US20150103399A1 - Method of producing glass substrate and glass substrate - Google Patents

Method of producing glass substrate and glass substrate Download PDF

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Publication number
US20150103399A1
US20150103399A1 US14/552,053 US201414552053A US2015103399A1 US 20150103399 A1 US20150103399 A1 US 20150103399A1 US 201414552053 A US201414552053 A US 201414552053A US 2015103399 A1 US2015103399 A1 US 2015103399A1
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Prior art keywords
layer
glass substrate
thin film
low
glass
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Abandoned
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US14/552,053
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English (en)
Inventor
Hiroshi HANEKAWA
Nobutaka Aomine
Yuki Aoshima
Hirotomo Kawahara
Kazunobu Maeshige
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AGC Inc
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Asahi Glass Co Ltd
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Assigned to ASAHI GLASS COMPANY, LIMITED reassignment ASAHI GLASS COMPANY, LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AOSHIMA, YUKI, KAWAHARA, Hirotomo, MAESHIGE, KAZUNOBU, AOMINE, NOBUTAKA, HANEKAWA, Hiroshi
Publication of US20150103399A1 publication Critical patent/US20150103399A1/en
Priority to US15/730,448 priority Critical patent/US10239783B2/en
Abandoned legal-status Critical Current

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    • 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
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • 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
    • C03C17/3657—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 multilayer coating having optical properties
    • C03C17/366—Low-emissivity or solar control coatings
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • 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
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • 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
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • 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
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • C03C2218/153—Deposition methods from the vapour phase by cvd by plasma-enhanced cvd

Definitions

  • the present invention relates to a method of producing a glass substrate having one or two or more layers deposited on its surface by a low-temperature CVD process, and to a glass substrate having one or two or more layers deposited on its surface by a low-temperature CVD process.
  • the CVD (chemical vapor deposition) process is a technique that deposits a film of a target substance onto a substrate using a chemical reaction of a source gas.
  • the CVD process is characterized by its capability to deposit a relatively uniform film even when a substrate surface has irregularities, and has been widely used in various kinds of fields.
  • Non-Patent Document 1 describes the technique of depositing a SiO 2 film on a glass substrate at high speed by a plasma-enhanced CVD (PECVD) process, which is a kind of CVD process at low temperatures.
  • PECVD plasma-enhanced CVD
  • a method of producing a glass substrate having a first layer formed on a surface of the substrate by low-temperature CVD includes preparing the glass substrate and forming the first layer on the glass substrate by the low-temperature CVD.
  • an integrated value after a baseline correction in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 in a peak due to OH groups obtained by an FTIR measurement on the first layer is 9.0 or less, and the C content of the first layer is 1.64 at % or less.
  • a glass substrate has a first layer formed on a surface of the glass substrate by low-temperature CVD.
  • an integrated value after a baseline correction in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 in a peak due to OH groups obtained by an FTIR measurement on the first layer is 9.0 or less, and the C content of the first layer is 1.64 at % or less.
  • FIGS. 1A , 1 B, 1 C and 1 D are schematic diagrams for illustrating a problem caused when a glass substrate with a thin film produced by a conventional low-temperature CVD process is subjected to a heat treatment;
  • FIG. 2 is a flowchart schematically illustrating a method of producing a thin film material
  • FIG. 3 is a cross-sectional view schematically illustrating a configuration of a glass substrate with a thin film
  • FIG. 4 is a cross-sectional view schematically illustrating a configuration of a second glass substrate with a thin film
  • FIG. 5 is a cross-sectional view schematically illustrating a configuration of a third glass substrate with a thin film
  • FIG. 6 is a cross-sectional view schematically illustrating an example of infrared reflecting glass
  • FIG. 7 is a cross-sectional view schematically illustrating an example of visible light anti-reflection glass
  • FIG. 8 is a cross-sectional view schematically illustrating an example of Low-E glass
  • FIG. 9 is a cross-sectional view schematically illustrating another example of Low-E glass.
  • FIG. 10 is a chart illustrating an FTIR measurement result in a sample (Sample 1) according to Example 1;
  • FIG. 11 is a chart illustrating an FTIR measurement result in a sample (Sample 2) according to Example 2;
  • FIG. 12 is a chart illustrating an FTIR measurement result in a sample (Sample 3) according to Example 3;
  • FIG. 13 is a chart illustrating an FTIR measurement result in a sample (Sample 4) according to Example 4;
  • FIG. 14 is a chart illustrating an FTIR measurement result in a sample (Sample 5) according to Comparative Example 1;
  • FIG. 15 is a chart illustrating an FTIR measurement result in a sample (Sample 6) according to Comparative Example 2;
  • FIG. 16 is a graph illustrating the relationship between the integrated values of a peak due to OH groups and the haze values after heat treatment obtained in Samples 1 through 6.
  • high-speed low-temperature CVD process As described above, recently, a study has been made in particular of the technique of depositing a film of a target substance onto a glass substrate at high speed by a CVD process at low temperatures (hereinafter referred to as “high-speed low-temperature CVD process”).
  • the inventors of the present invention have found a problem in that a layer deposited by such a “high-speed low-temperature CVD process” has a relatively poor heat resistance. For example, it has been observed that a large number of cracks are generated in the SiO 2 film when a glass substrate having the SiO 2 film deposited by the method illustrated in Non-Patent Document 1 described above is heated to approximately 650° C. to 750° C.
  • a method of producing a glass substrate having a layer with relatively good heat resistance formed on its surface by the low-temperature CVD process is provided.
  • a glass substrate having a layer with relatively good heat resistance formed on its surface by the low-temperature CVD process is provided.
  • a method of producing a glass substrate having a first layer formed on its surface by low-temperature CVD includes (1) the step of preparing a glass substrate and (2) the step of forming a first layer on the glass substrate by the low-temperature CVD, where, in the glass substrate after the step (2), an integrated value after a baseline correction in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 in a peak due to OH groups obtained by an FTIR measurement on the first layer is 9.0 or less, and the C content of the first layer is 1.64 at % or less.
  • the “low-temperature CVD process (low-temperature CVD)” means CVD processes according to which a film deposition process is performed under a condition at relatively low substrate temperatures such as 100° C. or less, unlike high-temperature CVD processes such as thermal CVD processes.
  • Examples of the “low-temperature CVD process (low-temperature CVD)” include plasma-enhanced CVD (PECVD) processes.
  • a large increase in substrate temperature may result during pre-processing of a substrate before a CVD process and the CVD process.
  • Such a case as well is included in the “low-temperature CVD process (low-temperature CVD)” as long as a “positive” heating process up to temperatures exceeding 400° C. is not included.
  • high-speed low-temperature CVD process As described above, a study has been made of the technique of depositing a film of a target substance at high speed by the low-temperature CVD process (hereinafter referred to as “high-speed low-temperature CVD process”). As described below, however, there is a problem in that normally, films deposited by such a “high-speed low-temperature CVD process” have relatively poor heat resistance.
  • the inventors of the present application have found that in a glass substrate on which a thin film-like layer is formed by the low-temperature CVD process, there is a correlation between the area of a peak due to OH groups obtained by FTIR spectroscopy on the layer and the heat resistance of the layer.
  • the FTIR absorbance of the layer is measured by performing an FTIR spectroscopy measurement on a glass substrate on which a film is deposited and a glass substrate of the same kind on which no film is deposited and taking a difference between their respective absorbances.
  • the inventors of the present application have found that it is possible to obtain a glass substrate on which a layer having good heat resistance is formed when the layer is formed in such a manner as to make the peak area due to OH groups have a predetermined value or less, thus arriving at the present invention.
  • the glass substrate with a thin film produced by the method according to the present invention is characterized in that the integrated value (after a baseline correction) of a peak due to OH groups in the wavenumber range of 2600 cm ⁇ to 3800 cm ⁇ 1 obtained by an FTIR measurement on the thin film is controlled to 9.0 or less. That is, according to the method of producing a glass substrate with a thin film according to the present invention, the content of OH groups contained in the thin film is significantly controlled.
  • the glass substrate with a thin film produced by the method according to the present invention is characterized in that the content of C (carbon) contained in the first layer is controlled to 1.64 at % or less (normally, C (carbon) is mixed into the thin film from the precursor side).
  • the effect is attained that the heat resistance of the glass substrate with a thin film is significantly improved.
  • FIGS. 1A through 1D schematically illustrate how a SiO 2 thin film deposited on a glass substrate by the conventional low-temperature CVD process changes when being subjected to a heat treatment.
  • FIG. 1A illustrates a state before a glass substrate 110 with a SiO 2 thin film is heated.
  • a SiO 2 thin film 120 deposited by the low-temperature CVD process is placed over the glass substrate 110 .
  • an organometallic compound gas of tetramethyldisiloxane or the like is used as a source gas.
  • the film deposition temperature is relatively low (for example, approximately 20° C. to 100° C.) by the low-temperature CVD process, it is assumed that OH groups 125 originating from the organometallic compound gas that is a precursor are captured into the deposited SiO 2 thin film 120 .
  • OH groups 125 originating from the organometallic compound gas that is a precursor are captured into the deposited SiO 2 thin film 120 .
  • the SiO 2 thin film 120 is deposited by a high-speed film deposition process, a large amount of OH groups 125 may be captured into the SiO 2 thin film 120 as a result of an increase in the amount of an unreacted precursor.
  • the glass substrate 110 with the SiO 2 thin film 120 is still heated. Therefore, the holes 130 formed in the SiO 2 thin film 120 are reduced with progress in the sintering and densification of the SiO 2 thin film 120 , so as to disappear. As indicated by arrows A of FIG. 1C , because the volume of the SiO 2 thin film 120 is reduced by the densification, the SiO 2 thin film 120 becomes smaller in size than the glass substrate 110 .
  • the glass substrate 110 expands because of heating. That is, as illustrated in FIG. 1C , the glass substrate 110 expands to extend in the directions of arrows B during heating. Because of such expansion of the glass substrate 110 in the directions of arrows B, tensile forces are also applied to the densified SiO 2 thin film 120 in the directions of arrows B. This causes microscopic or macroscopic breakage in the densified SiO 2 thin film 120 .
  • defects such as cracks 140 are assumed to be formed in the densified SiO 2 thin film 120 as illustrated in FIG. 1D .
  • the content of OH groups contained in a thin film deposited by the low-temperature CVD process is significantly controlled. Therefore, in the glass substrate with a thin film produced by the method according to the present invention, the reaction of OH groups to change to water is less likely to occur at the time of performing heat treatment. Furthermore, because the amount of water discharged outside is reduced, the number of holes formed in the thin film during heat treatment is reduced, so that the thin film is less likely to be densified. It is assumed that as a result, defects such as cracks are less likely to be caused in the thin film even when heat treatment is performed, so that the heat resistance of the glass substrate with a thin film improves.
  • FIGS. 1A through 1D The behavior illustrated in FIGS. 1A through 1D is merely a model thought up from experimental results by the inventors of the present application at this point. Accordingly, it is necessary to note that the heat resistance of the glass substrate with a thin film produced by the method according to the present invention may have been improved by other mechanisms.
  • a C component originating from a precursor when, for example, a C component originating from a precursor is present in the thin film, it is highly likely that such a C component is present, being attached to H atoms like, for example, a —CH 3 group. Accordingly, when such a C component originating from a precursor is present in the first layer, the C component becomes moisture and carbon dioxide at the time of heat treatment so as to be removed from inside the thin film like in the above-described case of OH groups. Furthermore, resultant holes are combined to densify the thin film. It is assumed that as a result, defects such as cracks are more likely to be caused in the thin film after heat treatment.
  • the glass substrate with a thin film produced by the method according to the present invention is characterized in that the content of C (carbon) contained in the first layer is controlled to 1.64 at % or less. Therefore, in the glass substrate with a thin film produced by the method according to the present invention, a phenomenon as described above is less likely to occur, so that the heat resistance of the thin film improves.
  • FIG. 2 is a flowchart schematically illustrating one example of the method of producing a glass substrate with a thin film according to the present invention.
  • one example of the method of producing a glass substrate with a thin film according to the present invention includes (1) the step (step S 110 ) of preparing a glass substrate and (2) the step (step S 120 ) of forming a first layer on the glass substrate by a low-temperature CVD process, where in the obtained glass substrate, an integrated value after a baseline correction in a wavenumber range of 2600 cm ⁇ to 3800 cm ⁇ 1 in a peak due to OH groups obtained by an FTIR measurement on the first layer is 9.0 or less and the C content of the first layer is 1.64 at % or less.
  • an integrated value after a baseline correction means an integrated value after correcting a baseline in the raw measurement data obtained by an FTIR measurement in the above-described wavenumber range.
  • a glass substrate on which a film is to be deposited is prepared.
  • the size and material of the glass substrate are not limited in particular.
  • the glass substrate may be, for example, soda-lime glass, alkali-free glass or the like.
  • the production method of a glass substrate is not limited in particular.
  • the glass substrate may be produced by a conventionally known common method such as a float process.
  • a first layer is formed on the glass substrate by the low-temperature CVD.
  • the low-temperature CVD may be, for example, a plasma-enhanced CVD (PECVD) process or the like.
  • a plasma gas may be, for example, oxygen gas.
  • the glass substrate prepared at step S 110 described above is placed in a film deposition chamber. Normally, when the first layer is formed by the low-temperature CVD process, a source gas that serves as the material of the first layer is supplied into the film deposition chamber.
  • the inside of the film deposition chamber may be either a normal pressure environment or a reduced pressure environment.
  • a plasma-enhanced CVD (PECVD) process the inside of the film deposition chamber is caused to be a reduced pressure environment by depressurization.
  • PECVD plasma-enhanced CVD
  • the deposited first layer is not limited to a particular kind.
  • the first layer may be, for example, oxide, nitride and/or oxynitride.
  • oxides include SiO 2 , TiO 2 , ZnO, SnO and/or Al 2 O 3 .
  • nitrides include Si 3 N 4 , TiN and AlN.
  • oxynitrides include SiON and TiON.
  • the source gas may contain, for example, an organic metal precursor.
  • the organic metal precursor may have, for example, a siloxane bond and/or an alkoxide bond. Furthermore, the organic metal precursor may contain at least one component selected from the group consisting of a —CH 3 group, a —OH group, and a —H group. Furthermore, the organic metal precursor may contain at least one component selected from the group consisting of Si, Ti, Zn, Sn and Al. In this case, it is possible to deposit films of oxides, nitrides and oxynitrides of silicon, titanium, zinc, tin and aluminum.
  • the film deposition process is performed so that an integrated value after a baseline correction in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 in a peak due to OH groups obtained by an FTIR measurement on the first layer is 9.0 or less.
  • Such control of the amount of OH groups may be performed relatively easily by, for example, controlling the amount of a precursor supplied at the time of forming the first layer to be in a predetermined range.
  • SiO 2 thin film from organic metal precursors such as tetramethyldisiloxane and/or hexamethyldisiloxane
  • the integrated value after a baseline correction in a wavelength range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 in a peak due to OH groups is preferably 7.0 or less and more preferably 5.5 or less.
  • the film deposition process is performed so that the C (carbon) content of the first layer is 1.64 at % or less.
  • C may be detected in the deposited first layer as an impurity.
  • the content of C originating from such an impurity is expected to be not more than approximately 3.2 ppm. Accordingly, the above-described C (carbon) content condition (C ⁇ 1.64 at %) is satisfied as long as a material containing a C component, such as an organic metal precursor, is not used as a material at the time of forming the first layer.
  • the content of C originating from a precursor is more preferably 1 at % or less.
  • the C content of the first layer may be measured by ESCA. That is, normally, the glass substrate itself contains no C. Therefore, the value obtained through the measurement result of an ESCA analysis of the whole glass substrate with a thin film may be understood as the C content of the first layer.
  • FIG. 3 illustrates a schematic cross-sectional view of a glass substrate with a thin film according to the present invention.
  • a glass substrate with a thin film 300 includes a glass substrate 310 and a first layer 320 formed on a surface 312 of the glass substrate 310 .
  • the glass substrate 310 is not limited to a particular kind.
  • the glass substrate 310 may be, for example, soda-lime glass, alkali-free glass or the like.
  • the first layer 320 is formed by the low-temperature CVD process such as PECVD.
  • the material of the first layer 320 is not limited in particular.
  • the thin film material may be, for example, oxide, nitride and/or oxynitride.
  • oxides include SiO 2 , TiO 2 , ZnO, SnO and Al 2 O 3 .
  • nitrides include Si 3 N 4 , TiN and AlN.
  • oxynitrides include SiON and TiON.
  • the glass substrate with a thin film 300 is characterized in that an integrated value after a baseline correction in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 in a peak due to OH groups obtained by an FTIR measurement on the first layer 320 is 9.0 or less.
  • This integrated value is preferably 7.0 or less and more preferably 5.5 or less.
  • the content of C originating from a precursor contained in the first layer 320 is controlled to 1.64 at % or less.
  • the content of C contained in the first layer 320 is preferably 1 at % or less.
  • the glass substrate with a thin film 300 having such characteristics is characterized in that defects such as cracks are less likely to be caused in the first layer 320 , that is, the heat resistance is significantly high, because the densification of the first layer 320 due to removal of OH groups is less likely to occur at the time of heat treatment.
  • the glass substrate with a thin film 300 according to the present invention has an extremely low haze value, for example, a haze value of 0.2% or less, even after being retained at 650° C. for 10 minutes or more.
  • the glass substrate with a thin film 300 according to the present invention may be significantly applied in usage in which application of heat treatment follows.
  • the thickness of the first layer 320 is not limited in particular.
  • the thickness of the first layer 320 may be, for example, in a range of 5 nm to 1000 nm.
  • multiple layers may be formed on a surface of a glass substrate with a thin film.
  • FIG. 4 schematically illustrates a configuration of a second glass substrate with a thin film according to the present invention.
  • a second glass substrate with a thin film 400 includes a glass substrate 410 , a first layer 420 placed on a surface 412 of the glass substrate 410 , and a second layer 430 placed on the first layer 420 .
  • the glass substrate 410 may be a glass substrate like the above-described glass substrate 310 illustrated in FIG. 3 .
  • the first layer 420 is formed by the low-temperature CVD process such as PECVD. Furthermore, the second layer 430 as well is formed by the low-temperature CVD process such as PECVD. The material of the first layer 420 may be different from that of the second layer 430 . Each of the layers 420 and 430 may have a thickness in a range of 5 nm to 1000 nm.
  • the glass substrate with a thin film 400 is characterized in that an integrated value after a baseline correction in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ in a peak due to OH groups obtained by an FTIR measurement on the first layer 420 and the second layer 430 is 9.0 or less. That is, in the second glass substrate with a thin film 400 , the total amount of the OH groups contained in the first layer 420 and the second layer 430 is significantly controlled.
  • the total content of C originating from a precursor contained in the first layer 420 and the second layer 430 is controlled to 1.64 at % or less.
  • the second glass substrate with a thin film 400 having such characteristics as well, it is possible to obtain the same effect as that of the above-described glass substrate with a thin film 300 , that is, good heat resistance, because the densification of the first layer 420 and the second layer 430 due to removal of OH groups is less likely to occur at the time of heat treatment.
  • the second glass substrate with a thin film 400 it is difficult to understand the content of C originating from a precursor contained in each of the first layer 420 and the second layer 430 .
  • the glass substrate itself normally contains no C
  • the value obtained through the measurement result of an ESCA analysis of the whole glass substrate with a thin film 400 may be understood as the total content of C contained in the first layer 420 and the second layer 430 .
  • this total C content it is possible to increase the heat resistance of the second glass substrate with a thin film 400 .
  • each of the first layer 420 and the second layer 430 is a layer formed by the low-temperature CVD process.
  • one of the first layer 420 and the second layer 430 may be a layer formed by a method other than the low-temperature CVD process.
  • Methods other than the low-temperature CVD process may be, but are not limited to, for example, physical vapor deposition such as sputtering and non-low-temperature CVD processes such as thermal CVD.
  • the second layer 430 when the second layer 430 is a layer formed by a method other than the low-temperature CVD process, it is considered that the second layer 430 hardly contains OH groups. In other words, it is considered that the peak due to OH groups obtained by an FTIR measurement on the first layer 420 and the second layer 430 originates from the first layer 420 .
  • the second layer 430 hardly contains a C component. Therefore, the value of the amount of C obtained through the measurement result may be presumed to be the amount of the C component contained in the first layer 420 .
  • the second glass substrate with a thin film 400 having such a configuration, it is possible to increase the heat resistance of the glass substrate with a thin film by controlling an integrated value after a baseline correction in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 in a peak due to OH groups obtained by an FTIR measurement on the first layer 420 and the second layer 430 to be 9.0 or less and by controlling the measured amount of a C component to be 1.64 at % or less.
  • FIG. 5 schematically illustrates a configuration of a third glass substrate with a thin film according to the present invention.
  • a third glass substrate with a thin film 500 includes a glass substrate 510 , a first layer 520 placed on a surface 512 of the glass substrate 510 , a second layer 530 placed on the first layer 520 , and a third layer 540 placed on the second layer 530 .
  • the glass substrate 510 may be a glass substrate like the above-described glass substrate 310 illustrated in FIG. 3 and/or glass substrate 410 illustrated in FIG. 4 .
  • the first layer 520 is formed by the low-temperature CVD process such as PECVD. Furthermore, the third layer 540 also is formed by the low-temperature CVD process. The first layer 520 and the third layer 540 may be of the same material or different materials. On the other hand, the second layer 530 is formed by a non-low-temperature CVD process.
  • Each of the first layer 520 and the third layer 540 may have a thickness in a range of 5 nm to 1000 nm. Furthermore, the second layer 530 may have a thickness in a range of 5 nm to 1000 nm.
  • the glass substrate with a thin film 500 is characterized in that an integrated value after a baseline correction in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 in a peak due to OH groups obtained by an FTIR measurement on the first layer 520 through the third layer 540 is 9.0 or less.
  • the total content of C originating from a precursor contained in the first layer 520 and the third layer 540 is controlled to 1.64 at % or less.
  • the second layer 530 hardly contains OH groups and a C component originating from a precursor.
  • the peak due to OH groups obtained by an FTIR measurement on the first layer 520 through the third layer 540 originates from the first layer 520 and the third layer 540 .
  • the total amount of the OH groups contained in the first layer 520 and the third layer 540 formed by the low-temperature CVD process and the total amount of C contained in both layers are significantly controlled.
  • the densification of the first layer 520 and the third layer 530 due to removal of OH groups is less likely to occur at the time of heat treatment. Accordingly, it will be clear that according to the third glass substrate with a thin film 500 as well, it is possible to obtain the same effect as that of the above-described glass substrates with a thin film 300 and 400 , that is, good heat resistance.
  • the configuration of the third glass substrate with a thin film 500 is not limited to this.
  • the first layer 520 alone may be a layer formed by the low-temperature CVD process and the second layer 530 and the third layer 540 may be layers formed by a non-low-temperature CVD process.
  • the second layer 530 alone may be a layer formed by the low-temperature CVD process and the first layer 520 and the third layer 540 may be layers formed by a non-low-temperature CVD process.
  • the third layer 540 alone may be a layer formed by the low-temperature CVD process and the first layer 520 and the second layer 530 may be layers formed by a non-low-temperature CVD process.
  • all of the first layer 520 through the third layer 540 may be layers formed by the low-temperature CVD process.
  • the number of layers is not limited to three, and the number of layers may be four or more.
  • FIG. 6 schematically illustrates a cross-sectional view of infrared reflecting glass.
  • infrared reflecting glass 600 includes a glass substrate 610 and a laminated body 620 of multiple dielectric layers placed on this glass substrate 610 .
  • the laminated body 620 of dielectric layers is formed by laminating, from the side closer to the glass substrate 610 , a first dielectric layer 630 , a second dielectric layer 640 , a third dielectric layer 650 , a fourth dielectric layer 660 , and a fifth dielectric layer 670 .
  • the first dielectric layer 630 has a first refractive index n 1
  • the second dielectric layer 640 has a second refractive index n 2
  • the third dielectric layer 650 has a third refractive index n 3
  • the fourth dielectric layer 660 has a fourth refractive index n 4
  • the fifth dielectric layer 670 has a fifth refractive index n 5 .
  • the first refractive index n 1 of the first dielectric layer 630 is higher than the second refractive index n 2 of the second dielectric layer 640
  • the third refractive index n 3 of the third dielectric layer 650 is higher than the second refractive index n 2 of the second dielectric layer 640 and the fourth refractive index n 4 of the fourth dielectric layer 660
  • the fifth refractive index n 5 of the fifth dielectric layer 670 is higher than the fourth refractive index n 4 of the fourth dielectric layer 660 .
  • the first dielectric layer 630 , the third dielectric layer 650 , and/or the fifth dielectric layer 670 may be, for example, a TiO 2 layer. Furthermore, the second dielectric layer 640 and/or the fourth dielectric layer 660 may be, for example, a SiO 2 layer.
  • the first dielectric layer 630 , the third dielectric layer 650 , and the fifth dielectric layer 670 may be the same layers, and the second dielectric layer 640 and the fourth dielectric layer 660 may be the same layers.
  • the laminated body 620 formed of five layers in total is placed on the glass substrate 610 .
  • the laminated body 620 may have six or more layers.
  • the infrared reflecting glass 600 of such a configuration exhibits high reflectance with respect to the radiation of the infrared region.
  • the infrared reflecting glass 600 includes a glass substrate with a thin film according to the present invention.
  • the glass substrate 610 of the infrared reflecting glass 600 may correspond to the glass substrate 310 of the glass substrate with a thin film 300 according to the present invention illustrated in FIG. 3
  • one of the first dielectric layer 630 through the fifth dielectric layer 670 of the infrared reflecting glass 600 may be the first layer 320 of the glass substrate with a thin film 300 according to the present invention illustrated in FIG. 3 .
  • the glass substrate 610 of the infrared reflecting glass 600 may correspond to the glass substrate 410 of the second glass substrate with a thin film 400 according to the present invention illustrated in FIG. 4
  • successive two layers of the first dielectric layer 630 through the fifth dielectric layer 670 of the infrared reflecting glass 600 may correspond to the first layer 420 and the second layer 430 of the second glass substrate with a thin film 400 illustrated in FIG. 4 .
  • the glass substrate 610 of the infrared reflecting glass 600 may correspond to the glass substrate 510 of the third glass substrate with a thin film 500 according to the present invention illustrated in FIG. 5
  • successive three layers of the first dielectric layer 630 through the fifth dielectric layer 670 of the infrared reflecting glass 600 may correspond to the first layer 520 through the third layer 540 of the third glass substrate with a thin film 500 illustrated in FIG. 5 .
  • the infrared reflecting glass 600 includes such a glass substrate with a thin film according to the present invention, it is possible to increase the heat resistance of the infrared reflecting glass 600 . Accordingly, it is possible to subject the infrared reflecting glass 600 to heat treatment, for example, for bending.
  • FIG. 7 schematically illustrates a cross-sectional view of visible light anti-reflection glass.
  • visible light anti-reflection glass 700 includes a glass substrate 710 , a first laminated body 730 placed on this glass substrate 710 , and a second laminated body 760 placed on this first laminated body 730 .
  • the first laminated body 730 is formed by laminating a first dielectric layer 740 having a first refractive index n 1 and a second dielectric layer 745 having a second refractive index n 2 in this order.
  • the first refractive index n 1 of the first dielectric layer 740 is higher than the second refractive index n 2 of the second dielectric layer 745 .
  • the first dielectric layer 740 may be, for example, a TiO 2 layer
  • the second dielectric layer 745 may be, for example, a SiO 2 layer.
  • the second laminated body 760 has the same configuration as the first laminated body 730 . That is, the second laminated body 760 is formed by laminating a third dielectric layer 770 having a third refractive index n 3 and a fourth dielectric layer 775 having a fourth refractive index n 4 in this order.
  • the third refractive index n 3 of the third dielectric layer 770 is higher than the fourth refractive index n 4 of the fourth dielectric layer 775 .
  • the third dielectric layer 770 may be, for example, a TiO 2 layer
  • the fourth dielectric layer 775 may be, for example, a SiO 2 layer.
  • the first laminated body 730 and the second laminated body 760 may have the same configuration.
  • the two laminated bodies 730 and 760 are placed on the glass substrate 710 .
  • the visible light anti-reflection glass 700 of such a configuration exhibits low reflectance with respect to visible light.
  • the visible light anti-reflection glass 700 includes a glass substrate with a thin film according to the present invention.
  • the glass substrate 710 of the visible light anti-reflection glass 700 may correspond to the glass substrate 310 of the glass substrate with a thin film 300 according to the present invention illustrated in FIG. 3
  • one of the first dielectric layer 740 through the fourth dielectric layer 775 of the visible light anti-reflection glass 700 may be the first layer 320 of the glass substrate with a thin film 300 according to the present invention illustrated in FIG. 3 .
  • the glass substrate 710 of the visible light anti-reflection glass 700 may correspond to the glass substrate 410 of the second glass substrate with a thin film 400 according to the present invention illustrated in FIG. 4
  • two of the first dielectric layer 740 through the fourth dielectric layer 775 of the visible light anti-reflection glass 700 may correspond to the first layer 420 and the second layer 430 of the second glass substrate with a thin film 400 illustrated in FIG. 4 .
  • the glass substrate 710 of the visible light anti-reflection glass 700 may correspond to the glass substrate 510 of the third glass substrate with a thin film 500 according to the present invention illustrated in FIG. 5
  • three of the first dielectric layer 740 through the fourth dielectric layer 775 of the visible light anti-reflection glass 700 may correspond to the first layer 520 through the third layer 540 of the third glass substrate with a thin film 500 illustrated in FIG. 5 .
  • the visible light anti-reflection glass 700 includes such a glass substrate with a thin film according to the present invention, it is possible to increase the heat resistance of the visible light anti-reflection glass 700 . Accordingly, it is possible to subject the visible light anti-reflection glass 700 to heat treatment, for example, for bending.
  • FIG. 8 schematically illustrates a cross-sectional view of Low-E glass.
  • Low-E glass 800 includes a glass substrate 810 , a silver layer 830 , and a top layer 850 placed at the top of the Low-E glass.
  • the silver layer 830 is interposed between a lower first dielectric layer 820 and an upper second dielectric layer 840 .
  • the top layer 850 is formed of a layer of a dielectric such as SiO 2 , and has the function of controlling reflection of visible light.
  • Low-E glass 800 of such a configuration because radiation from the glass is controlled, it is possible to obtain high heat shielding and heat insulation characteristics.
  • the Low-E glass 800 includes a glass substrate with a thin film according to the present invention.
  • the glass substrate 810 and the top layer 850 of the Low-E glass 800 may be the glass substrate 310 and the first layer 320 , respectively, of the glass substrate with a thin film 300 according to the present invention illustrated in FIG. 3 .
  • the glass substrate 810 and the top layer 850 of the Low-E glass 800 may be the glass substrate 410 and the second layer 430 , respectively, of the second glass substrate with a thin film 400 according to the present invention illustrated in FIG. 4 .
  • the first layer 420 of the second glass substrate with a thin film 400 may correspond to the first dielectric layer 820 or the second dielectric layer 840 .
  • the glass substrate 810 and the top layer 850 of the Low-E glass 800 may be the glass substrate 510 and the third layer 540 , respectively, of the third glass substrate with a thin film 500 according to the present invention illustrated in FIG. 5 .
  • the first layer 520 of the third glass substrate with a thin film 500 may correspond to the first dielectric layer 820
  • the second layer 530 of the third glass substrate with a thin film 500 may correspond to the second dielectric layer 840 .
  • the Low-E glass 800 includes such a glass substrate with a thin film according to the present invention, it is possible to increase the heat resistance of the Low-E glass 800 . Accordingly, it is possible to subject the Low-E glass 800 to heat treatment, for example, for bending.
  • the Low-E glass 800 of the configuration illustrated in FIG. 8 is a mere example, and the Low-E glass may have other configurations.
  • FIG. 9 schematically illustrates a cross-sectional view of Low-E glass of another configuration.
  • this Low-E glass 900 is formed by laminating a glass substrate 910 , a bottom layer 920 placed on the glass substrate 910 , a first dielectric layer 930 placed on the bottom layer 920 , a silver layer 940 placed on the first dielectric layer 930 , and a second dielectric layer 950 placed on the silver layer 940 in this order.
  • the bottom layer 920 has the function of controlling diffusion of an alkali metal from the glass substrate 910 toward the silver layer 940 .
  • the bottom layer 920 is formed of a layer of a dielectric such as SiO 2 .
  • the Low-E glass 900 includes a glass substrate with a thin film according to the present invention.
  • the glass substrate 910 and the bottom layer 920 of the Low-E glass 900 may be the glass substrate 310 and the first layer 320 , respectively, of the glass substrate with a thin film 300 according to the present invention illustrated in FIG. 3 .
  • the Low-E glass 900 includes such a glass substrate with a thin film according to the present invention, it is possible to increase the heat resistance of the Low-E glass 900 . Accordingly, it is possible to subject the Low-E glass 900 to heat treatment, for example, for bending.
  • the glass substrate 910 and the bottom layer 920 of the Low-E glass 900 may be the glass substrate 410 and the first layer 420 , respectively, of the second glass substrate with a thin film 400 according to the present invention illustrated in FIG. 4 .
  • the second layer 430 of the second glass substrate with a thin film 400 may correspond to the first dielectric layer 930 or the second dielectric layer 950 .
  • the glass substrate 910 and the bottom layer 920 of the Low-E glass 900 may be the glass substrate 510 and the first layer 520 , respectively, of the third glass substrate with a thin film 500 according to the present invention illustrated in FIG. 5 .
  • the second layer 530 of the third glass substrate with a thin film 500 may correspond to the first dielectric layer 930
  • the third layer 540 of the third glass substrate with a thin film 500 may correspond to the second dielectric layer 950 .
  • Sample 1 was made by depositing a SiO 2 thin film on a substrate and its characteristics were evaluated in the following manner.
  • a PECVD apparatus was used to deposit a SiO 2 thin film.
  • the plasma gas was oxygen gas (of a flow rate of 2000 sccm/m), and the plasma power was 20 kW/m.
  • Tetramethyldisiloxane was used as a source gas.
  • the flow rate of the source gas was 250 sccm/m.
  • a soda-lime glass substrate of 300 mm in length, 300 mm in width, and 2 mm in thickness was used as the substrate.
  • the substrate was not heated at the time of film deposition.
  • a SiO 2 thin film of approximately 226 nm in thickness was formed on the substrate by the PECVD process.
  • the deposition rate calculated from the deposition time and the thickness of the SiO 2 thin film was 226 nm ⁇ m/min.
  • Example 1 the plasma power, the flow rate of a precursor, the flow rate of an oxygen gas for plasma, the deposition rate, and the thickness of a SiO 2 thin film at the time of making Sample 1 are shown together.
  • an FTIR spectroscopy measurement was performed on the SiO 2 thin film of obtained Sample 1.
  • the FTIR absorbance of the SiO 2 thin film was measured by performing the FTIR spectroscopy measurement on Sample 1 and the same kind of glass substrate as used for Sample 1 and taking a difference between their respective absorbances.
  • An FTIR spectrometer (Nicolet 6700 FT-IR, manufactured by Thermo Scientific Inc.) was used for the FTIR spectroscopy measurement.
  • FIG. 10 illustrates an enlarged view of part of the result of the FTIR measurement.
  • This drawing illustrates data after correction of the baseline of the measurement result.
  • the baseline correction was performed by the automatic baseline correction of software (OMNIC software, manufactured by Thermo Scientific Inc.) accompanied to the FTIR spectrometer.
  • OMNIC software manufactured by Thermo Scientific Inc.
  • an operation to remove inclination or undulation generated in a spectral waveform because of the effect of the light scattering of a sample and the like by approximating the inclination or undulation by a polynomial curve is performed.
  • the C content was measured by ESCA instrument (PHI 5000 VersaProbe II, manufactured by ULVAC-PHI, INCORPORATED).
  • the content of C contained in the SiO 2 thin film was 0.55 at %.
  • haze is one of the indices of the transparency of a sample, and is used in expressing the turbidity (cloudiness) of a sample.
  • turbidity cloudiness
  • the turbidity of the sample increases so as to increase a haze value. Accordingly, it is possible to evaluate the heat resistance of the sample by measuring a haze value.
  • Heat treatment was performed by retaining Sample 1 at 650° C. and at 700° C. for 17 minutes in the atmosphere. Furthermore, haze values of Sample 1 were measured with a haze meter (Haze Meter HZ-2, manufactured by Suga Test Instruments Co., Ltd.).
  • the haze value of Sample 1 by the heat treatment at 650° C. was 0.16, and it was found that the turbidity of Sample 1 after the heat treatment at 650° C. was extremely low. Furthermore, abnormalities such as cracks were not recognized in particular in the SiO 2 thin film of Sample 1 in a visual observation. From this result, it was determined that Sample 1 has extremely good heat resistance with defects such as cracks being hardly caused after the heat treatment at 650° C.
  • the haze value by the heat treatment at 700° C. was 1.01, and it was found that the turbidity of Sample 1 after the heat treatment at 700° C. was low. Thus, it was determined that Sample 1 has good heat resistance even after the heat treatment at 700° C.
  • Example 1 the integrated value of a peak due to OH groups, the haze values after heat treatment at 650° C. and 700° C., and the C content are shown together.
  • Sample 2 was made by depositing a SiO 2 thin film on a substrate and its characteristics were evaluated in the same manner as in Example 1. In this Example 2, however, the plasma power was 25 kW/m, the deposition rate was 221 nm ⁇ m/min, and the thickness of the SiO 2 thin film was 221 nm. The other conditions are the same as in the case of Example 1.
  • FIG. 11 illustrates an enlarged view of the result of an FTIR measurement on the SiO 2 thin film of Sample 2 (after a baseline correction).
  • the integrated value of a peak in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 m was determined, and the peak integrated value was 7.7.
  • the C content was 0.21 at %.
  • the haze value of Sample 2 after heat treatment at 650° C. was 0.16. Furthermore, abnormalities such as cracks were not recognized in particular in the SiO 2 thin film of Sample 2 in a visual observation. From this result, it was determined that Sample 2 has extremely good heat resistance with defects such as cracks being hardly caused after the heat treatment at 650° C. Furthermore, the haze value of Sample 2 heat-treated at 700° C. was 0.55, and it was found that the turbidity of Sample 2 after the heat treatment at 700° C. was low. Thus, it was determined that Sample 2 has good heat resistance even after the heat treatment at 700° C.
  • Example 2 In the row of “Example 2” of Table 1 described above, the typical deposition conditions, the integrated value of a peak due to OH groups, the haze values after heat treatment at 650° C. and 700° C., and the C content of Sample 2 are shown together.
  • Sample 3 was made by depositing a SiO 2 thin film on a substrate and its characteristics were evaluated in the same manner as in Example 1.
  • the plasma power was 25 kW/m
  • the flow rate of a precursor was 187.5 sccm/m
  • the flow rate of an oxygen plasma gas was 1500 sccm/m
  • the deposition rate was 151 nm ⁇ m/min
  • the thickness of the SiO 2 thin film was 216 nm.
  • the other conditions are the same as in the case of Example 1.
  • FIG. 12 illustrates an enlarged view of the result of an FTIR measurement on the SiO 2 thin film of Sample 3 (after a baseline correction).
  • the integrated value of a peak in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 was determined, and the peak integrated value was 7.0.
  • the C content was 0.24 at %.
  • the haze value of Sample 3 after heat treatment at 650° C. was 0.10. Furthermore, abnormalities such as cracks were not recognized in particular in the SiO 2 thin film of Sample 3 in a visual observation. From this result, it was determined that Sample 3 has extremely good heat resistance with defects such as cracks being hardly caused after the heat treatment at 650° C. Furthermore, the haze value of Sample 3 heat-treated at 700° C. was 0.20, and it was found that the turbidity of Sample 3 after the heat treatment at 700° C. also was extremely low. Furthermore, abnormalities such as cracks were not recognized in particular in the SiO 2 thin film of Sample 3 in a visual observation. From this result, it was determined that Sample 3 has extremely good heat resistance with defects such as cracks being hardly caused even after the heat treatment at 700° C.
  • Example 3 In the row of “Example 3” of Table 1 described above, the typical deposition conditions, the integrated value of a peak due to OH groups, the haze values after heat treatment at 650° C. and 700° C., and the C content of Sample 3 are shown together.
  • Sample 4 was made by depositing a SiO 2 thin film on a substrate and its characteristics were evaluated in the same manner as in Example 1.
  • the plasma power was 25 kW/m
  • the flow rate of a precursor was 125 sccm/m
  • the flow rate of an oxygen plasma gas was 1000 sccm/m
  • the deposition rate was 90 nm ⁇ m/min
  • the thickness of the SiO 2 thin film was 224 nm.
  • the other conditions are the same as in the case of Example 1.
  • FIG. 13 illustrates an enlarged view of the result of an FTIR measurement on the SiO 2 thin film of Sample 4 (after a baseline correction).
  • the integrated value of a peak in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 was determined, and the peak integrated value was 5.1.
  • the C content was 0.24 at %.
  • the haze value of Sample 4 after heat treatment at 650° C. was 0.06. Furthermore, abnormalities such as cracks were not recognized in particular in the SiO 2 thin film of Sample 4 in a visual observation. From this result, it was determined that Sample 4 has extremely good heat resistance with defects such as cracks being hardly caused after the heat treatment at 650° C. Furthermore, the haze value of Sample 4 in heat treatment at 700° C. was 0.13, and it was found that the turbidity of Sample 4 after the heat treatment at 700° C. also was extremely low. Furthermore, abnormalities such as cracks were not recognized in particular in the SiO 2 thin film of Sample 4 in a visual observation. From this result, it was determined that Sample 4 has extremely good heat resistance with defects such as cracks being hardly caused even after the heat treatment at 700° C.
  • Example 4 In the row of “Example 4” of Table 1 described above, the typical deposition conditions, the integrated value of a peak due to OH groups, the haze values after heat treatment at 650° C. and 700° C., and the C content of Sample 4 are shown together.
  • Sample 5 was made by depositing a SiO 2 thin film on a substrate and its characteristics were evaluated in the same manner as in Example 1.
  • the plasma power was 10 kW/m
  • the flow rate of a precursor was 100 sccm/m
  • the flow rate of an oxygen plasma gas was 800 sccm/m
  • the deposition rate was 252 nm ⁇ m/min
  • the thickness of the SiO 2 thin film was 252 nm.
  • the other conditions are the same as in the case of Example 1.
  • FIG. 14 illustrates an enlarged view of the result of an FTIR measurement on the SiO 2 thin film of Sample 5 (after a baseline correction).
  • the integrated value of a peak in a wavenumber range of 2600 cm ⁇ 1 to 3800 cm ⁇ 1 was determined, and the peak integrated value was 8.1.
  • the C content was 4.30 at %.
  • the haze values after heat treatment at 650° C. and 700° C. were 0.61 and 1.92, respectively. From this, it was found that the turbidity of Sample 5 after heat treatment markedly increases. Furthermore, in a visual observation, it was recognized that a large number of cracks were caused in the SiO 2 thin film of Sample 5 after the heat treatment at 650° C. and 700° C. From this result, it was determined that Sample 5 does not exhibit good heat resistance.
  • Sample 6 was made by depositing a SiO 2 thin film on a substrate and its characteristics were evaluated in the same manner as in Comparative Example 1.
  • the plasma power was 15 kW/m
  • the deposition rate was 240 nm-m/min
  • the thickness of the SiO 2 thin film was 240 nm.
  • the other conditions are the same as in the case of Comparative Example 1.
  • FIG. 15 illustrates an enlarged view of the result of an FTIR measurement on the SiO 2 thin film of Sample 6 (after a baseline correction).
  • the integrated value of a peak in a wavenumber range of 2600 cm ⁇ to 3800 cm ⁇ 1 was determined, and the peak integrated value was 9.8.
  • the C content was 1.64 at %.
  • the haze values after heat treatment at 650° C. and 700° C. were 0.45 and 1.86, respectively. From this, it was found that the turbidity of Sample 6 after heat treatment is high. Furthermore, in a visual observation, it was recognized that a large number of cracks were caused in the SiO 2 thin film of Sample 6 after the heat treatment at 650° C. and 700° C. From this result, it was determined that Sample 6 does not exhibit good heat resistance.
  • FIG. 16 illustrates the relationship between the integrated values of a peak due to OH groups and the haze values after heat treatment at each of 650° C. and 700° C. obtained in Samples 1 through 6. Sample 5 is not plotted because the C content exceeds 1.64%.
  • the haze values after heat treatment of the samples are kept low values less than 0.2 when the integrated value of a peak due to OH groups is approximately 9.0 or less. From this, it has been determined that the heat resistance of the samples significantly increases when the integrated value of a peak due to OH groups is approximately 9.0 or less.
  • the haze values after heat treatment of the samples are kept low values less than 0.2 when the integrated value of a peak due to OH groups obtained by an FTIR measurement is approximately 0.7 or less. From this, it has been determined that the heat resistance at 700° C. of the samples significantly increases when the integrated value of a peak due to OH groups is approximately 7.0 or less.
  • the present invention may be used for film deposition techniques using CVD processes, and so forth.

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07188930A (ja) * 1993-12-27 1995-07-25 Hoya Corp 化学気相成長法および位相シフトマスクブランクの製造方法
US5821001A (en) * 1996-04-25 1998-10-13 Ppg Industries, Inc. Coated articles
JP2007113031A (ja) * 2005-10-18 2007-05-10 Hitachi Metals Ltd 酸化物膜の形成方法
WO2010098200A1 (fr) * 2009-02-26 2010-09-02 セントラル硝子株式会社 Article à couches multiples

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3291401B2 (ja) * 1994-09-07 2002-06-10 三洋電機株式会社 光起電力装置及び光起電力装置の製造方法
DE19732978C1 (de) * 1997-07-31 1998-11-19 Ver Glaswerke Gmbh Low-E-Schichtsystem auf Glasscheiben mit hoher chemischer und mechanischer Widerstandsfähigkeit
JP2002105641A (ja) 2000-10-03 2002-04-10 Murakami Corp 複合材およびその製造方法
JP2002348145A (ja) * 2001-05-24 2002-12-04 Nippon Sheet Glass Co Ltd 近赤外線遮断ガラス
JP4133353B2 (ja) * 2002-07-26 2008-08-13 株式会社神戸製鋼所 シリコン酸化薄膜またはチタン酸化薄膜の製造方法
JP2006215081A (ja) * 2005-02-01 2006-08-17 Seiko Epson Corp 光学物品及び製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07188930A (ja) * 1993-12-27 1995-07-25 Hoya Corp 化学気相成長法および位相シフトマスクブランクの製造方法
US5821001A (en) * 1996-04-25 1998-10-13 Ppg Industries, Inc. Coated articles
JP2007113031A (ja) * 2005-10-18 2007-05-10 Hitachi Metals Ltd 酸化物膜の形成方法
WO2010098200A1 (fr) * 2009-02-26 2010-09-02 セントラル硝子株式会社 Article à couches multiples

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10654746B2 (en) 2015-12-03 2020-05-19 AGC Inc. Glass plate with antireflection film

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US20180044229A1 (en) 2018-02-15
WO2013176132A1 (fr) 2013-11-28
JPWO2013176132A1 (ja) 2016-01-14
EP2857370A4 (fr) 2015-12-02
EP2857370A1 (fr) 2015-04-08

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