WO2017018393A1 - 銀反射鏡並びにその製造方法及び検査方法 - Google Patents
銀反射鏡並びにその製造方法及び検査方法 Download PDFInfo
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- WO2017018393A1 WO2017018393A1 PCT/JP2016/071784 JP2016071784W WO2017018393A1 WO 2017018393 A1 WO2017018393 A1 WO 2017018393A1 JP 2016071784 W JP2016071784 W JP 2016071784W WO 2017018393 A1 WO2017018393 A1 WO 2017018393A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0808—Mirrors having a single reflecting layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
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- 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
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- 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
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- 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
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- 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
- C23C14/081—Oxides of aluminium, magnesium or beryllium
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- 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
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- 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
- C23C14/10—Glass or silica
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/221—Ion beam deposition
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/225—Oblique incidence of vaporised material on substrate
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/48—Ion implantation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
- G01M11/00—Testing of optical apparatus; Testing structures by optical methods not otherwise provided for
- G01M11/005—Testing of reflective surfaces, e.g. mirrors
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
Definitions
- the present invention relates to a silver reflector that has durability when used in a high-temperature and high-humidity environment and can suppress deformation of an optical surface due to film stress, and a manufacturing method and an inspection method thereof.
- Patent Document 1 discloses a light reflecting mirror in which a reflective film containing silver is formed on the surface of a plastic substrate, the plastic substrate is a thermosetting resin molded product, and the adhesion improving film is Cr, Al. It is formed of 2 O 3 , LaTiO 3 or the like and the reflection increasing layer is composed of Y 2 O 3 , Al 2 O 3 or other plural layers.
- each film constituting the reflective film is formed by vapor deposition using plasma.
- Patent Document 2 discloses a reflecting mirror having a structure in which a film mainly composed of aluminum oxide is directly formed on both sides of a silver film, and both of the films mainly composed of aluminum oxide are aluminum oxide or aluminum oxynitride. What consists of is described. Here, all the films mainly composed of aluminum oxide are formed by sputtering, ion beam assisted deposition, or the like.
- Patent Document 3 discloses a laser having a base material layer, a stress adjustment film formed on the base material layer to deform the base material layer into a convex shape, and a reflective film formed on the stress adjustment film.
- An optical mirror for light is described in which the stress adjusting film contains any of zinc sulfide, cerium oxide, or silicon oxide.
- the stress adjusting film is formed by physical assistance including ions or plasma.
- Patent Document 1 Although the resistance of the reflective film to the environment is mentioned, there is a specific method or a quantitative explanation as to how much high durability can be achieved by what configuration. Absent.
- Patent Document 2 the reflectance is improved by heat treatment at 50 ° C. to 200 ° C. However, for conditions including moisture resistance, only a change in reflectance is measured at a temperature of 70 ° C. and a humidity of 90%. There is no disclosure of a specific method for improving moisture resistance.
- Patent Document 3 the structure of the convex surface is suppressed by a stress adjusting film having a tensile stress that cancels the tensile stress of the Ag film.
- a stress adjusting film having a tensile stress that cancels the tensile stress of the Ag film is disclosed. There is no.
- the present invention has been made in view of the above-described background art, and can maintain high reflection characteristics achieved by using silver even in a high-temperature and high-humidity environment, and can suppress film deformation to a low level to reduce surface deformation of an optical surface.
- An object of the present invention is to provide a silver reflector that can be used.
- Another object of the present invention is to provide a method for producing a silver reflector having high durability and performance and a method for inspecting the same.
- a silver reflecting mirror uses a base adhesion layer, a main silver layer formed on the adhesion layer, and an increased reflection layer formed on the main silver layer as a reflection film.
- the main silver layer is formed of either silver or an alloy mainly containing silver, and the film stress after the formation of the reflective film is in the range from +100 MPa to ⁇ 100 MPa,
- the film stress after the film is put in a high temperature dry environment of 110 ° C. for 24 hours is in the range from +100 MPa to ⁇ 100 MPa, and the reflective film after being put in the high temperature dry environment of 110 ° C. is high temperature and high humidity of 85 ° C. and 85% RH.
- the film stress after being put into the environment for 24 hours is in the range from +100 MPa to -100 MPa, and the film stress value after being put into the high temperature dry environment of 110 ° C. for 24 hours and the high temperature and humidity environment of 85 ° C. and 85% RH After 24 hours
- the absolute value of the variation between the film stress value is less than or equal to 40 MPa.
- drying in a high temperature drying environment means 20% RH or less.
- the film stress after film formation is in the range from +100 MPa to ⁇ 100 MPa, but also the film stress after the reflection film is put in a high-temperature dry environment of 110 ° C. for 24 hours, Since the reflective film after being put in a high temperature dry environment at 85 ° C. is in the range of +100 MPa to ⁇ 100 MPa after being put in a high temperature and high humidity environment of 85 ° C. and 85% RH for 24 hours, it is applied to the base material etc. The surface deformation of the optical surface can be suppressed small. Furthermore, the absolute value of the amount of change between the film stress value after being put in a high temperature and dry environment of 110 ° C.
- the film stress value after being put in a high temperature and high humidity environment of 85 ° C. and 85% RH is 40 MPa or less. Therefore, it is considered that the change in the film state due to the entry and exit of moisture accompanying the change in the changing environment is suppressed, and it is considered that shearing stress is less likely to occur at the interface between the reflective film and the base, preventing deterioration such as peeling of the reflective film.
- high reflection characteristics can be maintained even in a hot and humid environment. Specifically, for example, even after undergoing a durability test for 1000 hours in an environment of 85 ° C. and 85% RH, no substantial decrease in reflectivity is observed, and almost no appearance defects such as cracks and film floating occur. .
- a method for inspecting a silver reflecting mirror according to the present invention includes a base adhesive layer, a main silver layer formed on the adhesive layer, and an increased reflection layer formed on the main silver layer.
- the film stress value after the reflection film is put in a high temperature drying environment at 110 ° C. for 24 hours and the reflection film after the reflection film is put in a high temperature drying environment at 110 ° C. for 24 hours It is determined whether or not the absolute value of the change amount between the film stress value and the film stress value after being put in a high-temperature and high-humidity environment at 85 ° C. and 85% RH is 40 MPa or less.
- the film stress after film formation is in the range from +100 MPa to ⁇ 100 MPa, and the stress applied to the substrate or the like is reduced to reduce the surface deformation of the optical surface. It can be confirmed whether or not it is a silver reflecting mirror that can suppress the above. Furthermore, the absolute value of the amount of change between the film stress value after being put in a high temperature and dry environment of 110 ° C. for 24 hours and the film stress value after being put in a high temperature and high humidity environment of 85 ° C. and 85% RH is 40 MPa or less. Whether it is a silver reflector that can prevent deterioration such as peeling of the reflective film due to the entry and exit of moisture due to changes in the changing environment and maintain high reflection characteristics even in a hot and humid environment You can check whether or not.
- a method for producing a silver reflecting mirror according to the present invention includes a base adhesive layer, a main silver layer formed on the adhesive layer, and an increased reflection layer formed on the main silver layer.
- the film stress value after the reflection film was put in a high temperature drying environment of 110 ° C. for 24 hours and the reflection film was put in a high temperature drying environment of 110 ° C. for 24 hours and then the reflection film was 85 ° C. and 85% RH.
- the absolute value of the amount of change between the film stress value after being put in a high-temperature and high-humidity environment for 24 hours is 40 MPa or less.
- the film stress after film formation is in the range from +100 MPa to ⁇ 100 MPa, and the stress applied to the substrate or the like can be reduced to suppress surface deformation of the optical surface. Furthermore, the absolute value of the amount of change between the film stress value after being put in a high temperature and dry environment of 110 ° C. for 24 hours and the film stress value after being put in a high temperature and high humidity environment of 85 ° C. and 85% RH is 40 MPa or less.
- FIG. 2 is a conceptual cross-sectional view illustrating an environmental test apparatus used for inspection or evaluation of the silver reflecting mirror of FIG. 1.
- FIG. 2 is a conceptual cross-sectional view illustrating a film stress measuring device used for evaluation of the silver reflecting mirror of FIG. 1.
- the silver reflecting mirror 10 of the present embodiment includes a flat substrate 20 and a reflective film 30 that is a thin film formed on the substrate 20.
- the substrate 20 is a plate-like member, for example, and has a flat or curved optical surface 21 covered with the reflective film 30.
- the substrate 20 does not have to be light transmissive.
- the substrate 20 is formed of a resin material such as polycarbonate (PC), cycloolefin polymer (COP), acrylic resin (PMMA), or polyethylene terephthalate (PET). You may form with another inorganic material.
- the reflective film 30 includes an adhesion layer 31 formed as a base on the optical surface 21 of the substrate 20, a main silver layer 32 formed on the adhesion layer 31, and an increased reflection layer 33 formed on the main silver layer 32. With. That is, the main silver layer 32 is sandwiched between the adhesion layer 31 and the increased reflection layer 33.
- the adhesion layer 31 is preferably composed of two or more layers. By making the adhesion layer 31 into two or more layers, the effect of blocking water from the substrate 20 can be enhanced.
- the term “two or more layers” means a layer of material having good adhesion to the upper main silver layer 32 and a layer of material having good adhesion to the lower substrate 20.
- the adhesion layer 31 has a single layer configuration, it is necessary to select a material having good adhesion for both the main silver layer 32 and the substrate 20, but in this case, it becomes difficult to control film quality and stress. Furthermore, in order to improve the environmental resistance of the main silver layer 32, the influence of moisture from the substrate 20 must be taken into account.
- the number of layers may be three or more.
- the adhesion layer 31 there are several media for blocking moisture, but one has been found to be preferably a layer mainly composed of aluminum oxide.
- the layer mainly composed of aluminum oxide “Substance M2” or “Substance M3” manufactured by Merck Co., Ltd.
- La 2 O 3 is mixed with aluminum oxide in an amount of about 5 to 10% is used in addition to pure aluminum oxide.
- the present inventor decided to use ion assist to densify the film, aiming to achieve both a moisture blocking effect and a stress adjusting effect.
- the resistance to high temperature and high humidity can be improved by adjusting the film formation conditions such as the ion assist output and the film formation rate in consideration of the correlation with the film stress of the entire layer.
- a layer mainly composed of aluminum oxide formed by using the ion assist method is preferable as the layer constituting the lower side of the adhesion layer 31.
- the layers constituting the upper contact layer 31 a material having good adhesion with the silver, it was found that it is preferable to use a LaTiO 3, CeO 2, Y 2 O 3, SnO 2. Use of these materials facilitates adhesion and facilitates stress adjustment.
- the adhesion layer 31 includes at least one layer mainly composed of aluminum oxide, and the layer mainly composed of aluminum oxide is formed using an ion assist method.
- the film stress of the layer mainly composed of aluminum oxide is compressive stress. Thereby, some moisture can be allowed to pass through the aluminum oxide layer to increase resistance to high-temperature and high-humidity environment, and a certain degree of denseness and strength can be ensured by using compressive stress.
- the specific adhesion layer 31 includes a first layer 31a on the substrate 20 side and a second layer 31b on the main silver layer 32 side. Both layers 31a and 31b have a thickness of about 10 nm to 200 nm, more preferably 20 nm to 100 nm.
- the first layer 31a is a thin film layer that directly adheres to the substrate 20 and has a role of a buffer layer that allows some permeation while blocking moisture, and the second layer 31b is directly connected to the main silver layer 32. It is a thin film layer that has a role of adhering and reliably blocking moisture.
- the first layer 31a on the substrate 20 side is a layer mainly made of aluminum oxide as described above, and is formed using an ion assist method.
- the second layer 31b in direct contact with the main silver layer 32 is a layer formed of a material selected from at least one of LaTiO 3 , CeO 2 , Y 2 O 3 and SnO 2 as described above, and is an ion assist method. Is used to form a film.
- both layers 31a and 31b have an effect of improving adhesion even if the film thickness is 20 nm or less as a whole, if the film thickness is 20 nm or less, the thin film is being grown and sufficient moisture is formed from the continuity of the film.
- the film thickness is preferably 20 nm or more.
- the film thickness is preferably controlled to 100 nm or less.
- the adhesion layer 31 includes at least one adjustment layer related to the film stress and includes two or more layers, one adjustment layer (corresponding to one of the first and second layers 31a and 31b will be described in detail later).
- one adjustment layer corresponding to one of the first and second layers 31a and 31b will be described in detail later.
- the film stress after being put in a high-temperature and high-humidity environment at 85 ° C. and 85% RH is more compressive than the film stress after being put in a high-temperature dry environment at 110 ° C. for 24 hours. It changes in the negative direction.
- one adjustment layer is realized by applying a material with a relatively low density at which the film stress changes in the negative direction (for example, applying an ion assist method and balancing various conditions relating to film formation and ion supply at that time) With the aluminum oxide), it is possible to secure a state that allows a slight drainage of water and to improve resistance to high temperature and humidity.
- the other adjustment layer (corresponding to the other of the first and second layers 31a and 31b) is 85 ° C. against the film stress after being put in a high temperature drying environment of 110 ° C. for 24 hours in a single layer state.
- the film stress after being put in a hot and humid environment of 85% RH for 24 hours changes in the positive direction.
- the other adjustment layer has a high density and can reliably block moisture, and the strength of the adjustment layer itself is increased.
- the first layer 31a is made of a material having a density lower than that of the second layer 31b, and thus allows water to pass therethrough somewhat while blocking water. That is, the first layer 31a has a better water drainage than the second layer 31b, has a function of preventing peeling as a buffer against moisture, and the reflective film 30 for high temperature and humidity environment. Can increase resistance.
- the first layer 31a is an adjustment layer for balancing the film stress and has a relatively weak negative film stress.
- the negative film stress means a state in which a compressive stress is applied, and is intended to extend in the extending direction of the film, and corresponds to a state having a relatively high density with respect to the base material. Furthermore, as the first layer 31a, in a single layer state, with respect to the film stress after being put in a high temperature dry environment with an ambient temperature of 110 ° C. and a relative humidity of 20% RH or less (specifically, substantially zero humidity) for 24 hours.
- the film stress is selected such that the film stress changes in the negative direction after being put in a high-temperature and high-humidity environment with an ambient temperature of 85 ° C. and a relative humidity of 85% RH for 24 hours.
- the first layer 31a has a compressive stress increased by the above-described humidity increase type environmental test, and is determined to have ensured proper drainage or moisture penetration.
- the first layer 31a is desirably combined with the second layer 31b in which the film stress changes in the positive direction from the viewpoint of adjusting the film stress and other points.
- the second layer 31b is formed of a material having a higher density than that of the first layer 31a, thereby securing a state in which water drainage is not as good as that of the second layer 31b. 32 can be protected, and the resistance of the reflective film 30 to a hot and humid environment can be increased.
- the second layer 31b is an adjustment layer for balancing the film stress, and has a negative film stress of a certain level or more. Further, as the second layer 31b, in a single layer state, with respect to the film stress after being put in a high temperature dry environment with an ambient temperature of 110 ° C. and a relative humidity of 20% RH or less (specifically, substantially zero humidity) for 24 hours.
- the film stress is selected such that the film stress changes in the positive direction after being put in a high-temperature and high-humidity environment with an atmospheric temperature of 85 ° C. and a relative humidity of 85% RH for 24 hours.
- the compressive stress is slightly reduced by the humidity increasing environmental test as described above, and it is determined that the moisture blocking effect is high.
- the main silver layer 32 is a thin film formed only of silver.
- the main silver layer 32 has a thickness of about several tens of nm to 100 nm, more preferably about 50 nm to 100 nm.
- the main silver layer 32 may be formed of an alloy mainly containing silver within a range in which the reflectance does not decrease when it is desired to further enhance the metal corrosion resistance.
- the additive material for the silver alloy include Bi, Pd, Cu, Au, Ge, Nd, and Al.
- the material of the first layer 33f that is in direct contact with the main silver layer 32 is mainly aluminum oxide. This is because, in the multilayer film design for increasing the reflectance of the main silver layer 32, if the layer having a high refractive index is in the first layer, the reflection performance may be deteriorated.
- Aluminum oxide is a relatively low-refractive material (low-refractive index material in a broad sense) and is desirable for optical design, and has a relatively good adhesion to the main silver layer 32.
- Materials such as LaTiO 3 , CeO 2, Y 2 O 3, and SnO 2 used in the adhesion layer 31 have a refractive index as high as 1.8 or more, and the first layer is inappropriate for thin film design.
- the layer laminated on the first layer 33f is two or more layers using a high-refractive index material and a low-refractive index material in design for the purpose of increasing reflection. It was.
- the increased reflection layer 33 includes at least three layers.
- the specific reflection increasing layer 33 is a dielectric multilayer film in which a high refractive index material layer 33a and a low refractive index material layer 33b are alternately stacked on the lowermost first layer 33f, and the uppermost layer has a low refractive index.
- the rate material layer 33b is formed.
- the first layer 33f in contact with the main silver layer 32 can be regarded as a medium refractive index material layer in terms of a higher refractive index than the uppermost low refractive index material layer 33b. It shall be called a low refractive index material layer in relation to the material layer 33a.
- the high refractive index material layer 33a has a refractive index of 1.8 or higher
- the low refractive index material layer 33b has a refractive index of 1.55 or lower
- the first layer 33f is 1.55 or higher.
- the material of the low refractive index material layer 33b is selected from at least one of a mixed material in which aluminum oxide is mixed with SiO 2 and SiO 2 .
- the material of the high refractive index material layer 33a is selected from at least one of TiO 2 , Nb 2 O 5 , Ta 2 O 5 , LaTiO 3 , ZrO 2 , and a mixed material of these materials.
- the first layer 33f is formed of a material mainly made of aluminum oxide as described above.
- the high-refractive index material layer 33a and the low-refractive index material layer 33b are set to have a film thickness corresponding to the refractive index for each layer by optical design, and the same refractive index material layers 33a and 33b may have different thicknesses. . Further, when the increased reflection layer 33 is composed of a plurality of high refractive index material layers 33a and a plurality of low refractive index material layers 33b, for example, the plurality of high refractive index material layers 33a are formed of different materials having different refractive indexes. can do.
- the single low refractive index material layer 33b can be composed of a plurality of types of low refractive index material layers, and similarly, the single high refractive index material layer 33a is composed of a plurality of types of high refractive index material layers. You can also
- the increased reflection layer 33 may include at least one adjustment layer, similar to the adhesion layer 31. That is, the first layer 33f constituting the increased reflection layer 33 and the high refractive index material layer 33a thereon can also be used as an adjustment layer for balancing the film stress.
- the first layer 33 f adjacent to the main silver layer 32 can be an adjustment layer having a relatively weak negative film stress, like the first layer 31 a of the adhesion layer 31.
- the first layer 33f is in a single layer state with respect to the film stress after being put in a high temperature dry environment having an ambient temperature of 110 ° C. and a relative humidity of 20% RH or less (specifically, substantially zero humidity) for 24 hours.
- the film stress after being put in a high temperature and high humidity environment with an atmospheric temperature of 85 ° C. and a relative humidity of 85% RH can change in the negative direction.
- the high refractive index material layer 33a on the first layer 33f can be an adjustment layer having a negative film stress of a certain level or more, like the second layer 31b of the adhesion layer 31.
- the high refractive index material layer 33a has an atmospheric temperature of 110 ° C. and a relative humidity of 20% RH or less (specifically, substantially zero humidity).
- a film is selected that changes its film stress in the positive direction after being put in a high temperature and high humidity environment with an atmospheric temperature of 85 ° C. and a relative humidity of 85% RH for 24 hours.
- the film stress of the entire reflective reflection layer 33 is preferably in a state of being negatively greater than ⁇ 50 MPa from the viewpoint of preventing cracks in a high temperature environment.
- the tolerance of the increased reflection layer 33 with respect to the expansion and contraction of the substrate 20 is increased, and it is possible to prevent the cracks from being easily generated due to being placed in a high temperature drying environment for a long time.
- the illustrated film forming apparatus 100 includes a vapor deposition source 51 as a film forming material source, a vapor deposition holder 52 that supports and rotates a plurality of workpieces W, and a film thickness with respect to the meridian direction of the vapor deposition holder 52 in a vacuum container 59.
- a film thickness correcting plate 54 for adjustment, an ion gun 56 for irradiating the workpiece W with an ion beam during film formation, and a neutralizing gun 57 for neutralizing ions are provided.
- the film forming apparatus 100 includes, in addition to the vacuum vessel 59, a deposition source driving unit 61 that controls the operation of the deposition source 51, a holder driving unit 62 that rotationally drives the deposition holder 52, and the posture of the film thickness correction plate 54.
- a correction plate driving unit 64 that adjusts the ion gun 56, an ion gun driving unit 65 that operates the ion gun 56, a gas supply unit 66 that supplies gas to the ion gun 56, and the like, a gas discharge unit 67 that decompresses the inside of the vacuum vessel 59,
- a control unit 69 that controls the operation of each unit constituting the membrane device 100.
- the vapor deposition source 51 enables vacuum deposition of various film forming materials, and is fixed on the stage at the bottom of the vacuum vessel 59.
- the vapor deposition source 51 has a container (not shown) for holding the evaporated substance, and the evaporated substance 51a in the container is heated by an electron gun or resistance heating. From the vapor deposition source 51, the vapor EM of the evaporating substance can be injected upward.
- the vapor deposition source 51 is operated by the vapor deposition source driving unit 61.
- the vapor deposition source 51 is accompanied by a shutter 51d, and the vapor EM emission timing can be arbitrarily set.
- the ratio of the additive present in the thin film after film formation depends on the difference in evaporation temperature. It can be adjusted by the temperature and the timing of opening and closing the shutter 51d.
- the vapor deposition holder 52 is disposed above the vapor deposition source 51 in the vacuum vessel 59.
- the vapor deposition holder 52 has a dome shape or a conical shape as a whole, and holds a number of workpieces W via a number of support jigs 52a.
- the vapor deposition holder 52 is rotated about the axis Z by the holder driving unit 62 so that the workpieces W are periodically opposed to the vapor deposition source 51.
- the vapor deposition holder 52 inclines the surface Wa of the workpiece W with respect to the vapor deposition source 51 by a predetermined angle ⁇ (specifically, 45 °). This is because the incident angle of the light beam on the reflective film 30 is an angle ⁇ in the product in which the silver reflecting mirror 10 is incorporated.
- the film thickness correction plate 54 is disposed between the vapor deposition source 51 and the vapor deposition holder 52.
- the posture of the film thickness correction plate 54 in the vacuum vessel 59 is controlled by the correction plate driving unit 64.
- the film thickness correction plate 54 can be operated from the outside by a mechanical mechanism 54a, and can be raised and lowered as appropriate so that the inclination of the axis X increases and decreases, and if necessary, can be further rotated around the axis X. You can also.
- the film thickness correction plate 54 is raised and disposed above the vapor deposition source 51, the portion of the support jig 52 a that is behind the film thickness correction plate 54 is not vapor-deposited, and the film thickness difference with respect to the longitudinal direction of the vapor deposition holder 52. Can be adjusted.
- the ion gun 56 extracts ions in the plasma by applying a voltage or the like and discharges the ions to the outside of the ion gun 56. Specifically, the ion gun 56 ionizes the gas supplied from the gas supply unit 66 and applies a beam voltage between the anode 56 a and the cathode 56 b of the ion gun 56.
- the ion gun 56 allows ionized gas (for example, positive ions) to approach and pass the cathode 56b side and emits it into the vacuum container 59 as an ion beam IB.
- the emitted ion beam IB is irradiated onto the surface Wa of the work W supported by the vapor deposition holder 52. As a result, the surface Wa of the workpiece W is activated or the thin film on the surface Wa of the workpiece W is rearranged, and the thin film on the surface Wa of the workpiece W can be made dense while being more closely adhered.
- the gas supplied from the gas supply unit 66 to the ion gun 56 can be obtained by adding a reactive gas to an inert gas.
- a reactive gas for example, various gases such as argon (Ar), nitrogen (N 2 ), helium (He), and a mixed gas thereof can be used. Further, for example, oxygen (O 2 ) or the like can be used as the reactive gas.
- the neutralizing gun 57 is for neutralizing ions in the ion beam IB and suppressing the influence of electric field distribution.
- An ionizing gas is introduced into the neutralizing gun 57 from the gas supply unit 66, and the introduced gas is ionized.
- electrons generated by ionization are emitted to the vacuum container 59, gas molecules ionized by the ion gun 56 and emitted to the vapor deposition holder 52 side are neutralized by the electrons.
- a neutralizing grid may be used.
- the gas discharge unit 67 depressurizes the inside of the vacuum vessel 59, and the oxygen introduction port 58 provided at the bottom of the vacuum vessel 59 supplies oxygen gas or the like into the vacuum vessel 59.
- An auto pressure controller (not shown) is provided between the oxygen inlet 58 and the gas discharge part 67, and the oxygen pressure in the vacuum vessel 59 can be made substantially constant during film formation.
- the vapor deposition source driving unit 61 operates the vapor deposition source 51 to inject the vapor EM of the evaporated substance upward.
- the holder driving unit 62 rotates the vapor deposition holder 52 around the central axis Z during the formation of the vapor EM by the vapor deposition source 51.
- the correction plate drive unit 64 adjusts the rotation and other postures of the film thickness correction plate 54 during vapor deposition by the vapor deposition source 51.
- the ion gun driving unit 65 operates the ion gun 56 to irradiate the surface Wa of the workpiece W with the ion gun 56 and forms the neutralization gun 57 to neutralize the periphery of the workpiece W during the formation of the vapor EM by the vapor deposition source 51. Do.
- the control unit 69 operates the vapor deposition source 51 via the vapor deposition source driving unit 61 while rotating the vapor deposition holder 52 by the holder driving unit 62, thereby forming a thin film of evaporated material on the surface Wa of the workpiece W.
- the control unit 69 operates the ion gun 56 and the like via the ion gun driving unit 65 so that the evaporated substance thin film formed on the surface Wa of the workpiece W has high adhesion to the workpiece W.
- the thin film of the evaporating substance is made dense.
- the film forming apparatus 100 described above enables vapor deposition by an ion assist method (that is, ion beam assisted vapor deposition), and mainly forms the first layer 31a and the second layer 31b constituting the adhesion layer 31. Used for.
- the density or density of the first and second layers 31a and 31b can be adjusted by adjusting the degree of irradiation with the ion beam IB.
- the element film and the main silver layer 32 constituting the increased reflection layer 33 can also be formed using the film forming apparatus 100.
- the low refractive index material layer 33b and the main silver layer 32 of the increased reflection layer 33 can be easily formed using a normal vapor deposition apparatus that does not use the ion gun 56 or the like.
- the illustrated environmental test apparatus 200 includes a humidity control chamber 71 that has a heat insulating wall and forms a sealed space, an air circulation fan 73, an auxiliary temperature control unit 74 that performs auxiliary temperature control, and an indoor temperature and humidity.
- a temperature / humidity sensor 75 to be measured, an air adjusting unit 77 for keeping the temperature and humidity in the humidity control chamber 71 constant, and a control device 79 for controlling them are provided.
- work W2 tested with the environmental test apparatus 200 may be the silver reflecting mirror 10 which is a finished product, the 1st layer 31a, the 2nd layer 31b, etc. which comprise the contact
- the humidity control chamber 71 stores a plurality of workpieces W2 supported by the shelf 71a. At that time, while the air circulation fan 73 circulates the atmosphere in the humidity control chamber 71, the temperature and humidity in the humidity control chamber 71 are monitored by the temperature / humidity sensor 75.
- the auxiliary temperature adjustment unit 74 auxiliaryly heats or cools the air around the workpiece W ⁇ b> 2 based on the detection result of the temperature / humidity sensor 75.
- the air adjusting unit 77 takes in the air in the humidity control chamber 71 and sends it out into the humidity control chamber 71 as air having a target temperature and humidity.
- the air adjusting unit 77 can monitor the change in characteristics of the silver reflecting mirror 10 or the like under a high temperature or high temperature and high humidity environment.
- the environment achieved by the air adjusting unit 77 includes, firstly, a high-temperature drying environment where the ambient temperature is 110 ° C. and the humidity is substantially zero, and secondly, the ambient temperature is 85 ° C. and the relative humidity is 85%.
- a high-temperature and high-humidity environment of RH is included, and in addition, a high-temperature dry environment with an atmospheric temperature of 85 ° C. and a humidity of almost zero is also included.
- the high-temperature drying atmosphere or the high-temperature and high-humidity atmosphere formed by the air adjusting unit 77 is made uniform by the air circulation fan 73 and sent around the workpiece W2.
- the control device 79 appropriately operates the air adjustment unit 77 and the like, for example, holds the workpiece W2 in a first environment (that is, in a high temperature dry environment with an atmospheric temperature of 110 ° C. and a humidity of substantially zero) for 24 hours, W2 is maintained for 24 hours in a second environment (that is, in a high-temperature and high-humidity environment with an atmospheric temperature of 85 ° C. and a relative humidity of 85% RH).
- a first environment that is, in a high temperature dry environment with an atmospheric temperature of 110 ° C. and a humidity of substantially zero
- W2 is maintained for 24 hours in a second environment (that is, in a high-temperature and high-humidity environment with an atmospheric temperature of 85 ° C. and a relative humidity of 85% RH).
- a second environment that is, in a high-temperature and high-humidity environment with an atmospheric temperature of 85 ° C. and a relative humidity of 85% RH.
- the control device 79 can also hold the workpiece W2 in a stable state for a long period of time, such as 1000 hours, in a high-temperature dry environment or a high-temperature and high-humidity environment by operating the air adjusting unit 77.
- the temperature of the workpiece W2 can be gradually changed at the start of the first environment or at the end of the second environment. Further, when switching from the first environment to the second environment later, the environment test apparatus 200 itself can be changed. Further, when switching from the first environment to the second environment later, it is also possible to perform an operation of once returning to normal temperature and stabilizing the state.
- the workpiece W2 to be tested by the illustrated environmental test apparatus 200 is not limited to the silver reflector 10 of the product, and a specific reflective layer or constituent layer constituting the reflective film 30 is formed alone on the substrate 20. You can also
- the illustrated stress measuring apparatus 300 includes a pair of support members 81 that support both ends of a strip-shaped workpiece W2 from below, a laser light source 82 that irradiates laser light P1 vertically on the surface Wa of the workpiece W2, and a workpiece W2.
- the pair of support members 81 support the workpiece W2 at two points separated by a length L.
- the tops of the two support members 81 have the same height, and the workpiece W2 extends in the horizontal direction when bending is ignored.
- the laser light source 82 is disposed vertically above one of the support members 81, emits a laser beam P1 toward the support member 81, and forms a light spot on the surface Wa of the workpiece W2.
- the reflected light sensor 83 detects laser light P2 that is specularly reflected light from the light spot on the surface Wa of the workpiece W2.
- the reflected light sensor 83 has a support portion (not shown), and can move the laser light P2 to a height position where it can be detected most strongly, and the height H can be measured.
- the curvature radius R of the bent workpiece W2 is approximately 2H, and the incident point of the laser beam P1 viewed from the origin O of the curvature of the workpiece W2 Is approximately given by L / 4H using the chord length L.
- the control device 85 calculates the film stress of the thin film formed on the surface Wa of the workpiece W2 based on the opening angle ⁇ of the workpiece W2.
- the Stoney formula was used for the calculation of the film stress performed by the controller 85. That is, in the strip-shaped workpiece W2, when the thickness of the substrate 20 of the workpiece W2 is D and the thickness of the reflective film F of the workpiece W2 is d, the thickness d is extremely thin and D >> d. .
- the opening angle ⁇ is obtained as the deflection angle of the reflected laser beam P2 as long as the workpiece W2 is assumed to be bent in an arc shape.
- the change in stress before and after the formation of the reflective film F is calculated. Is considered to be a film stress, and the film stress can be expressed by the following equation using the difference ⁇ in the opening angle before and after coating. ⁇ (Es ⁇ D 2 ) / [6d (1-v) L / (2sin ⁇ )]
- the workpiece W2 measured by the illustrated stress measuring apparatus 300 is for measuring the film stress of the reflective film 30 in the product silver reflecting mirror 10 or its constituent elements, and has the same shape as the product silver reflecting mirror 10. There is no need, and the material of the substrate 20 can also be different from the substrate material of the silver reflector 10 of the product. However, it can be said that the measurement of the film stress of the reflective film 30 or its constituent elements tends to have relatively high accuracy when performed in a situation close to the silver reflector 10 of the product.
- the substrate 20 having the optical surface 21 is prepared, and the first layer 31a and the second layer 31b are sequentially formed on the optical surface 21 by using the film forming apparatus 100 shown in FIG.
- the main silver layer 32 is formed on the adhesion layer 31 using the same film forming apparatus 100.
- the reflective reflection layer 33 is formed on the main silver layer 32 using the same film forming apparatus 100.
- a test piece (work W2) for environmental testing is also prepared. In this test piece, for example, a reflective film 30 is formed on a strip-shaped substrate 20 under the same conditions.
- first layer 31a which is one of the adhesion layers 31 is formed on the strip-shaped substrate 20
- second layer 31b which is the other of the adhesion layers 31 is formed on the strip-shaped substrate 20.
- Things are also prepared as test pieces.
- substrate 20 is also prepared as a test piece.
- the film stress is measured for the test piece (work W2) that has not been subjected to the humidity increase type environmental test and the test piece (work W2) that has undergone the humidity increase type environmental test. That is, the test piece (work W2) is set in the stress measuring device 300, and the stress of the thin film on the surface of the test piece is measured.
- the stress of the thin film on the surface of the test piece satisfies the predetermined condition
- the silver reflecting mirror 10 completed under the same conditions as the test piece is determined to have sufficient resistance to environments such as high temperature and high humidity. Is done.
- the film stress of the reflecting film 30 after film formation is in the range of +100 MPa to ⁇ 100 MPa, and the first It is important as a premise to ensure the quality of the silver reflecting mirror 10 that the film stress of the reflective film 30 after being kept for 24 hours in this environment is in the range from +100 MPa to ⁇ 100 MPa. Further, after the test piece (work W2) was put in the second environment, the film stress of the reflective film 30 after being put in a high temperature and high humidity environment of 85 ° C. and 85% RH for 24 hours was from +100 MPa to ⁇ 100 MPa. It is also determined whether it is within the range.
- test piece in which the first layer 31a of the adhesion layer 31 is formed as a single layer and the test piece in which the second layer 31b of the adhesion layer 31 is formed as a single layer are also described above.
- the stress of the thin film on the surface of the test piece is measured before and after the humidity increase type environmental test in which the sample is held in the first environment for 24 hours and then held in the second environment for 24 hours.
- the change difference as an absolute value of the film stress value is negative (compressive stress).
- the completed silver reflector 10 or the test piece is (1) 1000 ° C in a high-temperature dry environment (first environment) having an atmospheric temperature of 110 ° C. and a humidity of almost zero.
- first environment having an atmospheric temperature of 110 ° C. and a humidity of almost zero.
- second environment with an atmospheric temperature of 85 ° C. and a relative humidity of 85% RH
- High-temperature dry environment with an atmospheric temperature of 85 ° C. and a substantially zero humidity.
- the test is held for 1000 hours.
- a model GENER-1300 manufactured by Optolan equipped with an ion gun or the like was used as the film forming apparatus 100.
- polycarbonate H-3000R manufactured by Mitsubishi Engineering Plastics Co., Ltd. which was molded to a thickness of 3 mm with a diameter of 30 mm was used as a film formation target, that is, a workpiece W.
- the substrate 20 is placed in an inclined state of 45 degrees with respect to the surface orthogonal to the vapor deposition source 51 or the support surface of the vapor deposition holder 52 because the film formation surface of the assumed actual product is located at a vapor deposition incident angle of 45 degrees. It was done.
- an ion assist method is used for the purpose of further enhancing the moisture blocking effect and adjusting the overall stress for the aluminum oxide layer having good adhesion with the substrate and having a high moisture blocking effect.
- a film was formed.
- a film of LaTiO 3 (Substance H4) having good adhesion to the main silver layer was formed.
- LaTiO 3 (Substance H4) has a function of blocking moisture by itself, but an ion assist method was used for the purpose of further enhancing the blocking effect and adjusting the overall stress.
- Aluminum oxide and LaTiO 3 (Substance H4) were formed with a film thickness of 40 nm to 60 nm from the viewpoint of stress adjustment. However, if the thickness is in the range of 10 nm to 200 nm, the thickness can be changed to adjust the overall stress. It has been found that there is no significant impact on environmental resistance.
- a main silver layer was formed on the LaTiO 3 (Substance H4) film.
- Experimental Examples 1 to 8 a pure silver film was formed.
- film formation was performed using an alloy material (specifically, an Ag-Bi material (manufactured by Kobelco Kaken)) containing 1% of bismuth (Bi) in silver (Ag).
- film formation was performed using an alloy material containing 0.25% bismuth in silver (specifically, an Ag—Bi material (manufactured by Kobelco Kaken)).
- the thickness of the main silver layer is 60 nm, there is no problem if it is thin or thick as long as the reflectance can be secured.
- the resistance heating method is used for forming the main silver layer, vapor deposition using an electron gun may be performed.
- a reflective layer was formed on the main silver layer.
- two types of multilayer film designs are implemented for stress adjustment.
- an aluminum oxide layer having a refractive index of 1.55 to 1.65 is deposited as a lower refractive index material layer at a thickness of 120 nm, and then a high refractive index layer having a refractive index of 1.
- An 8-2.2 LaTiO 3 (Substance H4) layer was deposited to 80 nm, and finally a SiO 2 layer having a refractive index of 1.42-1.5 was deposited to 30 nm for the main purpose of scratch resistance. A total of three layers was used.
- an aluminum oxide layer having a refractive index of 1.55 to 1.65 is formed to a thickness of 35 nm, and then, as a high refractive index layer, LaTiO 3 (Substance H4) layer is deposited to 75 nm, then a SiO 2 layer having a refractive index of 1.42 to 1.5 is deposited to 20 nm, and then a LaTiO 3 (Substance H4) layer is deposited to 80 nm.
- a SiO 2 layer having a refractive index of 1.42 to 1.5 was formed to a thickness of 30 nm to form a total of five layers.
- the effect of increased reflection was observed, and the reflectivity for P-polarized light having a wavelength of 870 nm and incident at 45 degrees satisfied 95% or more.
- a substrate 30 having a diameter of 30 mm and a thickness of 3 mm was prepared.
- a measurement substrate a glass substrate D263 manufactured by Schott Corp. and processed into a thin strip-shaped glass substrate having a thickness of 50 mm ⁇ 10 mm and a thickness of 0.1 mm was used as a film formation target, that is, a workpiece W.
- a stable glass glass material that is hardly affected by water absorption and other external influences was used.
- the film stress measurement substrate was also placed and formed in a state inclined at 45 degrees with respect to the surface orthogonal to the vapor deposition source 51 or the support surface of the vapor deposition holder 52.
- Table 1 below summarizes the film forming conditions.
- the “Material Condition” column means a film material constituting the reflective film
- Al 2 O 3 -A” to “Al 2 O 3 -F” mean aluminum oxide films having different film forming conditions.
- “H4” means LaTiO 3 (Substance H4) manufactured by Merck
- “SiO2” means a silicon oxide film or silica film
- “Ag” means a main silver layer.
- EB means film formation by electron beam evaporation
- EB + IAD means ion-assisted electron beam evaporation
- RH means film formation by resistance heating.
- the column “O2-APC (Pa)” means an adjustment value of the oxygen partial pressure during film formation.
- the oxygen partial pressure is set to 2.00 ⁇ 10 ⁇ 2 Pa. It is shown.
- the “rate (angstrom / sec)” column means the film forming speed.
- the degree of vacuum at the start of film formation was 2.0 ⁇ 10 ⁇ 3 Pa, and the substrate was not heated during film formation.
- the “IAD” column shows the ion assist conditions
- Voltage (V) means the beam voltage of the ion gun 56
- Current (mA) means the beam current of the ion gun 56
- Acc (V) means acceleration voltage
- Ar (GAS1) (SCCM)”, “Ar (GAS2) (SCCM)”, and “Ar (GAS3) (SCCM)” indicate supply flow rates of oxygen and argon.
- Ar (GAS2) indicates the supply amount of the argon gas component to the ion gun 56
- Ar (GAS3) indicates the supply amount of the argon gas to the neutralization gun 57. Since the materials “Al 2 O 3 -A”, “Al 2 O 3 -B”, “SiO 2”, and “Ag” are not subjected to ion assist film formation, the value in the “IAD” column is blank.
- the refractive indexes of the films obtained from the above “Al 2 O 3 -A” to “Al 2 O 3 -F” were 1.5768, 1.5763, 1.588, 1.576, 1.5897, and 1.6102, respectively. . That is, the refractive index of the aluminum oxide layer using the ion assist method is in the range of 1 to 1.025 times the refractive index when the film is formed without using the ion assist method.
- Table 2 below explains the film structure in the reflective films of Examples 1 to 10 and Comparative Examples 1 to 4, and Table 3 below shows the film elements constituting the reflective films of Examples and Comparative Examples It summarizes the film thickness.
- Table 3 [Table 3]
- the layer number means the order of the layers from the substrate.
- the substrate is basically made of polycarbonate (PC), but in the case of a measurement substrate (test piece) for measuring film stress, it may be made of glass material D263.
- Table 4 summarizes the results of environmental resistance tests for the silver reflectors of Examples 1 to 10 and Comparative Examples 1 to 4.
- “85 ° C. DRY-1000H” means that the atmosphere was kept in a high-temperature dry environment with an atmospheric temperature of 85 ° C. and a humidity of almost zero for 1000 hours.
- “110 ° C. DRY-1000H” It means that it has been kept for 1000 hours in a high-temperature dry environment with substantially zero humidity.
- “85 degrees 85% -1000H” means that it has been kept for 1000 hours in a high-temperature and high-humidity environment with an ambient temperature of 85 ° C. and a relative humidity of 85% means.
- “Appearance determination” is a result of appearance measurement, and visual observation under a fluorescent lamp, normal stereoscopic microscope observation, and 1000-times microscope observation with a VHX2000 manufactured by Keyence Corporation were performed. Cracks, film floatation, cloudiness, and discoloration exist as the main evaluation items as the types of appearance defects, but clouding and discoloration are excluded from the target because differences appear depending on reflectance, and cracks and film floatation are evaluation items. It was. In other words, regarding the above cracks and film floating, each of which is acceptable is marked with ⁇ , where a relatively shallow crack occurs at several mm or less is marked with ⁇ , and when either one is unacceptable, marked with x. Evaluation was performed.
- “Reflectance” is a result of reflectance measurement, and a P-polarized light reflected at 45 degrees in a wavelength of 870 nm ⁇ 30 nm band was measured using a spectrophotometer MCPD3000 manufactured by Otsuka Electronics Co., Ltd. This is a shape that matches the form in which the silver reflector is incorporated into the product.
- evaluation was performed with a mark indicating a reflectivity of 95% or more as a whole in the band, and a mark indicating less than 95% as a mark x.
- the numerical value of 95% assumes a reflective optical system as a form of incorporation into a product, and is a value that is sufficiently acceptable as the optical performance of a target product group. In general, reflecting mirrors using silver have a very high reflectance, and 95% is a satisfactory numerical value.
- the “tape test” is an experiment in which a tape provided with an adhesive surface is once attached to the reflective film and then peeled off. I made an evaluation.
- Examples 6 to 10 passed without any problem (circle mark), and Examples 1 to 5 were several mm. Shallow cracks were observed below, but at a level that was not a problem for practical use ( ⁇ mark). In addition, Comparative Examples 1 to 4 were also acceptable ( ⁇ mark) or practically problematic ( ⁇ mark).
- the results of the film stress test are summarized in Table 6 for each layer (see Table 1) constituting the example of the reflective film 30.
- the aluminum oxide films “Al 2 O 3 -A” to “Al 2 O 3 -F” constitute the first layer 31 a of the adhesion layer 31 and the first layer 33 f of the increased reflection layer 33 in Examples and Comparative Examples.
- the first column shows the results of testing the environmental change of the film stress (unit “MPa”) in the case where the first layer of Al 2 O 3 constituting the adhesion layer was produced as a single layer on the substrate. Show. First, in the first step (“one week”), the test piece was left at room temperature for one week to stabilize the film state.
- the test piece was kept in a high-temperature dry environment with an atmospheric temperature of 110 ° C. and a humidity of substantially zero for 24 hours to once dry the reflective film.
- the third step (“85 ° C. 85% 24H”), the test piece was kept in a high temperature and high humidity environment with an ambient temperature of 85 ° C. and a humidity of 85% for 24 hours to humidify the reflective film.
- the “difference” column is a value obtained by subtracting the film stress after the process of “85 ° C. 85% 24H” from the film stress after the process of “110 ° C. 24H”. This difference is obtained by inverting the sign of the amount of change in film stress.
- the film stress of the adhesion layer first layer is decreased by 137 MPa by switching from the high temperature drying environment for 24 hours to the high temperature and high humidity environment for 24 hours, and the change amount of the film stress is negative ( It corresponds to the direction of (compressive stress).
- the second column shows the results of testing the environmental change of the film stress (unit: “MPa”) in the case where the second layer of LaTiO 3 (H4) constituting the adhesion layer was produced as a single layer on the substrate.
- the meanings of “one week” (first step), “110 ° C. 24H” (second step), “85 ° C. 85% 24H” (third step), and “difference” are the same as those in the first column.
- the film stress of the second layer of the adhesion layer increases by 29 MPa by switching from the high temperature dry environment of 24 hours to the high temperature and high humidity environment of 24 hours, and the change amount of the film stress is positive ( It corresponds to the direction of (tensile stress).
- the arrow in the table means the same value as in the left column.
- the third column shows the environmental change of the film stress (unit “MPa”) in the case where only the enhanced reflection layer (made of Al 2 O 3 , LaTiO 3 (H4), SiO 2 ) is produced as a multilayer film on the substrate.
- the test results are shown.
- the meanings of “one week” (first step), “110 ° C. 24H” (second step), “85 ° C. 85% 24H” (third step), and “difference” are the same as those in the first column.
- Example 1 by switching from a high temperature drying environment of 24 hours to a high temperature and high humidity environment of 24 hours, the film stress of the increased reflection layer is reduced by 116 MPa, and the change amount of the film stress is negative (compressive stress). )
- the film stress of the increased reflection layer is reduced by 116 MPa, and the change amount of the film stress is negative (compressive stress).
- the fourth column shows the results of testing the environmental change of the film stress (unit: “MPa”) in the case where the entire reflective film was produced as a multilayer film on the substrate.
- the meanings of “one week” (first step), “110 ° C. 24H” (second step), “85 ° C. 85% 24H” (third step), and “difference” are the same as those in the first column.
- Example 1 by switching from a high temperature drying environment for 24 hours to a high temperature and high humidity environment for 24 hours, the total film stress is reduced by 18 MPa, and the amount of change in film stress is in the negative (compressive stress) direction. It is equivalent.
- the film stress is 100 MPa or less in “one week” (first step), “110 ° C. 24H” (second step), and “85 ° C. 85% 24H” (third step). It is a criterion for success. This is because the PV value of the optical surface exceeds the allowable range of the optical performance when, for example, the product exceeds 100 MPa for an assumed product. For example, when a film is formed on one side of a polycarbonate having a diameter of 40 mm and a thickness of 3 mm as in the embodiment, the deformation due to a film stress of 100 MPa is about 1 ⁇ m.
- the film stress is preferably adjusted to 100 MPa or less for a mirror used in a precise reflection optical system.
- the film stress is not limited to the case where the entire reflective film is formed as in the fourth column, but also in the case where a part of the reflective film is formed as in the first to third columns. Low is desirable.
- Examples 1 to 10 and Comparative Examples 1 to 3 are films in which the stress value of the entire reflection film is close to 0 and the surface deformation can be reduced. It was.
- membrane stress was very large and became a stress value which is concerned about surface deformation. This is considered to be due to the fact that the film formation conditions of the highly reflective Al 2 O 3 of Comparative Example 4 used strong ion assist.
- Examples 1 to 5 show that the film stress is in the positive direction.
- No. 10 indicates that the film stress changes in the negative direction. This result is considered that the influence of the increased reflection layer is conspicuous.
- Examples 6 to 10 since the film thickness of Al 2 O 3 used in the increased reflection layer is thin, LaTiO 3 (H4 From the above, it can be judged that the influence of the film stress has been received.
- Examples 1 to 10 had an absolute value of 40 MPa or less. It was. On the other hand, Comparative Examples 1 to 3 were 40 MPa or more.
- the absolute value of the difference in film stress is 40 MPa.
- the absolute value of the change amount is 40 MPa or less.
- membrane stress is a positive direction (tensile-stress side)
- the absolute value of the change amount is 40 Mpa or less.
- the absolute value of the difference in film stress is 40 MPa or less, but the original film stress is very large, and there is a concern about surface deformation.
- the film stress after 110 ° C. and 24H treatment that is held for one day in a high temperature dry state and the film stress after 85 ° C. and 85% 24H treatment that is held for one day in a high temperature and wet state are complex at multiple levels. It has been found that film deterioration due to environmental changes can be prevented by realizing a layer configuration state in which the change is small and the fluctuation is small.
- the film stress after the formation of the reflective film is in the range from +100 MPa to ⁇ 100 MPa
- the absolute value of the amount of change between the film stress value after being put in a high-temperature dry environment at 110 ° C. for 24 hours and the film stress value after being put in a high-temperature and high-humidity environment at 85 ° C. and 85% RH is 24 MPa or less. It turns out that it is important that each condition of a certain is met.
- the film stress after the reflection film is put into a 110 ° C.
- high temperature dry environment for 24 hours is in the range from +100 MPa to ⁇ 100 MPa, and (4) the reflection after the high temperature dry environment at 110 ° C. It is also important that the film stress after the film is put in a high temperature and high humidity environment of 85 ° C. and 85% RH for 24 hours is in the range from +100 MPa to ⁇ 100 MPa.
- the inventor of the present application analyzes various prototypes from the viewpoint of the behavior of the film stress with respect to environmental changes, and from the consideration of the state change in the single layer and the multilayer state, the extremely reliable silver mirror is the composition, film
- the change in film stress at high temperature drying and high temperature humidity was small. That is, the inventor of the present application determines a highly reliable silver mirror selection method by determining the balance of the layer configuration in which the change in film stress at high temperature drying and high temperature humidity is small, and by determining the quantitative value of such change amount.
- a highly reliable silver mirror selection method by determining the balance of the layer configuration in which the change in film stress at high temperature drying and high temperature humidity is small, and by determining the quantitative value of such change amount.
- the film mainly composed of aluminum oxide constituting the adhesion layer 31 or the like can be formed not only by the above-described deposition by the ion assist method but also by other film forming methods. Specifically, it can be formed by sputtering, RF vapor deposition, ion plating, cluster ion beam (IonizedICluster) vapor deposition, plasma ion beam vapor deposition, or the like.
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Abstract
Description
図面を参照して、本発明の一実施形態に係る銀反射鏡及びその製造方法等について説明する。
σ=(Es×D2)/[6d(1-v)R]
ただし、Esは、基板20のヤング率であり、vは、基板20のポアソン比である。
σ≒(Es×D2)/[6d(1-v)L/(2sinθ)]
と近似することができる。
σ≒(Es×D2)/[6d(1-v)L/(2sinΔθ)]
以下、本発明に係る銀反射鏡の具体的な実施例について説明する。
[表1]
上記表1において、「材料条件」欄は、反射膜を構成する膜材料を意味し、「Al2O3-A」~「Al2O3-F」は、成膜条件が異なる酸化アルミニウム膜を意味する。「H4」は、Merck社製のLaTiO3(Substance H4)を意味し、「SiO2」は、酸化シリコン膜又はシリカ膜を意味し、「Ag」は、主銀層を意味する。「Method」欄において、「EB」は電子ビーム蒸着による成膜を意味し、「EB+IAD」は、イオンアシストタイプの電子ビーム蒸着を意味し、「RH」は、抵抗加熱による成膜を意味する。「O2-APC(Pa)」欄は、成膜中における酸素分圧の調整値を意味し、例えばAl2O3-Aの場合、酸素分圧が2.00×10-2Paに設定されたことが示されている。「rate(オングストローム/sec)」欄は、成膜速度を意味する。なお、表1には記載していないが、成膜開始時の真空度は2.0×10-3Paであり、成膜に際して基板の加熱は行わなかった。
[表2]
[表3]
表2及び表3において、層番号は、基板からの層の順番を意味する。なお、基板は、基本的にポリカーボネート(PC)製であるが、膜応力測定用の測定基板(テストピース)の場合、硝材D263製となる場合もある。
[表4]
表4において、「85℃DRY-1000H」は、雰囲気温度85℃で湿度略ゼロの高温乾燥環境に1000時間保持されたことを意味し、「110℃DRY-1000H」は、雰囲気温度110℃で湿度略ゼロの高温乾燥環境に1000時間保持されたことを意味し、「85度85%-1000H」は、雰囲気温度85℃で相対湿度85%RHの高温多湿環境に1000時間保持されたことを意味する。
[表6]
表5において、第1欄は、密着層を構成する第1層のAl2O3を基板上に単層で作製した場合について、膜応力(単位「MPa」)の環境変化を試験した結果を示す。まず、第1工程(「一週間」)では、テストピースを室温で一週間放置して膜状態を安定させた。次に、第2工程(「110℃24H」)では、テストピースを雰囲気温度110℃で湿度略ゼロの高温乾燥環境に24時間保持して反射膜を一旦乾燥させた。最後に、第3工程(「85℃85%24H」)では、テストピースを雰囲気温度85℃で湿度85%の高温高湿環境に24時間保持して反射膜に加湿を行った。「差分」欄は、「110℃24H」の処理後の膜応力から「85℃85%24H」の処理後の膜応力を引いた値である。この差分は、膜応力の変化量の符号を反転させたものとなっている。つまり、実施例1の場合、24時間の高温乾燥環境から24時間の高温高湿環境への切り替えによって、密着層第1層の膜応力が137MPaだけ減少し、膜応力の変化量は、負(圧縮応力)方向に相当するものとなっている。
Claims (16)
- 下地の密着層と、前記密着層上に形成される主銀層と、前記主銀層上に形成される増反射層とを反射膜として備える銀反射鏡であって、
前記主銀層は、銀及び銀を主とする合金のいずれかで形成され、
前記反射膜の成膜後の膜応力が、+100MPaから-100MPaまでの範囲にあり、
前記反射膜を110℃の高温乾燥環境に24時間投入した後の膜応力が、+100MPaから-100MPaまでの範囲にあり、
前記110℃の高温乾燥環境に投入後の前記反射膜を85℃85%RHの高温多湿環境に24時間投入した後の膜応力が、+100MPaから-100MPaまでの範囲にあり、かつ、
前記110℃の高温乾燥環境に24時間投入後の膜応力値と、前記85℃85%RHの高温多湿環境に24時間投入した後の膜応力値との間の変化量の絶対値が、40MPa以下である銀反射鏡。 - 前記密着層は、酸化アルミニウムを主とする層を少なくとも1層含み、当該酸化アルミニウムを主とする層は、イオンアシスト法を用いて成膜されており、当該酸化アルミニウムを主とする層の膜応力は、圧縮応力である、請求項1に記載の銀反射鏡。
- 前記密着層及び前記増反射層のいずれかは、少なくとも1層の調整層を含み、当該調整層は、単層の状態において、110℃の高温乾燥環境に24時間投入後の膜応力に対して、85℃85%RHの高温多湿環境に24時間投入した後の膜応力が、負方向に変化する、請求項1及び2のいずれか一項に記載の銀反射鏡。
- 前記密着層及び前記増反射層のいずれかは、少なくとも1層の調整層を含み、当該調整層は、単層の状態において、110℃の高温乾燥環境に24時間投入後の膜応力に対して、85℃85%RHの高温多湿環境に24時間投入した後の膜応力が、正方向に変化する、請求項1~3のいずれか一項に記載の銀反射鏡。
- 前記銀を主とする合金の添加材料は、Bi、Pd、Cu、Au、Ge、Nd、及びAlのいずれかである、請求項1~4のいずれか一項に記載の銀反射鏡。
- 前記密着層は、少なくとも2層以上を含み、前記密着層を構成する各層の材料は、酸化アルミニウムを主とする材料、LaTiO3、CeO2、Y2O3及びSnO2のうち少なくとも一種から選ばれる、請求項1~5のいずれか一項に記載の銀反射鏡。
- 前記密着層のうち、前記主銀層と直接密着する層の材料が、LaTiO3、CeO2、Y2O3及びSnO2のうち少なくとも一種から選ばれる、請求項6に記載の銀反射鏡。
- 前記増反射層は、少なくとも3層以上を含み、前記増反射層のうち、前記主銀層と直接密着する層が、酸化アルミニウムを主とする材料で形成されている、請求項1~7のいずれか一項に記載の銀反射鏡。
- 前記増反射層の膜応力が、-50MPaよりも負に大きい、請求項1~8のいずれか一項に記載の銀反射鏡。
- 前記酸化アルミニウムを主とする層の屈折率が、1.55~1.65である、請求項2に記載の銀反射鏡。
- 前記増反射層は、3層以上を含み、酸化アルミニウムを主とする材料で形成され前記主銀層と密着する層の上に、高屈折率材料の層と低屈折率材料の層とを交互に積層した構造を有し、前記高屈折率材料は、TiO2、Nb2O5、Ta2O5、LaTiO3、ZrO2、及びこれらの材料の混合材料のうち少なくとも一種から選ばれ、前記低屈折率材料は、SiO2及びSiO2に酸化アルミニウムを混ぜた混合材料のうち少なくとも一種から選ばれる、請求項1~10のいずれか一項に記載の銀反射鏡。
- 下地の密着層と、前記密着層上に形成される主銀層と、前記主銀層上に形成される増反射層とを反射膜として備える銀反射鏡の検査方法であって、
前記主銀層は、銀及び銀を主とする合金のいずれかで形成され、
前記反射膜の成膜後の膜応力が、+100MPaから-100MPaまでの範囲にあるか否かを判定するとともに、
前記反射膜を110℃の高温乾燥環境に24時間投入した後の膜応力値と、前記反射膜を110℃の高温乾燥環境に24時間投入した後に前記反射膜を85℃85%RHの高温多湿環境に24時間投入した後の膜応力値との間の変化量の絶対値が、40MPa以下であるか否かを判定する銀反射鏡の検査方法。 - 前記反射膜を110℃の高温乾燥環境に24時間投入した後の膜応力が、+100MPaから-100MPaまでの範囲にあるか否かを判定し、
前記110℃の高温乾燥環境に投入後の前記反射膜を85℃85%RHの高温多湿環境に24時間投入した後の膜応力が、+100MPaから-100MPaまでの範囲にあるか否かを判定する、請求項12に記載の銀反射鏡の検査方法。 - 前記密着層がイオンアシスト法を用いて成膜された酸化アルミニウムを主とする層を含む場合に、当該酸化アルミニウムを主とする層の膜応力が圧縮応力であるか否かを判定する、請求項13に記載の銀反射鏡の検査方法。
- 下地の密着層と、前記密着層上に形成される主銀層と、前記主銀層上に形成される増反射層とを反射膜として備える銀反射鏡の製造方法であって、
前記主銀層は、銀及び銀を主とする合金のいずれかで形成され、
前記反射膜の成膜後の膜応力を、+100MPaから-100MPaまでの範囲にするとともに、
前記反射膜を110℃の高温乾燥環境に24時間投入した後の膜応力値と、前記反射膜を110℃の高温乾燥環境に24時間投入した後に前記反射膜を85℃85%RHの高温多湿環境に24時間投入した後の膜応力値との間の変化量の絶対値を、40MPa以下する銀反射鏡の製造方法。 - 前記銀反射鏡と同一の構造を有するテストピースを作製して、膜応力の計測を行う、請求項15に記載の銀反射鏡の製造方法。
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WO2023190477A1 (ja) * | 2022-03-30 | 2023-10-05 | 日東電工株式会社 | 複層構造体 |
Also Published As
Publication number | Publication date |
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EP3330749A1 (en) | 2018-06-06 |
JPWO2017018393A1 (ja) | 2018-05-17 |
EP3330749A4 (en) | 2018-08-15 |
US20180217303A1 (en) | 2018-08-02 |
US10444414B2 (en) | 2019-10-15 |
CN107850705A (zh) | 2018-03-27 |
CN107850705B (zh) | 2020-02-14 |
JP6799282B2 (ja) | 2020-12-16 |
EP3330749B1 (en) | 2022-09-21 |
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