JPH03187735A - Selective permeable membrane - Google Patents

Abstract

PURPOSE:To obtain a selectively permeable membrane with improved surface smoothness and scuff resistance and excellent durability by constituting a protective membrane of an amorphous membrane wherein an oxide contg. at least one selected from a group of titanium, zirconium, hafnium, tin and tantalum and at least one selected from boron and silicon is a main ingredient. CONSTITUTION:A selectively permeable membrane 4 is prepd. by forming a thin membrane consisting of at least two layers which are a selectively permeable functional membrane 2 and a protective membrane 3 from a base 1 side. The protective membrane 3 is an amorphous membrane wherein an oxide contg. at least one selected from a group of titanium, zirconium, hafnium, tin and tantalum and at least one selected from boron and silicon is a main ingredient. As the base sheet 1, a glass, a plastic etc., can be used. As the selectively permeable functional membrane 2, a metal, a nitride membrane, an electrically conductive indium oxide, an electrically conductive tin oxide, Cd2SnO4 dielectric body/Ag and a nitride membrane/a dielectric body are cited. Scuff resistance can be improved by forming an amorphous membrane with excellent durability on the outermost layer of the air side on the transparent substrate 1 and chem. durability can be also improved by getting rid of crystal grain boundaries.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a selectively transmitting film that selectively transmits or reflects a portion of light (electromagnetic waves) to control incoming or outgoing light energy. It is.

[Prior art] Conventionally, selective transmission films have been used as heat mirrors for construction heat rays, reflective glass, etc., heat mirrors for construction low-E glass, front glass of solar water heaters, or viewing window glass for ovens, etc., and fresh foods. There are some known cold mirrors used in lamps.

What is called a heat mirror reflects heat rays and passes visible light, and is sometimes called Low-E.

Typical examples of these include dielectric/silver/dielectric (A type), conductive metal oxides doped with indium oxide, tin oxide, etc. (B type), and metal thin films of 100 Å or less. There are nitride films (C type), etc.
These materials have high electrical conductivity and utilize the ability to reflect in the infrared region due to plasma vibration of electrons. Among these, type A has sufficiently high reflective performance even in the near-infrared region, so it can be used as bare glass or laminated glass as heat ray reflective glass for sunlight.

[Problem to be solved by the invention J The A type uses Ties, ZnO1Sn as a dielectric material.
An oxide film with a relatively high refractive index, such as O□, is used to reduce reflection in the visible range by utilizing interference. On the other hand, this oxide film also serves to protect the Ag film, which is not durable.

Despite being sandwiched and protected by dielectric films in this way, Ag films are susceptible to damage during storage from deposition to bare or laminated glass, from scratches due to careless handling, or sometimes after being paired or laminated glass. Moisture infiltration from the peripheral edges sometimes caused cloudiness due to silver oxidation, which caused problems.

Since type B is originally an oxide film, it is resistant to oxidation, so it can be used as a single plate depending on the usage environment, including type C. However, there were problems such as dissolution in chemicals, especially acids such as sulfuric acid, and insufficient scratch resistance.

[Means for Solving the Problems] The present invention attempts to solve the above-mentioned problems that the prior art had, and includes a thin film consisting of at least two layers, a selectively permeable functional film and a protective film from the substrate side. In the selectively permeable membrane formed by forming a protective film, at least one selected from the group of titanium, zirconium, hafnium, tin, and tantalum.
The present invention provides a selectively permeable membrane characterized in that it is an amorphous membrane whose main component is an oxide containing a seed and at least one of boron and silicon.

FIG. 1 shows a cross-sectional view of one example of the selectively permeable membrane of the present invention. The substrate l on which the selectively permeable membrane of the present invention is formed includes glass,
Plastic etc. can be used.

As the selective permeation functional film 2, metal, nitride film, conductive indium oxide, conductive tin oxide, Cdx5nO<dielectric/A
g or nitride film/dielectric material. Cr as a metal,
AI, SUS, Au, Pt, etc. are used, and TiN, ZrN, etc. are used as the nitride film. Further, the film thickness of the 0 selective permselective functional film, which may be the metal or nitride film mentioned above instead of Ag, may be adjusted depending on the desired performance.

FIG. 3 is a sectional view of another example of the permselective membrane (A type) of the present invention. 11 is a dielectric film such as Zr0g or Ties; 12 is a permselective functional film containing at least one of gold, silver, and platinum; and 13 is a protective film.

The protective film 3 is an oxide film made of at least one member selected from the group consisting of titanium, zirconium, hafnium, tin, and tantalum, and at least one member selected from the group consisting of boron and silicon. When the selectively permeable film has a multilayer structure such as dielectric/Ag/dielectric (type A), the protective film 3 may also serve as the outermost dielectric layer. In addition, this multilayer film has 3
It goes without saying that the number of layers is not limited to just one, and that three or more layers may be used in order to adjust optical performance or improve adhesion between the eyebrows and the substrate. The thickness of the protective film 3 should be set at 10 because if it is too thin, the effect will not be sufficient.
The refractive index of the protective film is 0 Å or more, preferably 150 Å or more, especially 2n0 Å or more, although there is no particular restriction on the thickness.
It may be determined by taking into consideration changes in appearance due to this interference, productivity, etc.

The composition of the protective film 3 is not particularly limited7, but in order to make the film amorphous and improve scratch resistance and reliability, oxide films of titanium, zirconium, hafnium, tin, tantalum, boron, and silicon may be used. TiO□, ZrO.

Hf0i, 5nOa, Ta*Os, B1Os, Stem
When expressed as, Ti0a, Zr0i, Hfol,
A total of 10 oxides selected from 5nOi and Ta5ks
For 0 parts, B, 0. , the total molar ratio of oxides selected from SiO□ is 5 parts or more, preferably 10 parts or more,
In particular, it is good to have 2n parts or more. Also B2n. In the case of T, reliability decreases if there are too many T
ilt, ZrOs, Hf0m.

A total of 10 oxides selected from 5nOs and Ta*Os
The molar ratio to 0 parts is 2n0 parts or less, preferably 100 parts or less, particularly 50 parts or less. In the case of Stem, if too much Ti is used, the durability against alkali will decrease.
e, ZrO, HfOllSnow and 5 kg of Ta in a molar ratio of 190 parts to a total of 100 parts of oxides.
It is preferably 0 parts or less, preferably 900 parts or less, particularly 400 parts or less.

Table 1 specifically shows the properties of various amorphous oxide films most suitable for the protective film of the present invention.

Films were formed by reactive sputtering using targets with the compositions listed in the table. Crystallinity is
Observation was made by thin film X-ray diffraction. Furthermore, the scratch resistance is the result of a rubbing test using a sand eraser, where O indicates that there were almost no scratches, and X indicates that scratches occurred easily.

As for wear resistance, as a result of a taper test (wearing wheel C5-10F, load 500 g, 1000 rotations), a haze within 4% was rated O, and a haze exceeding 14% was rated x. Acid resistance was determined by immersion in 0.1N HSO4 for 240 hours.
If the change rate of Tv (visible light transmittance) and Rv (visible light reflectance) is within 1% compared to before immersion, 0 is 011~4%, Δ is, and if the film has dissolved and disappeared is × And so. Alkali resistance is 0. As a result of immersion in IN NaOH for 240 hours, the rate of change in Tv and Rv from before immersion was 1.
% or less, △ if the film was within 2%, and X if the film was dissolved. The boiling test is 1 atm.
After being immersed in water at 00°C for 2 hours, when the change rate of Tv and Rv from before immersion is within 1%, ○, when more than 1 layer is ×
And so.

Regarding the ZrBxOy film, as is clear from Table 1,
It can be seen that when the amount of B in the film is small, a crystalline film tends to be formed, and when the amount of B is large, an amorphous film tends to be formed. It can be seen that the crystalline film has poor scratch resistance and abrasion resistance, whereas the amorphous film has excellent scratch resistance and abrasion resistance. This is an amorphous film.
This is thought to be due to the smooth surface. Therefore, Zr
ByoOy film (atomic ratio X of B to Zr in the film is 0.1
0 < x) has excellent scratch resistance and abrasion resistance.
Since the Bias film is hygroscopic and dissolves by absorbing moisture in the air, it is preferable that x<3 for the ZrBxOy film.

There is no particular limit to the atomic ratio of 0 (oxygen) to Zr in the ZrBxOy film, but if it is too high, the film structure will become rough and uneven, and if it is too low, the film will become metallic and the transmittance will decrease. Zr0m and B2O3
It is preferable that the amount is such that a composite system of ZrO*+XBO+,s is obtained.
When X is included in atomic ratio to r, y=2+1.5x
It is preferable that the degree of

Furthermore, from Table 1, it can be seen that as the amount of B in the ZrBxOy film increases, the refractive index of the film tends to decrease. The relationship between the composition of the film and the refractive index n is shown in FIG. 2(a). By increasing the amount of B in the film, the refractive index n decreases from about 2.1 to about 1.5.

Therefore, ZrBxOy with 0.10<x<4.2<y<8
The film is an amorphous oxide film suitable for the purpose of the present invention, which has good scratch resistance and abrasion resistance, and whose refractive index can be freely selected depending on the amount of B.

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 deterioration occurs in the boiling test. Therefore, Zr
A protective film of BxOy (x<2.3) is preferred.

As described above, by adding boron oxide B2O3 to the ZrO* film, the film becomes amorphous and the surface becomes smooth, which is thought to contribute to the improvement of wear resistance and scratch resistance. In addition, the refractive index can be adjusted by adjusting the amount of B, and furthermore,
Compared to the ZrO□ film, the internal stress is smaller, so it is advantageous in terms of adhesion with the adjacent film. This is especially advantageous when forming thick films.

Next, regarding the ZrStmOy film, it is real amorphous and has high scratch resistance and wear resistance.

The refractive index varies depending on the composition ratio between ZrO* (n = 2.14) and 5ift (n = 1.46) (see Figure 2 (b)).
In the Zr5iaOy film, 0.05≦2 (Zr in the film
It is preferable that the atomic ratio of SL to SL is <19.

If z<0.05, the film will not become amorphous and sufficient physical durability will not be obtained. Moreover, when 2≧19, alkali resistance deteriorates. In addition, y (atomic ratio of O to Zr in the ZrSxxOy film) is approximately y=2+2z when the atomic ratio of SL to Zr is 2 for the same reason as described for the ZrBxOy film. is preferred.

Further, a ZrBxSixO film is also suitable for the purpose of the present invention. If the atomic ratio x of B to Zr in such a film and the atomic ratio y of 2% O in SL are X+Z≧0.05, the film becomes amorphous and has high scratch resistance and wear resistance. This is preferable.

In addition, if x+z<19, the alkali resistance is also good, so in the Z r B x S 1 m Oy film,
It is preferable that 0.05≦x+z<19. however,
As mentioned above, B2O3 is hygroscopic and dissolves by absorbing moisture in the air, so it is better not to contain too much in the ZrBxSixOy film. If B is included to the extent that Zr<25 atomic % and SL<25 atomic % and the remainder is B with respect to the total of Z, B, and Si, the chemical durability will be insufficient. That is, Zr:B:St in the ZrBxSxxOy film
If (atomic ratio) is l:x:z, then 1/(1+x+z
)<0.25 and Z/(1+x+z)<0.25. That is, a composition in which x+z-3>O and x-32+1>0 is unfavorable in terms of chemical durability. y is ZrO* + B for the same reason as mentioned in the case of ZrBxOy.
Considering it as a composite system of tus + 5ift, y is 2+1.
It is preferable that it is about 5 Shown in (c).

Metals other than Zr, i.e. Ti, Hf, Sn, Ta
, In, and at least one of B and SL also becomes amorphous, providing sufficient scratch resistance and abrasion resistance. A Ti5izOy film is shown as sample 28 in Table 1 as an example.

Above, ZrBxOy system, Zr5izOy system, ZrB, l
The amount of B or SL added may be adjusted so that the 51m0y-based film has a refractive index necessary as the above-mentioned protective film.

The method for forming the selectively permeable membrane 3 of the present invention is not particularly limited, and any of the methods such as vapor deposition, ion blasting, and sputtering are possible. For large-area applications, sputtering is advantageous because of the uniformity of the film distribution.

[Function] The present invention is characterized in that an amorphous film with excellent durability is formed as the outermost air-side layer on the transparent substrate.

In general, T x O * + Zr O * is a chemically stable material, but it tends to form a crystalline film (the surface becomes uneven and does not have sufficient scratch resistance. Also, since grain boundaries are formed, Moisture, acid, alkali, etc. permeate through the membrane, oxidizing or dissolving the metal, nitride film, or conductive indium oxide formed on the lower side, which may deteriorate the performance as a selectively permeable membrane.This invention By mixing glass constituent elements such as boron and silicon, the film is made amorphous and scratch resistance is improved.Furthermore, chemical durability is also improved by eliminating crystal grain boundaries.

In the A-type configuration, ZrO, which has a high refractive index, is used as the dielectric material.
, , TiO□, etc. are used. The refractive index of the protective film of the present invention can be selected quite freely by adjusting the boron or silicon content. Therefore, as a dielectric film, Zn
The same film as the protective film of the present invention can also be used instead of O, Ti0z.

This makes it possible to further improve reliability.

[Example 1] A selectively permeable membrane 2 in which about 4,000 ITO (indium oxide containing tin) was formed on a glass substrate was set in a vacuum chamber and evacuated to I.times.10-'Torr or less. A Zr5ii target was then reactively sputtered in a mixed gas of argon and oxygen at 2 x 10-'' Torr to form a Zr51m, ops, o film (refractive index of about 1.7).
3 Approximately 400 people formed. In order to examine the durability of this permselective membrane, it was immersed in 0.1N H, SO, and NaOH solutions for 24 hours. No change in appearance was observed after the test, and the change in optical performance was within 1% compared to before the test. Furthermore, in the scratch resistance test using a sand eraser, there were almost no scratches, showing excellent performance.

[Example 2] As in Example 1, Zr- was deposited on ITO (4000 people).
ZrBo from B target (atomic ratio 70-30),
About 400 people formed 4srs, s films (refractive index of about 2.05). Similar to Example 1, it exhibited excellent durability and scratch resistance.

[Example 3] In the same manner as in Example 1, about 282n people of ITO and then Z
A Zr5i40+o film (refractive index 1.57) was sputtered using an r-5i target (atomic ratio 2n to 80).
0 people formed. The TV (visible light transmittance), TE (sunlight transmittance), Rvr (film surface visible light reflectance), and REF (film surface solar ray reflectance) of this glass with a selective transmission film are 86.71.11. It was 15 (%). Durability was similar to Example 1.

[Example 4] A glass substrate was set in a vacuum chamber, and I
Exhausted to below rr. Approximately 690 ZrSiO4 films (refractive index approximately 1.75) were formed by reactive sputtering of a Zr-5i target (atomic ratio 1:1) in a mixed gas of argon and oxygen at 2 x 10-'' Torr.Next Sputtering Ag in argon gas to form an Ag film with a thickness of about 70%
After forming the layer, approximately 60 layers of the same ZrSiO4 film as the first layer was added.
0 people were formed to create a selectively permeable membrane. The TV (visible light transmittance), T, (sunlight transmittance), RvF (film surface visible light reflectance), REF (film surface solar ray reflectance), and Rva (glass surface visible light reflectance) of such glass with a selective transmission film are reflectance), R
EO (glass surface solar reflectance) is 82.5 respectively.
．． 68.3°12.6, 19.7, 12.6, 19.7
(%).In order to examine its storage stability, it was left at 50° C. and 95% RH for 24 hours. After the test, some haze was observed in some areas, but it was not at a problematic level.

[Example 5J A glass substrate was set in a vacuum chamber, and
Zr5iO<
A film (refractive index of about 1.7) was formed by sputtering Ag in 0-order argon gas to form an Ag film of about 7O
After forming A, the same Zr5iO film as the first layer was deposited at about 57 cm.
Five people formed a selectively transmitting film and measured the TV (visible light transmittance), T, (sunlight transmittance), RVF (film surface visible light reflectance), and REF (of the glass with the selectively transmitting film). Film surface sunlight reflectance), Rva (glass surface visible light reflectance), R
to (glass surface sunlight reflectance) is 82.1, respectively.
．． 67, 0°13.0.2n. 9,12.9.21.0
(%).In order to examine its storage stability, it was left at 50° C. and 95% RH for 24 hours. After the test, some haze was observed in some areas, but it was not at a problematic level.

[Example 6] A glass substrate was set in a vacuum chamber, and I
ZrSiO4 was formed by reactive sputtering of a Zr-5t target (atomic ratio 1:1) in a mixed gas of argon and oxygen at e 2
Approximately 775 films (refractive index: 1.75) were formed. Next, sputter Ag in argon gas to form an Ag film of about 7
After forming 0 people (second layer), the same ZrSiO as the first layer
4 films were formed by approximately 875 people (3rd layer), then Ag films were formed by approximately 70 people (4th layer) in the same manner as the 2nd layer, and then 1.3 layers were formed by approximately 70 people (4th layer).
Approximately 490 ZrSiO4 films (5th layer)
A selectively transmitting membrane consisting of five layers was formed.The TV (visible light transmittance), T, (
(sunlight transmittance), R, F (film surface visible light reflectance), RE
F (film surface solar ray reflectance), Rv, (glass surface visible light reflectance), REa (glass surface solar ray reflectance) are 83.0.55.1, 10.0.31.6, 9, respectively. .9,
It was 31.6 (%). In order to examine its storage stability, it was left at 50° C. and 95% RH for 24 hours. After the test, some haze was observed in some areas, but it was not at a problematic level.

[Comparative Example 1] Z was added as a protective film to the ITO substrate used in Example 1.
About 400 ZrO* films were formed by reactive sputtering of r. This selectively permeable membrane was subjected to the same durability test as in Example 1, and when changes in appearance were examined, it was found that a considerable amount of haze had occurred. Also, in the sand eraser test, there were large scratches in some places, which was problematic.

[Comparative Example 2] Approximately 400 people (7
) A selectively permeable membrane similar to that of Example 3 was made except that ZnO was used. In order to investigate the storage stability of this, 5゜”C9
When left in 5% RH for 24 hours, considerable haze occurred over the entire surface.

[Effects of the Invention] As described above, in the present invention, by overcoating with an amorphous oxide layer containing boron and silicon, surface smoothness and scratch resistance are improved. In addition, the disappearance of grain boundaries prevents moisture, acids, alkalis, etc. from penetrating into the interior.
Furthermore, in the case of materials that migrate easily, such as Ag, it is prevented from diffusing to the surface through grain boundaries and deteriorating. As a result, a selectively permeable membrane with excellent durability can be obtained.

By appropriately selecting the amount of boron, silicon, or a combination of both, the refractive index can be adjusted over a wide range of 1.5 to 2.1, making it possible for the protective film to also have the function of an optical film. . This increases the degree of freedom in optical design and also simplifies the film configuration, making a large contribution to improving productivity.

[Brief explanation of drawings]

FIG. 1 is a sectional view of an example of a selectively permeable membrane of the present invention. FIG. 2(a) is a diagram showing the relationship between the amount of Bσ' in the ZrB+tOy film and the refractive index n of the film. Figure 2(b) shows the relationship between the SL content in the Zr5ixOy film and n, and Figure 2(c) shows the relationship between the Si content in the ZrB+51i0y film and n. (d) is Ti51m0y
FIG. 2 is a diagram showing the relationship between the St content in the film and n. Figure 3 (a
) and (b) are cross-sectional views of another example of the selectively permeable membrane of the present invention. Substrate 2: Permselective function membrane 3: Protective membrane 4: Permselective membrane 11: Dielectric film 12: Permselective function membrane 13: Protective membrane 14: Permselective membrane Figure 1 (a) Figure (F) )) 'i! , 2rQ2+5tOz'' in rSiHChRN
irox+Ba Os Diagram (a) 2r 61 S: 10 Rito City's S'=(h HrOx-+ 5jOz (MoIshiγ・) Diagram (C)

Claims (5)

[Claims] (1) In a permselective membrane formed by forming a thin film consisting of at least two layers of a permselective functional membrane and a protective film from the substrate side,
The protective film is an amorphous film mainly composed of an oxide containing at least one member selected from the group of titanium, zirconium, hafnium, tin, and tantalum, and at least one member of boron and silicon. selectively permeable membrane. (2) The permselective functional membrane contains at least one selected from silver, gold, platinum, titanium nitride, zirconium nitride, conductive indium oxide, or conductive tin oxide. selectively permeable membrane. (3) A selectively permeable film consisting of at least three layers, in which a dielectric film is laminated from the base side, a selectively permeable functional film containing at least one of silver, gold, and platinum, and then a protective film, wherein the protective film is laminated. A selective transmission film characterized by being an amorphous film mainly composed of an oxide containing at least one member selected from the group of titanium, zirconium, hafnium, tin, and tantalum, and at least one member of boron and silicon. film. (4) A dielectric film is laminated on the (2n+1)th layer (n≧0) from the substrate side, and a permselective functional film containing at least one of silver, gold, and platinum is laminated on the second nth layer (n≧1). A selectively permeable membrane consisting of a total of (2n+1) layers in which a protective film is formed on a coating consisting of a total of 2n layers, the protective film comprising titanium, zirconium, hafnium,
A selectively permeable membrane characterized in that it is an amorphous membrane whose main component is an oxide containing at least one selected from the group of tin and tantalum and at least one of boron and silicon. (5) the dielectric film includes at least one member selected from the group of titanium, zirconium, hafnium, tin, and tantalum;
5. The selectively permeable membrane according to claim 3, wherein the membrane is mainly composed of an oxide containing at least one of boron and silicon.