WO2011121922A1

WO2011121922A1 - Glass plate provided with transparent conductive film and method for manufacturing the glass plate

Info

Publication number: WO2011121922A1
Application number: PCT/JP2011/001575
Authority: WO
Inventors: 田中智; 瀬戸康徳; 大谷強; 平田昌宏
Original assignee: 日本板硝子株式会社
Priority date: 2010-03-31
Filing date: 2011-03-17
Publication date: 2011-10-06
Also published as: JP2011212988A

Abstract

Disclosed is a glass plate provided with a transparent conductive film, wherein an increase of the roughness of the surface can be suppressed, even if the haze rate of the transparent conductive film is increased. The glass plate provided with the transparent conductive film is provided with the glass plate, and the transparent conductive film formed on the glass plate. The transparent conductive film has a transparent conductive layer (transparent conductive layer (A)), and a transparent conductive layer (transparent conductive layer (B)), the transparent conductive layer (B) is formed on the transparent conductive layer (A), the transparent conductive film includes a plurality of holes, and each of the holes is formed by having the transparent conductive layer (B) cover a recessed section in the surface of the transparent conductive layer (A).

Description

Glass plate with transparent conductive film and method for producing the same

The present invention relates to a glass plate with a transparent conductive film used for a photoelectric conversion element and the like and a method for producing the same.

From the viewpoint of reducing the burden on the environment, solar cells capable of generating clean energy have attracted attention. Furthermore, from the viewpoint of resource saving, there is an increasing expectation for thin film solar cells that use less semiconductor material. Thin-film solar cell generally on a transparent substrate such as a glass plate, tin oxide (SnO ₂₎ transparent conductive film (surface electrode) made of, of amorphous semiconductor such as amorphous silicon or amorphous silicon germanium A photoelectric conversion layer and a conductive film (back electrode) are sequentially stacked.

Various ideas have been made to improve the photoelectric conversion efficiency of thin film solar cells. An example is a technique for obtaining a light confinement effect by scattering incident light in a transparent conductive film having a high haze ratio before the incident light reaches the photoelectric conversion layer. For example, Patent Document 1 discloses a thin film solar cell in which a first underlayer having holes on a glass plate, a second underlayer, and a transparent conductive film are formed in this order. The second underlayer is depressed in the holes in the first underlayer, and the portion of the second underlayer that is depressed in the holes acts as a growth nucleus for efficiently forming the transparent conductive film. As a result, large irregularities are formed on the surface of the transparent conductive film, the haze ratio of the transparent conductive film is increased by the irregularities, and the light confinement effect in the transparent conductive film is improved. Patent Document 2 discloses a thin film solar cell in which irregularities are formed on the surface by etching the surface of a transparent conductive film formed of zinc oxide using hydrochloric acid.

Patent Document 3 discloses a thin-film solar cell in which fine irregularities are provided on the irregularities on the surface of a transparent conductive film. The unevenness on the surface contributes to the light confinement of sunlight in the wavelength range of 600 nm to 800 nm, and the minute unevenness contributes to the light confinement of sunlight from 400 nm to 600 nm. Thereby, the photoelectric conversion efficiency with respect to the wide wavelength range of sunlight is improved.

Moreover, in the thin film solar cell currently disclosed by patent document 4, the light confinement effect is acquired by disperse | distributing an inorganic scattering particle to the inorganic binder matrix layer between a transparent substrate and a transparent conductive film instead of a surface shape. I am going to do that.

JP 2001-053307 A JP 2008-160165 A JP 2009-140930 A JP 2009-212507 A

In order to improve the photoelectric conversion efficiency of the thin film solar cell, it is desirable to increase the haze ratio of the transparent conductive film and prevent the surface roughness of the transparent conductive film from becoming too large. This is because the surface of the transparent conductive film and the surface of the photoelectric conversion layer are in contact with each other, and thus the shape of the surface of the transparent conductive film affects the characteristics of the photoelectric conversion layer. Specifically, when the surface roughness of the surface of the transparent conductive film is too large, defects are likely to occur in the photoelectric conversion layer. In Patent Documents 1, 2, and 3, irregularities on the surface of the transparent conductive film are used to increase the haze ratio. For this reason, the surface roughness of the surface increases as the haze ratio of the transparent conductive film increases. When the technique disclosed in Patent Document 4 is used, the surface roughness of the surface of the transparent conductive film can be kept low even if the haze ratio is increased. However, the technique of Patent Document 4 requires inorganic scattering fine particles (for example, alumina fine particles) separately from the binder matrix (for example, silica). Moreover, in order to achieve a high haze ratio, it is necessary to thicken the inorganic binder matrix layer that does not contribute to the improvement of conductivity.

In view of such circumstances, the present invention improves the transparent conductive film itself, and even if the haze ratio of the transparent conductive film is increased, the glass plate with a transparent conductive film that can suppress the surface roughness of the surface can be suppressed. The purpose is to provide.

The present invention comprises a glass plate and a transparent conductive film formed on the glass plate, the transparent conductive film having a transparent conductive layer A and a transparent conductive layer B, and the transparent conductive layer B is The transparent conductive layer A is formed on the transparent conductive layer A, the transparent conductive film includes a plurality of holes, and each of the plurality of holes fills the concave portion on the surface of the transparent conductive layer A with the transparent conductive layer B A glass plate with a transparent conductive film is provided.

Moreover, this invention is a manufacturing method of the glass plate with a transparent conductive film provided with the glass plate and the transparent conductive film containing the several void | hole formed on the said glass plate from the other side surface, A plurality of surfaces of the transparent conductive layer a are supplied by supplying an etching gas containing an etching component capable of etching the transparent conductive layer a to the surface of the transparent conductive layer a formed in advance on the glass plate. Forming a transparent conductive layer A having a plurality of recesses from the transparent conductive layer a by retreating the region in the film thickness direction by the etching component, and the surface of the transparent conductive layer A is oxidized to be a metal oxide The metal is formed on the transparent conductive layer A so as to close the plurality of recesses by supplying a film-forming gas containing an oxidizable component capable of generating oxidant and an oxidant capable of oxidizing the oxidizable component. By forming a transparent conductive layer B containing compound and forming a plurality of holes, a method of manufacturing a transparent conductive film-attached glass plate, provides.

Moreover, this invention is a manufacturing method of the glass plate with a transparent conductive film provided with the glass plate and the transparent conductive film containing the several void | hole formed on the said glass plate from another side surface, An etching component capable of etching the transparent conductive layer a on a surface of the transparent conductive layer a previously formed on the glass plate, an oxidizable component capable of being oxidized to form a metal oxide, and the oxidizable By supplying a mixed gas containing an oxidant capable of oxidizing the component, a plurality of regions on the surface of the transparent conductive layer a are caused to recede in the film thickness direction by the etching component, and a plurality of regions are removed from the transparent conductive layer a. The transparent conductive layer A having recesses is formed, and the transparent holes are formed by forming the transparent conductive layer B containing the metal oxide on the transparent conductive layer A so as to close the plurality of recesses. To see through METHOD FOR PRODUCING glass sheet with a conductive film to provide.

According to the present invention, it is possible to achieve a high haze ratio required for a thin film solar cell substrate while suppressing an increase in surface roughness of the surface of the transparent conductive film.

Cross-sectional schematic diagram of an example of a glass plate with a transparent conductive film of the present invention The schematic diagram for demonstrating the manufacturing method of the glass plate with a transparent conductive film of this invention. Sectional view of a glass plate with a transparent conductive film observed using a scanning electron microscope (SEM) Sectional view of glass plate with transparent conductive film observed using SEM

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

FIG. 1A is a schematic cross-sectional view of an example of a glass plate with a transparent conductive film of the present invention. As shown in FIG. 1A, a glass plate 10 with a transparent conductive film includes a glass plate 11, a base film 12 formed on the surface of the glass plate 11, and a transparent conductive film formed on the surface of the base film 12. 15. The base film 12 includes a first base layer 12a and a second base layer 12b in this order from the glass plate 11 side. The transparent conductive film 15 includes a first transparent conductive layer (transparent conductive layer A) 13 and a second transparent conductive layer (transparent conductive layer B) 14 in order from the glass plate 11 side.

The glass plate 10 with a transparent conductive film is preferably provided with a base film 12, and the transparent conductive film 15 is preferably formed on the glass plate 11 through the base film 12. Thereby, the alkali component of the glass plate 11 can be prevented from entering the transparent conductive film 15. Further, the base film 12 may be composed of one layer, and in that case, it is preferable that silicon oxide, silicon oxycarbide, silicon nitride, aluminum oxide, silicon oxynitride, or tin-doped silicon oxide be a main component. Further, the base film 12 may be composed of two layers, a first base layer 12a and a second base layer 12b. In that case, the first underlayer 12a is preferably composed mainly of silicon oxide, titanium oxide, zinc oxide, or silicon oxycarbide, and particularly preferably composed mainly of tin oxide. The second underlayer 12b is preferably composed mainly of silicon oxide or aluminum oxide, and particularly preferably composed mainly of silicon oxide. The “main component” refers to a component having a composition component content of 50% by mass or more according to common usage. Furthermore, if the film thickness and refractive index of these

foundation layers

12a and 12b are appropriately adjusted, the reflectance and reflection interference color of the glass plate 10 with a transparent conductive film can be reduced. The film thickness of the first underlayer 12a is preferably 10 to 100 nm, particularly 20 to 70 nm. The refractive index of the first base layer 12a is preferably 1.8 to 2.4. The thickness of the second underlayer 12b is preferably 5 to 80 nm, particularly 10 to 40 nm. The refractive index of the second underlayer 12b is preferably 1.4 to 1.7.

The transparent conductive film 15 is composed of at least two transparent

conductive layers

13 and 14. The transparent conductive layer A13 preferably contains zinc oxide as a main component. However, the material constituting the transparent conductive layer A13 is not particularly limited as long as it is conductive and can be etched by an etching component described later. The etching component may be selected as appropriate depending on the material to be etched, but hydrogen chloride, silicon chloride, or the like may be used. As an etching component of zinc oxide, hydrogen chloride is suitable.

The thickness of the transparent conductive layer A13 is preferably from 180 nm to 600 nm, more preferably from 200 nm to 600 nm, particularly preferably from 300 nm to 500 nm. If the transparent conductive layer A13 is too thin, the size of the

pores

13a and 13b in the film thickness direction is the wavelength of sunlight that should cause scattering as described later (depending on the photoelectric conversion layer used, for example, a wavelength of about 800 nm) In comparison, it becomes too small. On the other hand, if the thickness of the transparent conductive layer A13 is excessively thick, there is a possibility that the visible light transmittance is reduced, or the stress in the film is increased to deteriorate the durability.

Holes

13 a and 13 b are formed in the transparent conductive layer A 13, and the

holes

13 a and 13 b scatter light that enters from below in FIG. 1 and reaches the photoelectric conversion layer formed above the transparent conductive film 15. Contribute to. The

holes

13a and 13b are formed by the transparent conductive layer B14 closing the recess 13h, which is generated when a part of the surface 13s of the transparent conductive layer A13 recedes in the film thickness direction (specifically, downward in the drawing) from above. Is formed. The surface 13s of the transparent conductive layer A13 may recede over the entire thickness range (hole 13a) or may recede to a partial thickness range (hole 13b). In order to efficiently scatter light, at least some of the plurality of vacancies extend over the entire film thickness of the transparent conductive layer A13, in other words, at least some of the vacancies of the plurality of vacancies. It is preferable that the hole has a height equal to the film thickness of the transparent conductive film A13.

FIG. 1B is an enlarged view of the region 13c in the transparent conductive film 15 of FIG. The hole 13a has a needle-like body 13d extending from the surrounding wall surface toward the inside of the hole 13a. The needle-like body 13d is typically formed so as to hang down from the bottom surface of the transparent conductive layer B14. The needle-like body 13d is assumed to have grown by the deposition of the material constituting the transparent conductive layer B14. However, depending on the film forming conditions of the transparent conductive film 15, the needle-like body 13d may not be formed. In some cases, the needle-like body grows not from above the hole 13a but from the side surface of the hole 13a. Needle-like bodies may be formed not only in the holes 13a but also in the holes 13b.

Hereinafter, the size of the

holes

13a and 13b will be described. The size of the

holes

13a and 13b when the transparent conductive film 15 is observed along the film thickness direction (in other words, from the direction perpendicular to the film surface) is calculated by converting the average area into a circle (the diameter ( (Hereinafter referred to as “diameter A”), preferably 0.5 μm to 10 μm, and more preferably 1.0 μm to 5.0 μm. This diameter can be measured by a method using EPMA described later. The size of the

holes

13a and 13b appearing in the cross section obtained by cutting the transparent conductive film 15 along the film thickness direction is expressed by a diameter (hereinafter referred to as “diameter B”) calculated by converting the average area into a circle. It is preferably 0.1 μm or more and 0.6 μm or less. This diameter can be measured by cross-sectional observation with an SEM. Further, the ratio of the total area of the

holes

13a and 13b to the area of the transparent conductive layer A13 when observed along the film thickness direction is preferably 10% or more and 40% or less. When the size and area ratio of the

holes

13a and 13b are in an appropriate range, the incident light can be efficiently scattered and the strength of the transparent conductive layer A13 can be maintained.

The ratio of diameter A to diameter B (diameter A / diameter B) is preferably 3 or more and 10 or less. If the ratio of the diameter A to the diameter B is out of the above range, the incident light scattering effect may not be sufficiently obtained.

When the transparent conductive film 15 is observed along the film thickness direction, the number of holes in a region of 100 μm × 100 μm is preferably 100 or more and 1000 or less. A larger number of pores is not preferable because it is difficult to maintain the mechanical strength of the film. On the other hand, if the number of holes is smaller than this, the effect of light scattering is lowered, which is not preferable.

The transparent conductive layer B14 is made of a transparent and conductive material. The transparent conductive layer B14 preferably contains tin oxide as a main component and also contains fluorine. By adding fluorine, the conductivity of the transparent conductive layer B14 can be improved. In order to increase the conductivity of the transparent conductive layer B14, other trace components such as antimony may be added together with fluorine or instead of fluorine. Examples of the component to be oxidized (tin raw material) to be added to the film forming gas to produce tin oxide by chemical vapor deposition (CVD) include tin chloride, dimethyltin dichloride, and monobutyltin trichloride. Examples of the oxidizing agent to be added to the film forming gas in order to oxidize the tin raw material include oxygen and water vapor.

The thickness of the transparent conductive layer B14 is preferably 200 nm to 1000 nm, more preferably 200 nm to 800 nm, and particularly preferably 250 nm to 700 nm. If the transparent conductive layer B14 is too thin, the conductivity of the transparent conductive film 15 may be too low. On the other hand, if the transparent conductive layer B14 is too thick, the light transmittance of the glass plate with the transparent conductive film is too low, the surface roughness of the surface of the transparent conductive film 15 is excessive, or the residual stress in the film is large. And durability may deteriorate.

In the present embodiment, the surface of the transparent conductive film 15 is formed by the surface of the transparent conductive layer B14. The surface roughness Ra on the surface of the transparent conductive film 15 is preferably 40 nm or less, and more preferably 5 nm or more and 30 nm or less. When the surface roughness Ra on the surface of the transparent conductive film 15 exceeds 40 nm, the surface of the transparent conductive film 15 tends to cause defects in the photoelectric conversion layer, which is not preferable. The surface of the transparent conductive film 15 may be constituted by the surface of a transparent conductive layer (transparent conductive layer C) other than the transparent conductive layer B14 further laminated on the transparent conductive layer B14. The surface roughness of the transparent conductive film 15 is preferably in the above range. The transparent conductive layer C may be, for example, an ITO film or a zinc oxide film doped with aluminum.

The haze ratio of the transparent conductive film 15 is preferably 10% or more, more preferably 15% or more, and particularly preferably 20% or more. The haze rate means a haze rate in the wavelength range of 400 nm to 800 nm.

Further, the sheet resistance Rs on the surface of the transparent conductive film 15 is preferably 30Ω / □ or less, more preferably 20Ω / □ or less, and particularly preferably 5Ω / □ or more and 15Ω / □ or less.

An example of the process of forming the transparent conductive film 55 will be described with reference to FIG. FIG. 2A shows a preformed body 50 a in which only the base film 52 is formed on the glass plate 51. The base film 52, that is, the base layers 52a and 52b can be formed on the glass plate 51 by sputtering, CVD, or the like. However, it is not always necessary to form the base film 52.

A transparent conductive layer (transparent conductive layer a) 57 is formed on the preform 50a to obtain a preform 50b shown in FIG. The transparent conductive layer 57 is preferably a zinc oxide film formed by a sputtering method, but may be formed by other methods such as a CVD method.

Thereafter, a mixed gas containing an etching component for etching the transparent conductive layer 57 and an oxidizable component and an oxidizing component for forming an additional transparent conductive layer is sprayed on the transparent conductive layer 57 by a CVD method. A transparent conductive layer (transparent conductive layer A) 53 having a recess is obtained by retreating a part of the surface of the transparent conductive layer 57, and a transparent conductive layer (transparent conductive layer B) 54 is formed, and the transparent conductive layer having pores 53a. A glass plate 50 with a transparent conductive film provided with the film 55 is obtained (FIG. 2D). In the middle of film formation using the mixed gas, as shown in FIG. 2C, a part of the surface of the transparent conductive layer 57 is retreated, and the transparent conductive layer B grows thereon, so that the preform 50c is formed. It is thought that is formed.

In addition, when forming the thick transparent conductive layer 54, the transparent conductive layer 54 may be formed in two or more steps. In that case, it is preferable to spray a film-forming gas obtained by removing the etching component from the above-mentioned mixed gas at the time of forming the transparent conductive layer 54 for the second time and thereafter. When a film-forming gas that does not include such an etching component is sprayed when the transparent conductive layer 54 is formed for the second time or later, a mixed gas containing an etching component is sprayed when the transparent conductive layer 54 is formed for the second time or later. In comparison, the film formation rate is increased, and the transparent conductive layer 54 is easily grown to a sufficient thickness. Further, by spraying a film forming gas not containing an etching component during the second and subsequent transparent conductive layer 54 film formation, the surface characteristics such as the surface roughness Ra and the sheet resistance of the transparent conductive layer 54 can be improved. In addition, the electron mobility in the transparent conductive layer 54 can be improved.

When the transparent conductive layer C is further formed on the transparent conductive layer 54, the transparent conductive film C may be formed by a CVD method, but formed by a physical vapor deposition method (PVD method) such as a sputtering method. You can also

The transparent conductive layer 53 is preferably composed mainly of zinc oxide. Moreover, when forming the transparent conductive layer 54 using mixed gas, it is preferable that mixed gas contains the tin raw material and oxidizing agent which are to-be-oxidized components, and also hydrogen chloride. The molar ratio of hydrogen chloride to the tin raw material in the mixed gas is preferably 0.24 or more and 0.72 or less. When the molar ratio of hydrogen chloride is smaller than this, vacancies are hardly formed and it is difficult to achieve a desired haze ratio. On the other hand, if the molar ratio of hydrogen chloride is larger than this, by-products are generated excessively from the transparent conductive layer 57, the conductivity of the formed transparent conductive film 55 is lowered, or the pores 53a are too large. The mechanical strength of the transparent conductive film 55 may decrease.

The temperature of the glass plate when supplying the mixed gas is preferably 400 ° C. or higher and 800 ° C. or lower, particularly preferably 600 ° C. or higher and 750 ° C. or lower.

In the above description, the transparent conductive layer 54 is formed using a mixed gas containing an etching component and a film forming component (oxidized component and oxidizing agent). However, an etching gas containing an etching component and a film forming gas containing a film forming component are used. May be sequentially supplied to form the transparent conductive layer 54.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

Example 1
A first underlayer (SnO ₂ film: thickness 25 nm) and a second underlayer (SiO ₂ film: thickness 25 nm) are formed on a glass plate (thickness 3.2 mm) made of soda lime silica glass by a CVD method. The layers were laminated in this order, and then a transparent conductive layer a (ZnO film: thickness 368 nm) was formed by a sputtering method to obtain a preform. This preform was put into a substrate transfer type atmospheric pressure CVD apparatus, and the glass plate was heated to 660 ° C., and dimethyltin dichloride (hereinafter referred to as “DMT”) (1.68 mol%), water vapor (water vapor relative to DMT). Molar ratio: 10), oxygen (molar ratio of oxygen to DMT: 12), hydrogen chloride (molar ratio of hydrogen chloride to DMT: 0.72), hydrogen fluoride (molar ratio of hydrogen fluoride to DMT: 0. 30) and a mixed gas consisting of nitrogen as a carrier gas was supplied. As a result, a part of the surface of the transparent conductive layer a is retreated in the film thickness direction to form a transparent conductive film A having a recess, and a transparent conductive layer B (fluorine-doped tin oxide film) is formed on the transparent conductive layer A. And the glass plate with a transparent conductive film which has a hole in a transparent conductive film was obtained.

(Example 2)
A glass plate with a transparent conductive film having pores in the transparent conductive film was obtained in the same manner as in Example 1 except that the concentration of hydrogen chloride in the mixed gas was changed so that the molar ratio to DMT was 0.48.

(Example 3)
A glass plate with a transparent conductive film having pores in the transparent conductive film was obtained in the same manner as in Example 1 except that the concentration of hydrogen chloride in the mixed gas was changed so that the molar ratio to DMT was 0.96.

Example 4
A glass plate with a transparent conductive film having pores in the transparent conductive film was obtained in the same manner as in Example 1 except that the concentration of hydrogen chloride in the mixed gas was changed so that the molar ratio to DMT was 1.20.

(Example 5)
A glass plate with a transparent conductive film having pores in the transparent conductive film was obtained in the same manner as in Example 1 except that the thickness of the transparent conductive layer a was changed to 231 nm.

(Example 6)
In the same manner as in Example 1, except that the thickness of the transparent conductive layer a was changed to 458 nm and the concentration of oxygen in the mixed gas was increased so that the molar ratio with respect to DMT was 24, pores were formed in the transparent conductive film. A glass plate with a transparent conductive film was obtained.

(Example 7)
In the same manner as in Example 1, except that the thickness of the transparent conductive layer a was changed to 540 nm and the concentration of water vapor in the mixed gas was increased so that the molar ratio with respect to DMT was 15. A glass plate with a transparent conductive film was obtained.

(Example 8)
The first film formation was performed in the same manner as in Example 1 except that the thickness of the transparent conductive layer a was changed to 458 nm and the concentration of hydrogen fluoride in the mixed gas was changed so that the molar ratio to DMT was 0.10. Went. Subsequently, hydrogen chloride is removed from the mixed gas used in the first film formation (that is, using a film forming gas obtained by removing hydrogen chloride from the mixed gas), and the second transparent film is formed in the same manner as in the first time. Conductive layer B was formed to obtain a glass plate with a transparent conductive film having pores in the transparent conductive film.

(Comparative Example 1)
A glass plate with a transparent conductive film was obtained in the same manner as in Example 1 except that hydrogen chloride was removed from the mixed gas (that is, a film forming gas from which hydrogen chloride was removed from the mixed gas was used).

(Comparative Example 2)
A glass plate with a transparent conductive film was obtained in the same manner as in Example 2 except that the transparent conductive layer a was not formed.

(Comparative Example 3)
A glass plate with a transparent conductive film was obtained in the same manner as in Example 7 except that hydrogen chloride was removed from the mixed gas (that is, a film forming gas from which hydrogen chloride was removed from the mixed gas was used).

For the glass plates with a transparent conductive film of Examples 1 to 8 and Comparative Examples 1 to 3, the thickness of the transparent conductive layer B, the haze ratio, the shape of the pores, the surface roughness Ra, the sheet resistance, and the light beam are as follows. The transmittance and durability were examined. Moreover, the cross section of the glass plate with a transparent conductive film was image | photographed using the scanning electron microscope (SEM). Photos corresponding to Example 1 and Comparative Example 1 are shown in FIGS.

[Thickness of transparent conductive layer B]
The thickness of the transparent conductive layer B was measured by observing the cross section along the film thickness direction of the transparent conductive layer B using SEM. Note that the thickness of the transparent conductive layer a (which becomes the transparent conductive layer A after the supply of the mixed gas) does not change even after the transparent conductive layer B is formed using the mixed gas. Has been confirmed.

[Haze rate]
Using a haze meter (NDH 2000 manufactured by Nippon Denshoku Industries Co., Ltd.), light was incident on the glass plate with a transparent conductive film from the glass plate side, and the haze ratio of the glass plate with the transparent conductive film was measured.

[Hole shape and distribution]
Using an electron probe microanalyzer (EPMA), measure the area of 100 μm × 100 μm on the surface of the transparent conductive film of the glass plate with a transparent conductive film, and map the zinc to the part where zinc does not exist Detected. Since the EPMA probe penetration depth is about 1 μm, the presence or absence of zinc in the transparent conductive layer A can be detected even from above the transparent conductive layer B. Next, the portion where zinc was not present was determined as a hole by image processing, the number of holes was measured, and the area of each hole was measured. The diameter (diameter A) when the average area of each measured pore was regarded as a perfect circle was calculated. Moreover, the ratio (area ratio) of the measured total area of the void | hole with respect to the area of the transparent conductive layer A whole was computed. Next, the cross section along the film thickness direction of the glass plate with the transparent conductive film was observed by SEM, the area of the voids in the transparent conductive layer A that appeared in the range of 4 mm in the cross section direction was measured, and this average area was true. The diameter (diameter B) when considered as a circle was calculated. However, in the calculation of the diameter A and the area ratio, only the part where the area of the part where zinc does not exist is 1 μm ² or more was regarded as a hole.

[Surface roughness]
Using an atomic force microscope (AFM, SPA-400 manufactured by SII Nano Technology), a 10 μm × 10 μm region of the surface of the transparent conductive film on the glass plate with a transparent conductive film was observed, and analysis software (AFM, SII The surface roughness Ra of the surface of the transparent conductive film B was measured using Nano Navi).

[Sheet resistance]
The sheet resistance of the surface of the transparent conductive layer B was measured using MCP-TESTER LORESTA-FP manufactured by Dia Instruments.

[Light transmittance]
Based on JIS B 7107, the light transmittance of the glass plate with a transparent conductive film was measured using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.).

[durability]
A glass plate with a transparent conductive film is put into a pressure cooker test (PCT) machine (TPC-411, manufactured by Tabay Espec Co., Ltd.), one of constant temperature and humidity tests, and left for 65 hours under conditions of a temperature of 125 ° C and a humidity of 85%. Then, the presence or absence of peeling of the transparent conductive film was visually observed. In addition, based on the ECDL test (Electrochemical delamination test) reported in SPIE (SPIE-The International Society for Optical Engineering) (Proceedings of SPIE, Reliability of Photovoltaic Cells, Modules, Components, and 13-13Au, 11-13, August 13-13). Lecture No. 70480M), whether or not the transparent conductive film is peeled off after being held at 185 ° C. for 15 minutes with a DC voltage of 100 V applied between the glass plate surface of the transparent conductive film and the surface of the transparent conductive layer B Was visually observed. In the ECDL test, the number of holding times until the transparent conductive film peeled was recorded.

For the glass plates with a transparent conductive film of Examples 1 to 8 and Comparative Examples 1 to 3, the thickness of the transparent conductive layer B, the haze ratio, the shape and distribution of the holes, the surface roughness Ra, the sheet resistance as described above Table 1 shows the results of measurement of light transmittance and durability. In addition, about the haze rate of the glass plate with a transparent conductive film of Example 8, a hole shape and distribution, surface roughness Ra, sheet resistance, light transmittance, and durability, the composition of the second transparent conductive layer B is formed. Only the measurement results after the film are described.

Voids were formed in any of the transparent conductive films of the glass plates with the transparent conductive film of Examples 1 to 8. On the other hand, no pores were formed in the glass plates with transparent conductive films of Comparative Examples 1 to 3.

When Examples 1 to 8 containing hydrogen chloride in the mixed gas were compared with Comparative Examples 1 and 3 not containing hydrogen chloride, the glass plates with transparent conductive film of Examples 1 to 8 were transparent conductive films of Comparative Examples 1 and 3. The haze rate was higher than that of the attached glass plate. In particular, considering that the difference between the glass plate with a transparent conductive film of Example 7 and the glass plate with a transparent conductive film of Comparative Example 3 is only the presence or absence of hydrogen chloride in the mixed gas in the production process, It can be seen that hydrogen chloride contributes to the formation of vacancies.

Since the transparent conductive layer A does not exist in the glass plate with a transparent conductive film of Comparative Example 2, no pores are formed. In the glass plate with a transparent conductive film in which no pores are formed, the surface roughness Ra increases as the haze ratio increases because the surface irregularities are the main factor determining the haze ratio.

Claims

A glass plate, and a transparent conductive film formed on the glass plate,
The transparent conductive film has a transparent conductive layer A and a transparent conductive layer B,
The transparent conductive layer B is formed on the transparent conductive layer A,
The transparent conductive film includes a plurality of pores;
Each of the plurality of holes is one in which the transparent conductive layer B blocks a recess in the surface of the transparent conductive layer A.
A glass plate with a transparent conductive film.
The glass plate with a transparent conductive film according to claim 1, wherein at least some of the plurality of holes are spread over the entire film thickness of the transparent conductive layer A.
Further comprising a base film formed on the glass plate,
The transparent conductive film was formed on the glass plate through the base film,
The glass plate with a transparent conductive film according to claim 1.
The surface roughness Ra of the surface of the transparent conductive film is 40 nm or less,
The haze rate is 10% or more,
The glass plate with a transparent conductive film according to claim 1.
2. The glass plate with a transparent conductive film according to claim 1, wherein a diameter A calculated by converting an average area of the plurality of pores into a circle when observed along the film thickness direction is 0.5 μm or more and 10 μm or less.
The transparent conductive film according to claim 1, wherein a diameter B calculated by converting an average area of the plurality of holes appearing in a cross section cut along the film thickness direction into a circle is 0.1 μm or more and 0.6 μm or less. Glass plate.
The glass plate with a transparent conductive film according to claim 1, wherein the ratio of the total area of the plurality of pores to the area of the transparent conductive film when observed along the film thickness direction is 10% or more and 40% or less.
The glass plate with a transparent conductive film according to claim 1, wherein the transparent conductive layer A contains zinc oxide as a main component.
The glass plate with a transparent conductive film according to claim 1, wherein the transparent conductive layer B contains tin oxide as a main component and contains fluorine.
The glass plate with a transparent conductive film according to claim 1, wherein the thickness of the transparent conductive layer A is 180 nm or more and 600 nm or less.
The glass plate with a transparent conductive film according to claim 1, wherein the thickness of the transparent conductive layer B is 200 nm or more and 1000 nm or less.
The glass plate with a transparent conductive film according to claim 1, wherein the transparent conductive film further has a transparent conductive layer C on the transparent conductive layer B.
Each of the plurality of holes is formed by a part of the surface of the transparent conductive layer A receding in the film thickness direction and the transparent conductive layer B closing the part of the area. The glass plate with a transparent conductive film according to claim 1.
A method for producing a glass plate with a transparent conductive film, comprising a glass plate and a transparent conductive film containing a plurality of pores formed on the glass plate,
By supplying an etching gas containing an etching component capable of etching the transparent conductive layer a to the surface of the transparent conductive layer a formed in advance on the glass plate, a plurality of surfaces on the surface of the transparent conductive layer a Forming a transparent conductive layer A having a plurality of recesses from the transparent conductive layer a by retreating the region in the film thickness direction by the etching component;
By supplying to the surface of the transparent conductive layer A a film forming gas containing an oxidizable component that can be oxidized to form a metal oxide, and an oxidizing agent that can oxidize the oxidizable component, Forming a plurality of pores by forming a transparent conductive layer B containing the metal oxide on the transparent conductive layer A so as to close the recess,
The manufacturing method of a glass plate with a transparent conductive film.
A method for producing a glass plate with a transparent conductive film, comprising a glass plate and a transparent conductive film containing a plurality of pores formed on the glass plate,
An etching component capable of etching the transparent conductive layer a on the surface of the transparent conductive layer a previously formed on the glass plate, an oxidizable component capable of being oxidized to form a metal oxide, and the oxidizable component By supplying a mixed gas containing an oxidizing agent that can oxidize a plurality of regions on the surface of the transparent conductive layer a, the etching component causes the etching component to recede in the film thickness direction to form a plurality of recesses from the transparent conductive layer a. And forming the plurality of pores by forming the transparent conductive layer B containing the metal oxide on the transparent conductive layer A so as to close the plurality of recesses. ,
The manufacturing method of a glass plate with a transparent conductive film.
The film forming gas containing an oxidizable component capable of being oxidized to generate a metal oxide and an oxidant capable of oxidizing the oxidizable component is further supplied to the surface of the transparent conductive layer B. Manufacturing method of a glass plate with a transparent conductive film.