JP2019214479A - Substrate with film, and method for manufacturing substrate with film - Google Patents

Abstract

To provide a substrate with a film having a titanium oxide-containing film, in which ablation resistance is improved compared to prior art.SOLUTION: There is provided a substrate with a film having a substrate and a film placed on the substrate, in which the film is a titanium oxide-containing film, and further contains tin oxide, the film has a concentration part of the tin oxide on an outermost surface, a ratio P(Sn)/P(Ti) is 0.1 or higher and 2.4 or lower, where tin concentration is P(Sn) and titanium concentration is P(Ti) on the outermost surface, obtained by an X ray photoelectron spectroscopy (XPS), and a haze ratio measured from a film side of the substrate with the film is 0.8% or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a substrate with a film and a method for producing the substrate with a film.

A substrate with a film formed by forming a thin film of titanium oxide (TiO ₂ ) on a substrate is expected to be applied to various uses because of the significant characteristics of the TiO ₂ thin film. For example, when the substrate is a glass substrate, such a substrate with a film is expected to be applied to heat reflection glass, antifouling glass, and the like.

The substrate with a TiO ₂ thin film can be manufactured by, for example, forming a thin TiO ₂ film on the substrate by a CVD process. Patent Document 1 proposes that the deposition rate of a TiO ₂ thin film can be increased by using a specific source gas in an atmospheric pressure CVD process.

JP 2005-235552 A

As described above, a substrate with a film having a TiO ₂ thin film is expected to be applied to various uses.

However, the conventional substrate with a TiO ₂ thin film as described in Patent Document 1 has a problem that the ablation resistance is relatively poor because the thickness of the TiO ₂ thin film is small. However, on the other hand, if the thickness of the TiO ₂ thin film is increased, the advantage that the TiO ₂ is a thin film is impaired, and problems such as an increase in reflectance and / or an increase in haze may occur.

Therefore, there is a demand for a film-coated base material that can exhibit good ablation resistance without excessively increasing the thickness of the TiO ₂ thin film.

  The present invention has been made in view of such a background, and an object of the present invention is to provide a film-coated substrate having a titanium oxide-containing film with improved ablation resistance as compared with the related art. I do. Another object of the present invention is to provide a method for producing such a substrate with a film.

In the present invention, a substrate with a film having a substrate and a film disposed on the substrate,
The film is a titanium oxide-containing film, further includes a tin oxide,
The film has a concentrated portion of tin oxide on the outermost surface,
When the tin concentration at the outermost surface obtained by X-ray photoelectron spectroscopy (XPS) is P _s (Sn) and the titanium concentration is P _s (Ti), the ratio P _s (Sn) / P _s (Ti ) Is not less than 0.1 and not more than 2.4,
A substrate with a film is provided, wherein the haze ratio measured from the film side of the substrate with a film is 0.8% or less.

Further, the present invention provides a method for producing a film-coated substrate having a titanium oxide-containing film on a substrate by a normal pressure CVD process,
In the CVD process, a mixed gas of titanium tetraisopropoxide (TTIP) and tin chloride is used as a source gas,
A concentration ratio of the tin chloride to the TTIP is in a range of 0.18 mol% to 0.5 mol%;
A method is provided wherein a haze ratio measured from the film side of the manufactured substrate with a film is 0.8% or less.

  According to the present invention, it is possible to provide a film-coated substrate having a titanium oxide-containing film, which has improved ablation resistance as compared with the related art. Further, the present invention can provide a method for producing such a substrate with a film.

It is the figure which showed typically the cross section of the base material with a film by one Embodiment of this invention. FIG. 3 is a diagram schematically illustrating an example of an element concentration profile in a depth direction of a film when a base material is formed of a glass substrate. It is the figure which showed typically the flow of the manufacturing method of the base material with a film by one Embodiment of this invention. 5 is a depth profile of each element concentration in a film of Sample 1 obtained by X-ray photoelectron spectroscopy (XPS). Is a plot showing the relationship between the haze ratio for the ratio _{P s (Sn) / P s} (Ti) in the membrane of each sample. 5 is a plot showing the relationship between the reflectance difference ΔR and the ratio P _s (Sn) / P _s (Ti) in the film of each sample.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

(Substrate with film according to one embodiment of the present invention)
FIG. 1 schematically shows a cross section of a substrate with a film (hereinafter, referred to as “first substrate with a film”) according to an embodiment of the present invention.

  As shown in FIG. 1, the first base material with a film 100 includes a base material 110 and a film 120.

  The substrate 110 has a first surface 112 and a second surface 114 facing each other, and the film 120 is disposed on the first surface 112 of the substrate 110.

  The substrate 110 is not particularly limited as long as it is transparent. The substrate 110 may be, for example, a glass substrate. The thickness of the film 120 is, for example, in a range of 10 nm to 100 nm.

  Here, the first base material 100 with a film has a feature that the haze ratio measured from the side of the film 120 is 0.8% or less.

In the first base material 100 with a film, the film 120 is a titanium oxide-containing film and further contains tin oxide. Further, the film 120 has a concentrated portion of tin oxide on the outermost surface 122. More specifically, the film 120 is formed of a single layer, and the tin (Sn) concentration at the outermost surface 122 obtained by X-ray photoelectron spectroscopy (XPS) is P _s (Sn), and titanium (Ti) when the concentration of) was _P s (Ti), the ratio _{P s (Sn) / P s} (Ti) is 0.1 or more, has a characteristic that is 2.4 or less.

As described above, the conventional substrate with a TiO ₂ thin film has a problem in ablation resistance. In addition, when the TiO ₂ thin film is made thick, problems such as an increase in reflectance and / or an increase in haze may occur.

On the other hand, in the first base material with a film 100, the film 120 is mainly composed of titanium oxide, but has a concentrated portion of tin oxide on the outermost surface 122, and the above-mentioned ratio P _s (Sn) / P _s (Ti) is characterized by being 0.1 or more.

  When the film 120 is configured in this manner, the ablation resistance of the film 120 can be significantly improved due to the presence of the tin oxide concentrated portion on the outermost surface 122.

Further, in the first film-substrate 100, the aforementioned ratio _P s at the outermost surface 122 of the membrane _{120 (Sn) / P s (} Ti) is controlled to 2.4 or less. For this reason, in the first substrate with a film 100, the haze ratio can be 0.8% or less.

  By the above effects, in one embodiment of the present invention, it is possible to obtain a film-coated base material having improved ablation resistance as compared with the related art without excessively increasing the thickness of the film 120 containing titanium oxide. Can be.

  Next, each member constituting the first base material with a film 100 will be described in detail.

(Base material 110)
As described above, the substrate 110 is not particularly limited as long as it is a transparent material, and the substrate 110 may be, for example, a ceramic substrate, a plastic substrate, or a glass substrate. Examples of the glass substrate include soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, and alkali-free glass.

  When the substrate 110 is a glass substrate, the glass substrate may be transparent or colored. Such a first base material 100 with a film can be used, for example, for a window glass for a house.

When the base 110 is formed of a glass substrate, an alkali barrier layer formed of, for example, silica (SiO ₂ ) may be provided on the first surface 112 of the base 110. Thereby, durability can be improved. When providing an alkali barrier layer, the thickness of the alkali barrier layer is, for example, in a range of 10 nm to 100 nm.

  However, the alkali barrier layer is an optional layer and may be omitted. That is, the film 120 may be provided on the first surface 112 of the base 110 via the alkali barrier layer, or the film 120 may be provided directly.

  In addition, the thickness of the base material 110 is not particularly limited.

(Membrane 120)
As described above, in the first substrate with a film 100, the film 120 is mainly composed of titanium oxide, but the outermost surface 122 includes a concentrated portion of tin oxide.

  The thickness of the film 120 is, for example, in a range of 10 nm to 50 nm. Preferably, the thickness of the film 120 is less than 30 nm.

  FIG. 2 schematically shows an example of an element concentration profile in the depth direction of the film 120 when the substrate 110 is formed of a glass substrate in the first film-coated substrate 100. FIG. 2 shows the concentration profiles of titanium (Ti), tin (Sn), and silicon (Si).

  In FIG. 2, the horizontal axis represents a distance d (nm) in the depth direction from the outermost surface 122 of the film 120, and d = 0 corresponds to the outermost surface 122 of the film 120. The index on the horizontal axis is equivalent to the sputtering time of the sample surface by the XPS method.

  On the other hand, the vertical axis represents the concentration of each element obtained by the XPS method. In FIG. 2, for clarity, each element is schematically depicted such that the maximum height of each concentration (the highest concentration) is equal to each other. However, actually, the maximum concentration of each element is different (for example, see FIG. 4 below).

  As shown in FIG. 2, the concentration profile of Ti gradually increases from the outermost surface 122, becomes almost constant, and then gradually decreases. Further, Sn shows a maximum value at the outermost surface 122 and thereafter shows a behavior of gradually decreasing. On the other hand, since Si is an element derived from the glass substrate, it is almost zero in a region near the outermost surface 122 where Ti and Sn are present, and shows a behavior of gradually increasing from a depth region where the decrease of Ti starts. . Note that when the substrate 110 is formed of a glass substrate having an alkali barrier layer on the first surface 112, Si behaves similarly.

Here, according to the above description, the concentration of tin (Sn) on the outermost surface 122 is represented by P _s (Sn), and the concentration of titanium (Ti) is represented by P _s (Ti). Therefore, _ideally, P s (Sn) and _P s (Ti) corresponds to a respective element concentration of the distance d = 0.

However, due to the accuracy of the analysis by the XPS method, the concentration of each element at the position of the distance d = 0 may include a corresponding error. Therefore, in the present application, the “Sn concentration at the outermost surface”, that is, P _s (Sn), is defined as the maximum value of the Sn concentration in the range of the distance d = 0 to 5 nm, and the “concentration of Ti at the outermost surface”, that is, P _s (Ti) is defined as the minimum value of the Ti concentration in the range of the distance d = 0 to 5 nm.

As described previously, the ratio _{P s (Sn) / P s} (Ti) is 0.1 or more and 2.4 or less.

  Referring again to FIG. 2, the profile of Ti and the profile of Si intersect at a certain distance d. In the present application, the depth position L at which the intersection occurs is defined as the thickness of the film 120.

Further, in FIG. 2, two horizontal lines _{F 1} and _{F 2} is depicted.

Of these, the horizontal line _{F 1} is at a distance d = 0 to L range (i.e. the thickness), represents the average value of Ti concentration, which is expressed as _P ave (Ti) or later. A straight line _{F 2} is at a distance d = 0 to L range (i.e. the thickness), represents the average value of Sn concentration, which is expressed as _P ave (Sn) or later.

In this case, the film 120 preferably has a ratio {P _s (Sn) / P _s (Ti)} / {P _ave (Sn) / P _ave (Ti)} of 4 or more. In this case, a more conspicuous portion of tin oxide is formed on the outermost surface 122 of the film 120.

(First substrate 100 with film)
As described above, the first base material with a film 100 has a haze ratio of 0.8% or less.

The first coated substrate 100 has a visible light reflectance R ₁ (%) measured from the film 120 before the ablation test, and a visible light measured from the film 120 after the ablation test. When the reflectance is R ₂ (%), the reflectance difference ΔR = R ₁ −R ₂ is 3% or less.

Here, the ablation test is performed as follows:
First, a substrate with a film having a size of 100 mm × 100 mm (also referred to as “sample”) is placed horizontally on a table so that the film faces upward.
Next, 1 ml of the test solution is dropped on the film of the sample. The test liquid is prepared by adding 1.0 g of powder specified in JIS Z8901 and 2 drops of neutral detergent to 1 liter of tap water.
Next, using a polishing cloth (wool buff) having a contact surface of 30 mm × 11 mm, the polishing cloth is linearly reciprocated 420 times while applying a load of 1100 g / cm ² to the sample.

The measurement of the visible light reflectance _{R 1} and _{R 2} of the sample which is performed after the ablation test is performed in conformity with JIS Z 8722.

  Since the first substrate with a film 100 has good ablation resistance, it is possible to significantly suppress a decrease in the reflectance difference ΔR. Further, in the first base material 100 with a film, the haze ratio can be significantly suppressed without increasing the film thickness too much.

(Method of manufacturing a substrate with a film according to one embodiment of the present invention)
Next, an example of a method for manufacturing a base material with a film according to an embodiment of the present invention will be described with reference to FIG.

  FIG. 3 schematically shows a flow of a method for manufacturing a substrate with a film according to one embodiment of the present invention (hereinafter, referred to as a “first manufacturing method”).

As shown in FIG. 3, the first manufacturing method includes:
(1) a step of preparing a substrate having a first surface (step S110);
(2) a step of forming a film on the first surface (step S120);
Have

  Hereinafter, each step will be described.

  Here, for the sake of clarity, the first manufacturing method will be described using the first film-coated base material 100 as shown in FIG. 1 as an example. Therefore, the reference numerals shown in FIG. 1 are used to represent each member.

(Step S110)
First, the base material 110 is prepared. As described above, the substrate 110 may be a transparent substrate, for example, a glass substrate.

  The substrate 110 has a first surface 112 on which the film 120 will be placed in a later step.

When the substrate 110 is a glass substrate, an alkali barrier layer (SiO ₂ layer) may be provided on the first surface 112 of the substrate 110.

  In addition, the method of installing the alkali barrier layer is well known to those skilled in the art. Therefore, it will not be described further here.

(Step S120)
Next, a film 120 is formed on the first surface 112 of the substrate 110. When the substrate 110 is a glass substrate and has an alkali barrier layer, the film 120 may be provided directly on the alkali barrier layer.

  The film 120 is formed by a normal pressure CVD process. More specifically, the following processing is performed.

  First, the substrate 110 is heated to a predetermined temperature.

  Next, a reactive gas is supplied to the first surface 112 of the substrate 110. The reaction gas contains a source gas and oxygen. The source gas includes a titanium source gas and a tin source gas. Among them, the titanium source gas contains titanium tetraisopropoxide (TTIP). In addition, the tin source gas contains tin chloride, for example, tin tetrachloride and / or monobutyltin trichloride (MBTC).

  The film formation temperature is, for example, in the range of 500 ° C to 700 ° C, and preferably in the range of 550 ° C to 600 ° C.

  In this step, the film 120 is formed while the substrate 110 is being transported. The transport speed of the substrate 110 is, for example, in a range of 1 m / min to 20 m / min. The supply rate of the reaction gas is adjusted so that the thickness of the film 120 is in the range of 10 nm to 50 nm. For example, the supply amount of TTIP may be in a range of 0.05 mol% to 1.2 mol%.

  Here, the concentration ratio of tin chloride to TTIP contained in the reaction gas is adjusted in the range of 0.18 mol% to 0.5 mol%.

By forming a film under such conditions, a thin film 120 of titanium oxide in which tin oxide is concentrated can be formed on the outermost surface 122. That is, by forming a film under such conditions, the aforementioned ratio _{P s (Sn) / P s} (Ti) is capable of forming a 0.1 or more films 120. Further, a substrate with a film having a haze ratio of 0.8% or less can be obtained.

  Through such a normal pressure CVD process, the first base material with a film 100 can be manufactured.

  In the above description, the film formation step (step S120) was performed using the base material 110 prepared in advance, and the base material with a film 100 was thus manufactured (so-called “batch processing”).

  However, when the substrate 110 is a glass substrate, the film-forming step (step S120) may be performed during the manufacturing process of the glass substrate to manufacture the substrate 110 with a film (so-called “continuous processing”).

For example, when manufacturing a glass substrate, a glass ribbon is moved slowly over a molten tin bath, then slowly cooled, and then cut into predetermined dimensions. During the movement of the glass ribbon, the film 120 may be formed on the upper surface (corresponding to the first surface 112) of the glass ribbon by a normal pressure CVD process. If necessary, before forming the film 120, an alkali barrier layer (SiO ₂ ) may be formed on the upper surface of the glass ribbon by a normal pressure CVD process.

  In such a manufacturing method, since the temperature of the substrate 110 (glass ribbon) has already been increased at the time of film formation, the heating process of the substrate 110 can be omitted. Further, a large number of base materials with a film 110 can be continuously manufactured.

  Next, examples of the present invention will be described. However, the present invention is not limited to these.

  In the following description, Examples 1 to 3 are Examples, and Examples 4 to 6 are Comparative Examples.

(Example 1)
According to the following method, a titanium oxide-containing film was formed on a substrate using a normal pressure CVD method, and a substrate with a film was manufactured.

  A glass substrate (transparent soda lime glass) was used as a base material.

  The normal pressure CVD process was performed by blowing a source gas and oxygen onto one surface (first surface) of the substrate. The source gas was a mixed gas of titanium tetraisopropoxide (TTIP) and monobutyltin trichloride (MBTC), and the concentration ratio of MBTC to TTIP (MBTC / TTIP) was 0.25 mol%.

  The temperature of the substrate was 560 ° C. The target film thickness was 20 nm.

  Thus, a substrate with a film (hereinafter, referred to as “sample 1”) was manufactured.

(Example 2)
In the same manner as in Example 1, a substrate with a film (hereinafter, referred to as “sample 2”) was produced.

  However, in Example 2, the concentration ratio of MBTC to TTIP (MBTC / TTIP) was 0.50 mol% in the normal pressure CVD process.

(Example 3)
In the same manner as in Example 1, a substrate with a film (hereinafter, referred to as “sample 3”) was produced.

  However, in Example 3, the target film thickness was 30 nm.

(Example 4)
In the same manner as in Example 1, a substrate with a film (hereinafter, referred to as “sample 4”) was produced.

  However, in Example 4, the concentration ratio of MBTC to TTIP (MBTC / TTIP) was set to 0.05 mol% in the normal pressure CVD process.

(Example 5)
In the same manner as in Example 1, a substrate with a film (hereinafter, referred to as “sample 5”) was produced.

  However, in Example 5, the concentration ratio of MBTC to TTIP (MBTC / TTIP) was 0.05 mol% in the normal pressure CVD process. The target film thickness was 30 nm.

(Example 6)
In the same manner as in Example 1, a substrate with a film (hereinafter, referred to as “sample 6”) was produced.

  However, in Example 6, the concentration ratio of MBTC to TTIP (MBTC / TTIP) was set to 0.50 mol% in the normal pressure CVD process. The target film thickness was 35 nm.

(Evaluation)
The following evaluation was performed using each sample manufactured as described above.

(Measurement of element profile in film)
Using the XPS method, the concentration profiles of tin, titanium, and silicon in the film thickness direction of each sample were measured. For the measurement, a scanning X-ray photoelectron spectrometer (PHI 5000 VersaProbe, manufactured by ULVAC-PHI, Inc.) was used, and the beam diameter was 100 μm.

  FIG. 4 shows an example of the measurement results obtained in Sample 1.

  In FIG. 4, the horizontal axis is the sputtering time t (min), and the vertical axis is the concentration (atomic%) of tin, titanium, and silicon. Here, the total amount of tin, titanium, silicon, calcium, sodium, carbon, and oxygen is set to 100 atomic%.

  As shown in FIG. 4, in Sample 1, the tin concentration in the film showed a maximum value at a position where the sputtering time t was 0, and then showed a profile that gradually decreased. In addition, the titanium concentration showed a profile in which the sputtering time t gradually increased until the sputtering time t was from 0 to 5 minutes, became substantially constant thereafter in the range of 5 minutes to 15 minutes, and gradually decreased after t was 15 minutes. . On the other hand, the silicon concentration gradually increased from the position where the sputtering time t was about 15 minutes, and at the position where the sputtering time t was about 20 minutes, the silicon concentration showed a behavior reverse to the titanium concentration.

  From this, it was found that the film of Sample 1 had titanium (oxide) as a main component and a tin (oxide) enriched portion on the outermost surface. From the above definition, it was found that the film thickness L of the film was about 18.3 nm (corresponding to a sputtering time t = 20 minutes).

  In samples 2 and 3, almost similar profiles were obtained. On the other hand, in Samples 4 and 5, enrichment of tin oxide on the outermost surface of the film was not recognized.

From the results obtained in each sample, the thickness L, the ratio _{P s (Sn) / P s} (Ti), and the ratio _{{P s (Sn) / P} s (Ti)} / {P ave (Sn) / P _ave (Sn)} was determined.

  The results obtained for each sample are shown in Table 1 below together with the film forming conditions.

（ヘイズ率の測定）
各サンプルに対して、ヘイズメータを用いてヘイズ率の測定を行った。

(Measurement of haze ratio)
The haze ratio of each sample was measured using a haze meter.

(Ablation test)
An ablation test was performed on each sample in the manner described above. Also, from the measurement results of the visible light reflectance R ₁ (%) measured from the film side before the ablation test and the visible light reflectance R ₂ (%) measured from the film side after the ablation test, The rate difference ΔR = R ₁ −R ₂ was determined.

  Table 2 below summarizes the values of the haze ratio and the reflectance difference ΔR obtained for each sample.

表２から、サンプル１〜５では、いずれもヘイズ率は、０．４以下となっており、ヘイズ率が低く抑えられていることがわかる。一方、サンプル６では、約１％の高いヘイズ率を示した。

From Table 2, it can be seen that the haze ratios of Samples 1 to 5 are all 0.4 or less, and the haze ratios are kept low. On the other hand, Sample 6 showed a high haze ratio of about 1%.

  Samples 1 to 3 all have a reflectance difference ΔR of 3% or less, while samples 4 and 5 have a reflectance difference ΔR of more than 3%. .

  FIG. 5 shows the results of the haze ratio obtained for each sample. In FIG. 5, the horizontal axis is the ratio Ps (Sn) / Ps (Ti) in the film of each sample, and the vertical axis is the haze ratio. Each plot in FIG. 5 shows the sample number (1 to 6).

  FIG. 6 collectively shows the values of the reflectance difference ΔR obtained in each sample. In FIG. 6, the horizontal axis is the ratio Ps (Sn) / Ps (Ti) in the film of each sample, and the vertical axis is the reflectance difference ΔR. Each plot in FIG. 6 shows the sample number (1 to 6).

  FIG. 5 shows that the haze ratio tends to increase as the ratio Ps (Sn) / Ps (Ti) increases. When the ratio Ps (Sn) / Ps (Ti) exceeds about 2.4, the haze ratio becomes zero. It turns out that it exceeds 0.8%.

  Also, from FIG. 6, the reflectance difference ΔR shows a tendency to decrease as the ratio Ps (Sn) / Ps (Ti) increases, and when the ratio Ps (Sn) / Ps (Ti) falls below about 0.1, It can be seen that the reflectance difference ΔR exceeds 3%.

  As described above, it was confirmed that by appropriately adjusting the concentration ratio of MBTC to TTIP (MBTC / TTIP) and the film thickness L in the CVD process, a concentrated portion of tin oxide can be obtained on the outermost surface of the film. It was also confirmed that when such CVD process conditions were employed, a haze ratio was low, and a substrate with a film having excellent ablation resistance was obtained.

100 Base material with a film 110 Base material 112 First surface 114 Second surface 120 Film 122 Top surface according to one embodiment of the present invention

Claims (13)

A substrate, a substrate with a film having a film disposed on the substrate,
The film is a titanium oxide-containing film, further includes a tin oxide,
The film has a concentrated portion of tin oxide on the outermost surface,
When the tin concentration at the outermost surface obtained by X-ray photoelectron spectroscopy (XPS) is P _s (Sn) and the titanium concentration is P _s (Ti), the ratio P _s (Sn) / P _s (Ti ) Is not less than 0.1 and not more than 2.4,
A substrate with a film, wherein a haze ratio measured from the film side of the substrate with a film is 0.8% or less.   The base material with a film according to claim 1, wherein the base material is a glass substrate.   The base material with a film according to claim 2, wherein the glass substrate has an alkali barrier layer on the side of the film.   The film-coated substrate according to any one of claims 1 to 3, wherein the film has a thickness in a range of 10 nm to 50 nm. In the film, the average value of the tin concentration over the thickness L of the film obtained by the X-ray photoelectron spectroscopy (XPS) method is P _ave (Sn), and the average value of the titanium concentration over the thickness L of the film is when was the _P ave (Ti), the ratio _{{P s (Sn) / P} s (Ti)} / {P ave (Sn) / P ave (Ti)} is 4 or more, according to claim 1 to 4 The substrate with a film according to any one of the above. A method for producing a substrate with a film having a titanium oxide-containing film on the substrate by a normal pressure CVD process,
In the CVD process, a mixed gas of titanium tetraisopropoxide (TTIP) and tin chloride is used as a source gas,
A concentration ratio of the tin chloride to the TTIP is in a range of 0.18 mol% to 0.5 mol%;
The method, wherein a haze ratio measured from the film side of the manufactured substrate with a film is 0.8% or less. The tin chloride, tin tetrachloride (SnCl ₄₎ and / or monobutyltin trichloride (MBTC), The method of claim 6.   The method according to claim 6, wherein the titanium oxide-containing film has a thickness in a range of 10 nm to 50 nm.   The method according to any one of claims 6 to 8, wherein the substrate is a glass substrate.   The method according to claim 9, further comprising forming an alkali barrier layer on the base material before forming the titanium oxide-containing film.   The method according to claim 9, wherein the atmospheric pressure CVD process is performed during a manufacturing process of the glass substrate, and the titanium oxide-containing film is formed on a glass ribbon.   The method according to any one of claims 6 to 11, wherein a temperature of the substrate during the formation of the titanium oxide-containing film is in a range of 500C to 700C.   The method according to any one of claims 6 to 11, wherein a temperature of the substrate during the formation of the titanium oxide-containing film is in a range of 550 ° C to 600 ° C.

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