JPS6230148B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improvement in a glass body with an alkali diffusion-preventing silica film that prevents alkali ions from diffusing from the glass base of an alkali-containing glass. Glass plates as a transparent material are chemically stable, have excellent surface hardness, can withstand high temperatures of about 500℃ to 700℃, and have excellent electrical insulation and chemical properties, so they are used for construction and vehicles. , as well as aircraft window glass materials, optical parts, electrical parts,
Used in electronic parts, etc. In particular, recently, conductive glass plates with conductive coatings formed on the glass plate surfaces have been used for display elements such as liquid crystal elements, electrochromic elements, and electroluminescent elements, amorphous solar cell substrates, and the like. As the glass substrate for these conductive glass plates, there is a tendency to use soda lime silica glass plates, which are the most commonly used and inexpensive. Since it contains alkaline components such as sodium and potassium, it has the disadvantage that the performance of the coated conductive film deteriorates due to the diffusion of alkali ions from the glass base to the surface after long-term use. for example,
The conductive film of the conductive glass plate may become cloudy or lose its transparency, or the resistance value of the conductive film may increase or its chemical and physical durability may decrease. In other words, in liquid crystal display elements, alkali diffused from glass causes a redox reaction on the surface of the display electrode, altering the indium oxide film (ITO film) or tin oxide film (NESA film), which are the transparent electrode materials, and furthermore. The liquid crystal itself also deteriorates due to electrolysis. Electrochromic elements also wear out their electrodes for the same reason, causing electrolytic corrosion and deterioration of the electrochromic materials such as tungsten oxide and molybdenum oxide, leading to deterioration of the element. Furthermore, in the case of an electroluminescent device, alkali released from the glass surface by diffusion penetrates the conductive film and enters the phosphor material, changing the luminous efficiency and even the luminous color. Furthermore, in the case of amorphous solar cells, it is said that the alkali that comes out through the electrodes may diffuse into the amorphous silicon and reduce the conversion efficiency. Alternatively, in alkali-containing glasses such as soda lime silica glass, alkali ions tend to move easily during high-temperature processing, and due to the diffusion of alkali ions during high-temperature processing in the structure of conductive glass or various coated glasses. Another drawback is that the performance of the conductive film or various coating films is degraded. Three solutions are conventionally available to compensate for these drawbacks of plain glass. One method is to use plate glass with a composition in which alkali diffusion is not a problem, such as silica glass, high silica glass (Vycor), alkali-free aluminosilicate glass (CGW#7059, etc.), or low alkali borosilicate (Pyrex, etc.). It is.
However, these glasses are expensive, not always readily available, and have poor surface smoothness, requiring the surface to be re-polished. In fact, in extreme cases, because it is difficult to obtain glass in the form of thin sheets, glass several millimeters thick is shaved and polished to obtain sheets of 1 mm. This is a very unfavorable situation from the point of view of saving material resources and energy. The second solution is to remove or reduce the alkali component from the soda lime silica glass surface layer in advance, by contacting it with sulfur powder at high temperature, or by heating it to a temperature of 300°C or higher in a vacuum and applying a DC electric field to remove Na ⁺ Methods that have been proposed include sweeping ions to the side opposite to the ITO (NESA) coated surface, and boiling them in acids such as hydrochloric acid or sulfur. This method is time consuming and has insufficient reproducibility. The third solution is to form a thin film on the surface of ordinary soda-lime silica glass to prevent some kind of alkali diffusion, and silica film is generally used. The reason why a silicon oxide film (e.g., SiO ₂ film) is used to prevent alkali diffusion is that the film is amorphous, and when another thin film, such as a conductive film, is formed on top of it, it is essentially the same film that is formed on glass. This is because the refractive index of the silicon oxide film is slightly lower than that of glass, but it is close to that of glass, and because it is transparent to a wider range of light than normal plate glass, the transparency of glass is not impaired. The silicon oxide film mentioned above has a broad meaning, and in detail, it can be a pure silicon oxide film or a silicon oxide film mixed with appropriate impurities, such as a silicon oxide film mixed with a small amount of boron or phosphorus to increase its ability to prevent the diffusion of alkali ions. There is a silicon oxide film. Methods for forming such a silicon oxide film for preventing alkali diffusion include the sputtering method, vacuum evaporation method, ion plating method, or CVD method under as high a vacuum as possible to make the film denser and increase the alkali blocking ability. A method of forming a pure silicon oxide film such as pure SiOx (0<x≦2), a method of forming the same pure silicon oxide film using the sol/gel method, or a method of easily incorporating additives such as boron or phosphorus. Typical methods include forming a boron-containing silicon oxide film or a phosphorus-containing silicon oxide film by a sol/gel method. As described above, silicon oxide films for preventing alkali diffusion formed by various methods have alkali diffusion inhibiting effect to some extent, although the degree of effectiveness varies, but it is still not sufficient, and the performance may vary depending on the manufacturing method, manufacturing conditions, etc. They had the disadvantage of being very different. As mentioned above, the present inventors have discovered that the conventional alkali diffusion-preventing silicon oxide films have various drawbacks, such as severe manufacturing constraints such as manufacturing condition control, composition control, and raw material adjustment during formation of the alkali diffusion-preventing silicon oxide film. As a result of research into an alkali diffusion prevention silicon oxide film that has no defects and has a higher alkali diffusion prevention effect than conventional alkali diffusion prevention silicon oxide films, we found that fluorine combined with silicon (Si) in the silicon oxide film or this fluorine By containing a combination of hydrogen and hydrogen bonded to silicon, in other words, by making Si-F bonds exist in a part of -O-Si-O- bonds in the silicon oxide film, or by combining them with Si-F bonds. Si
-H bond, it was discovered that the diffusion of alkali in glass could be suppressed more than the silicon oxide film containing phosphorus and boron, which was known to have an excellent alkali diffusion inhibiting effect, and the present invention was made based on the present invention. This is what we have come to propose. That is, the present invention provides a glass in which an alkali diffusion-preventing silicon oxide film is formed on the surface of the alkali-containing glass to suppress alkali diffusion from the glass, in which the alkali diffusion-preventing silicon oxide film is made of fluorine or fluorine bonded to silicon. This invention relates to a glass body with a silicon oxide film for preventing alkali diffusion, characterized in that it contains fluorine bonded to silicon and hydrogen bonded to silicon. The reason why the silicon oxide film for preventing alkali diffusion of the present invention increases the ability to prevent alkali diffusion from glass is not clear, but -O-Si-
By having a -Si-F bond or a -Si-F bond and a -Si-H bond in some of the O- bonds, the network structure of the silicon oxide film becomes denser and there are no structural defects, and the terminal Due to the effect that F or F and H are positively charged and obstruct the movement of alkali ions such as Na ⁺ and K ⁺ , there is a concentration difference between the inside of the glass and the coating material coated on the surface, or an electrical This is thought to be to prevent alkali ions from leaching to the glass surface due to triggers. In the present invention, the content of fluorine or fluorine and hydrogen that participates in bonding with silicon in the alkali diffusion preventing silicon oxide film is preferably in the range of 0.01 to 20%. More preferably, the optimum content is 0.1 to 10%.
The existence of such Si-F bonds or Si-F bonds and Si-H bonds can be confirmed by, for example, infrared spectroscopy. As a result of investigating the relationship with the amount of alkali diffusion using this detection method, it was found that, as mentioned above, there is excellent alkali blocking ability with a fluorine content of 0.01% to 20% or a fluorine and hydrogen content. did. If the fluorine content or the fluorine and hydrogen content exceeds 20%, the hardness of the alkali diffusion-preventing silicon oxide film decreases and the film becomes easily scratched, which is undesirable. For example, when an alkali diffusion-preventing silicon oxide film is applied to a transparent electrode plate of a display element, the hardness of the film decreases, which poses a problem in terms of ease of handling during the manufacturing process, which is undesirable. Also, if it is less than 0.01%,
This is not preferable because the ability to prevent alkali diffusion is weakened. Note that in addition to fluorine or hydrogen bonded to silicon, fluorine or hydrogen contained in the form of F ₂ or H ₂ may also exist in the silicon oxide film, but in the silicon oxide film of the present invention, The fluorine content and hydrogen content are fluorine or hydrogen combined with silicon, i.e.
It represents the content of fluorine or hydrogen that forms Si-F bonds or Si-H bonds. The thickness of the silicon oxide film for preventing alkali diffusion of the present invention is preferably 50 Å or more so as to exhibit sufficient alkali diffusion inhibiting ability. Among them, 100
A range of Å to 5000 Å is most practical. In addition, the most commonly used glass to which the alkali diffusion prevention silicon oxide film of the present invention can be applied is
Examples include soda lime silica glass containing 10 to 20 wt% of Na and K, as well as various other alkali-containing glasses. Further, methods for forming the alkali diffusion preventing silicon oxide film of the present invention include vacuum evaporation method, sputtering method,
PVD method such as ion plating method, CVD method,
In addition to the low pressure CVD method and the sol/gel method, various film formation methods can be used. In addition, in the case of PVD method,
In addition to the method of depositing SiO ₂ on the deposition source target, methods such as reactive vapor deposition or reactive sputtering using Si or SiO as the deposition source target are adopted. Methods for introducing fluorine or hydrogen into the silicon oxide film include vacuum evaporation, sputtering, and ion plating.
In the PVD method, fluorine gas, fluorine compound gas, hydrogen gas, or hydride compound gas is introduced into a vacuum chamber to form Si-F bonds or Si-F bonds and Si-H bonds during film formation. How to do it, and
In _the CVD method, Si-
A typical method is to form an F bond or a Si-F bond and a Si-H bond, but in addition to these methods, after forming a silicon oxide film, it may be formed in a fluorine atmosphere or in a fluorine and hydrogen atmosphere. For example, after forming a silicon oxide film, fluorine ions or fluorine ions and hydrogen ions are introduced by ion implantation. The alkali diffusion-preventing silicon oxide film of the present invention does not contain additives in the form of solid components like conventional alkali diffusion-preventing silicon oxide films containing additives, but is in an amorphous state and its tertiary form. It differs from conventional alkali diffusion prevention films in that a part of the original network structure includes Si--F bonds, or both Si--F and Si--H bonds. Therefore, since the alkali-diffusion silicon oxide film of the present invention does not contain solid additives, it is easy to work in the raw material preparation stage, and the film formation process does not require fractional distillation or other problems that tend to occur in vacuum evaporation. There is no need to worry about the dissipation of additive components during sputtering, and the film formation process becomes easier. Next, examples of the present invention will be described. Example 1 Alkaline component R ₂ O (R:
An ordinary glass plate (soda lime silica glass plate) containing 15% Na, K) was thoroughly washed with detergent, washed with water, and dried. After placing this glass plate in a vacuum chamber of a vacuum evaporation device and evacuating the chamber to 1×10 ^-5 torr, argon gas containing 15% hydrogen gas and 5% CF ₄ gas was introduced. At 2×10 ^-4 torr, a high-frequency electromagnetic field (frequency 13.56 MHz) was applied to ionize the introduced gas, while the evaporation source (SiO ₂ powder) was heated by electron beam heating at a deposition rate of about 10 Å/sec. By high frequency ion plating method, approx.
A 1000 Å SiO ₂ film was formed. Next, dry air was introduced into the vacuum chamber from the variable leak valve to a pressure of 3 x 10 ^-3 torr, and then about 2000 Å of SnO was deposited using the ordinary vacuum evaporation method using tin oxide added with antimony oxide as the evaporation source. ₂ conductive films were formed.
Note that the distance between the evaporation source and the glass substrate during the formation of the SiO ₂ film and the SnO ₂ film was 40 cm, and the substrate temperature was set to room temperature. Table 1 shows the fluorine content, hydrogen content, and alkali diffusion inhibiting ability of Sample 1 thus obtained. Example 2 A glass plate similar to Example 1 was thoroughly washed with a detergent, washed with water, and dried. This glass plate was placed in the vacuum chamber of the RF2 pole sputtering device, and the inside of the chamber was
15% hydrogen gas and 5% after exhausting to 10 ^-5 torr
3x by introducing argon gas containing _CF4 gas.
RF2 using a fused silica target at 10 ^-2 torr.
An approximately 1000 Å SiO ₂ film was formed using the polar sputtering method. Next, the glass substrate on which the SiO ₂ film was formed was transferred to a vacuum evaporation apparatus, and after setting the inside of this vacuum chamber to 3 × 10 ^-4 torr, it was subjected to ordinary vacuum evaporation using tin oxide added with antimony oxide as a evaporation source. Approximately 2000Å
A SnO ₂ conductive film was formed. Note that the glass substrate temperature during sputtering was approximately 300°C, and the glass substrate temperature during vapor deposition was room temperature. Table 1 shows the fluorine content, hydrogen content, and alkali diffusion inhibiting ability of Sample 2 thus obtained. Example 3 A glass plate similar to Example 1 was thoroughly washed with detergent, washed with water, and dried. This glass plate was placed in a vacuum chamber of an RF magnetron sputtering device, and after the chamber was evacuated to 1×10 ^-5 torr, argon gas containing 15% hydrogen gas and 5% CF ₄ gas was introduced. 3×10 ^-3 torr using a fused silica target.
A 1000 Å SiO ₂ film was formed using the RF magnetron sputtering method. Next, the glass substrate on which the SiO ₂ film was formed was transferred to a vacuum evaporation device, and the inside of this vacuum chamber was heated 3×.
After reducing the temperature to 10 ^-4 torr, it was evaporated using a normal vacuum evaporation method using tin oxide to which antimony oxide was added as a evaporation source.
A 2000 Å SnO ₂ conductive film was formed. Note that the glass substrate temperature during sputtering was approximately 300°C, and the glass substrate temperature during vapor deposition was room temperature. Table 1 shows the fluorine content, hydrogen content, and alkali diffusion inhibiting ability of Sample 3 thus obtained. Example 4 A glass plate similar to Example 1 was thoroughly washed with detergent, washed with water, and dried. This glass plate surface was coated with approximately 5% SiF ₄ , SiH ₄ gas and O ₂ gas by CVD
1000Å SiO ₂ film at substrate temperature of 300℃, 400℃, 450℃
℃, formed at 550℃. Note that O ₂ :(SiH ₄ +
SiF ₄ ) ratio was approximately 10:1. Then these
The glass substrate on which the SiO ₂ film has been formed is placed in a vacuum chamber of a vacuum evaporation device, and the inside of this vacuum chamber is heated to 3×10 ^-4 torr.
After that, a film of about 2000 Å was deposited using the normal vacuum evaporation method using tin oxide added with antimony oxide as the evaporation source.
A SnO ₂ conductive film was formed. Note that the glass substrate temperature during vapor deposition was room temperature. Among these four samples, the substrate temperature was set to 300
Sample 4 is the one with SiO ₂ film formed at ℃.
Sample 5 has a SiO ₂ film formed at a substrate temperature of 400°C, Sample 6 has a SiO ₂ film formed at a substrate temperature of 450°C, and Sample 7 has a SiO ₂ film formed at a substrate temperature of 550°C. And so. Table 1 shows the fluorine content, hydrogen content, and alkali diffusion inhibition ability for each of these samples. Example 5 A glass plate similar to Example 1 was thoroughly washed with a detergent, washed with water, and dried. This glass plate was placed in a vacuum chamber of a vacuum evaporation device, and the chamber was evacuated to 1×10 ^-5 torr, and then SiF ₄ gas was introduced and 2×
With the vacuum chamber heated to 10 ^-4 torr and 200°C, a high-frequency electromagnetic field (frequency 13.56MHz) is applied to ionize the introduced gas, while the evaporation source (SiO ₂ powder) is heated by electron beam heating. A SiO ₂ film with a thickness of about 1000 Å was formed by high-frequency ion plating at a deposition rate of about 10 Å/sec. Next, dry air was introduced into the vacuum chamber from the variable leak valve to a pressure of 3×10 ^-3 torr, and then
A SnO ₂ conductive film with a thickness of approximately 2000 Å was formed by a normal vacuum deposition method using tin oxide doped with antimony oxide as a deposition source. Note that the distance between the evaporation source and the glass substrate during the formation of the SiO ₂ film and the SnO ₂ film was 40 cm, and the substrate temperature was set to room temperature. Table 1 shows the fluorine content and alkali diffusion inhibiting ability of Sample 8 thus obtained. Example 6 A glass plate similar to Example 1 was thoroughly washed with detergent, washed with water, and dried. This glass plate was placed in the vacuum chamber of the RF2 pole sputtering device, and the inside of the chamber was
After exhausting to 10 ^-5 torr, SiF ₄ gas was introduced and 3×
A SiO ₂ film of about 1000 Å was formed using a fused silica target by the RF two-pole sputtering method under conditions of 10 ^-2 torr and heating the vacuum chamber to 200°C. next
The glass substrate on which the SiO ₂ film was formed was transferred to a vacuum evaporation apparatus, and the inside of this vacuum chamber was set to 3 × 10 ^-4 torr, and then a film of about 2,000 Å was deposited using a normal vacuum evaporation method using tin oxide added with antimony oxide as the evaporation source. A SnO ₂ conductive film was formed. Note that the glass substrate temperature during sputtering was approximately 300°C, and the glass substrate temperature during vapor deposition was room temperature. Table 1 shows the fluorine content and alkali diffusion inhibiting ability of Sample 9 thus obtained. Example 7 A glass plate similar to Example 1 was thoroughly washed with detergent, washed with water, and dried. This glass plate was placed in a vacuum chamber of an RF magnetron sputter device, and the chamber was evacuated to 1×10 ^-5 torr, and then SiF ₄ gas was introduced to reduce the pressure to 3×10 ^-3 torr, and the vacuum chamber was closed. RF using a fused silica target heated to 200℃
An approximately 1000 Å SiO ₂ film was formed using the magnetron sputtering method. Next, the glass substrate on which the SiO ₂ film was formed was transferred to a vacuum evaporation device, and the inside of this vacuum chamber was heated 3×.
After reducing the temperature to 10 ^-4 torr, it was evaporated using a normal vacuum evaporation method using tin oxide to which antimony oxide was added as a evaporation source.
A 2000 Å SnO ₂ conductive film was formed. Note that the glass substrate temperature during sputtering was set to room temperature. Table 1 shows the fluorine content and alkali diffusion inhibiting ability of Sample 10 thus obtained. Example 8 A glass plate similar to Example 1 was thoroughly washed with detergent, washed with water, and dried. This glass plate surface is coated with SiF ₄ gas, O ₂ gas and water vapor using CVD method.
1000Å SiO ₂ film at substrate temperature of 350℃, 450℃, 550℃
It was formed with. The ratio of O ₂ :SiF ₄ :H ₂ O is 10:
I did it at 1:0.1. Next, the glass substrate on which these SiO ₂ films have been formed is placed in a vacuum chamber of a vacuum evaporation device,
After setting the inside of this vacuum chamber to 3×10 ^-4 torr, a SnO ₂ conductive film of about 2000 Å was formed by a normal vacuum evaporation method using tin oxide to which antimony oxide was added as a evaporation source. Note that the glass substrate temperature during vapor deposition was room temperature. Among these three samples, the substrate temperature was set to 350
Sample 11 is the one with SiO ₂ film formed at ℃.
Sample 12 was a sample in which a SiO ₂ film was formed at a substrate temperature of 450°C, and Sample 13 was a SiO ₂ film formed at a substrate temperature of 550°C. Table 1 shows the fluorine content and alkali diffusion inhibiting ability of each of these samples. Comparative Example 1 A glass plate similar to Example 1 was thoroughly washed with detergent, washed with water, and dried. This glass plate was placed in a vacuum chamber of a vacuum evaporation device, and the chamber was evacuated to 5×10 ^-5 torr, and then the evaporation source (SiO ₂ powder) was heated by electron beam heating at approximately 10 Å/second. A SiO ₂ film with a thickness of approximately 1000 Å was formed using a conventional vacuum evaporation method at a deposition rate of . Next, dry air was introduced into the vacuum chamber from the barrier pull leak valve to 3×10 ^-3 torr.
After that, a film with a thickness of about 2000 Å was deposited using a normal vacuum evaporation method using tin oxide added with antimony oxide as a deposition source.
A SnO ₂ conductive film was formed. Note that the distance between the evaporation source and the glass substrate during the formation of the SiO ₂ film and the SnO ₂ film was 40 cm, and the substrate temperature was set to room temperature. Table 1 shows the alkali diffusion inhibiting ability of Sample 14 thus obtained. Comparative Example 2 A glass plate similar to Example 1 was thoroughly washed with detergent, washed with water, and dried. This glass plate was placed in the vacuum chamber of the RF2 pole sputtering device, and the inside of the chamber was
After evacuation to 10 ^-5 torr, argon gas was introduced to bring the pressure to 3 x 10 ^-2 torr, and a SiO ₂ film of about 1000 Å was formed by RF bipolar sputtering using a fused silica target. Next, the glass substrate on which the SiO ₂ film was formed was transferred to a vacuum evaporation device, and the inside of this vacuum chamber was heated to 3×10 ^-4 torr.
After that, a film of approximately 2000 Å was deposited using the ordinary vacuum evaporation method using tin oxide added with antimony oxide as the evaporation source.
A SnO ₂ conductive film was formed. Note that the glass substrate temperature during sputtering was approximately 300°C, and the glass substrate temperature during vapor deposition was room temperature. Table 1 shows the alkali diffusion inhibiting ability of Sample 15 thus obtained. Comparative Example 3 A glass plate similar to Example 1 was thoroughly washed with detergent, washed with water, and dried. This glass plate was placed in a vacuum chamber of a vacuum evaporation device, and the chamber was evacuated to 3×10 ^-3 torr, and then heated using an electron beam heating method using tin oxide added with antimony oxide as a deposition source. A SnO ₂ conductive film with a thickness of approximately 2000 Å was formed using a conventional vacuum evaporation method. Note that the distance between the evaporation source and the glass substrate during formation of the SnO ₂ film was 40 cm, and the substrate temperature was room temperature. Table 1 shows the alkali diffusion inhibiting ability of Sample 16 thus obtained.

[Table] The fluorine content (%) and hydrogen content (%) in the SiO ₂ film in the above table are determined by infrared spectroscopy to determine the percentage of fluorine that forms Si-F bonds in the SiO ₂ film. and the content of hydrogen forming Si-H bonds, and the alkali diffusion inhibition ability is
The evaluation was based on the amount of alkali leached through the SiO ₂ membrane, and the measurement method was to heat each sample at 550℃.
heat treatment for 30 minutes to promote alkali diffusion from the glass, then the surface SnO ₂ film was eluted with an etching solution of (HCl + Zn), and the sodium contained in the eluted solution was measured by atomic absorption spectrometry. This is what I did. As is clear from the table above, the glass body with a silicon oxide film for preventing alkali diffusion of the present invention is produced by introducing fluorine bonded to silicon or fluorine and hydrogen into the silicon oxide film. It is recognized that leaching of alkali can be prevented compared to a silicon oxide film that does not introduce hydrogen or hydrogen. Moreover, it has performance equivalent to or superior to that of the phosphorous-containing SiO ₂ film formed by the sol/gel method, which was conventionally considered to have the best ability to inhibit alkali diffusion. Moreover, the glass body with a silicon oxide film for preventing alkali diffusion of the present invention has fewer restrictions on manufacturing methods, manufacturing conditions, etc., and can obtain high alkali diffusion inhibiting ability. Furthermore, the glass body with an alkali-diffused silicon oxide film of the present invention has hardness, adhesion, light stability, and thermal stability up to about 400°C with respect to the glass body.
It is sufficiently stable under various environmental conditions and processing conditions. The glass body with an alkali-diffusion silicon oxide film of the present invention is particularly suitable as an alkali-diffusion prevention film for conductive glasses used in display devices such as liquid crystal devices, electrochromic devices, and electroluminescent devices, and amorphous solar cell substrates. , such a display element,
It is stable and does not deteriorate during the manufacturing process of solar cells, etc. and during various environmental conditions thereafter. Of course, in addition to these, we also provide electrically conductive coatings, heat ray reflective coatings, and non-conductive coatings for glass plates for automobiles, aircraft, railway vehicles, and other various transportation vehicles, for construction, for various devices, for optical parts, for electrical parts, and for electronic parts. It can be usefully applied to base coats for forming antireflective coatings, reflective coatings, colored coatings, and other coatings with various functions.

Claims (1)

[Scope of Claims] 1. A glass in which an alkali diffusion-preventing silicon oxide film is formed on the surface of the alkali-containing glass to suppress alkali diffusion from the glass, wherein the alkali diffusion-preventing silicon oxide film is composed of fluorine bonded to silicon. A glass body formed with an alkali diffusion-preventing silicon oxide film, characterized by containing: 2. A glass body on which a silicon oxide film for preventing alkali diffusion is formed according to claim 1, wherein the silicon oxide film for preventing alkali diffusion contains fluorine bonded to silicon and hydrogen bonded to silicon. 3 The content of fluorine that participates in bonding with silicon in the silicon oxide film for preventing alkali diffusion is 0.01 to 20
%. A glass body on which a silicon oxide film for preventing alkali diffusion is formed according to claim 1. 4 The sum of fluorine and hydrogen that participates in bonding with silicon in the alkali diffusion prevention silicon oxide film is 0.01~
Claim 2 characterized in that 20%
A glass body on which a silicon oxide film for preventing alkali diffusion is formed as described in 2.