JPH04154647A - Transparent electrically conductive laminate - Google Patents

Abstract

PURPOSE:To form an undercoat layer, providing a transparent electrically conductive laminate having large area free from color unevenness. by sputtering method in a short time by making a transparent film having specific film thickness and low refractive index and a transparent film having high refractive index between a transparent electrically conductive film and a transparent substrate. CONSTITUTION:In a laminate wherein a transparent electrically conductive film 11 (refractive index n: >=1.8 and thickness d: >=0.15mum) is formed on a transparent substrate 10 such as glass substrate, a transparent film 12 having low refractive index (n=1.35-1.55, d=0.045-0.075mum) is arranged in such a way that the transparent film having low refractive index is brought into contact with the transparent electrically conductive film 11 between the transparent substrate 10 and the transparent electrically conductive film 11 and further a transparent film 13 having high refractive index (n=1.8-2.5, d=0.015-0.045mum) is laid so that this film is contacted with the transparent substrate 10 to give a transparent electrically conductive laminate.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a transparent conductive laminate.

[Prior Art] Conventionally, a transparent conductive film is formed on a glass surface and used as a display electrode or low-emission glass.For example, indium film formed on a glass substrate by ion blating method - Tin oxide (ITO) is often used as a transparent electrode for display elements such as liquid crystals.

Furthermore, fluorine-doped tin oxide (SnO,:F) films and antimony-doped tin oxide (SnOa:Sb) films formed on glass substrates by a spray method are used as low-emission glass for housing. Recently, new applications for transparent conductive films have been considered, such as electrode shielding glass for buildings, electrically heated windshield windows for automobiles, and transparent conductive substrates for consumer solar cells. These are all applications that require large-area glass substrates.

However, the material constituting the transparent conductive film is ITOlS.
There are nOa:F, 5nOz:Sb and aluminum-doped zinc oxide (ZnO:Al), but all of these transparent oxide materials have a refractive index of 1.8 to 2.2, which is larger than glass, so interference may occur. The reflectance at wavelengths that satisfy the conditions becomes large.

That is, when these transparent oxides are formed on a glass substrate to a certain thickness or more, maximum and minimum waves (ripples) appear in the spectral reflection (transmission) spectrum. For this reason, when these thin films are formed on a large-area glass substrate, due to in-plane film thickness variations (unevenness), the wavelength of the maximum reflection (transmission) shifts, resulting in color unevenness in the reflected (transmission) color that can be perceived by the eye. will be done.

Although the film thickness distribution on the glass surface depends on the method of film formation, for example, when considering glass of 1 m x 1 m, the current situation is that extremely advanced technology is required to suppress the film thickness distribution to within ±50% using vapor deposition or CVD.

According to our research, assuming this level of film thickness distribution, when the transparent conductive film described above is deposited on a substrate on a glass base to a thickness of approximately 0.15 μm or more, in-plane color unevenness reaches a level that becomes a problem. On the other hand, as the film thickness increases, the saturation of the reflected (transmitted) color begins to decrease.At a thickness of approximately 0.6 μm or more, the vividness decreases (but the level at which it can be recognized as color unevenness begins to decrease). In order to exceed this, a film thickness of 3 μm or more, preferably 5 μm or more is required.

Further, even if the film thickness distribution could be controlled extremely uniformly, a large ripple in the 1-minute spectrum would remain, so a film thickness of 3 μm or less would be perceived as a vivid color by the eye. If this is formed on a large area of glass, the maximum reflection (transmission) wavelength will shift depending on the angle (viewing angle) between the glass surface and the line of sight, causing a change in color, which will also be perceived as color unevenness. Therefore, it is desirable to suppress the ripple itself in the optical spectrum to a small level.

When the film thickness is thinner than 0.15 μm, the amount of change in film thickness distribution is about ±75 people, so in-plane color unevenness due to film thickness variation is hardly perceivable, but color unevenness due to viewing angle is still a problem. becomes.

As described above, when a transparent conductive film is formed to be thicker than a certain level on a glass substrate, color unevenness may be observed on the glass due to in-plane film thickness fluctuations or changes in viewing angle, which may significantly impair marketability. In order to prevent this, several proposals have been made so far. Japanese Patent Publication No. 63-39535 proposes a layer with n = 1.7 to 1.8 between the transparent conductive film and the glass substrate. A method of forming the film to a thickness corresponding to the residual wavelength is shown.The same publication also describes a method of forming the film to a thickness corresponding to the residual wavelength.
= Counterfeit with a thickness corresponding to the wavelength of 1.6 to 1.7 and n =
A method is shown in which a layer having a thickness corresponding to a wavelength of 1.8 to 1.9 is successively formed in this order from the glass substrate side.

Furthermore, JP-A-1-201046 discloses a method of forming a StCmOy film as a practical means of forming a layer with n=1.7 to 1.8 between a transparent conductive film and a glass substrate. . This method assumes a float method as a manufacturing process for plate glass, in which a mixed gas of silane, unsaturated hydrocarbon compound, and carbon dioxide is applied to the glass surface in a tin window. This is a method of forming a transparent film.

In either case, the thickness of the underlying layer of the transparent conductive film must be at least equivalent to % wavelength of visible light. Therefore, in both cases, atmospheric pressure CVD is described as the forming means in the embodiments. Film formation by atmospheric pressure CVD is said to be a very effective method, especially in terms of cost, when a large amount of glass is processed continuously (so-called on-line) during a manufacturing process. However, on the other hand, it has the disadvantage that it is not suitable for high-mix, low-volume production or multilayer film formation.

For this reason, current heat-reflecting glass for buildings and automobiles is often manufactured using a sputtering method.

Furthermore, in the case of transparent conductive substrates for display purposes, a vacuum process is usually used from the viewpoint of quality. Advantages of the vacuum process include high quality, ease of high-mix low-volume production, ease of multilayer film formation, and excellent controllability of film thickness.However, when considering uniform coating on large-area substrates, in-line sputtering method can be said to be the best. Another advantage is that it is easy to combine vapor deposition or plasma CVD with other vacuum processes in terms of equipment design. For this reason, it is desirable that the base layer as described above can be formed by a sputtering method.

On the other hand, a drawback of the sputtering method is that the film formation rate is slow, and currently, research is being actively conducted to improve the film formation rate of sputtering. Among them, the biggest drawback of the 200,000 type is that the film formation rate is extremely slow when forming an oxide film by reactive sputtering from a metal target. We have found a transparent material with an intermediate refractive index that is stable, durable, and has a fast film formation rate, and have proposed using it as the base layer, but in terms of production tact, there is a more desirable solution. It was wanted.

[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned problems and to obtain a large-area transparent conductive laminate in which color unevenness is prevented by forming a base layer by a vacuum process, particularly by a sputtering method. The purpose of this invention is to provide a new method for forming the film in a shorter time than conventional methods.

[Means for solving the problem] For this reason, the present invention has a refractive index of 1.8 or more and a thickness of 0.15.
In a laminate in which a transparent conductive film of μm or more is formed on a transparent substrate, n = 1 between the transparent conductive film and the transparent substrate.
．． 35 to 1.55 low refractive index transparent film with n d = 0.35 to 1.55.
A high refractive index transparent film with a film thickness of 0.045 to 0.075 um and n = 1.8 to 2.5 is in contact with the transparent conductive film and a film thickness of nd = 0.015 to 0.045 um. The present invention provides a transparent conductive laminate characterized in that the transparent conductive laminate is formed so as to be in contact with the transparent substrate.

FIG. 1 is another cross-sectional view of the transparent conductive laminate of the present invention.

As the transparent conductive film 11 of the present invention, ITOlSnow
:F, Snow:Sb, ZnO:Al, etc. are typically used, but the scope of the present invention is not limited thereto. These include heated mirrors for architecture, transparent conductive substrates for solar cells, transparent conductive substrates for displays, electromagnetic shielding glass, electric heated windshield glass for automobiles, aircraft, and vehicles.
It can be used as UV cut glass, etc.

The transparent thin film 12 with n = 1.35 to 1.55 of the present invention may include MgF, SiO□, a mixture thereof, or 5i(
Composite oxides mainly composed of h, such as Zr5txOy,
Ti5ixOy, etc. can be used, but the scope of the present invention is not limited thereto.In particular, considering that the film is formed by sputtering, SiO, which also has durability, can be used.
□ or 5L (composite oxide containing h as the main component, such as Zr5t
xOy is advantageous.

As the transparent thin film 13 of the present invention with n=1.8 to 2.5,
zrOs, Ti0z, TazOs, ZnO, In20
Although there are many candidates such as a, 5nOa, and ITO, the scope of the present invention is not limited thereto.Especially when considering film formation by sputtering, price,
It is necessary to select considering durability etc., TiO□,
SnO□, etc. are promising. On the other hand, when considering productivity, it is also worth considering the possibility that the process can be standardized by using the same material as the transparent conductive film in the subsequent stage.

[Function] The cause of color unevenness is the interference effect of light at the upper and lower interfaces of the high refractive index thin film when a transparent thin film having a sufficiently larger refractive index than the substrate is formed on a transparent substrate. Therefore, maximums and minimums (ripples) of reflection (transmittance) occur in the optical spectrum. Here, when the film thickness of the high refractive index thin film changes, the position (wavelength) of the maximum and minimum
This change is observed as a change in color tone. Similarly, when the viewing angle changes, changes in the positions (wavelengths) of the maximum and minimum in the spectroscopic spectrum are observed as changes in color tone.

In the present invention, the high refractive index thin film 11 and the transparent substrate 10
A low/high refractive index transparent film formed between the two layers functions to prevent reflection at the interface between the high refractive index film and the transparent substrate. As a result, equivalently, this interface has disappeared, and the interference effect of light within the high refractive film has disappeared (
Therefore, ripples in reflection (transmission) disappear. Therefore, changes in color tone due to changes in film thickness and viewing angle are no longer perceived.

In general, the reflectance due to interference in a thin film is r + + r * eXl) (-iδ)1 + r+ for amplitude reflectance.
Denoted as rx exp(-iδ), where rl
is the Fresnel coefficient of the air/thin film interface, r is the Fresnel coefficient of the thin film/substrate interface, δ is the phase difference within the thin film layer n: the refractive index of the thin film d: the thickness of the thin film θ: the amount of light within the thin film Angle λ between the traveling direction and the normal to the substrate surface: Expressed as the wavelength of light in vacuum. I'm currently thinking about transparent substrates and transparent thin films, so r+, r2. Both δ are real numbers. The reflectance measured is the energy reflectance, which is the square of the absolute value of the amplitude reflectance. Here l r+ rx I<
<1, the denominator is approximated to 1 and R= l r l ” ~ l rI+r2exp(-i
δ)12=l rll”+lr*12+21r
It can be written as +I r*1cosδ. This is because the ripple size due to film thickness variation (i.e., due to change in δ) is 41r, I
ral. In other words, the magnitude of the ripple is proportional to the product of the Fresnel coefficients at the upper and lower interfaces of the thin film. Therefore, if the Fresnel coefficient at either the upper or lower interface can be made zero, the ripple will disappear. Setting the Fresnel coefficient of the interface to zero is nothing but making this interface antireflective. The simplest type of anti-reflection coating is a single-layer anti-reflection coating, which is made of a material that has a refractive index that is the square root of the product of the refractive indices of the two materials that form the interface (an intermediate refractive index). This is achieved by forming the optical thickness of the wavelength corresponding to the wavelength to be prevented from reflecting. This is the meaning of the underlayer used in the ripple suppressing glass in the prior art described above.

In the present invention, the overall film thickness is intended to be reduced by using a transparent two-layer film having a low/high refractive index instead of the λ layer having an intermediate refractive index. In other words, an intermediate refractive index single-layer film required an optical film thickness of about 0.13 μm, but by creating a low/high two-layer film, the total thickness of the two layers can be reduced as described in claim 1. 0.065-0.12μm
It is possible to do this.

Such a transparent conductive laminate can also be constructed as a laminated glass laminated with another glass substrate via a plastic interlayer, with the side on which the thin film is formed facing inside.

Strictly speaking, this anti-reflection effect only exists at a specific single wavelength (dominant wavelength), so the anti-reflection effect is not perfect at other surrounding wavelengths (some ripples remain. Therefore, Some of the color changes mentioned above may also remain and be perceivable.

Therefore, as a more effective way to prevent ripples,
It is conceivable to provide an antireflection layer also on the upper layer of the high refractive index film. By doing so, both the upper and lower interfaces of the high refractive index thin film disappear, and the residual ripple can be further reduced.

FIG. 2 is a cross-sectional view of another example of the transparent conductive laminate of the present invention, in which 20 is a glass substrate, 21 is a high refractive index transparent conductive film (the same thin film as 11 in FIG. 1), and 22 is a low refractive index transparent conductive film. 23 is a high refractive index transparent base film (the same thin film as 13 in FIG. 1), and 24 is a low refractive index transparent upper film.

The refractive index of this low refractive index transparent upper layer film is air (refractive index = 1.
If n+=1.0Xne due to the anti-reflection condition at the 0)/transparent conductive film (refractive index = n c ) interface, then by forming this upper layer film to an optical thickness of n+d+ = 4λ, this in E. The reflectance of the interface can be made completely O. That is, the ripple at λ1 can be reduced to O.

The transparent conductive laminate thus formed has reflectances lr, l, and I at the upper and lower interfaces of the high refractive index transparent conductive film.
r21 is both low (suppressed), and as a result, it is possible to almost completely eliminate ripples in the reflection (transmission) spectrum.

Further, the transparent upper layer film 24 (refractive index n l + optical film thickness n
, d, ) is the main wavelength for antireflection (λ1=4n+d+)
and the transparent base two-layer film 22 (refractive index n l + optical film thickness n1di) and 23 (refractive index n3 + optical film thickness n1di)
The dominant wavelength for anti-reflection (λ2: This is difficult to express mathematically. Measure the spectral reflection (transmission) spectrum with the configuration shown in Figure 1, and choose the wavelength at which the ripple is the smallest.) By appropriately shifting, the wavelength range in which residual ripples are sufficiently suppressed can be expanded, and the anti-glare effect can be further enhanced.

For example, λ1≧0.55μm and 50.55μm,
Alternatively, by setting the thickness to 50.55 μm and 2≧0.55 μm, residual ripples can be sufficiently suppressed over a wide wavelength range in the visible region.

In this case, it is more preferable that λ1 and λ2 differ by 0.05 μm or more. This is because the upper film can suppress ripples at wavelengths near λ, and the base film can suppress ripples at wavelengths near λ.

In addition, if you particularly dislike the color tone that corresponds to a certain wavelength range, set the wavelength 2- within that wavelength range, and add the upper layer film and the base 2 layer so that these correspond to 2 and λ2. The refractive index and layer thickness of the film can be adjusted. For example, if you dislike the color tone of red Qi-tong,
, E2=0.65 μm, etc., it is possible to suppress ripples in the length range in this range.

Such a transparent conductive laminate can also be constructed as a laminated glass with the side on which the thin film is formed facing inside and laminated with another glass substrate with a plastic interlayer interposed therebetween. FIG. 3 is a sectional view of an example of a transparent conductive laminate (laminated glass) of the present invention. 30 is a glass substrate, 3
1 is a high refractive index transparent conductive film (FIG. 1 11, same as FIG. 2 2), 32 is a low refractive index transparent base film (FIG. 1 12, FIG. 2 2)
2), 33 is a high refractive index transparent base film (Fig. 1 13,
23), 34 is a transparent upper layer film (same as in FIG. 2 24), and 35 is a plastic intermediate film.

In this case, since it is not air but the plastic intermediate film that is in contact with the upper layer film, the antireflection conditions at this interface are different from those shown in FIG. 2. Therefore, if the laminate shown in FIG. 2 is combined with a plastic interlayer film as is, the antireflection effect of the upper layer film will be relatively reduced. In this case, in order to suppress reflection at the interface between the high refractive index transparent conductive film 31 and the plastic intermediate film 35, the transparent upper layer film 34 has a refractive index n = + = 1.65 to 1.8 and an optical film thickness. From the viewpoint of ripple prevention, it is preferable to change the value so that n d =0.1 to 0.18 μm.

Figure 4 shows the transparent conductive laminate (laminated glass) of the present invention.
FIG. 3 is a cross-sectional view of another example of FIG. 40 is a glass substrate, 41 is a high refractive index transparent conductive film, 42 is a low refractive index transparent conductive film, 43
4 is a high refractive index transparent film, and 44 is a plastic intermediate film.

In this example, in order to prevent reflection at the interface between the high refractive index transparent conductive film 41 and the plastic intermediate film 44,
The layers are formed on the high refractive index transparent conductive film 41 in reverse order.

Also in these cases, the wavelength range in which residual ripples are sufficiently suppressed can be expanded by appropriately shifting the dominant wavelengths for antireflection at the upper and lower interfaces of the high refractive index transparent conductive film, as in the example shown in FIG.

[Example] Example 1 A glass substrate was set in a vacuum chamber, and
After exhausting the air to a temperature of 100 mA orr, a mixed gas of Ar and oxygen was introduced, and a titanium target was DC sputtered at a pressure of I x 10 -3 to I x 10 -'' Torr to form a Ti (h) film on a glass substrate at 120 m The refractive index of this film is 2.4, which corresponds to n d =0.029 μm.

Then the same <1×10″3~I of a mixed gas of Ar and oxygen
Zr: Si=1 at a pressure of X 10-”Torr
: Zr5ix by DC sputtering 9 alloy target
400 Oy films were formed. The refractive index of this film is 1.5
2, which corresponds to n d = 0.061 μm. On top of this, a thin ITO film is applied by ion blasting.
Formed o people. Separately, the refractive index of an ITo film formed in the same manner was measured and found to be 2.0. Sample this
(configuration shown in Figure 1). The spectral reflection/transmission characteristics of this sample are shown at 81 in FIG. From this graph, determine the dominant wavelength for ripple prevention.

=0.63 μm.

Example 2 900 SiO□ films were formed on Sample 1 by vapor deposition. Separately, the refractive index of a 5iOa thin film formed in the same manner was 1.47, nd = 0.13 μm, λ, = 0.52
Corresponds to μm. This was designated as sample 2 (configuration shown in Figure 2).

Example 3 Using a Zr:Si=1:9 alloy target on sample 1, a mixed gas of Ar and oxygen was applied to I
800 films of Zr5ixC1y were formed by DC sputtering under a pressure of "~l x 10-" Torr. The refractive index of this film is 1.52, and nd=0.12μ
m, λ, corresponds to =0.49 μm. This is sample 3
(configuration shown in Figure 2).

Example 4 The sample was laminated glass using a PVB (polyvinyl butyral) interlayer film, and this was designated as sample 4 (3rd sample).
Figure configuration).

Example 5 Using an alloy target of Zr:Si=l:2 on sample 1, IXto- of a mixed gas of Ar and oxygen was applied.
700 films of Zr5ixOy were formed by DC sputtering at a pressure of 3 to 10-'' Torr.

The refractive index of this film is 1.74, and nd=0.12μm
, λ1: corresponds to 0.49 μm. This sample was bonded to another glass via a PVB interlayer to create a laminated glass. This was designated as sample 5 (configuration shown in FIG. 3).

Example 6 First, Zr5x was applied on sample 1 under the same conditions as Example 1.
300 people formed a film of xOy. The refractive index of this film is 1.
52, which corresponds to nd=0.046 μm. Next, 90 people formed TiOi films. The refractive index of this film is 2.
4, which corresponds to nd=0.022 μm. Since this is the film thickness of the base film of 374 mm, the main wavelength for ripple prevention is:
Eh, it corresponds to =0.47 μm. This was bonded to another glass via a PVB interlayer to form sample 6 (
(Configuration in Figure 4).

Comparative Example 1 ITO was deposited on the glass substrate 50 by ion blasting.
8,000 people formed the thin film 51. The refractive index of this film is 2.
It was 0. This was designated as sample 7 (configuration shown in Figure 5)
.

Comparative Example 2 An alloy target of Zr:5i=1:2 was used on a glass substrate in a mixed atmosphere of Ar and oxygen.
A Zr5txOy film 62 was formed by DC sputtering under a pressure of
m, corresponds to λ1=0.63 μm. 8,000 ITO thin films 61 were formed on this by ion blasting. This was designated as sample 8 (configuration shown in FIG. 6).

Comparative Example 3 Sample 7 was bonded to another glass 70 via a PVB interlayer 72 to create a laminated glass. This was designated as sample 9 (configuration shown in FIG. 7).

The spectral reflection spectrum of sample 1.2.3 is shown in FIG. 8, and 81.82.83 in figure 0 corresponds to sample 1.2.3. 1st O showing the spectral reflection spectrum of sample 7
It can be seen that ripples are clearly suppressed in the case (81) in which the transparent underlayer film according to the present invention is applied compared to the lot shown in the figure, and there is an effect of preventing glare. Furthermore, when a transparent upper layer film is applied (82, 83), the effect of suppressing ripples becomes remarkable.

1 in Figure 1O showing the spectral reflection spectrum of sample 8
Compared to 02, when the transparent underlayer film of the present invention was applied (81
) shows equivalent performance despite the lower film thickness being thinner, and when the transparent upper film of the present invention is further applied (82, 83), it can be seen that excellent performance is shown.

The spectral reflection spectrum of sample 4.5.6 is shown in FIG. 9, and 91.92.93 in FIG. 0 corresponds to sample 4.5.6. Compared to 103 in Figure 1O, which shows the spectral reflection spectrum of sample 9, when the transparent lower layer film according to the present invention was applied (91), the effect of suppressing ripples was observed to be the same, and when the transparent upper layer film was further applied (92, 93) It can be seen that the effect becomes even greater.

[Effects of the Invention] As can be seen from the Examples above, the present invention has the effect of suppressing ripples that appear in the optical spectrum when a transparent conductive film with a high refractive index is formed on a glass substrate to a certain thickness or more.

This provides the effect of preventing unevenness in film thickness of the high refractive index transparent conductive film and unevenness in color (glow) due to changes in viewing angle. This has a remarkable effect especially when the present invention is applied to a large-area glass substrate.

In addition, in the present invention, reflection at the (upper) and lower interfaces of the high refractive index transparent conductive film is prevented in order to suppress ripples in the spectral spectrum, so the overall reflectance level is reduced and the transmittance is increased. be able to. This meets the "high transmittance" generally required of glass substrates. In particular, the present invention is effective in transparent conductive substrates for display, since high transmittance is required from the viewpoint of ease of viewing one screen. Furthermore, the present invention is effective in transparent conductive substrates for solar cells, which require not only low resistance but also high transmittance in order to improve conversion efficiency. Also, in electric heated windshield windows for automobiles, high transmittance is desired in order to ensure safety as well as uniform appearance, and it is effective to apply the present invention. Also, high transmittance is required for electromagnetic shielding glass so as not to impair the transparency of the glass.
The present invention is effective.

In these specific applications, the application of the present invention is particularly effective since, as mentioned above, when a transparent conductive film is applied to a large area substrate, the problem of color unevenness always occurs.

Also, one of the major effects of the present invention is that compared to the achromatic glass that we previously proposed (Japanese Patent Application No. 2-201148), by dividing the transparent underlayer film into two layers, the overall film thickness can be reduced. It can be made smaller and the time for forming it can be shortened.Thereby, productivity can be improved.

By using the present invention to form a transparent conductive laminate on a large-area glass substrate without color unevenness, a heat mirror for architectural use,
It can be applied to electromagnetic shielding glass, electric heated windshield glass for automobiles, transparent conductive substrates for displays, ultraviolet ray blocking glass, etc. without damaging the appearance and improving productivity (large area applications).

[Brief explanation of drawings]

1 to 4 schematically show cross sections of an embodiment of the present invention. In the figure, 1O120, 30, 40
is a glass substrate, 11.21.31.41 is a transparent conductive film,
12.22.24.32.42 is a low refractive index transparent film, 13
．． 23, 33, and 43 are high refractive index transparent films, 34 are intermediate refractive index transparent films, and 35.44 are plastic intermediate films. 5 to 7 schematically show cross sections of conventional examples. In the figure, 50.60.70 is a glass substrate,
51, 61, and 71 are transparent conductive films, 62 is an intermediate refractive index transparent film, and 72 is a plastic intermediate film. FIG. 8 shows the spectral reflection characteristics of Samples 1 to 3 of Examples according to the present invention. In the figure, 81, 82, and 83 correspond to samples 1 and 2.3, respectively. FIG. 9 shows the spectral reflection characteristics of Samples 4 to 6 of Examples according to the present invention. In the figure, 91, 92, and 93 correspond to samples 4, 5, and 6, respectively. FIG. 1O shows the spectral reflection characteristics of samples 7 to 9 as comparative examples. In FIG. 1O, 101, 102, and 103 correspond to samples 7, 8, and 9, respectively.

Claims (1)

[Claims] 1. In a laminate in which a transparent conductive film with a refractive index n of 1.8 or more and a thickness d of 0.15 μm or more is formed on a transparent substrate, between the transparent conductive film and the transparent substrate , n=1.35~1
．． 55 low refractive index transparent film with nd=0.045 to 0.07
in contact with the transparent conductive film to a film thickness of 5 μm, and n=
A high refractive index transparent film of 1.8 to 2.5 with nd=0.015 to
A transparent conductive laminate, characterized in that it is formed to a thickness of 0.045 μm so as to be in contact with the transparent substrate. 2. In the laminate according to claim 1, a low refractive index transparent film with n = 1.35 to 1.55 and a film thickness of nd = 0.08 to 0.15 μm is provided at the interface between the transparent conductive film and air. A transparent conductive laminate characterized by being formed. 3. In the laminate according to claim 2, the dominant wavelength of the low refractive index transparent film on the transparent conductive film is λ_1=4nd, and the dominant wavelength of the low refractive index transparent film on the lower layer of the transparent conductive film is λ_1=4nd. When the dominant wavelength of the two-layer film is defined as λ_2 = (the wavelength with the smallest ripple in the spectrum without forming the upper low-refractive index transparent film), λ_1≧0.55 μm and λ_2≦0.55 μm, or A transparent conductive laminate characterized by satisfying λ_1≦0.55 μm and λ_2≧0.55 μm. 4. A transparent electromagnetic shielding plate comprising a lead-out electrode for connecting the transparent conductive film to ground at an end of the transparent conductive laminate according to any one of claims 1 to 3. 5. An electrically heated windshield window comprising an electrode for supplying electricity to the transparent conductive film of the transparent conductive laminate according to any one of claims 1 to 3. 6. A solar cell comprising amorphous silicon or polysilicon formed on the transparent conductive film of the transparent conductive laminate according to claim 1, and a back electrode formed thereon. 7. A transparent conductive laminate obtained by adhering the transparent conductive laminate according to any one of claims 1 to 3 to another transparent substrate via an intermediate film. 8. The transparent conductive laminate according to claim 2 or 3,
The low refractive index transparent film formed on the transparent conductive film is n=1.
．． 65 to 1.8, nd = 0.1 to 0.18 μm A transparent conductive laminate made of a medium refractive index transparent film is bonded to another transparent substrate via an intermediate film. Conductive laminate. 9. The transparent conductive laminate according to claim 7 or 8,
A transparent conductive laminate formed by reversing the order of forming multilayer thin films on a transparent substrate. 10. On the laminate according to claim 1, n=1.35 to 1.
55 low refractive index transparent film with nd=0.045 to 0.075
in contact with the transparent conductive film with a film thickness of μm, and n=1
．． A high refractive index transparent film of 8 to 2.5, nd=0.015 to 0
．． A transparent conductive laminate formed by forming a film with a thickness of 0.045 μm so as to be in contact with the low refractive index transparent film, and then adhering this to another transparent substrate via an intermediate film. 11. The transparent conductive laminate according to any one of claims 7 to 10, which is an electrically heated windshield window comprising an electrode for supplying electricity to the transparent conductive film. 12. A solar cell obtained by adhering the solar cell according to claim 6 to another transparent substrate with the multilayer film on the inside through an intermediate film.