JP2014130294A - Member with metal oxide film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a member with a metal oxide film having a laminated film containing at least one metal oxide film layer formed on a base material, which exhibits reduced temporal change in a function of the metal oxide film.SOLUTION: A member with a metal oxide film includes a laminated film containing at least one metal oxide film layer formed on a base material. The laminated film includes a monolayer of an organic compound containing fluorine atoms in bonds thereof located on an upper layer side of the metal oxide film layer. The organic compound monolayer may be the upper most layer of the laminated film, for example.

Description

  The present invention relates to a member including a metal oxide film provided with a laminated film including at least one metal oxide film layer formed on a substrate.

Various products using metal oxide films, such as optical parts and electrical / electronic parts, are known. As the metal oxide film, for example, TiO ₂ (titanium oxide (IV)), Ta ₂ O ₅ (tantalum oxide), Nb ₂ O ₅ (niobium oxide), SiO ₂ (silicon dioxide), SiO (silicon monoxide), SnO ₂ (tin oxide (IV)), ITO (indium tin oxide), IGZO (indium gallium zinc oxide), and the like. The metal oxide film is stoichiometrically represented by MnOm. Here, M is a metal, O is oxygen, and n and m are positive integers. Further, a thin film of metal oxide film in an oxygen deficient state is represented by MnOm-x. Here, x is a positive integer or decimal and m> x.

  Metal oxide films are used in optical parts having functional films such as an antireflection function, an increased reflection function, and a filter function, for example. The optical component provided with such a functional film is, for example, an optical lens, a prism, a filter, a transparent conductive film, or the like.

In electric / electronic parts, a metal oxide film is used as a transparent conductive film, for example. For example, a transparent conductive film such as SnO ₂ , ITO, or IGZO may be formed in a slightly oxygen deficient state for the purpose of improving conductivity (reducing sheet resistance).

  Also, metal thin films are often used in electronic / electrical parts. Typical examples are aluminum wiring and copper wiring. Industrially, measures such as covering the metal thin film with a resin material have been implemented in order to prevent the metal thin film from being deteriorated, and it is used for actual use.

On the other hand, for example, in the case of a functional film such as an antireflection film or an increased reflection film of an optical component, the uppermost layer (SiO ₂ film having good wettability is considered in consideration of the durability improvement and the bonding process performed in a later process. A membrane layer that is in contact with air). In the case of electrical / electronic parts, for example, the uppermost layer of the functional film is usually a metal oxide film, or the metal film is left as it is.

  The composition formula of the metal oxide film indicates a stoichiometric bonding state. However, the actually formed metal oxide film cannot take a stoichiometric bond state, and is in an oxygen deficient state.

  For example, a metal oxide film as an optical thin film can be formed by a vacuum deposition method, a sputtering method, an ion plating method, a plasma deposition method, a CVD (Chemical Vapor Deposition) method or the like (not limited to this). To be implemented. Both methods are methods in which energy is supplied from the outside to the material before film formation to “evaporate with heat” or “evaporate by exchanging energy”. In this case, a stoichiometric bond state cannot be obtained by supplying a small amount of high energy from the outside. Specifically, the bond with oxygen molecules is broken. As a result, the formed metal oxide film is in an oxygen deficient state.

  As a method for supplementing the oxygen deficiency state of the metal oxide film, there is an ion assist method in an oxygen atmosphere. However, even when the metal oxide film is formed in an oxygen atmosphere, an effect of oxygen uptake sufficient to achieve a stoichiometrically bonded state cannot be obtained, and the metal oxide film is in an oxygen deficient state.

  Oxygen-deficient metal oxide films change over time due to oxygen or moisture uptake in long-term use environments, or change in chemical composition due to some external stimulus such as in reliability tests . This is to return from the oxygen deficient state to a more stable stoichiometrically bonded state. This phenomenon is a phenomenon generally called wavelength shift in the thin film field. As a specific function change, spectral characteristics change such as a decrease in transmittance and a deviation from a design function.

  An object of the present invention is to reduce a change in the function of a metal oxide film over time in a member including a metal oxide film having a laminated film including at least one metal oxide film layer formed on a substrate. And

  A member including a metal oxide film according to the present invention includes a laminated film including at least one metal oxide film layer formed on a substrate, and the laminated film is on an upper layer side than the metal oxide film layer. And a monomolecular layer of an organic compound containing a fluorine atom in the bond, which is disposed in the structure.

  In the member including the metal oxide film of the present invention, an example in which the monomolecular layer of the organic compound is disposed in the uppermost layer of the laminated film can be given. However, the monomolecular layer of the organic compound may constitute an intermediate layer of the laminated film, and one or more other layers may be formed on the upper layer side of the monomolecular layer of the organic compound.

  A member including a metal oxide film according to the present invention includes a monomolecular layer of an organic compound including a fluorine atom in a bond, which is disposed on an upper layer side of a metal oxide film layer in a laminated film including a metal oxide film layer. Therefore, intrusion of moisture and air components into the metal oxide film can be reduced, and changes in the function of the metal oxide film over time can be reduced.

It is a graph which shows the result which put together the durability test result of Table 1 and Table 2 according to the theoretical formula of the Arrhenius plot. It is a graph which shows the result which put together the durability test result of Table 4 and Table 5 according to the theoretical formula of the Arrhenius plot. It is a graph which shows the result which put together the durability test result of sample 1 and sample 1 'according to the theoretical formula of the Arrhenius plot. It is a graph which shows the result which put together the durability test result of sample 2 and sample 2 'according to the theoretical formula of the Arrhenius plot. It is a graph which shows the result which put together the endurance test result of sample 3 and sample 3 'according to the theoretical formula of the Arrhenius plot.

  The chemical composition change of the oxygen-deficient metal oxide film is considered to be caused by moisture or oxygen entering from the outside (for example, in the air) due to a change in the external environment. The member including the metal oxide film of the present invention penetrates from the outside by forming a thin film substance / thin film material composed of molecules with low surface free energy at a place where an external environmental change factor may enter. The effect of moisture and oxygen is reduced.

  Here, the thin film substance / thin film material composed of molecules with low surface free energy is a monomolecular layer of an organic compound containing fluorine (F) atoms in the bond. There are organic compounds containing many fluorine atoms in the world. As an example, the following “fluorine-based coating material, water / oil repellent treatment agent” was used.

(1) Product name: OPTOOL DSX (manufactured by Daikin Industries),
(2) Product name: Cytop (manufactured by AGC Asahi Glass),
(3) Product name: Fluorosurf (manufactured by Fluoro Technology),
(4) Product name: NOVEC (manufactured by 3M),
(5) Chemical substances: triazine thiol compounds and triazine dithiol compounds having fluorine atoms in the side chain,
(6) Chemical substances: acrylic compounds and epoxy compounds having fluorine atoms in the side chain.
However, in the member including the metal oxide film of the present invention, the organic compound including a fluorine atom in the bond is not limited thereto.

These compounds are deposited on the products described below. The film forming method may be either a dry film forming method or a wet film forming method.
In the “dry film formation method”, a target product is introduced into a vacuum chamber by a vacuum deposition method or the like, and the fluorine-based coating agent is evaporated to form a film uniformly on the product surface. Examples of the “wet film forming method” include a so-called dip film forming method and a spinner film forming method.

  The products (1) to (4) can be subjected to the “dry film formation method” and the “wet film formation method”. For the compounds of (5) and (6), the “wet film formation method” is often not feasible, and the “dry film formation method” is performed.

The surface reaction of the above compound will be described.
The chemical molecular structure of the compounds (1) to (6) is such that the main main chain is a hydrocarbon group, the side chain has a carbon-fluorine bond, and all the hydrogen atoms in the hydrocarbon group or Fluoroalkyl groups partially substituted with fluorine atoms are bonded. This molecular structure can cover the surface with a carbon-fluorine bond having a low surface free energy. Since the carbon-fluorine bond has a large bond energy, it can realize excellent heat resistance, weather resistance, and chemical resistance. Further, since the carbon-fluorine bond has a low polarizability, the intermolecular cohesive force is reduced and a low surface free energy surface can be formed. For example, a fluoroalkyl group has a driving force that minimizes the surface free energy at the air interface, and the —CF ₃ group tends to segregate on the air interface side. By this effect, the carbon-fluorine bond having a low surface free energy serves to prevent moisture and air components from entering from the surface.

The above compounds (1) to (6) have two functional groups. One functional group is a reactive group (functional group) for bonding to the substrate. The other is a fluoroalkyl group that forms a low surface free energy surface.
One functional group of the compounds (1) to (4) is a —Si—OR group (R is hydrogen or an alkyl group). When the substrate is a glass-based material, this functional group reacts with —Si—OH of the substrate to form a Si—O—Si bond. Since this reaction can form a strong bond, the compounds (1) to (4) are fixed on the substrate. If necessary, a strong immobilization process may be performed by heat treatment. Further, even when the substrate is a non-glass material, when the surface treatment such as the silane coupling treatment is performed, the above-described reaction occurs because the chemical composition of the surface is -Si-OH. Thereby, an immobilization reaction is performed.

  In the chemical molecular structure of the compound (5), the main main chain is a hydrocarbon group, but the skeleton is a triazine ring, and a fluoroalkyl group is bonded to the upper part of the triazine ring. This molecular structure can cover the surface with a carbon-fluorine bond having a low surface free energy. This carbon-fluorine bond having a low surface free energy functions to prevent moisture and air components from entering from the surface.

  The reactive group (functional group) for bonding to the substrate in the compound (5) is a triazine ring-SH group. In the case of a triazine thiol compound, there is one SH group, and in the case of a triazine dithiol compound, there are two SH groups. This triazine ring-SH functional group reacts with the substrate. When the substrate is a metal oxide, the -SH functional group reacts with -Me-OH on the surface of the metal (described as Me) of the substrate to form a bond of -Me-S-triazine ring. Since this reaction can form a strong bond, the compound (5) is fixed on the substrate. If necessary, a strong immobilization process may be performed by heat treatment.

  In the chemical molecular structure of the acrylic compound or epoxy compound of (6) above, the main main chain is hydrocarbon-based and a fluoroalkyl group is bonded to the side chain. This molecular structure can cover the surface with a carbon-fluorine bond having a low surface free energy. This carbon-fluorine bond having a low surface free energy functions to prevent moisture and air components from entering from the surface. Moreover, the double bond and the epoxy group are arrange | positioned at another side chain.

  In the compound (6), the reactive group (functional group) for bonding to the substrate is a —C—OR group (R is an alkyl group). In the case where the substrate is a glass-based material, the functional group and —Si—OH of the substrate react to form a Si—O—C bond. Since this reaction can form a strong bond, the compound (6) is fixed on the substrate. If necessary, a strong immobilization process may be performed by heat treatment. Further, even when the substrate is a non-glass material, when the surface treatment such as the silane coupling treatment is performed, the above-described reaction occurs because the chemical composition of the surface is -Si-OH. Thereby, an immobilization reaction is performed. In the case where the substrate is a metal oxide, a —C—OR group reacts with —Me—OH on the surface of the metal (described as Me) of the substrate to form a bond of —Me—O—C—.

  The thickness of the organic compound containing the fluorine atom in the bond shown above is a monomolecular layer (1 nm (nanometer) to several tens of nm), which is sufficiently thinner than the wavelength of light, that is, the wavelength of light is not felt. Since it is thin enough, there is no optical effect. In other words, there is no optical influence because it seems that the organic compound does not exist for the wavelength of light. In addition, the organic compound formed on the surface of the substrate chemically has low surface free energy, so that the influence of moisture and oxygen entering from the outside on the substrate is reduced.

Next, the result of verifying the effect when a monomolecular layer of an organic compound containing fluorine atoms in a bond is formed on a laminated film including at least one metal oxide film layer will be described.
After molding a plastic flat substrate made of ZEONEX (manufactured by Nippon Zeon Co., Ltd.), the laminated film shown in Table 1 below was formed by vacuum deposition within 24 hours. The plastic flat substrate has a plane size of □ 50 × 50 mm (millimeters) and a thickness of 3 mm. The design wavelength (λ) is 550 nm. Table 1 shows the materials and film thicknesses (in parentheses) of Samples 1-9. A first layer, a second layer, a third layer, and a fourth layer were formed in that order on the substrate. The fourth-layer fluorine-based organic film (organic compound containing fluorine atoms in the bond) is a monomolecular layer. As the fourth layer, a fluorine-based organic film was formed by a vacuum deposition method. In addition, about the fluorine-type organic film | membrane, the same film | membrane can be formed also by the method of apply | coating an organic liquid.

Three samples 1 to 3 were prepared and subjected to a durability test. Samples 1 to 3 were formed by forming a SiO ₂ film on the first layer, an ITO film on the second layer, a SiO ₂ film, a SiO film or a Si film on the third layer, and a fluorine-based organic film (optool) on the fourth layer. It is an example.

  Table 2 shows the results of the durability test of Samples 1 to 3 for a maximum of 10 hours (h) under a high temperature and high humidity condition where the temperature is 100 ° C. and the humidity is 85%. Table 3 shows the results of the durability test of Samples 1 to 3 for up to 1000 hours (h) under a high temperature and high humidity condition where the temperature is 80 ° C. and the humidity is 85%. The evaluation was performed by observing the occurrence of cracks (thin film floats and cracks) in the laminated film. In Table 2 and Table 3, “◯” indicates “no change”, and “●” indicates “crack generation”. “Coat” indicates a film (third layer) formed on a metal oxide film (ITO). “Life (h)” assumes an approximate life time in consideration of the time when one or two of the three samples having the same structure are cracked.

  The observation evaluation results were tabulated and the durability test results were quantitatively evaluated. Degradation of film adhesion (cracking) occurs when a thin film in an oxygen-deficient state changes its chemical composition when given external stimuli, such as in a reliability test, and changes over time in a long-term use environment. To do. This is to return from the oxygen deficient state to a more stable stoichiometrically bonded state.

  FIG. 1 is a graph showing the results of the durability test results of Tables 1 and 2 summarized according to the Arrhenius plot theoretical formula. The vertical axis represents the logarithm of life (Ln (life)), and the horizontal axis represents the reciprocal of absolute temperature (1 / absolute temperature).

For sample 1, the logarithm of the lifetime (6.6 hours) when the temperature condition is 100 ° C. is about 1.887, and the logarithm of the lifetime (967 hours) when the temperature condition is 80 ° C. is about 6.874.
For sample 2, the logarithm of the lifetime (4.3 hours) when the temperature condition is 100 ° C. is about 1.459, and the logarithm of the lifetime (533 hours) when the temperature condition is 80 ° C. is about 6.279.
For sample 3, the logarithm of the lifetime (2.0 hours) when the temperature condition is 100 ° C. is about 0.693, and the logarithm of the lifetime (133 hours) when the temperature condition is 80 ° C. is about 4.890.
The reciprocal of 100 ° C. (about 373 K) is about 0.000026 and the reciprocal of 80 ° C. (about 353 K) is about 0.0023.

From Tables 2 and 3, it can be seen that the 100 ° C. test has a shorter life than the 80 ° C. test, that is, the durability time until cracking becomes shorter as the temperature increases. In addition, the durability varies depending on the material of the third layer (metal oxide film coating layer), and it is understood that the third layer is improved in the order of SiO ₂ >SiO> Si. Furthermore, it can be seen from FIG. 1 that the activation energies indicated by the slopes of the graphs of Samples 1 to 3 increase in descending order of durability.

Three samples 4 to 6 shown in Table 1 were prepared, and a durability test was performed under the same conditions as described above. Samples 4 to 6 were formed by forming a SiO ₂ film on the first layer, a SiO ₂ film, a SiO film or a Si film on the second layer, an ITO film on the third layer, and a fluorine-based organic film (optool) on the fourth layer. It is an example.
The durability test results of Samples 4 to 6 were the same as those of Samples 1 to 3. From the above, it can be seen that the durability is improved in the order of SiO ₂ >SiO> Si in the second layer (underlayer of the metal oxide film).

Three samples 7 to 9 shown in Table 1 were prepared, respectively, and a durability test was performed under the same conditions as described above. Samples 7 to 9 consist of a CrO ₂ film as the first layer, a SiO ₂ film, a SiO film or Si film as the second layer, a CrO film as the third layer, and a fluorine-based organic film (triazine dithiol compound) as the fourth layer. This is an example of film formation.
The durability test results of Samples 7 to 9 were the same as those of Samples 1 to 3. From the above, it can be seen that the durability is improved in the order of SiO ₂ >SiO> Si in the second layer (underlayer of the metal oxide film).

  From the above, a thin film (metal oxide film) that is a member having a laminated film including a metal oxide film layer and cannot be stoichiometrically bonded and is in an oxygen deficient state enters from the outside. It can be seen that due to moisture and oxygen, the chemical composition changes in an attempt to return to a more stable stoichiometric bonded state from the oxygen deficient state.

Next, the result of verifying the effect of the fluorine-based organic film will be described.
Three samples 1 ′ to 3 ′ each having no fourth layer (fluorine-based organic film) were prepared for the samples 1 to 3, and a durability test was performed. Samples 1 ′ to 3 ′ are examples in which a SiO ₂ film is formed as a first layer, an ITO film is formed as a second layer, and a SiO ₂ film, a SiO film, or a Si film is formed as a third layer.

  Table 4 shows the results of the durability test of the samples 1 'to 3' for up to 10 hours (h) under a high temperature and high humidity condition where the temperature is 100 ° C and the humidity is 85%. Table 5 shows the results of the durability test of Samples 1 'to 3' for up to 1000 hours (h) under a high temperature and high humidity condition where the temperature is 80 ° C and the humidity is 85%. The evaluation methods in Table 4 and Table 5 and the display in the table are the same as the evaluation methods in Table 2 and Table 3 and the display in the table.

  FIG. 2 is a graph showing the results of the durability test results of Tables 4 and 5 summarized according to the Arrhenius plot theoretical formula. The vertical axis represents the logarithm of life (Ln (life)), and the horizontal axis represents the reciprocal of absolute temperature (1 / absolute temperature).

For sample 1 ′, the logarithm of the lifetime (3.0 hours) when the temperature condition is 100 ° C. is about 1.099, and the logarithm of the lifetime (300 hours) when the temperature condition is 80 ° C. is about 5.704.
For sample 2 ′, the logarithm of the lifetime (2.0 hours) when the temperature condition is 100 ° C. is about 0.693, and the logarithm of the lifetime (133 hours) when the temperature condition is 80 ° C. is about 4.890.
For sample 3 ′, the logarithm of the lifetime (1.2 hours) when the temperature condition is 100 ° C. is about 0.182, and the logarithm of the lifetime (58 hours) when the temperature condition is 80 ° C. is about 4.060.
The reciprocal of 100 ° C. (about 373 K) is about 0.000026 and the reciprocal of 80 ° C. (about 353 K) is about 0.0023.

From Tables 4 and 5, it can be seen that the 100 ° C. test has a shorter life than the 80 ° C. test, that is, the durability time until cracking becomes shorter as the temperature increases. In addition, the durability varies depending on the material of the third layer (metal oxide film coating layer), and it is understood that the third layer is improved in the order of SiO ₂ >SiO> Si. Furthermore, it can be seen from FIG. 2 that the activation energies indicated by the slopes of the graphs of the samples 1 ′ to 3 ′ are higher in descending order of durability.

  FIG. 3 is a graph showing the results of the durability test results of Sample 1 and Sample 1 'summarized according to the Arrhenius plot theoretical formula. FIG. 4 is a graph showing the results of the durability test results of Sample 2 and Sample 2 'summarized according to the Arrhenius plot theoretical formula. FIG. 5 is a graph showing the results of the durability test results of Sample 3 and Sample 3 'summarized according to the Arrhenius plot theoretical formula. 3 to 5, the vertical axis represents the logarithm of life (Ln (lifetime)), and the horizontal axis represents the reciprocal of absolute temperature (1 / absolute temperature).

  3 to 5, it can be seen that the 100 ° C. test has a shorter life than the 80 ° C. test, that is, the durability time until cracking becomes shorter as the temperature increases. In addition, when the fluorinated organic film is formed on the fourth layer (Samples 1 to 3), the lifetime may be longer than when the fluorinated organic film is not formed (Samples 1 ′ to 3 ′). Recognize. In addition, the activation energy indicated by the slope of the graph of each sample is higher in the descending order of durability, and the fluorine-based organic film is formed in the fourth layer (samples 1 to 3). It can be seen that it is higher than when no film is formed (samples 1 ′ to 3 ′).

  Samples 4 to 9 were also verified for the effect of the presence or absence of a fluorine-based organic film. And the verification result similar to the samples 1-3 was obtained also about the samples 4-9.

Based on the above, a thin film substance / film material composed of molecules with low surface free energy, that is, a monomolecular layer of an organic compound containing fluorine atoms in the bond, is formed at a site where the environmental change factor may enter. By forming a film, the influence of moisture and oxygen entering from the outside can be reduced.
A carbon-fluorine bond with a low surface free energy is formed by a molecular structure having a carbon-fluorine bond in the side chain and a fluoroalkyl group in which all or part of the hydrogen molecules in the hydrocarbon group are replaced with fluorine atoms. The surface can be covered. This carbon-fluorine bond having a low surface free energy serves to prevent intrusion of moisture and air components from the surface of the laminated film including the metal oxide film. Thereby, the change with time of the function of the metal oxide film can be reduced.

  When samples 1 to 9 were used and the F-based organic film (fourth layer) was removed, the effect of the F-based organic film on the third layer, which is the uppermost layer, was evaluated. Furthermore, samples 10 to 12 were prepared, and the effect of the F-based organic film on the intermediate layer was investigated.

  Table 6 below shows the material and film thickness (in parentheses) of Samples 10-12. Similarly to Samples 1 to 9, after molding a plastic flat substrate made of ZEONEX (manufactured by Nippon Zeon Co., Ltd.), the laminated films shown in Samples 10 to 12 below were formed by vacuum deposition within 24 hours.

Three each of the samples 10 to 12 shown in Table 6 were prepared, and the test was performed under the same conditions as the durability test of the samples 1 to 9. Samples 10-12, SiO ₂ film in the first layer, SiO ₂ layer to the second layer, third layer CrO ₂ film, CrO or Cr film, SiO ₂ film in the fourth layer, a fluorine-based fifth layer This is an example in which an organic film (triazine dithiol compound) is formed.

  The durability test results of Samples 10 to 12 were the same as those of Samples 1 to 9. Further, when the effects of the presence or absence of the fluorine-based organic film (fifth layer) were examined for Samples 10 to 12, the same results as Samples 1 to 9 were obtained.

  As mentioned above, although the Example of this invention was described, this invention is not limited to these, A various change is possible within the range of this invention described in the claim.

  For example, the monomolecular layer of the organic compound containing a fluorine atom in the bond is not limited to those shown in the above examples, and is a fluorine-based organic polymer used for antifouling coating, water / oil repellent coating, etc. A compound (fluorine-based surfactant) can be used. Such a fluorinated organic polymer compound has an alkyl group, an alkenyl group or an alkynyl group partially or entirely substituted with fluorine.

  Moreover, the member containing a metal oxide film is an optical component, an electrical component, an electronic component, etc., for example. The present invention is particularly applicable to a member in which a laminated film including a metal oxide film is formed at a location that is not completely separated or blocked from the external environment, in other words, at a location that may be affected by the external environment. It is valid.

In the member including the metal oxide film of the present invention, the material of the substrate is not particularly limited, such as a glass material, a resin material, a metal material, a ceramic material, and the like.
In the member including the metal oxide film of the present invention, the thickness of the laminated film including the metal oxide film is, for example, 10 nm or more. The manufacturing method of this laminated film is not limited to the vacuum film forming method.

  Moreover, in the member including the metal oxide film of the present invention, the stacked film including the metal oxide film is not limited to the one shown in the above embodiment, and the number of stacked layers is as long as the stacked film includes at least the metal oxide film. There may be any number of layers. In addition, the laminated film may include one layer of metal oxide film, or may include two or more layers of metal oxide film. In the laminated film, the metal oxide film may be arranged anywhere in the laminated film, and may be arranged in any layer.

  The member including the metal oxide film of the present invention can prevent moisture and oxygen from entering the stacked film by the single layer film of the fluorine-based organic compound, and therefore can be applied to any member including the stacked film including the metal oxide film, Changes in the function of the metal oxide film over time can be reduced.

  Moreover, in the said Example, although the monomolecular layer of the fluorine-type organic compound is arrange | positioned in the uppermost layer of a laminated film, the member containing the metal oxide film of this invention is not limited to this. In the member including the metal oxide film of the present invention, the monomolecular layer of the fluorine-based organic compound constitutes an intermediate layer of the laminated film, and one or more other layers on the upper layer side of the monomolecular layer of the fluorine-based organic compound May be formed. Here, the other layer formed on the upper layer side of the monomolecular layer of the fluorine-based organic compound is not particularly limited, and is, for example, a Si layer or a resin layer.

  Even in this case, the monomolecular layer of the fluorine-based organic compound functions to prevent moisture and air components from entering the lower metal oxide film layer. Therefore, the monomolecular layer of the fluorine-based organic compound constituting the intermediate layer of the laminated film can reduce the penetration of moisture and air components into the metal oxide film on the lower layer side, and can reduce the temporal change in the function of the metal oxide film.

Claims (2)

A laminated film formed on a substrate and including at least one metal oxide film layer,
The member including a metal oxide film, wherein the laminated film includes a monomolecular layer of an organic compound including a fluorine atom in a bond, which is disposed on an upper layer side than the metal oxide film layer.   The member including the metal oxide film according to claim 1, wherein the monomolecular layer of the organic compound is disposed in an uppermost layer of the laminated film.

Images