO2010103914A1 WO 2010103914 A1 WO2010103914 A1 WO 2010103914A1 JP 2010052706 W JP2010052706 W JP 2010052706W WO 2010103914 A1 WO2010103914 A1 WO 2010103914A1
Authority
WO
WIPO (PCT)
Prior art keywords
thin film
oxide thin
tantalum oxide
glass
film
Prior art date
Application number
PCT/JP2010/052706
Other languages
French (fr)
Japanese (ja)
Inventor
徹 蘆田
和広 加藤
英雄 大本
Original Assignee
セントラル硝子株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by セントラル硝子株式会社 filed Critical セントラル硝子株式会社
Publication of WO2010103914A1 publication Critical patent/WO2010103914A1/en

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
    • 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
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
    • 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
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/218—V2O5, Nb2O5, Ta2O5
    • 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
    • C03C2218/155—Deposition methods from the vapour phase by sputtering by reactive sputtering

Definitions

  • the present invention relates to an amorphous tantalum oxide thin film formed on a substrate through a sputtering method.
  • a metal oxide thin film mainly composed of a metal oxide such as zinc oxide, tin oxide, titanium oxide, or indium oxide is a low-emission laminated body (for example, Patent Document 1) as a thin film laminated body laminated with a metal thin film. ), An optical filter, or a thin film laminated body in which different metal oxide thin films are laminated with each other, an electrochromic (hereinafter sometimes referred to as EC) film (for example, Patent Document 2) is used.
  • EC electrochromic
  • the stress generated in the thin film includes a thermal stress generated due to a difference in thermal expansion coefficient between the thin film and the substrate material, and an internal stress generated in a process in which the ratio between the substrate temperature and the melting point of the film material is small.
  • an object of the present invention is to provide a metal oxide thin film with low internal stress.
  • an amorphous tantalum oxide thin film is a promising candidate for obtaining a thin film with low internal stress.
  • the amorphous tantalum oxide thin film of the present invention is an amorphous tantalum oxide thin film formed on a transparent substrate by a sputtering method.
  • the theoretical density of the tantalum oxide thin film is ⁇ 0 and the measured density is ⁇ (The value represented by ⁇ / ⁇ 0 ) ⁇ 100 (hereinafter sometimes referred to as “densification degree”) is 75 to 95%.
  • the theoretical density ⁇ 0 of the tantalum oxide thin film is 8.3 g / cm 3 (the value listed in JCPDS (Joint Committee for Power Diffraction Standards) card number 54-0514 is adopted), and the measured density ⁇ is the X-ray reflectivity method. It is obtained by measuring the critical angle with and analyzing it.
  • the density measurement by the X-ray reflectance method is introduced in detail in Non-Patent Document 1, and can be derived by a general-purpose analysis program attached to the XRD measurement apparatus (RINT-UltimaIII manufactured by Rigaku).
  • the tantalum oxide thin film of the present invention was amorphous, the value of the crystal was adopted as the theoretical density ⁇ 0 in the above formula for obtaining the degree of densification.
  • the degree of densification becomes less than 100% when the crystallinity deteriorates, and a further decrease in value is observed in the amorphous state. Therefore, in order to obtain an index representing the degree of densification of the amorphous thin film, the crystal value may be adopted as the theoretical density ⁇ 0 .
  • “on the substrate” may be one in which the tantalum oxide thin film is in contact with the substrate, or another thin film interposed between the substrate and the tantalum oxide thin film.
  • the degree of densification is 75% to 95%, preferably 77% to 91%.
  • the degree of densification exceeds 95%, the internal stress cannot be said to be sufficiently reduced. Further, if the densification degree is too low, such as less than 75%, the film strength may be lowered.
  • the tantalum oxide thin film having a low degree of densification tended to have a lower refractive index than that having a high degree of densification.
  • a thin film with a low refractive index may reduce the glare of the thin film and improve the transmittance. Therefore, a tantalum oxide thin film with a low refractive index is a preferred form in the present invention. It can be said that there is.
  • the tantalum oxide thin film of the present invention preferably has a refractive index at a wavelength of 550 nm of 2.05 or less, and most preferably 2.00 or less.
  • the refractive index of the tantalum oxide thin film exceeds 2.05, the thin film may have a structure in which the degree of densification increases and the internal stress increases.
  • the lower limit of the refractive index is not particularly limited, but the refractive index has a correlation with the degree of densification, and when trying to obtain a low refractive index, the degree of densification is lowered and the film strength of the thin film is weakened. Sometimes. Therefore, the lower limit of the refractive index may be set to 1.90, preferably 1.95.
  • the amorphous tantalum oxide thin film of the present invention has a low internal stress, the adhesion with the substrate is improved, and the peeling of the film itself and the occurrence of warping of the substrate are suppressed. Moreover, when the tantalum oxide thin film and another metal thin film are laminated
  • a glass substrate is preferably used for the transparent substrate (having transparency to visible light).
  • glass substrates include windows and mirrors for buildings and vehicles, float glass made of soda lime silicate glass used for displays, or soda lime silicate manufactured by the roll-out method.
  • plate glass having inorganic transparency such as salt glass and alkali-free glass.
  • the shape of the substrate is not limited to a flat plate or a bent plate, and in addition to various tempered glass such as air-cooled tempered glass and chemically tempered glass. Knitted glass can also be used.
  • various glass substrates such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, zero expansion crystallized glass, TFT glass, PDP glass, and optical film substrate glass should be used. Can do.
  • inexpensive float glass such as polyethylene terephthalate resin, polycarbonate and high-transmission glass is suitable, but besides transparent glass, transparent resin substrate or film such as polycarbonate or polyethylene terephthalate. Etc. may be used.
  • the amorphous tantalum oxide thin film according to the present invention is preferably formed using a sputtering method.
  • a sputtering method known sputtering methods such as DC sputtering, RF sputtering, pulse sputtering, counter sputtering, and dual sputtering methods can be applied.
  • the tantalum oxide thin film having a densification degree of 95% or less can be obtained by adjusting the atmospheric gas during film formation. Further, when it is desired to reduce the densification degree more than the above, for example, O 2 and CO 2 It is also preferable to use the mixed gas because it can be easily reduced. When the mixed gas is used, particularly when the CO 2 flow ratio represented by the formula CO 2 / (O 2 + CO 2 ) ⁇ 100 is 20% by volume or more, the degree of densification is reduced to less than 90%. Is preferable.
  • the upper limit of the pressure of the atmospheric gas during film formation is preferably 1.0 Pa, and the lower limit is not particularly limited, It may be set to 0.1 Pa.
  • the thin film laminate having the thin film and a metal film layer such as silver is preferably used as a low emission laminate.
  • the Articles composed of a transparent base material and a thin film laminate formed on the transparent base material have a heat shielding property to prevent solar heat from flowing into the room in a building, or heat insulation to prevent the indoor temperature from flowing out of the room It is used as a window glass with added properties.
  • a window glass When used as a window glass, it is a multi-layer glass that is provided with heat-shielding properties by being constructed in the order of a glass with a low emission laminate, a dry air layer, and a transparent glass, or a surface that is installed outdoors. From the above, it is preferable to use as a double-glazed glass provided with heat insulation by constituting in order of a transparent glass, a dry air layer, and a glass with a low radiation laminate, and the glass with a low radiation laminate is a surface in contact with the dry air layer It is preferable to form a low emission laminate.
  • a thin film laminate including the thin film, an anode layer such as tungsten oxide, and a cathode layer such as iridium oxide is used as an EC layer.
  • An article in which a transparent base material and a transparent conductive film and an EC layer are sequentially laminated on the transparent base material are reversible by applying a current voltage to the article, or the color of the EC layer itself. It is preferable to be used as an all-solid-state EC element capable of changing. Specifically, for example, it is preferably used as an EC mirror for vehicles or home, an EC display device, a light control glass for vehicle or home window glass, and the like.
  • the substrate with a thin film laminate described above may be incorporated into articles such as double-glazed glass, laminated glass, EC mirror, etc. through processes such as distribution and storage.
  • the dirt may be washed with water.
  • the low emission laminate is often used including a silver layer, and contact with water is avoided when water contacts the laminate including the silver layer. It is preferable.
  • the glass with a low-emission laminate using the amorphous tantalum oxide thin film of the present invention as a protective film for the silver layer does not cause deterioration of the film surface at the time of cleaning in contact with water as described above.
  • the tantalum oxide thin film according to the present invention has a low internal stress due to its low densification degree, the influence on the substrate and other films is reduced. Therefore, it is preferably used for thin film laminates such as infrared shielding films, optical filters, and all solid-state EC elements. Specifically, it is preferably used as a protective film for a metal thin film such as silver or a base film for a metal film.
  • Example 1 The tantalum oxide thin film was formed using a DC magnetron sputtering apparatus having a schematic structure as shown in FIG. FIG. 1 shows a main part when the apparatus is observed from above.
  • a Ta target is used for the target 1 and a transparent base material (soda-lime silicate glass obtained by a float process) 3 is held by the base material holder 2, and then the inside of the vacuum chamber 8 is evacuated using a vacuum pump 5. did.
  • two targets 1 are drawn, but the number and type of installations are appropriately set according to the number of thin films stacked and the type of film.
  • O 2 gas is introduced from the gas introduction pipe 7.
  • the gas flow rate was controlled by a mass flow controller (not shown).
  • the pressure in the vacuum chamber 8 during film formation was adjusted to 0.3 Pa by the opening / closing valve 6. Furthermore, the output power of the DC power source was 3 kW.
  • the substrate holder 2 was transported on the transport roll 12 and passed by the side of the target 1. The passage speed at this time was adjusted to obtain a tantalum pentoxide thin film having a thickness of 37 nm.
  • Example 2 As the atmospheric gas in the vacuum chamber 8, O 2 and CO 2 gases are introduced from the gas introduction pipe 7, the gas flow rate is controlled by a mass flow controller (not shown), and the CO 2 flow ratio [ ⁇ CO 2 / ( O 2 + CO 2 ) ⁇ ⁇ 100] was 75% by volume.
  • a tantalum pentoxide thin film was obtained by the same procedure as in Example 1 except that the reactive gas flow ratio was changed.
  • Comparative Example 1 In Comparative Example 1, a tin oxide thin film was obtained in the same procedure as in Example 1 except that the tin oxide thin film was prepared with an O 2 flow rate ratio of 100% by volume.
  • (1) Evaluation of tantalum oxide thin film and tin oxide thin film obtained in Example 1 or 2 and Comparative Example 1 The density of the obtained thin film was evaluated by an X-ray reflectivity method using CuK ⁇ rays, The degree of densification was evaluated. The refractive index was evaluated by thin film optical simulation from the film surface reflectance, glass surface reflectance, and transmittance measured using a magnetic spectrophotometer (U-4000 manufactured by Hitachi, Ltd.).
  • (2) Evaluation of internal stress of thin film The internal stress of the thin film was evaluated by the cantilever method.
  • This method is a method for determining the internal stress of the film by measuring the amount of change in the warpage of the substrate before and after film formation.
  • the base material was a microsheet glass having a thickness of 0.1 mm, and a thin film was formed under the same conditions as in Examples 1 and 2 and Comparative Example 1. However, only one end of the glass substrate was fixed to the substrate holder 2.
  • the value of the internal stress is expressed as a negative value.
  • the magnitude of the internal stress is evaluated as an absolute value, it can be evaluated that the internal stress is smaller as the numerical value is closer to zero.
  • the evaluation results are shown in Table 1. Furthermore, the relationship between the densification degree and the internal stress of the thin film is shown in FIG. In each of Examples 1 and 2, the degree of densification was 95% or less, the absolute value of internal stress was 13.0 ⁇ 10 8 N / m 2 or less, and the refractive index was 2.05 or less.
  • Example 3 A thin film laminate was produced using a DC magnetron sputtering apparatus having a schematic structure as shown in FIG.
  • a Zn target was used as the upstream target 1
  • an Ag target was used as the downstream target 1
  • a ZnAlO (Al 4 wt% -containing ZnO) target was used as the downstream target 1
  • a Ta target was used as the most downstream target 1.
  • the inside of the vacuum chamber 8 was evacuated using the vacuum pump 5.
  • the atmosphere gas in the vacuum chamber 8 introduces O 2 gas from the gas introduction pipe 7, the gas flow rate is controlled by a mass flow controller (not shown), and the gas atmosphere is adjusted according to the laminate type of the laminate. did.
  • the pressure in the vacuum chamber 8 during film formation was adjusted by the open / close valve 6.
  • the output power of the DC power source was 1 kW.
  • the substrate holder 2 was transported on the transport roll 12 and passed by the side of the target 1. This adjusts the rate of passage of time by adjusting the thickness of each thin layer, a thin film in the order of ZnO / Ag / ZnAlO / Ta 2 O 5 has a laminated body that is laminated on the transparent substrate 3.
  • the zinc oxide thin film layer was a layer having a thickness of 37 nm.
  • the O 2 gas in the vacuum chamber 8 is evacuated, and then the Ar gas is controlled from the gas introduction pipe 7 by the mass flow controller while being placed in the vacuum chamber 8.
  • the pressure was set to 0.5 Pa.
  • the output power of the DC power source was 0.4 kW.
  • the Ag thin film layer is The film thickness was 10 nm.
  • the conditions for forming the ZnAlO thin film layer on the Ag thin film layer were the same as those for forming the Ag thin film layer.
  • the ZnAlO thin film layer had a thickness of 5 nm.
  • the Ar gas in the vacuum chamber 8 was evacuated, and then O 2 gas was introduced from the gas introduction pipe 7 so that the O 2 flow rate ratio was 100%.
  • the pressure in the vacuum chamber 8 during film formation was adjusted to 0.3 Pa by the opening / closing valve 6.
  • the tantalum oxide thin film layer had a thickness of 37 nm.
  • Example 4 A thin film laminate was obtained in the same procedure as in Example 5 except that the CO 2 flow ratio ⁇ [CO 2 / (O 2 + CO 2 )] ⁇ 100 ⁇ was changed to 75% by volume at the time of forming the tantalum oxide film.
  • Table 2 shows the internal stress and the number of defects of the tantalum oxide films in Examples 3 and 4 and Comparative Example 2. From Table 2, in Examples 3 and 4, the internal stress of the tantalum oxide film was small, resulting in a small number of defects.
  • Example 3 and 4 were fabricated from Example 3 and 4 with favorable moisture resistance.
  • the base material on which the thin film laminate was formed was washed with pure water at a temperature of 40 ° C. for 10 minutes using an ultrasonic cleaner, and hot air drying was performed after the washing. Even after the water washing and drying steps described above, no defects occurred on the surface of the thin film laminate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physical Vapour Deposition (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

In thin film laminates, delamination can occur over time at an interface between a metal oxide thin film and a metal thin film, or between a metal oxide thin film and a metal oxide thin film. Therefore, disclosed is an amorphous tantalum oxide thin film with a low internal stress. The amorphous tantalum oxide thin film is formed on a transparent substrate via a sputtering method, and where the theoretical density of said tantalum oxide thin film is ρ0 and the measured density is ρ, the value represented by (ρ / ρ0) x 100 is 75 - 95% by volume.

Description

酸化タンタル薄膜及び薄膜積層体Tantalum oxide thin film and thin film laminate
　本発明は、基材上にスパッタリング法を経て形成される非晶質酸化タンタル薄膜に関する。 The present invention relates to an amorphous tantalum oxide thin film formed on a substrate through a sputtering method.
発明の背景Background of the Invention
酸化亜鉛、酸化スズ、酸化チタン、酸化インジウム等のような金属酸化物を主成分とする金属酸化物薄膜は、金属薄膜と相互に積層した薄膜積層体として、低放射積層体（例えば特許文献１）や光学フィルタ、あるいは異なった金属酸化物薄膜同士を相互に積層した薄膜積層体として、エレクトロクロミック（以下ＥＣとすることもある）膜（例えば特許文献２）などに用いられている。薄膜積層体において、経時と共に金属酸化物薄膜と金属薄膜との界面、あるいは金属酸化物薄膜と金属酸化物薄膜との界面で剥離が生じることがある。 A metal oxide thin film mainly composed of a metal oxide such as zinc oxide, tin oxide, titanium oxide, or indium oxide is a low-emission laminated body (for example, Patent Document 1) as a thin film laminated body laminated with a metal thin film. ), An optical filter, or a thin film laminated body in which different metal oxide thin films are laminated with each other, an electrochromic (hereinafter sometimes referred to as EC) film (for example, Patent Document 2) is used. In the thin film laminate, peeling may occur over time at the interface between the metal oxide thin film and the metal thin film, or at the interface between the metal oxide thin film and the metal oxide thin film.
特開２００７－１９１３８４号公報JP 2007-191384 A 特開２００７－１０２１９７号公報JP 2007-102197 A
金属酸化物薄膜と金属薄膜、あるいは金属酸化物薄膜と金属酸化物薄膜との界面での経時による剥離は、薄膜内に存在する内部応力、特には金属酸化物膜内に存在する内部応力に起因することが本発明者らの検討によりわかってきた。薄膜に生じる応力としては、薄膜と基板材料の熱膨張係数の違いにより発生する熱応力、及び基板温度と膜材料の融点の比が小さいプロセスにおいて発生する内部応力がある。 Separation over time at the interface between a metal oxide thin film and a metal thin film or between a metal oxide thin film and a metal oxide thin film is caused by internal stress existing in the thin film, particularly internal stress present in the metal oxide film. This has been found by the inventors' investigation. The stress generated in the thin film includes a thermal stress generated due to a difference in thermal expansion coefficient between the thin film and the substrate material, and an internal stress generated in a process in which the ratio between the substrate temperature and the melting point of the film material is small.
また、スパッタリング法により得られる金属酸化物薄膜においては、内部応力が優勢となる。この内部応力が大きいと、金属酸化物薄膜と基板の密着性が低下することがあり、薄膜の基材からの剥離、基材の反り等が生じることがある。更に、金属酸化物薄膜と他の金属薄膜とが積層されている場合、金属酸化物薄膜の内部応力に起因して外観不良等の欠陥が生じることがある。 Moreover, in the metal oxide thin film obtained by sputtering method, internal stress becomes dominant. When this internal stress is large, the adhesion between the metal oxide thin film and the substrate may be lowered, and the thin film may be peeled off from the substrate, the substrate may be warped, and the like. Furthermore, when a metal oxide thin film and another metal thin film are laminated | stacked, defects, such as an external appearance defect, may arise due to the internal stress of a metal oxide thin film.
内部応力の小さい金属酸化物膜は、上記の問題点の改善に寄与するものである。従って、本発明は、内部応力が小さい金属酸化物薄膜を提供することを課題とする。 The metal oxide film having a small internal stress contributes to the improvement of the above problems. Therefore, an object of the present invention is to provide a metal oxide thin film with low internal stress.
本出願人は上記課題を解決するために鋭意検討した結果、非晶質の酸化タンタル薄膜が内部応力の小さい薄膜を得るための有望な候補であることを見出した。 As a result of intensive studies to solve the above problems, the present applicant has found that an amorphous tantalum oxide thin film is a promising candidate for obtaining a thin film with low internal stress.
　すなわち本発明の非晶質酸化タンタル薄膜は、スパッタリング法により透明基板上に形成される非晶質酸化タンタル薄膜であり、該酸化タンタル薄膜の理論密度をρ0、実測密度をρとしたとき(ρ／ρ0)×１００で表わされる値（以下、「緻密化度」と表記することがある）が７５～９５％であることを特徴とするものである。 That is, the amorphous tantalum oxide thin film of the present invention is an amorphous tantalum oxide thin film formed on a transparent substrate by a sputtering method. When the theoretical density of the tantalum oxide thin film is ρ 0 and the measured density is ρ ( The value represented by ρ / ρ 0 ) × 100 (hereinafter sometimes referred to as “densification degree”) is 75 to 95%.
酸化タンタル薄膜の理論密度ρ0は８．３ｇ／ｃｍ３（JCPDS（Joint Committee for Power Diffraction Standards）カード番号５４-０５１４に掲載された値を採用）とされ、実測密度ρは、Ｘ線反射率法で臨界角を測定し、これを解析することで求められる。Ｘ線反射率法による密度測定については、非特許文献１に詳細に紹介されており、ＸＲＤ測定装置（Ｒｉｇａｋｕ社製ＲＩＮＴ－ＵｌｔｉｍａIII）に付随した汎用の解析プログラムにより導き出すことができる。 The theoretical density ρ 0 of the tantalum oxide thin film is 8.3 g / cm 3 (the value listed in JCPDS (Joint Committee for Power Diffraction Standards) card number 54-0514 is adopted), and the measured density ρ is the X-ray reflectivity method. It is obtained by measuring the critical angle with and analyzing it. The density measurement by the X-ray reflectance method is introduced in detail in Non-Patent Document 1, and can be derived by a general-purpose analysis program attached to the XRD measurement apparatus (RINT-UltimaIII manufactured by Rigaku).
　なお、本発明の酸化タンタル薄膜は非晶質のものであったが、緻密化度を求める前記式において、結晶の値を理論密度ρ0として採用している。緻密化度は結晶性が悪くなると１００％未満となり、非晶質状態ではさらなる値の低下が見られる。従って、非晶質の薄膜の緻密化度を表す指標を得るために、結晶の値を理論密度ρ0として採用しても差し支えない。 Although the tantalum oxide thin film of the present invention was amorphous, the value of the crystal was adopted as the theoretical density ρ 0 in the above formula for obtaining the degree of densification. The degree of densification becomes less than 100% when the crystallinity deteriorates, and a further decrease in value is observed in the amorphous state. Therefore, in order to obtain an index representing the degree of densification of the amorphous thin film, the crystal value may be adopted as the theoretical density ρ 0 .
　また、「基板上」は、酸化タンタル薄膜が基板に接するものでも、基板と該
酸化タンタル薄膜との間に他の薄膜が介在するものでもよい。 Further, “on the substrate” may be one in which the tantalum oxide thin film is in contact with the substrate, or another thin film interposed between the substrate and the tantalum oxide thin film.
　本発明においては、緻密化度を７５％～９５％としており、好ましくは７７％～９１％と設定してもよい。緻密化度が９５％超では、内部応力の低減が十分とは言えないものであった。また、緻密化度が７５％未満と低くなりすぎると膜強度が低下するおそれが生じる。 In the present invention, the degree of densification is 75% to 95%, preferably 77% to 91%. When the degree of densification exceeds 95%, the internal stress cannot be said to be sufficiently reduced. Further, if the densification degree is too low, such as less than 75%, the film strength may be lowered.
また、緻密化度の低い酸化タンタル薄膜は、緻密化度の高いものよりも屈折率が低くなる傾向が見られた。一般的に、屈折率の低い薄膜は、薄膜のぎらつき感を低減させ、透過率を向上させることにも繋がる可能性があるため、屈折率が低い酸化タンタル薄膜は、本発明において好ましい形態であるとも言える。 In addition, the tantalum oxide thin film having a low degree of densification tended to have a lower refractive index than that having a high degree of densification. In general, a thin film with a low refractive index may reduce the glare of the thin film and improve the transmittance. Therefore, a tantalum oxide thin film with a low refractive index is a preferred form in the present invention. It can be said that there is.
上記の観点から、本発明の酸化タンタル薄膜は、波長５５０ｎｍにおける屈折率が２．０５以下とすることが好ましく、特に２．００以下とすることが最も好ましい。なお、酸化タンタル薄膜の屈折率が２．０５を超えると、緻密化度が高くなり内部応力が大きくなる構造を薄膜中にもたらすことがある。また、屈折率の下限は、特に限定されるものではないが、屈折率は緻密化度と相関性があり、低い屈折率を得ようとすると、緻密化度が低くなり薄膜の膜強度を弱めることがある。従って、屈折率の下限は１．９０、好ましくは１．９５と設定してもよい。 From the above viewpoint, the tantalum oxide thin film of the present invention preferably has a refractive index at a wavelength of 550 nm of 2.05 or less, and most preferably 2.00 or less. When the refractive index of the tantalum oxide thin film exceeds 2.05, the thin film may have a structure in which the degree of densification increases and the internal stress increases. Further, the lower limit of the refractive index is not particularly limited, but the refractive index has a correlation with the degree of densification, and when trying to obtain a low refractive index, the degree of densification is lowered and the film strength of the thin film is weakened. Sometimes. Therefore, the lower limit of the refractive index may be set to 1.90, preferably 1.95.
　本発明の非晶質酸化タンタル薄膜は、内部応力が小さいため、基板との密着性が向上し、膜自体の剥離や基板の反り発生を抑制する。また、酸化タンタル薄膜と他の金属薄膜とが積層されている場合、酸化タンタル薄膜の内部応力に起因する外観不良等の欠陥が低減される。 Since the amorphous tantalum oxide thin film of the present invention has a low internal stress, the adhesion with the substrate is improved, and the peeling of the film itself and the occurrence of warping of the substrate are suppressed. Moreover, when the tantalum oxide thin film and another metal thin film are laminated | stacked, defects, such as an external appearance defect resulting from the internal stress of a tantalum oxide thin film, are reduced.
ＤＣマグネトロンスパッタリング装置を上方から観察したときの要部を説明する図である。It is a figure explaining the principal part when a DC magnetron sputtering apparatus is observed from upper direction. 得られた非晶質酸化タンタル薄膜の緻密化度と内部応力との関係を示す図である。It is a figure which shows the relationship between the densification degree of the obtained amorphous tantalum oxide thin film, and internal stress.
１ ターゲット 
２ 基材ホルダー 
３ 透明基板 
４ カソードマグネット 
５ 真空ポンプ  1 target
2 Base material holder
3 Transparent substrate
4 Cathode magnet
5 Vacuum pump
透明基材（可視光に透過性を有するもの）には、ガラス基板が好適に使用される。ガラス基板の例としては、建築用や車両用をはじめとする窓や鏡、ディスプレイ用に使用されているソーダ石灰ケイ酸塩ガラスからなるフロート板ガラス、又はロールアウト法で製造されたソーダ石灰ケイ酸塩ガラス、無アルカリガラス等無機質の透明性がある板ガラスが挙げられる。  A glass substrate is preferably used for the transparent substrate (having transparency to visible light). Examples of glass substrates include windows and mirrors for buildings and vehicles, float glass made of soda lime silicate glass used for displays, or soda lime silicate manufactured by the roll-out method. Examples thereof include plate glass having inorganic transparency such as salt glass and alkali-free glass.
当該板ガラスには、無色のもの、着色のもの共に使用可能で、基材の形状は、平板、曲げ板を問わず、さらには、風冷強化ガラス、化学強化ガラス等の各種強化ガラスの他に編入りガラスも使用できる。さらには、ホウケイ酸塩ガラス、低膨張ガラス、ゼロ膨張ガラス、低膨張結晶化ガラス、ゼロ膨張結晶化ガラス、TFT用ガラス、PDP用ガラス、光学フィルム用基板ガラス等の各種ガラス基材を用いることができる。  For the plate glass, both colorless and colored can be used, and the shape of the substrate is not limited to a flat plate or a bent plate, and in addition to various tempered glass such as air-cooled tempered glass and chemically tempered glass. Knitted glass can also be used. In addition, various glass substrates such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, zero expansion crystallized glass, TFT glass, PDP glass, and optical film substrate glass should be used. Can do.
また、ガラス基板以外の例としては、ポリエチレンテレフタレート樹脂、ポリカーボネートや高透過ガラスなどの廉価なフロート板ガラスが好適であるが、透明ガラスのほかにも、ポリカーボネートやポリエチレンテレフタレート等の透明な樹脂基板あるいはフィルム等を用いてもよい。  Moreover, as an example other than the glass substrate, inexpensive float glass such as polyethylene terephthalate resin, polycarbonate and high-transmission glass is suitable, but besides transparent glass, transparent resin substrate or film such as polycarbonate or polyethylene terephthalate. Etc. may be used.
本発明に係る非晶質酸化タンタル薄膜は、スパッタリング法を用いて形成されることが好ましい。スパッタリング法には、DCスパッタリング、RFスパッタリング、パルススパッタリング、対向スパッタリング、デュアルスパッタリング法など公知のスパッタ方式が適応可能である。  The amorphous tantalum oxide thin film according to the present invention is preferably formed using a sputtering method. As the sputtering method, known sputtering methods such as DC sputtering, RF sputtering, pulse sputtering, counter sputtering, and dual sputtering methods can be applied.
緻密化度が９５％以下である該酸化タンタル薄膜は、成膜時の雰囲気ガスを調節することで得られ、さらに上記よりも緻密化度を低減させたい場合、例えば、Ｏ2とＣＯ2との混合ガスを用いることによっても、容易に低減させることが可能となるため好ましい。該混合ガスを用いる場合、特に、ＣＯ2／（Ｏ2＋ＣＯ2）×１００の式で表されるＣＯ2流量比が２０体積％以上であるとき、緻密化度を９０％未満に低減させることが可能となるため好ましい。  The tantalum oxide thin film having a densification degree of 95% or less can be obtained by adjusting the atmospheric gas during film formation. Further, when it is desired to reduce the densification degree more than the above, for example, O 2 and CO 2 It is also preferable to use the mixed gas because it can be easily reduced. When the mixed gas is used, particularly when the CO 2 flow ratio represented by the formula CO 2 / (O 2 + CO 2 ) × 100 is 20% by volume or more, the degree of densification is reduced to less than 90%. Is preferable.
一般的にスパッタ法などでは、金属ターゲットを用いてＯ2雰囲気中で酸化物薄膜を成膜させると、ターゲット表面で生成される酸素負イオンなどの高エネルギー粒子が、膜に打ち込まれるため、該膜は密度が高くなり、緻密化度は高くなる。  Generally, in a sputtering method or the like, when an oxide thin film is formed in an O 2 atmosphere using a metal target, high-energy particles such as oxygen negative ions generated on the target surface are implanted into the film. The film has a higher density and a higher degree of densification.
Ｏ2とＣＯ2との混合ガスを用いると、ＣＯ2はＯ2に比べて酸化力が弱いため、ターゲット表面の酸化を抑制する効果があると考えられる。その結果、ターゲット表面で生成される酸素負イオンなどの高エネルギー粒子が減少し、酸化タンタル膜の膜密度が減少すると考えられる。また、該混合ガスには放電を安定させるために、Ａｒ，Ｘｅ，Ｎｅ，Ｋｒなどのガスを加えてもよい。なお、酸化タンタル薄膜を形成するには成膜時の雰囲気ガスの圧力の上限を１．０Ｐaとすることが好ましく、下限は特に限定されるものではないが、
０．１Ｐaと設定してもよい。  When a mixed gas of O 2 and CO 2 is used, it is considered that CO 2 has an effect of suppressing oxidation of the target surface because CO 2 has a weaker oxidizing power than O 2 . As a result, it is considered that high-energy particles such as oxygen negative ions generated on the target surface are reduced and the film density of the tantalum oxide film is reduced. Further, in order to stabilize the discharge, a gas such as Ar, Xe, Ne, Kr may be added to the mixed gas. In order to form a tantalum oxide thin film, the upper limit of the pressure of the atmospheric gas during film formation is preferably 1.0 Pa, and the lower limit is not particularly limited,
It may be set to 0.1 Pa.
 本発明に係る非晶質酸化タンタル薄膜の膜厚が５ｎｍ以上、１００ｎｍ以下のとき、該薄膜と銀等の金属膜層とを有する薄膜積層体は、例えば、低放射積層体として好適に使用される。透明基材と該透明基材上に形成された薄膜積層体とからなる物品は、建物において日射熱が室内に流入することを防ぐ遮熱性、または室内の温度が室外へ流出することを防ぐ断熱性を付与した窓ガラスとして用いられる。  When the film thickness of the amorphous tantalum oxide thin film according to the present invention is 5 nm or more and 100 nm or less, the thin film laminate having the thin film and a metal film layer such as silver is preferably used as a low emission laminate. The Articles composed of a transparent base material and a thin film laminate formed on the transparent base material have a heat shielding property to prevent solar heat from flowing into the room in a building, or heat insulation to prevent the indoor temperature from flowing out of the room It is used as a window glass with added properties.
窓ガラスとして用いる場合、室外に設置される面から低放射積層体付きガラス、乾燥空気層、透明ガラスの順で構成することにより遮熱性が付与された複層ガラス、または室外に設置される面から、透明ガラス、乾燥空気層、低放射積層体付きガラスの順で構成することにより断熱性が付与された複層ガラスとして用いる事が好ましく、低放射積層体付きガラスは乾燥空気層に接する面に低放射積層体を形成することが好ましい。  When used as a window glass, it is a multi-layer glass that is provided with heat-shielding properties by being constructed in the order of a glass with a low emission laminate, a dry air layer, and a transparent glass, or a surface that is installed outdoors. From the above, it is preferable to use as a double-glazed glass provided with heat insulation by constituting in order of a transparent glass, a dry air layer, and a glass with a low radiation laminate, and the glass with a low radiation laminate is a surface in contact with the dry air layer It is preferable to form a low emission laminate.
　あるいは、該非晶質酸化タンタル薄膜の膜厚が１００ｎｍ以上、１０００ｎｍ以下のとき、該薄膜と、酸化タングステン等の陽極層、及び酸化イリジウム等の陰極層とを有する薄膜積層体は、ＥＣ層として使用され得る。透明基材と該透明基材上に透明導電膜、ＥＣ層と順次積層された物品は、該物品に電流電圧を印加することで、可逆的に透過率や反射率、あるいはＥＣ層自体の色を変化させることが可能な全固体型ＥＣ素子として利用されることが好ましい。具体的には、例えば、車両用や家庭用のＥＣミラー、ＥＣ表示装置、車両用や家庭用窓ガラスの調光ガラス等として用いられるのが好ましい。  Alternatively, when the amorphous tantalum oxide thin film has a film thickness of 100 nm or more and 1000 nm or less, a thin film laminate including the thin film, an anode layer such as tungsten oxide, and a cathode layer such as iridium oxide is used as an EC layer. Can be done. An article in which a transparent base material and a transparent conductive film and an EC layer are sequentially laminated on the transparent base material are reversible by applying a current voltage to the article, or the color of the EC layer itself. It is preferable to be used as an all-solid-state EC element capable of changing. Specifically, for example, it is preferably used as an EC mirror for vehicles or home, an EC display device, a light control glass for vehicle or home window glass, and the like.
　また、上記の薄膜積層体付き基材は、流通、保管などの過程を経て、複層ガラス、合わせガラスやＥＣミラー等といった物品に組み込まれることがあり、その際、ガラス表面の付着物等の汚れに対して、水を使用した洗浄を行うことがある。例えば、該低放射積層体は、銀層を含むものが多く使用されており、銀層を含む積層体に水を接触させると積層体が劣化することがあるため、水との接触は回避されることが好ましい。しかしながら、本発明の非晶質酸化タンタル薄膜を銀層の保護膜として使用した低放射積層体付きガラスは、上記のような水が接触する洗浄時に膜表面の劣化が生じないものであった。  In addition, the substrate with a thin film laminate described above may be incorporated into articles such as double-glazed glass, laminated glass, EC mirror, etc. through processes such as distribution and storage. The dirt may be washed with water. For example, the low emission laminate is often used including a silver layer, and contact with water is avoided when water contacts the laminate including the silver layer. It is preferable. However, the glass with a low-emission laminate using the amorphous tantalum oxide thin film of the present invention as a protective film for the silver layer does not cause deterioration of the film surface at the time of cleaning in contact with water as described above.
本発明に係る酸化タンタル薄膜は、緻密化度が低いことに起因して内部応力が小さいため、基材、他の膜に与える影響が小さくなる。従って、赤外線遮蔽膜、光学フィルタ、全固体型ＥＣ素子等の薄膜積層体へ使用されることが好ましい。具体的には、銀等の金属薄膜の保護膜、あるいは、金属膜の下地膜として用いられることが好ましい。  Since the tantalum oxide thin film according to the present invention has a low internal stress due to its low densification degree, the influence on the substrate and other films is reduced. Therefore, it is preferably used for thin film laminates such as infrared shielding films, optical filters, and all solid-state EC elements. Specifically, it is preferably used as a protective film for a metal thin film such as silver or a base film for a metal film.
　以下に、本発明の具体例を実施例および比較例にて説明する。  Hereinafter, specific examples of the present invention will be described with reference to Examples and Comparative Examples.
　 実施例１ 
酸化タンタル薄膜の成膜は、図１に示すような概略構造を有するＤＣマグネトロンスパッタリング装置を用いて行った。図１は、該装置を上方から観察したときの要部を示すものである。ターゲット１にＴａターゲットを用い、透明基材（フロート法で得られたソーダ石灰ケイ酸塩ガラス）３を基材ホルダー２に保持させた後、真空チャンバー８内を、真空ポンプ５を用いて排気した。尚、図１では、ターゲット１は２個描かれているが、設置数、種類は薄膜の積層数、膜種に応じて適宜設定を行った。  Example 1
The tantalum oxide thin film was formed using a DC magnetron sputtering apparatus having a schematic structure as shown in FIG. FIG. 1 shows a main part when the apparatus is observed from above. A Ta target is used for the target 1 and a transparent base material (soda-lime silicate glass obtained by a float process) 3 is held by the base material holder 2, and then the inside of the vacuum chamber 8 is evacuated using a vacuum pump 5. did. In FIG. 1, two targets 1 are drawn, but the number and type of installations are appropriately set according to the number of thin films stacked and the type of film.
真空チャンバー８内の雰囲気ガスは、ガス導入管７より、Ｏ2ガスを導入し、
ガス流量をマスフロコントローラー（図示せず）により制御した。成膜中の真空チャンバー８内の圧力は、開閉バルブ６により０．３Ｐａに調節した。さらに、ＤＣ電源の出力電力を３ｋＷとした。  As the atmospheric gas in the vacuum chamber 8, O 2 gas is introduced from the gas introduction pipe 7.
The gas flow rate was controlled by a mass flow controller (not shown). The pressure in the vacuum chamber 8 during film formation was adjusted to 0.3 Pa by the opening / closing valve 6. Furthermore, the output power of the DC power source was 3 kW.
基材ホルダー２は、搬送ロール１２上を搬送され、ターゲット１の横を通過した。この時の通過速度を調整し、膜厚３７ｎｍの五酸化タンタル薄膜を得た。  The substrate holder 2 was transported on the transport roll 12 and passed by the side of the target 1. The passage speed at this time was adjusted to obtain a tantalum pentoxide thin film having a thickness of 37 nm.
実施例２ 
真空チャンバー８内の雰囲気ガスは、ガス導入管７より、Ｏ2および
ＣＯ2ガスを導入し、ガス流量をマスフロコントローラー（図示せず）により制御し、ＣＯ2流量比［｛ＣＯ2／（Ｏ2＋ＣＯ2）｝×１００］を７５体積％とした。反応性ガス流量比を変更した以外は実施例１と同様の手順で五酸化タンタル薄膜を得た。  Example 2
As the atmospheric gas in the vacuum chamber 8, O 2 and CO 2 gases are introduced from the gas introduction pipe 7, the gas flow rate is controlled by a mass flow controller (not shown), and the CO 2 flow ratio [{CO 2 / ( O 2 + CO 2 )} × 100] was 75% by volume. A tantalum pentoxide thin film was obtained by the same procedure as in Example 1 except that the reactive gas flow ratio was changed.
比較例１ 
比較例１ではＯ2流量比を１００体積%で作製した酸化スズ薄膜とした以外は、実施例 １と同様の手順で酸化スズ薄膜を得た。 
（１）実施例１又は２及び比較例１で得られた酸化タンタル薄膜、酸化スズ薄膜の評価
 得られた薄膜の密度を、ＣｕＫα線を用いたＸ線反射率法にて評価し、薄膜の緻密化度を評価した。また、磁気分光光度計（日立製作所製Ｕ－４０００）を用いて測定した膜面反射率、ガラス面反射率および透過率から、薄膜光学シミュレーションによって屈折率を評価した。 
（２）薄膜の内部応力の評価 
薄膜の内部応力は、片持ち梁法によって評価された。該方法は、成膜前後の基板の反りの変化量を測定することにより、膜の内部応力を求める方法である。この評価の実施のために、基材を厚さ０．１ｍｍのマイクロシートガラスとし、実施例１、２及び比較例１と同様の条件で薄膜を形成した。ただし、該ガラス基材は、基材ホルダー２にその一端だけが固定された。  Comparative Example 1
In Comparative Example 1, a tin oxide thin film was obtained in the same procedure as in Example 1 except that the tin oxide thin film was prepared with an O 2 flow rate ratio of 100% by volume.
(1) Evaluation of tantalum oxide thin film and tin oxide thin film obtained in Example 1 or 2 and Comparative Example 1 The density of the obtained thin film was evaluated by an X-ray reflectivity method using CuKα rays, The degree of densification was evaluated. The refractive index was evaluated by thin film optical simulation from the film surface reflectance, glass surface reflectance, and transmittance measured using a magnetic spectrophotometer (U-4000 manufactured by Hitachi, Ltd.).
(2) Evaluation of internal stress of thin film
The internal stress of the thin film was evaluated by the cantilever method. This method is a method for determining the internal stress of the film by measuring the amount of change in the warpage of the substrate before and after film formation. In order to perform this evaluation, the base material was a microsheet glass having a thickness of 0.1 mm, and a thin film was formed under the same conditions as in Examples 1 and 2 and Comparative Example 1. However, only one end of the glass substrate was fixed to the substrate holder 2.
　該条件で薄膜を形成すると、薄膜内に生じた内部応力に応じて基材に反りが発生するので、非特許文献２で紹介されているように、該反り量から薄膜の内部応力が求められる。  When a thin film is formed under such conditions, warpage occurs in the base material in accordance with internal stress generated in the thin film, and as introduced in Non-Patent Document 2, the internal stress of the thin film is determined from the amount of warpage. .
　本実施例では、内部応力の値が負の値で表されるが、内部応力の大きさは絶対値で評価されるので、数値がゼロに近いほど内部応力が小さいものとして評価できる。評価結果を表１に示す。さらに、緻密化度と薄膜の内部応力との関係を図２に示す。実施例１および２のいずれも、緻密化度が９５％以下、内部応力の絶対値が１３．０×１０8Ｎ／ｍ2以下、屈折率も２．０５以下となった。  In this embodiment, the value of the internal stress is expressed as a negative value. However, since the magnitude of the internal stress is evaluated as an absolute value, it can be evaluated that the internal stress is smaller as the numerical value is closer to zero. The evaluation results are shown in Table 1. Furthermore, the relationship between the densification degree and the internal stress of the thin film is shown in FIG. In each of Examples 1 and 2, the degree of densification was 95% or less, the absolute value of internal stress was 13.0 × 10 8 N / m 2 or less, and the refractive index was 2.05 or less.
Figure JPOXMLDOC01-appb-T000001
 実施例３ 
薄膜積層体を、図２に示すような概略構造を有するＤＣマグネトロンスパッタリング装置を用いて作製した。上流側のターゲット１にＺｎターゲットを用い、その下流側ターゲット１にＡｇターゲット、さらに下流側ターゲット１にＺｎＡｌＯ（Ａｌ ４ｗｔ％含有ＺｎＯ）ターゲット、最下流のターゲット１にＴａターゲットを用いた。 
Figure JPOXMLDOC01-appb-T000001
 Example 3
A thin film laminate was produced using a DC magnetron sputtering apparatus having a schematic structure as shown in FIG. A Zn target was used as the upstream target 1, an Ag target was used as the downstream target 1, a ZnAlO (Al 4 wt% -containing ZnO) target was used as the downstream target 1, and a Ta target was used as the most downstream target 1.
透明基材（フロート法で得られたソーダ石灰ケイ酸塩ガラス）３を基材ホルダー２に保持させた後、真空チャンバー８内を、真空ポンプ５を用いて排気した。真空チャンバー８内の雰囲気ガスは、ガス導入管７より、Ｏ2ガスを導入し、ガス流量をマスフロコントローラー（図示せず）により制御し、ガス雰囲気を、積層体の積層種に応じて調整した。成膜中の真空チャンバー８内の圧力は、開閉バルブ６により調節した。また、ＤＣ電源の出力電力を
１ｋＷとした。  After the transparent substrate (soda lime silicate glass obtained by the float process) 3 was held on the substrate holder 2, the inside of the vacuum chamber 8 was evacuated using the vacuum pump 5. The atmosphere gas in the vacuum chamber 8 introduces O 2 gas from the gas introduction pipe 7, the gas flow rate is controlled by a mass flow controller (not shown), and the gas atmosphere is adjusted according to the laminate type of the laminate. did. The pressure in the vacuum chamber 8 during film formation was adjusted by the open / close valve 6. The output power of the DC power source was 1 kW.
　基材ホルダー２は、搬送ロール１２上を搬送され、ターゲット１の横を通過した。この時の通過速度を調整し各薄膜層の膜厚を調整し、透明基材３上にＺｎＯ／Ａｇ／ＺｎＡｌＯ／Ｔａ2Ｏ5の順で薄膜が積層された積層体を形成した。  The substrate holder 2 was transported on the transport roll 12 and passed by the side of the target 1. This adjusts the rate of passage of time by adjusting the thickness of each thin layer, a thin film in the order of ZnO / Ag / ZnAlO / Ta 2 O 5 has a laminated body that is laminated on the transparent substrate 3.
　基材上に酸化亜鉛薄膜を形成するときは、Ｏ2ガスのみとし、圧力を０．３Ｐａとした。該酸化亜鉛薄膜層は、３７ｎｍの膜厚を有する層とした。  When the zinc oxide thin film was formed on the substrate, only O 2 gas was used and the pressure was 0.3 Pa. The zinc oxide thin film layer was a layer having a thickness of 37 nm.
該酸化亜鉛薄膜層上にＡｇ薄膜層を形成するときは、真空チャンバー８内のＯ2ガスを排気した後、Ａｒガスをガス導入管７よりマスフロコントローラーにより制御しながら、真空チャンバー８内に導入し、圧力を０．５Ｐａとした。また、ＤＣ電源の出力電力を０．４ｋＷとした。該Ａｇ薄膜層は、
１０ｎｍの膜厚を有するものとした。  When the Ag thin film layer is formed on the zinc oxide thin film layer, the O 2 gas in the vacuum chamber 8 is evacuated, and then the Ar gas is controlled from the gas introduction pipe 7 by the mass flow controller while being placed in the vacuum chamber 8. The pressure was set to 0.5 Pa. The output power of the DC power source was 0.4 kW. The Ag thin film layer is
The film thickness was 10 nm.
該Ａｇ薄膜層上にＺｎＡｌＯ薄膜層を形成するときの条件は、Ａｇ薄膜層を形成するとき同様とした。該ＺｎＡｌＯ薄膜層は、５ｎｍの膜厚を有するものとした。  The conditions for forming the ZnAlO thin film layer on the Ag thin film layer were the same as those for forming the Ag thin film layer. The ZnAlO thin film layer had a thickness of 5 nm.
該ＺｎＡｌＯ薄膜層上に酸化タンタル薄膜層を形成するときは、真空チャンバー８内のＡｒガスを排気した後、ガス導入管７より、Ｏ2ガスを導入し、Ｏ2流量比１００％とした。成膜中の真空チャンバー８内の圧力は、開閉バルブ６により０．３Ｐａに調節した。該酸化タンタル薄膜層は、３７ｎｍの膜厚を有するものとした。  When the tantalum oxide thin film layer was formed on the ZnAlO thin film layer, the Ar gas in the vacuum chamber 8 was evacuated, and then O 2 gas was introduced from the gas introduction pipe 7 so that the O 2 flow rate ratio was 100%. The pressure in the vacuum chamber 8 during film formation was adjusted to 0.3 Pa by the opening / closing valve 6. The tantalum oxide thin film layer had a thickness of 37 nm.
実施例４ 
酸化タンタル膜を成膜時にＣＯ2流量比｛［ＣＯ2／（Ｏ2＋ＣＯ2）］×１００｝を７５体積％とした以外は実施例５と同様の手順で薄膜積層体を得た。  Example 4
A thin film laminate was obtained in the same procedure as in Example 5 except that the CO 2 flow ratio {[CO 2 / (O 2 + CO 2 )] × 100} was changed to 75% by volume at the time of forming the tantalum oxide film.
　比較例２ 
ＺｎＡｌＯ薄膜層上に酸化タンタル膜を形成する代わりに酸化スズ膜を形成
した以外は、実施例３と同様の手順で薄膜積層体を得た。 
（３）実施例３及び４、及び比較例２で得られた薄膜積層体の評価 
薄膜積層体が形成された透明基材を、温度３０℃、相対湿度９０％の環境下
で４週間保持し、２０ｃｍ角（２０ｃｍ×２０ｃｍ＝４００ｃｍ）の領域内に発生した直径０．３ｍｍ以上の欠陥数を計測した。  Comparative Example 2
A thin film laminate was obtained in the same procedure as in Example 3 except that a tin oxide film was formed on the ZnAlO thin film layer instead of forming a tantalum oxide film.
(3) Evaluation of thin film laminates obtained in Examples 3 and 4 and Comparative Example 2
The transparent base material on which the thin film laminate is formed is maintained for 4 weeks in an environment of a temperature of 30 ° C. and a relative humidity of 90%, and a diameter of 0.3 mm or more generated in a 20 cm square (20 cm × 20 cm = 400 cm) region. The number of defects was measured.
　表２に実施例３、４及び比較例２における酸化タンタル膜の内部応力と欠陥数を示す。表２から、実施例３及び４は、酸化タンタル膜の内部応力が小さく、これに起因して欠陥数が少なかった。  Table 2 shows the internal stress and the number of defects of the tantalum oxide films in Examples 3 and 4 and Comparative Example 2. From Table 2, in Examples 3 and 4, the internal stress of the tantalum oxide film was small, resulting in a small number of defects.
　また、耐湿性が良好であった実施例３及び４に関して、以下の水洗浄に関する評価を行った。  Moreover, the following water washing evaluation was performed about Example 3 and 4 with favorable moisture resistance.
　薄膜積層体が形成された基材を、超音波洗浄機を用いて、温度４０℃の純水で１０分間洗浄を行い、洗浄後に温風乾燥を行った。上記の水洗浄、乾燥工程を経ても、薄膜積層体表面に欠陥は生じなかった。  The base material on which the thin film laminate was formed was washed with pure water at a temperature of 40 ° C. for 10 minutes using an ultrasonic cleaner, and hot air drying was performed after the washing. Even after the water washing and drying steps described above, no defects occurred on the surface of the thin film laminate.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (5)

  1. スパッタリング法により透明基板上に形成される非晶質酸化タンタル薄膜であり、該酸化タンタル薄膜の理論密度をρ0、実測密度をρとしたとき（ρ／ρ0）×１００で表わされる値が７５～９５体積％であることを特徴とする非晶質酸化タンタル薄膜。  An amorphous tantalum oxide thin film formed on a transparent substrate by a sputtering method, where the theoretical density of the tantalum oxide thin film is ρ 0 , and the measured density is ρ, the value represented by (ρ / ρ 0 ) × 100 An amorphous tantalum oxide thin film characterized by being 75 to 95% by volume.
  2. 波長５５０ｎｍにおける屈折率が２．０５以下であることを特徴とする請求項１に記載の非晶質酸化タンタル薄膜。  2. The amorphous tantalum oxide thin film according to claim 1, wherein the refractive index at a wavelength of 550 nm is 2.05 or less.
  3. 膜厚が５～１０００ｎｍであることを特徴とする請求項１又は請求項２に記載の非晶質酸化タンタル薄膜。  The amorphous tantalum oxide thin film according to claim 1 or 2, wherein the film thickness is 5 to 1000 nm.
  4. 反応性ガスを用いてスパッタリング法により透明基板上に形成される非晶質酸化タンタル薄膜であり、該反応性ガスがＯ2およびＣＯ2からなる群から選ばれる少なくとも１種であることを特徴とする請求項１乃至請求項３のいずれか１項に記載の非晶質酸化タンタル薄膜。  An amorphous tantalum oxide thin film formed on a transparent substrate by a sputtering method using a reactive gas, wherein the reactive gas is at least one selected from the group consisting of O 2 and CO 2. The amorphous tantalum oxide thin film according to any one of claims 1 to 3.
  5. 請求項１乃至請求項４のいずれか１項に記載の非晶質酸化タンタル薄膜と金属薄膜とを有する薄膜積層体。 A thin film laminate comprising the amorphous tantalum oxide thin film according to any one of claims 1 to 4 and a metal thin film.
PCT/JP2010/052706 2009-03-10 2010-02-23 Tantalum oxide thin film and thin film laminate WO2010103914A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009056890A JP2010209413A (en) 2009-03-10 2009-03-10 Tantalum oxide thin film, and thin film layered product
JP2009-056890 2009-03-10

Publications (1)

Publication Number Publication Date
WO2010103914A1 true WO2010103914A1 (en) 2010-09-16

Family

ID=42728205

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/052706 WO2010103914A1 (en) 2009-03-10 2010-02-23 Tantalum oxide thin film and thin film laminate

Country Status (2)

Country Link
JP (1) JP2010209413A (en)
WO (1) WO2010103914A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115818977A (en) * 2022-11-03 2023-03-21 广西大学 Preparation method of tantalum oxide nanowire film for counter electrode of electrochromic device and electrochromic device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0656477A (en) * 1992-08-13 1994-03-01 Central Glass Co Ltd Radio wave transmitting-type heat shielding glass of grey color
JP2002194529A (en) * 2000-10-20 2002-07-10 Asahi Glass Co Ltd Manufacture method for optical thin film
JP2004228355A (en) * 2003-01-23 2004-08-12 Seiko Epson Corp Insulating film substrate, method and apparatus for manufacturing the same, electro-optical device and method for manufacturing the same
JP2005042160A (en) * 2003-07-22 2005-02-17 Matsushita Electric Ind Co Ltd Method and device for controlling film thickness

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0656477A (en) * 1992-08-13 1994-03-01 Central Glass Co Ltd Radio wave transmitting-type heat shielding glass of grey color
JP2002194529A (en) * 2000-10-20 2002-07-10 Asahi Glass Co Ltd Manufacture method for optical thin film
JP2004228355A (en) * 2003-01-23 2004-08-12 Seiko Epson Corp Insulating film substrate, method and apparatus for manufacturing the same, electro-optical device and method for manufacturing the same
JP2005042160A (en) * 2003-07-22 2005-02-17 Matsushita Electric Ind Co Ltd Method and device for controlling film thickness

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
B. P. HICHWA: "Quantitative measurement of film thickness, density and stoichiometry of multilayer thin films on thick substrates", NUCL. INSTRUM. METHODS PHYS. RES. B, vol. 24/25, no. 1, April 1987 (1987-04-01), pages 584 - 586 *
P. J. MARTIN ET AL.: "Properties of thin films of tantalum oxidede posited by ion-assisted deposition", THIN SOLID FILMS, vol. 239, no. 2, 1 March 1994 (1994-03-01), pages 181 - 185 *
W. D. WESTWOOD ET AL.: "Effect of pressure on the properties of reactively sputtered Ta205", J. VAC. SCI. TECHNOL., vol. 11, no. 1, 1974, pages 381 - 384 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115818977A (en) * 2022-11-03 2023-03-21 广西大学 Preparation method of tantalum oxide nanowire film for counter electrode of electrochromic device and electrochromic device
CN115818977B (en) * 2022-11-03 2024-04-30 广西大学 Preparation method of tantalum oxide nanowire film for counter electrode of electrochromic device and electrochromic device

Also Published As

Publication number Publication date
JP2010209413A (en) 2010-09-24

Similar Documents

Publication Publication Date Title
JP2625079B2 (en) Solar controlled durable thin film coating with low emissivity
JP5722346B2 (en) High quality radiation control coating, radiation control glass and manufacturing method
KR920007499B1 (en) High transmittance low emissivity article and method of preparation
US6899953B1 (en) Shippable heat-treatable sputter coated article and zinc cathode sputtering target containing low amounts of tin
US20180079681A1 (en) Tin oxide overcoat indium tin oxide coatings, coated glazings, and production methods
CN200958077Y (en) Low-radiant strengthened film-coating glass
JPH0715143B2 (en) High transmittance, low emissivity heat resistant window or windshield
WO1991002102A1 (en) Film based on silicon dioxide and production thereof
CN105130209A (en) High-transmittance low-cost color-adjustable low-radiation energy-saving glass and preparation method thereof
JP2007191384A (en) Low emissivity glass
US9296649B2 (en) Process for producing laminate, and laminate
CN201424436Y (en) Low-reflective coated glass
JP6601419B2 (en) Glass plate with laminated film and multilayer glass
WO2019157799A1 (en) Method for preparing low-radiation coated glass
JP2011173764A (en) Low radiation film
CN102336529A (en) High transmittance toughenable low radiation glass and manufacture method thereof
KR20110018069A (en) Transparent substrate having multilayer coating for anti-reflection and method for preparing the same
JPH07249316A (en) Transparent conductive film and transparent substrate using the transparent conductive film
WO2010103914A1 (en) Tantalum oxide thin film and thin film laminate
JP2018002564A (en) Gray color tone low radiation glass
WO2010098200A1 (en) Stack article
JP2008222507A (en) Multiple glass
JP2010031346A (en) Zinc oxide thin film and thin film laminate
JP2014124815A (en) Low-radiation film
JP2017132666A (en) Gray color tone radiation glass, and method for producing the gray color tone radiation glass

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10750668

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10750668

Country of ref document: EP

Kind code of ref document: A1