JP2950886B2 - Method for manufacturing glass with permselective membrane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a glass with a selectively permeable film that selectively transmits or reflects a part of light (electromagnetic wave) and controls light energy to flow in or out. And a method for producing the same.

[Prior art] Conventionally, as a permselective film, heat mirrors such as a construction heat ray, a reflection glass or the like, a construction low-E glass, a heat mirror such as a front glass of a solar water heater or a viewing window glass such as an oven, and fresh. Several things are known, such as cold mirrors used in grocery lamps.

What is called a heat mirror reflects heat rays and transmits visible light, and is sometimes called Low-E. Typical of these are dielectric / silver / dielectric (A type), doped metal oxides (B type) such as indium oxide and tin oxide, and thin films of metals of 100 ° or less, nitride films (C type). Type). These materials have high conductivity and utilize the reflection performance in the infrared region due to plasma vibration of electrons. Of these, the A type has sufficiently high reflection performance even in the near infrared region, so that it can be used as a double-glazed glass or a laminated glass or a heat ray reflective glass for sunlight.

[Problems to be Solved by the Invention] The A type uses an oxide film having a relatively high refractive index such as TiO ₂ , ZnO, or SnO ₂ as a dielectric, and reduces reflection in the visible region by using interference. On the other hand, this oxide film also serves to protect the durable Ag film.

Despite the fact that the Ag film is thus sandwiched and protected by the dielectric film, the storage state from the film formation to the laminated glass or laminated glass, scratches due to careless handling, and sometimes the laminated glass Alternatively, there may be a problem that silver oxidization causes white turbidity due to invasion of moisture from the peripheral edge after the vitrification.

Since the B type is originally an oxide film and is strong against oxidation, it can be used as a single plate depending on the use environment including the C type. However, there are problems such as dissolution in chemicals, particularly acids such as sulfuric acid, and insufficient scratch resistance.

Means for Solving the Problems The present invention is intended to solve the above-mentioned problems of the prior art, and a thin film comprising at least two layers of a selective permeation functional film and a protective film on a glass substrate from the substrate side. In the method for producing a glass with a selective permeable film formed by forming, all the films constituting the thin film are formed by a sputtering method, and at least one selected from the group consisting of silver, gold and platinum is used as a selective permeable functional film. And a protective film composed of an oxide containing at least one selected from the group consisting of titanium, zirconium, hafnium, tin, and tantalum, and at least one selected from the group consisting of boron and silicon. Provided is a method for producing glass with a permselective film, characterized by using an amorphous film as a component.

According to the present invention, further, 2n (n ≧ 1) layers of a dielectric film and a permselective functional film are alternately laminated on a glass substrate in this order from the substrate side, and a protective film is formed on the second nth layer. (2n + 1)
In a method for manufacturing a glass with a permselective film formed by forming a multilayer film composed of (n ≧ 1) layers, all films constituting the multilayer film are formed by a sputtering method, and silver, Using a film containing at least one selected from the group consisting of gold and platinum, as a protective film,
It is preferable to use an amorphous film containing, as a main component, an oxide containing at least one selected from the group consisting of titanium, zirconium, hafnium, tin, and tantalum and at least one selected from the group consisting of boron and silicon. Disclosed is a method for producing a glass with a selective permeable membrane.

FIG. 1 shows a cross-sectional view of one example of the glass with a selective permeable membrane. Glass is used as the substrate 1 on which the permselective film is formed. As the permselective film 2, a film containing at least one selected from the group consisting of silver, gold and platinum is used. The thickness of the permselective function film may be adjusted depending on the required performance.

FIG. 3 is a cross-sectional view of another example of the glass with the permselective membrane (A type). Reference numeral 11 denotes a dielectric film such as ZrO ₂ or TiO ₂ , 12 denotes a permselective functional film containing at least one of gold, silver, and platinum, and 13 denotes a protective film.

As the protective film 3, an oxide film including at least one selected from the group consisting of titanium, zirconium, hafnium, tin, and tantalum and at least one selected from the group consisting of boron and silicon is used.

When the permselective film has a multilayer structure such as a dielectric / Ag / dielectric (A type), the protective film 3 may also serve as the outermost dielectric. The multilayer film is not limited to only three layers, and may have three or more layers in order to adjust the optical performance or improve the adhesion between the layers and the substrate. The thickness of the protective film 3 is 100 ° or more, preferably 150 ° or more, particularly 200 ° or more, since the effect is not sufficient if the thickness is too small. The thickness is not particularly limited, but may be determined in consideration of the refractive index of the protective film, changes in appearance due to the interference, productivity, and the like.

The composition of the protective film 3 is not particularly limited. However, in order to make the film amorphous and improve scratch resistance and reliability, an oxide film of titanium, zirconium, hafnium, tin, tantalum, boron, or silicon is formed of TiO _2. , ZrO ₂ , HfO ₂ , SnO ₂ , Ta ₂ O ₅ , B ₂ O ₃ , S
When represented as iO ₂ , TiO ₂ , ZrO ₂ , HfO ₂ , SnO ₂ and Ta ₂ O ₅ , B ₂ O ₃ and SiO ₂
The total amount of the oxides selected from the above is in a molar ratio of 5 parts or more, preferably 10 parts or more, and more preferably 20 parts or more.

In the case of B ₂ O ₃ , if the amount is too large, the reliability decreases. Therefore, depending on the application, TiO ₂ , ZrO ₂ , HfO ₂ , SnO ₂ and Ta ₂ O
200 in molar ratio to 100 parts in total of oxides selected from ₅
Parts or less, preferably 100 parts or less, particularly 50 parts or less.

In the case of SiO ₂ , if it is too much, the durability against alkali decreases, so the molar ratio is 100 parts by weight with respect to the total of 100 parts of oxides selected from TiO ₂ , ZrO ₂ , HfO ₂ , SnO ₂ and Ta ₂ O _5. 1900 parts or less, preferably 900 parts or less, particularly 400 parts or less.

Table 1 shows properties of various amorphous oxide films that are optimal for the protective film of the present invention. Films were formed by reactive sputtering using targets having the compositions shown in the table.

 The crystallinity was observed by thin film X-ray diffraction.

The abrasion resistance is the result of a rubbing test with a sand eraser. ○ indicates that the scratch was hardly formed, and X indicates that the scratch was easily generated.

Abrasion resistance was measured using the Taber test (wear wheel CS-10F, weight 500
g, 1000 rotations), those with a haze of 4% or less were evaluated as ○, and those with a haze of more than 4% were evaluated as x.

Acid resistance is as a result of immersion in 0.1 N H ₂ SO ₂ for 240 hours, T
_{When the} change rate of _V (visible light transmittance) and R _V (visible light reflectance) with respect to before immersion was within 1%, the film was dissolved and disappeared. Those were marked as x.

Alkali resistance results were immersed for 240 hours in a NaOH of 0.1 N, T _V, ○ what change rate for the previous immersion R _V is within 1%, within 2% things △, membrane had dissolved Those were marked as x.

Boiling test, one atmosphere, was immersed for 2 hours in 100 ° C. water, when T _V, the rate of change for the previous immersion R _V is within 1% ○, and as × when 1 percent.

As is clear from Table 1, the ZrB _x O _y film tends to form a crystalline film when the amount of B in the film is small, and to form an amorphous film when the amount of B is large. It can also be seen that a crystalline film is poor in abrasion resistance and abrasion resistance, whereas an amorphous film is excellent. This is probably because the amorphous film has a smooth surface. Therefore, the ZrB _x O _y film (the
A film having an atomic ratio x of B to Zr of 0.10 <x) has scratch resistance,
Excellent wear resistance. Since the B ₂ O ₃ film is hygroscopic and absorbs and dissolves moisture in the air, x <3 in the ZrB _x O _y film.
The degree is preferred.

The atomic ratio of O (oxygen) to Zr in the ZrB _x O _y film is not particularly limited. However, if the amount is too large, the film structure becomes coarse and the film becomes uneven, and if it is too small, the film becomes metallic. It is preferable that the amount is about the amount of a composite system of ZrO ₂ and B ₂ O ₃ because the transmittance tends to decrease and the scratch resistance of the film tends to decrease. That is, the composite oxide is converted to Zr
When expressed as O ₂ + xBO _1.5 , when B is contained at an atomic ratio of x to Zr, it is preferable that y is about 2 + 1.5x.

From Table 1, as the increase in the amount of B in the ZrB _x O _y film and the refractive index of the film is seen to be prone to decrease. FIG. 2A shows the relationship between the film composition and the refractive index n. By increasing B in the film, the refractive index n becomes about 2.1 to 1.5.
To a degree.

Therefore, the ZrB _x O _y film of 0.10 <x <4,2 <y <8 has good scratch resistance and abrasion resistance, and the refractive index can be freely selected depending on the amount of B according to the present invention. It is an amorphous oxide film suitable for the purpose.

Furthermore, as shown in Table 1, as the content of B in the film increases, the acid resistance and alkali resistance tend to deteriorate. When x ≧ 2.3, the acid resistance deteriorates, and when x> 4, the alkali resistance decreases and the boiling test shows deterioration. Therefore, for applications that are used while exposed in air,
A protective film of a ZrB _x O _y film (x <2.3) is preferred.

As described above, by adding boron oxide B ₂ O ₃ to the ZrO ₂ film, the film becomes amorphous and the surface becomes smooth, which is considered to contribute to the improvement of wear resistance and scratch resistance. Can be Further, the refractive index can be adjusted by the amount of B, and further, ZrO ₂
Since the internal stress is smaller than that of the film, it is advantageous in terms of adhesion to the film in contact. This is particularly advantageous when forming a thick film.

Next, with respect to the ZrSi _z O _y film, a film which is also amorphous and has high scratch resistance and abrasion resistance can be obtained.

Regarding the refractive index, ZrO ₂ (n = 2.14) and SiO ₂ (n = 1.
46) depending on the composition ratio (see FIG. 2 (b)). More specifically, in the ZrSi _z O _y film, 0.0
It is preferable that 5 ≦ z (atomic ratio of Si to Zr in the film) <19. When z <0.05, the film does not become amorphous and sufficient physical durability cannot be obtained. When z ≧ 19, the alkali resistance becomes poor. Further, y (atomic ratio of O to Zr in the ZrSi _z O _y film) is determined by the same reason as described for the ZrB _x O _y film when z is included in the atomic ratio of Si to Zr. , Y = 2 + 2z.

Further, a ZrB _x Si _z O _y film is also a film suitable for the purpose of the present invention. If the atomic ratio x of B to Zr, the atomic ratio z of Si, and the atomic ratio y of O in this film are x + z ≧ 0.05, the film becomes amorphous and becomes a film having high scratch resistance and abrasion resistance. It is preferred.

If x + z <19, the alkali resistance is also good. Therefore, it is preferable that 0.05 ≦ x + z <19 in the ZrB _x Si _z O _y film. However, as described above, since B ₂ O ₃ is hygroscopic and absorbs moisture in the air and is dissolved, ZrB _x Si _z O _y
It is better not to contain too much in the film.

Specifically, Zr other than O (oxygen) in the film,
If Zr <25 at% and Si <25 at% with respect to the total of B and Si, and B is contained so that the remainder becomes B ₂ O ₃ , the chemical durability becomes insufficient.

That is, the ratio of Zr: B: Si (atomic ratio) in the ZrB _x Si _z O _y film is 1: x:
If z, 1 / (1 + x + z) <0.25 and Z / (1 + x +
z) <0.25, ie x + z-3> 0 and x-3z + 1
Compositions> 0 have poor chemical durability.

y is considered to be a composite system of ZrO ₂ + B ₂ O ₃ + SiO ₂ for the same reason as described in the case of ZrB _x O _y , and y is 2 + 1.
It is preferable to be about 5x + 2z. Therefore, almost 2 <y <
It is preferably about 40. The higher the content of B or Si, the lower the refractive index of the ZrB _x Si _z O _y film. FIG. 2C shows an example of the ZrB ₁ Si _z O _y film.

Metals other than Zr, ie, Ti, Hf, Sn, Ta, In, and B
Similarly, an oxide containing at least one of Si and Si also becomes amorphous, and sufficient scratch resistance and abrasion resistance are obtained. Ti
The Si _z O _y film is shown as an example in Sample 28 of Table 1.

As described above, in films of ZrB _x O _y system, ZrSi _z O _y system, ZrB _x Si _z O _y system, etc., if the addition amount of B or Si is adjusted so as to have a refractive index necessary as the above-mentioned protective film, Good.

The sputtering method is used to form the permselective film 3 in the present invention. For large area applications, sputtering is advantageous from the uniformity of the film distribution.

[Action] The present invention is characterized in that an extremely durable, high quality film is formed on the outermost layer on the air side on a transparent substrate.

In general, TiO ₂ and ZrO ₂ are chemically stable materials, but tend to form a crystalline film, the surface becomes uneven, and the scratch resistance is not sufficient. In addition, since crystal grain boundaries are formed, moisture,
Acids, alkalis, and the like may permeate, and the metal formed on the lower side may be oxidized or dissolved, thereby deteriorating the performance as a permselective membrane. In the present invention, the film is made amorphous by mixing glass constituent elements such as boron and silicon, and the scratch resistance is improved. Further, the disappearance of the crystal grain boundaries improves the chemical durability.

In the A type configuration, Zr having a high refractive index as a dielectric
O ₂ , TiO ₂ or the like is used. The protective film in the present invention,
The refractive index can be freely selected by adjusting the content ratio of boron or silicon. Therefore, as a dielectric film, Zn
O, the same film as the protective film in place of TiO ₂ can be used. Thereby, the reliability can be further improved.

Example Example 1 A glass substrate was set in a vacuum chamber and evacuated to 1 × 10 ⁻⁵ Torr or less. 2 × 10 ^-3 Torr in a mixed gas of argon and oxygen
A ZrSiO ₄ film (refractive index: about 1.75) was formed by about 690 ° by reactive sputtering of a Zr—Si target (atomic ratio: 1: 1).
Next, Ag is sputtered in argon gas to reduce the Ag film thickness.
After the formation of 70 °, the same ZrSiO ₄ film as the first layer was formed about 600 ° to form a permselective film.

T _V (visible light transmittance) of the glass with the permselective membrane,
T _E (sunlight transmittance), R _VF (film surface visible light reflectance), R _EF
(Film surface solar ray reflectance), R _VG (glass surface visible light reflectance), and R _EG (glass surface solar ray reflectance) are 82.
5, 68.3, 12.6, 19.7, 12.6, and 19.7 (%). This was left to stand at 50 ° C. and 95% RH for 24 hours to examine its storage stability. Although some haze was observed in the appearance after the test, it was not at a problematic level.

Example 2 A glass substrate was set in a vacuum chamber and evacuated to 1 × 10 ⁻⁵ Torr or less. 2 × 10 ^-3 Torr in a mixed gas of argon and oxygen
A Zr—Si target (atomic ratio 1: 2) was reactively sputtered to form a ZrSiO ₄ film (refractive index: about 1.7) at about 650 °. Next, Ag is sputtered in argon gas to reduce the Ag film to about 70%.
After the formation, the same ZrSiO ₄ film as the first layer was formed about 575 ° to form a permselective film.

T _V , T _E , R _VF , R _EF ,
R _VG, R _EG, respectively, 82.1,67.0,13.0,20.9,12.9,
21.0 (%). To check the storage stability of this
It was left in 50 ° C. and 95% RH for 24 hours. Although some haze was observed in the appearance after the test, it was not at a problematic level.

Example 3 A glass substrate was set in a vacuum chamber and evacuated to 1 × 10 ⁻⁵ Torr or less. 2 × 10 ^-3 Torr in a mixed gas of argon and oxygen
A Zr—Si target (atomic ratio 1: 1) was reactively sputtered to form a ZrSiO ₄ film (refractive index: about 1.75) about 775 °.
Next, Ag is sputtered in argon gas to reduce the Ag film thickness.
After the formation of 70 ° (second layer), the same ZrSiO ₄ film as that of the first layer is formed at about 875 ° (third layer), and then A is formed in the same manner as the second layer.
g film about 70Å (fourth layer), then Zr in the same manner as the first and third layers
An SiO ₄ film was formed at about 490 ° (fifth layer) to form a permselective film composed of five layers.

T _V , T _E , R _VF , R _EF ,
R _VG, R _EG, respectively, 83.0,55.1,10.0,31.6,9.9 ,,
It was 31.6 (%). To check the storage stability of this
It was left in 50 ° C. and 95% RH for 24 hours. Although some haze was observed in the appearance after the test, it was not at a problematic level.

Comparative Example 1 A permselective film similar to that of Example 1 was prepared except that the first and third layers of the ZrSiO ₄ film were changed to ZnO of about 400 °. In order to examine the storage stability of this, it was left in 50 ° C. and 95% RH for 24 hours, and considerable haze occurred over the entire surface.

[Effects of the Invention] As described above, in the present invention, by overcoating the amorphous oxide layer containing boron and silicon, the surface smoothness is improved and the scratch resistance is improved. In addition, it suppresses the penetration of moisture, acid, alkali, etc. into the interior due to the disappearance of the grain boundaries, and in the case of those that easily migrate, such as Ag, prevent them from diffusing to the surface through the grain boundaries and deteriorating. I'm preventing. Thereby, a glass with a permselective membrane having excellent durability can be obtained.

The refractive index can be adjusted in a wide range from 1.5 to 2.1 by appropriately selecting the amount of boron or silicon or the combined amount of both, so that the protective film can also have the function of a chemical film. As a result, the degree of freedom in optical design is increased and the structure of the film is simplified, which greatly contributes to improving productivity.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of the glass with a permselective membrane of the present invention. FIG. 2A shows the content of B in the ZrB _x O _y film and the refractive index n of the film.
FIG. FIG. 2 (b) is a diagram showing the relationship between the content of Si in the ZrSi _z O _y film and n. FIG. 2 (c) is a diagram showing the relationship between the Si content in the ZrB ₁ Si _z O _y film and n. FIG. 2 (d) is a view showing the relationship between the content of Si in the TiSi _z O _y film and n. 3 (a) and 3 (b) are cross-sectional views of another example of the glass with a selective permeable membrane of the present invention. 1: Base, 2: Permselective function membrane, 3: Protective film, 4: Selective permeate film, 11: Dielectric film, 12: Permselective function film, 13: Protective film, 14: Permselective film.

Claims (2)

(57) [Claims] 1. A method for manufacturing a glass with a permselective film, comprising forming a thin film composed of at least two layers of a permselective functional film and a protective film on a glass substrate from the substrate side, wherein all the films constituting the thin film are formed. Formed by the sputtering method, a film containing at least one selected from the group consisting of silver, gold and platinum is used as the permselective functional film, and a protective film is made of the group consisting of titanium, zirconium, hafnium, tin and tantalum. A method for producing a glass with a selectively permeable film, characterized by using an amorphous film containing, as a main component, an oxide containing at least one selected from the group consisting of at least one selected from the group consisting of boron and silicon. 2. A 2n (n.gtoreq.1) layer of a dielectric film and a permselective functional film are alternately laminated on a glass substrate in this order from the substrate side, and a protective film is formed on the 2nth layer. 2n + 1) (n
≧ 1) In a method of manufacturing a glass with a permselective film formed by forming a multilayer film composed of layers, all the films constituting the multilayer film are formed by a sputtering method, and silver, gold and A film containing at least one selected from the group consisting of platinum is used, and as the protective film, at least one selected from the group consisting of titanium, zirconium, hafnium, tin and tantalum, and at least one selected from the group consisting of boron and silicon A method for producing glass with a permselective film, comprising using an amorphous film containing an oxide containing at least one of the following as a main component.