JP6295957B2 - Method for producing glass substrate with conductive thin film - Google Patents

Description

  The present invention relates to a method for producing a glass substrate with a conductive thin film, a thin film solar cell, a low emission glass substrate, and a glass substrate with a conductive thin film.

  2. Description of the Related Art Conventionally, a glass substrate with a conductive thin film in which a conductive thin film is formed on a glass substrate is known, and is used for, for example, a solar cell module, architectural low radiation glass, and the like. In such a glass substrate with a conductive thin film, the conductive thin film may be peeled off during production or use, and various studies have been made to solve such problems.

For example, Patent Document 1 reflects an unevenness of the base film made of SiO ₂ and a metal oxide base film having a crystallinity of 150 mm or more to provide unevenness on an alkali-containing substrate glass. It is disclosed that the adhesion of a transparent conductive film is improved by forming a continuous alkali barrier film having a thickness and a transparent conductive film made of SnO ₂ doped with impurities and having a thickness of 5000 mm or more in that order. Yes.

Further, in Patent Document 1, SnO ₂ base film by thermal decomposition spray method or the CVD method is a film on a glass substrate, the unevenness is formed by the growth of crystal grains, film peeling by more uneven is prevented Is disclosed.

Japanese Unexamined Patent Publication No. 2000-261013

  However, in this method, it is difficult to control the size of the crystal grains, and as a result, the crystal grains become large and the density of the unevenness tends to be sparse. Therefore, it cannot be said that the film peeling resistance of the conductive thin film is sufficiently suppressed in an actual use environment, that is, in an environment where a voltage is applied to the conductive thin film at a high temperature. Moreover, since the crystal grains are large, the haze is likely to be large, and the transparency of the substrate with the conductive thin film is lowered. Moreover, the raw material for the base film for uneven | corrugated formation is also needed separately.

  In view of the above-described problems of the prior art, the present invention can suppress the occurrence of film peeling of the conductive thin film under a high temperature use environment, particularly in a use environment in which a voltage is applied to the conductive thin film, and haze can also be achieved. It aims at providing the glass substrate with the electroconductive thin film which suppressed.

In order to solve the above problems, the present invention
And undercoat layer on a surface of the glass substrate and next Ide conductive thin film are laminated,
Before Symbol glass substrate, the undercoat layer, the surface of the side where the conductive thin film is laminated, in the manufacturing method of the conductive thin film-coated glass substrate etching process is performed by the hydrogen fluoride,
Etching treatment with hydrogen fluoride
A gas containing hydrogen fluoride having a hydrogen fluoride concentration of 0.1% by volume or more and 10% by volume or less is applied to a sheet-like glass being conveyed at a temperature of 300 ° C. or more and 1 second or more and 2 minutes under normal pressure. A method for producing a glass substrate with a conductive thin film, which is performed by spraying below, is provided.

In addition, an undercoat layer containing silicon oxide is laminated on the surface of the glass substrate, and then a conductive thin film,
In the method of manufacturing a glass substrate with a conductive thin film in which the surface on the side on which the conductive thin film is laminated of the glass substrate with the undercoat layer containing silicon oxide is etched with hydrogen fluoride,
Etching treatment with hydrogen fluoride
A gas containing hydrogen fluoride having a hydrogen fluoride concentration of 0.1% by volume or more and 10% by volume or less is usually applied to a sheet-like glass on which an undercoat layer containing silicon oxide is formed. Provided is a method for producing a glass substrate with a conductive thin film, which is performed by spraying at 300 ° C. or higher for 1 second or more and 2 minutes or less .

  In the glass substrate with a conductive thin film of the present invention, the surface roughness of the glass substrate is fine and moderately fine, and the haze is small. Therefore, it is excellent in transparency, and the occurrence of film peeling of the conductive thin film can be suppressed in a use environment at a high temperature, particularly in a use environment in which a voltage is applied to the conductive thin film.

Sectional drawing of the glass substrate with an electroconductive thin film in the 1st Embodiment of this invention Sectional drawing of the thin film solar cell in the 3rd Embodiment of this invention Sectional drawing of the injector in the Example of this invention

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not departed from the scope of the present invention. Various modifications and substitutions can be made.
[First Embodiment]
In the present embodiment, a configuration example of the glass substrate with a conductive thin film of the present invention will be described.

  In the glass substrate with a conductive thin film of the present embodiment, an undercoat layer and then a conductive thin film are laminated on the surface of the glass substrate, and the haze of the glass substrate is 3% or less. The surface roughness (Ra) of the surface on which the undercoat layer and the conductive thin film are laminated is 0.5 nm or more and 50 nm or less.

  A specific configuration example of the glass substrate with a conductive thin film of the present embodiment will be described below with reference to FIG.

FIG. 1 schematically shows a cross-sectional view of a glass substrate with a conductive thin film of the present embodiment, and in order from the bottom in the figure, a glass substrate 11, an undercoat layer 12, a conductive thin film (top coat layer). 13 is laminated. Hereinafter, the configuration of the glass substrate and each layer will be described.
<Glass substrate>
It does not specifically limit as a glass substrate, It can select according to a use. Specifically, for example, soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, alkali-free glass, and other various glasses can be used.

  When providing a layer having an alkali barrier property as described below as the undercoat layer 12, the undercoat layer having an alkali barrier property usually diffuses the alkali component from the glass substrate containing the alkali component to the conductive thin film 13 or the like. It is provided for the purpose of suppression. For this reason, in view of such an object, in such a case, for example, an alkali glass containing an alkali metal oxide such as soda lime silicate glass can be suitably used.

  However, even when an undercoat layer having alkali barrier properties is provided, it does not exclude a glass substrate having a low or no alkali metal oxide content, and various glass substrates other than soda lime silicate glass can also be used. it can.

  In addition, like a glass substrate used for a photoelectric conversion element such as a solar cell or a liquid crystal display, when used for an application in which a transparent conductive oxide film is formed thereon, the glass substrate may have high light transmittance. preferable. Specifically, for example, it is preferable to have a light transmittance of 80% or more in a wavelength region of 350 to 800 nm.

  The thickness of a glass substrate can be suitably selected according to the use. In the case of a glass substrate used for a purpose in which a transparent conductive oxide film is formed thereon, such as a glass substrate used for photoelectric conversion elements such as solar cells and liquid crystal displays, the thickness of the glass substrate is 0.2. It is preferably ˜6.0 mm. It is because the intensity | strength of a glass substrate is strong in this range, and the light transmittance in the wavelength range mentioned above is high.

  The surface roughness (Ra) of the glass substrate on which the undercoat layer and the conductive thin film are laminated is 0.5 nm to 50 nm, more preferably 0.5 nm to 30 nm, and more preferably 4.0 nm. The thickness is particularly preferably 15 nm or more.

  The surface roughness (Ra) is the surface roughness (Ra) in the surface shape observed by AFM, and can be measured by a measuring method based on JIS B 0601 (1994).

  Thus, when the surface roughness (Ra) of the surface on which the glass substrate undercoat layer and the conductive thin film are laminated satisfies the above range, the voltage is applied to the conductive thin film at a high temperature. Even in a use environment, it is preferable because the occurrence of peeling of the conductive thin film can be suppressed.

  And the haze of a glass substrate is 3% or less, It is more preferable that it is 1% or less, It is especially preferable that it is 0.8% or less.

  The haze indicates the ratio of the amount of scattered transmitted light out of the light (total transmitted light amount) transmitted to the opposite surface when light is applied to the glass substrate, and is based on a method in accordance with JIS K 7136. Can be measured.

  That is, when the haze is in the above range, the degree of scattering of light transmitted through the glass substrate is small, which means that the glass substrate is transparent and does not cloud.

Thus, by providing fine irregularities on the side of the glass substrate on which the undercoat layer or the like is formed at least so as to hardly increase the ratio of the amount of scattered light transmitted through the glass substrate, transparency is improved. It is preferable because it can be preferably used for various uses such as a required glass substrate for solar cells, a glass substrate for display, a low emission glass substrate, and a low emission glass substrate for construction.
<Etching treatment with hydrogen fluoride>
And it is preferable that the surface 11A of the side of the glass substrate of this embodiment on which the undercoat layer and the conductive thin film are laminated is etched with hydrogen fluoride, thereby easily having the above characteristics. It can be a substrate.

  An etching process using hydrogen fluoride will be described.

  The etching treatment with hydrogen fluoride can be performed, for example, by spraying a gas containing hydrogen fluoride on the sheet-like glass being conveyed under normal pressure. At this time, the portion of the sheet-like glass to which the gas containing at least hydrogen fluoride is blown is 300 ° C. or higher, and the time for blowing the gas containing hydrogen fluoride to the treated portion of the glass is 1 second. It is preferably 2 minutes or less, and the hydrogen fluoride concentration contained in the gas containing hydrogen fluoride is preferably 0.1% by volume or more and 10% by volume or less. Here, the sheet-like glass includes a glass substrate manufactured through a cooling process, a cutting process, and the like after the molding process, and a glass ribbon that is not subjected to the cutting process after the molding process in the manufacturing process. It may be a form. In the case of a glass ribbon, a glass substrate having a desired size can be obtained by performing a cutting process after the etching process.

  In order to sufficiently advance the etching process, it is preferable that the sheet-like glass has a portion where the gas containing at least hydrogen fluoride is blown at 300 ° C. or higher as described above. In particular, 350 ° C. or higher is more preferable in order to increase the reactivity during the etching process.

  At this time, the upper limit of the temperature of the portion of the sheet-like glass to which the gas containing hydrogen fluoride is blown is not particularly limited. When a gas containing hydrogen fluoride is blown onto the sheet-like glass, it is preferable that the sheet-like glass is not deformed or broken. Moreover, after performing the etching process by blowing the gas containing hydrogen fluoride, it is preferable that the temperature is such that the shape does not change by other than the reaction. Specifically, for example, in view of the cost required for heating, the temperature is preferably 650 ° C. or lower, and more preferably 600 ° C. or lower.

  Of the sheet-like glass as described above, at least the portion that blows the gas containing hydrogen fluoride (the portion that performs the etching process) may be within the above temperature range, but the entire sheet-like glass is It is good also as temperature.

  In addition, the sheet-like glass can be heated to the above temperature by heating the glass substrate manufactured as described above. However, in the glass substrate manufacturing process, the glass substrate (glass ribbon) is caught at a timing within the above temperature range. Etching with hydrogen fluoride can also be performed. Specifically, it can be performed on, for example, a glass ribbon that has been molded in a float bath and has come out of the float bath, specifically, for example, a glass ribbon in a cooling process. Even in this case, heating may be performed as necessary.

  Thus, in the manufacturing process of a glass substrate, since it can save the energy which heating requires by performing when a glass substrate or a glass ribbon exists in a predetermined temperature range, it is preferable from a viewpoint of reduction of manufacturing cost and environmental impact. .

  The gas containing hydrogen fluoride may be a gas containing hydrogen fluoride at least on the surface of the sheet-like glass when sprayed on the sheet-like glass.

  As described above, any gas containing hydrogen fluoride at least on the surface of the sheet-like glass may be used. Therefore, as a material, that is, a substance discharged from a nozzle or the like on the sheet-like glass surface, What becomes a substance containing hydrogen fluoride can be used. Specifically, for example, a substance containing a molecule having a fluorine atom in its structure can be used. As such a substance, for example, hydrogen fluoride is preferable because of safety such as non-explosive properties and high reactivity with glass, and trifluoroacetic acid is preferable because of stability of raw materials themselves such as non-explosive properties and safety of pyrolysis reaction products. In addition, when using trifluoroacetic acid as a raw material, in order to accelerate | stimulate thermal decomposition, as for the part sprayed among sheet-like glass, 500 degreeC or more is preferable.

The gas containing hydrogen fluoride may contain various liquids other than the above substances and liquids and gases other than gases, and such liquids or gases do not react with molecules having fluorine atoms at room temperature, particularly hydrogen fluoride. A liquid or gas is preferred. Specific examples include N ₂ , air, H ₂ , O ₂ , Ne, Xe, CO ₂ , Ar, He, Kr, and the like, but are not limited to these. Moreover, 2 or more types of these gases can also be mixed and used. As a gaseous carrier gas containing hydrogen fluoride, it is preferable to use an inert gas such as N ₂ or argon.

Further, the gas containing hydrogen fluoride may further contain SO ₂ . SO ₂ is used when a glass substrate is continuously produced by a float process or the like, and has a function of preventing wrinkles from being generated on the glass due to the conveyance roller coming into contact with the glass substrate in the slow cooling region. Moreover, the gas decomposed | disassembled at high temperature may be included.

  Further, the gas containing hydrogen fluoride may contain water vapor or water. Water vapor can be extracted by bubbling an inert gas such as nitrogen, helium, argon, carbon dioxide in heated water. When a large amount of water vapor is required, it is also possible to take a method in which water is sent directly to the vaporizer and vaporized directly.

  When HF is used as a gas containing hydrogen fluoride and water is added thereto, the molar ratio of HF to water ([water] / [HF]) is preferably 50 or less. When HF and water coexist, it is considered that hydrogen bonds are formed between HF molecules and water molecules, and HF acting on the glass substrate is reduced. For this reason, when [water] / [HF] exceeds 50, the temperature at which film peeling occurs in the DHB test may not be sufficiently increased.

  [Water] / [HF] is preferably 40 or less, more preferably HF acting on the glass substrate, more preferably 30 or less.

  In addition, since it is not necessary to contain water, the lower limit of the molar ratio of [water] / [HF] may be 0 or more.

  The concentration of hydrogen fluoride contained in the gas containing hydrogen fluoride is not particularly limited, but is preferably 0.1% by volume or more and 10% by volume or less as described above, and 0.2 volume. % To 8% by volume, more preferably 0.5% to 6% by volume. The hydrogen fluoride concentration contained in the gas containing hydrogen fluoride here is at least the concentration in the sheet-like glass surface that is the object to be treated, and more preferably from the discharge port of the injector. It is preferable that the concentration is within the above range.

  The concentration of hydrogen fluoride can be selected according to the required reactivity and the depth and shape of the irregularities formed on the surface, but if the above range is satisfied, the peeling of the conductive thin film may occur. Since it can suppress especially, it is preferable.

  As described above, when water or other gas is added to the gas containing hydrogen fluoride, the whole can be mixed and sprayed onto the sheet-like glass. In addition, a partly mixed gas and / or each component gas is blown against a sheet-like glass from nozzles arranged close to each other, for example, at an injector portion described later, and substantially mixed on the sheet-like glass surface. You may spray as you do.

  Although it is not particularly limited as a method of spraying a gas containing hydrogen fluoride on the sheet-like glass, an injector is arranged on the conveyance path of the sheet-like glass being conveyed, It can spray from the provided discharge outlet.

  The injector may be used in any manner such as double-flow or single-flow, and two or more injectors may be arranged in series in the conveying direction of the sheet-like glass to treat the sheet-like glass surface.

  As shown in FIG. 3 described later, the double-flow injector is an injector in which the flow of gas from discharge to exhaust is equally divided in the forward direction and the reverse direction with respect to the sheet-like glass conveyance direction. A single-flow injector is an injector in which the flow of gas from discharge to exhaust is fixed in either the forward direction or the reverse direction with respect to the moving direction of the glass substrate. When a single-flow injector is used, it is preferable that the gas flow on the sheet-like glass and the movement direction of the glass substrate are the same in terms of airflow stability.

  Blowing a gas containing hydrogen fluoride under normal pressure means that the peripheral part of the sheet-like glass is not intended to be pressurized or reduced in pressure, such as a gas containing hydrogen fluoride. This does not exclude the occurrence of pressure fluctuations associated with the operation.

  Specifically, for example, exhaust (intake) is performed in response to blowing of a gas containing hydrogen fluoride, and the operation is performed in an environment that maintains the atmosphere around the sheet-like glass at normal pressure or in the vicinity thereof. preferable.

  In particular, in the present embodiment, the normal pressure when the gas containing hydrogen fluoride is blown is preferably performed in an atmosphere within a pressure range of atmospheric pressure ± 100 Pa, and a pressure of atmospheric pressure ± 50 Pa. More preferably, it is carried out in a range of atmospheres.

  The time for blowing the gas containing hydrogen fluoride to the treated portion of the sheet-like glass is 1 second in order to form unevenness on the sheet-like glass surface that can sufficiently suppress the occurrence of peeling of the conductive thin film. It is preferable that it is 2 minutes or less. In particular, it is more preferably 5 seconds or more and 60 seconds or less, and particularly preferably 5 seconds or more and 30 seconds or less.

  Here, the time for blowing the gas containing hydrogen fluoride to the treated portion of the sheet-like glass is that the sheet-like glass passes through the region where the gas containing hydrogen fluoride is blown. It means the time required. Specifically, it is calculated by (the length in the conveyance direction of the sheet-like glass in the region where the gas containing hydrogen fluoride is blown) / (the conveyance speed of the sheet-like glass).

  It does not specifically limit as a conveyance method of sheet-like glass, What is necessary is just to be able to convey, maintaining the shape of sheet-like glass in a desired shape. Specifically, it can be conveyed using, for example, a roller or a (belt) conveyor (hereinafter also referred to as “roller or the like”). By blowing a gas containing hydrogen fluoride onto the sheet-like glass substrate being conveyed in this way, it becomes possible to continuously perform the etching treatment, so that productivity can be increased.

The etching process using hydrogen fluoride may be performed on at least the surface on which the undercoat layer 12 and the conductive thin film 13 (topcoat layer) are laminated, but the surface other than the surface on which the undercoat layer 12 and the like are laminated. Similarly, the surface may be treated with hydrogen fluoride.
For this reason, the gas containing hydrogen fluoride is supplied to at least one side of the sheet-like glass being conveyed as described above on the side not touching the roller or the like and the side touching the roller or the like. Etching treatment may be performed. In addition, when performing an etching process on both sides of a sheet-like glass, the gas is supplied to both the side not touching the roller or the like and the side touching the roller or the like to perform the etching process. Also good.

  In addition, when supplying the said gas to the surface which is contacting a roller etc., it can carry out by arrange | positioning an injector so that sheet-like glass (its discharge port) may oppose, for example between rollers. In addition, when the sheet-shaped glass transport means is a conveyor, supply from the side touching the conveyor by using a mesh material that does not cover part of the sheet-shaped glass, such as a mesh belt, for the conveyor belt. May be.

  However, when the etching process is performed on the side where the roller or the like is in contact, in the subsequent transport process, the etched surface further contacts the roller or the like, so the shape of the etched part changes. there's a possibility that. For this reason, when performing an etching process only about one surface, it is preferable to supply the gas containing hydrogen fluoride with respect to the surface which conveyance means, such as a roller, are not contacting.

  The speed at the time of transporting the sheet-like glass is not particularly limited as long as the sheet-like glass can be sufficiently etched with hydrogen fluoride, and the sheet-like glass is treated. It is preferable to select the speed so that the time during which the gas containing hydrogen fluoride is sprayed on the part falls within the above range.

  By performing etching treatment with hydrogen fluoride on the glass substrate surface in this manner, fine irregularities can be formed on the glass substrate surface. By forming such irregularities, the adhesion (peeling resistance) of the undercoat layer and the conductive thin film can be increased, and the occurrence of peeling of the conductive thin film can be suppressed.

  This can first increase the adhesive strength of the undercoat layer to the glass substrate by providing the fine irregularities on the glass substrate surface. In this case, the undercoat layer formed on the surface of the glass substrate has a fine concavo-convex shape reflecting the concavo-convex shape of the glass substrate surface on the surface (surface on which the conductive thin film is formed). For this reason, it becomes possible to raise the adhesive strength with respect to the undercoat layer of an electroconductive thin film.

Accordingly, it is possible to increase the adhesion strength between the glass substrate, the undercoat layer, and the conductive thin film, and to improve the peeling resistance of these layers. In particular, the conductive thin film is easily peeled off in an environment where a voltage is applied. However, the above configuration makes it possible to suppress the peeling of the conductive thin film even in such an environment.
<Undercoat layer>
The undercoat layer 12 is a layer provided between the glass substrate 11 and the conductive thin film 13, and the configuration thereof is not particularly limited. However, the undercoat layer may have a layer containing at least silicon oxide. preferable. The layer containing silicon oxide here may contain silicon oxide, but it is more preferable to have a film containing silicon oxide as a main component. In this case, “main component” means that the component is contained in 90% or more in terms of mass percentage based on oxide.

  Thus, by providing the layer containing silicon oxide, it becomes possible to suppress the alkali component contained in the glass substrate from moving to the conductive thin film, and to suppress the deterioration of the characteristics of the conductive thin film. it can.

  In addition, when the alkali component moves from the glass substrate to the conductive thin film, the conductive thin film may peel off. However, by providing a layer containing such silicon oxide, the movement of the alkali component is suppressed, and the conductive thin film peels off. It can also be suppressed. For this reason, it works synergistically with the effect of the etching treatment with hydrogen fluoride applied to the surface of the glass substrate, and it becomes possible to further suppress the peeling of the conductive thin film, which is preferable.

As the structure of the undercoat layer having a layer containing silicon oxide, for example, a SiO ₂ film, a SiO ₂ / TiO ₂ film (which means a laminated structure of SiO ₂ film and TiO ₂ film, The order is not limited, and a film having a laminated structure will be described in the same manner as above), a structure including a SiOC film, and a SnO ₂ / SiO ₂ film. Any of these films can function as an alkali barrier film. Among them, the SiO ₂ / TiO ₂ film can be particularly preferably used because of its high alkali barrier performance. The undercoat layer forming method is particularly limited. Instead, there are a thermal decomposition method, a CVD method, a sputtering method, a vapor deposition method, an ion plating method, a spray method and the like.

The thickness of the undercoat layer is not particularly limited to be selected depending on the layer structure and its function, but when including an alkali barrier film as described above, 10 nm or more is preferable from the viewpoint of alkali barrier performance, More preferably, it is 20 nm or more. Moreover, from the point of adjustment of cost and visible light transmittance, 500 nm or less is preferable, and 100 nm or less and 50 nm or less are more preferable.
<Conductive thin film>
Although it does not specifically limit as the electroconductive thin film 13, Although it can select according to a use and the performance requested | required, in the glass substrate with an electroconductive thin film of this embodiment, the structural member by the side of a glass substrate In general, at least transparency in the visible light region is required. For this reason, it is preferable to use a transparent conductive film as the conductive thin film.

The transparent conductive film is preferably a film containing SnO ₂ as a main component, a film containing ZnO as a main component, a tin-doped indium oxide (ITO) film, or a film having a layer containing Ag having low radiation performance. Examples thereof include a film made of a silver alloy containing a metal element such as an Ag layer or Pd, and a film containing SnO ₂ as a main component is preferable from the viewpoint of raw material cost, mass productivity, and the like. Here, the “main component” means that the component is contained in 90% or more in terms of oxide based mass percentage.

Examples of the film containing SnO ₂ as a main component include a film made of SnO ₂ , a film made of fluorine-doped tin oxide (FTO), and a film made of antimony-doped tin oxide. These layers may have low radiation performance in addition to conductivity.

  Although it does not specifically limit as a formation method of a transparent conductive film, A thermal decomposition method, CVD method, sputtering method, a vapor deposition method, an ion plating method, a spray method etc. are mentioned.

The thickness of the transparent conductive film is preferably 5 nm or more and 1500 nm or less. In the case of a film containing SnO ₂ as a main component, the thickness is preferably 100 nm or more and 1200 nm or less, and more preferably 300 nm or more and 800 nm or less.
<Other layers>
In addition to the glass substrate, the undercoat layer, and the conductive thin film described above, the following layers can be optionally provided.

When an alkali barrier film is included as the undercoat layer as described above, a TiO ₂ film, a SnO ₂ film, or the like can be provided between the glass substrate and the alkali barrier film.

Furthermore, a mixed oxide or multilayer film of SiO ₂ and SnO ₂ can be provided between the alkali barrier film and the conductive thin film.

  An antireflection film or the like can be provided on the surface of the glass substrate opposite to the surface on which the conductive thin film is formed.

  The film itself provided between the glass substrate and the conductive thin film may have alkali barrier performance.

  Moreover, even when a film other than the undercoat layer and the conductive thin film is provided between the glass substrate and the conductive thin film as described above, the surface of each layer (surface on the conductive thin film side) is provided. Since the unevenness formed on the surface of the glass substrate is transferred (reflected), the adhesion between the respective layers can be enhanced. For this reason, even if it is a case where these films | membranes are provided, the objective of the glass substrate with a conductive thin film of this embodiment can be achieved.

The glass substrate with a conductive thin film according to the present embodiment has been described above, but the glass substrate with a conductive thin film according to the present embodiment preferably has a temperature at which film peeling occurs in a DHB test of 150 ° C. or higher. This will be described below.
<DHB test>
Hereinafter, the DHB test will be described.

  The DHB (Dump Heat Bias) test is a durability test that can estimate the ease of peeling of a conductive thin film, and is a test that simultaneously evaluates electrical and thermal attacks on a test piece coated with a conductive thin film. It is.

  Specifically, a glass substrate with a conductive thin film as a sample is heated for a sufficient period of time until it becomes stable at each set temperature (test temperature), and at the same time, an electric field is applied to the glass substrate with a conductive thin film. This is a test for examining the temperature (set temperature) at which film peeling occurs on the thin film. In other words, this is a test in which heating and voltage application are performed simultaneously to examine the temperature at which film peeling occurs on the conductive thin film.

  According to this test, it is possible to evaluate the durability of film peeling under an environment where temperature and voltage are applied at the same time. Can be evaluated.

  Specifically, for example, the DHB test can be performed by the following procedure.

  (1) The sample was placed between two electrodes. The side on which the conductive thin film is not formed (the glass substrate surface) is brought into contact with a copper electrode (anode) covered with aluminum, and the conductive thin film side is brought into contact with a graphite electrode (cathode). After heating the sample to the set temperature, the voltage is maintained at 500 V and the voltage application time is maintained for 15 minutes.

  (2) After cooling to room temperature, the conductive thin film side of the sample is exposed to an atmosphere of 100% relative humidity for 1 hour to cause aggregation on the conductive thin film side (moisture is condensed on the surface of the conductive thin film). The aggregation temperature and water temperature are 55 ° C., and the vaporization temperature is 50 ° C. ± 2 ° C.

  This operation is performed in a closed container, and water is maintained at the above water temperature at the bottom of the container, and the conductive thin film portion of the sample disposed at the top of the container is maintained at the above aggregation temperature. The vaporization temperature means the temperature of the steam in the container.

  (3) It is confirmed whether or not peeling of the conductive thin film occurs on the surface of the sample on the conductive thin film side. The presence or absence of peeling was defined as peeling when the area of the peeled portion that could be visually confirmed in the sample exceeded 10%.

(4) A plurality of other samples prepared under the same conditions were prepared, and the test was performed three times for each set temperature. A temperature at which the conductive thin film of the sample has been peeled is defined as T _max (° C.). Higher _Tmax means that the conductive thin film is less likely to peel for a long time (high durability).

  In the glass substrate with a conductive thin film of the present embodiment, the temperature at which film peeling occurs in the DHB test as described above is preferably 150 ° C. or higher, and more preferably 165 ° C. or higher.

According to the study of the inventors of the present invention, when the temperature at which film peeling occurs in the DHB test is equal to or higher than the above temperature, even in an application used under a severe use environment such as a solar cell, for a sufficient period of time. It can be set as the glass substrate with an electroconductive thin film which film peeling does not generate | occur | produce easily.
[Second Embodiment]
This embodiment demonstrates the other structural example of the glass substrate with an electroconductive thin film of this invention.

  The glass substrate with a conductive thin film of the present embodiment is a glass substrate having an undercoat layer containing silicon oxide and then a conductive thin film laminated on the surface of the glass substrate, and having the undercoat layer containing silicon oxide. The surface roughness (Ra) of the surface on which the conductive thin film is laminated of the glass substrate with the haze of 3% or less and the silicon oxide-containing undercoat layer is 0.5 nm or more and 50 nm or less. ing.

As a specific configuration of the glass substrate with a conductive thin film of the present embodiment, as in the first embodiment, as shown in FIG. 1, the glass substrate 11, the undercoat layer 12, and the conductive thin film (top coat) are sequentially arranged from the bottom. Layer) 13 is laminated. This will be specifically described below.
<Glass substrate, conductive thin film, undercoat layer>
As the glass substrate and the conductive thin film in the glass substrate with a conductive thin film of the present embodiment, the same ones as in the case of the first embodiment can be preferably used. At this time, the surface roughness and haze of the surface on which the undercoat layer of the glass substrate is laminated are not particularly limited, but have the same surface roughness and haze as in the first embodiment. Also good.

  Further, the same undercoat layer as that described in the first embodiment can be used, but in this embodiment, the undercoat layer has a layer containing at least silicon oxide. As used herein, the layer containing silicon oxide only needs to contain silicon oxide as described in the first embodiment. However, the layer containing silicon oxide as a main component is more preferable. preferable. In this case, “main component” means that the component is contained in 90% or more in terms of mass percentage based on oxide.

  Thus, by providing the layer containing silicon oxide, it becomes possible to suppress the alkali component contained in the glass substrate from moving to the conductive thin film, and to suppress the deterioration of the characteristics of the conductive thin film. it can. In addition, etching with hydrogen fluoride can be performed on the surface of the layer (film) containing silicon oxide.

  In addition, when the alkali component moves from the glass substrate to the conductive thin film, the conductive thin film may peel off. However, by providing a layer containing such silicon oxide, the movement of the alkali component is suppressed, and the conductive thin film peels off. It can also be suppressed. For this reason, it works synergistically with the effect of the etching treatment with hydrogen fluoride applied to the surface of the glass substrate, and it becomes possible to further suppress the peeling of the conductive thin film, which is preferable.

Note that, as described in the first embodiment, a layer other than the layer containing silicon oxide may be included. Examples of the configuration of the undercoat layer having a layer containing silicon oxide include a configuration including a SiO ₂ film, a SiO ₂ / TiO ₂ film, a SiOC film, and a SnO ₂ / SiO ₂ film. Any of these films can function as an alkali barrier film, and among them, a SiO ₂ / TiO ₂ film can be particularly preferably used because of its high alkali barrier performance.

  In addition, since the preferable thickness of the undercoat layer, a suitable formation method, and the like are as described in the first embodiment, they are omitted here.

  And the surface roughness (Ra) of the side by which the conductive thin film is laminated | stacked of the glass substrate on which the undercoat layer containing a silicon oxide was laminated | stacked is 0.5 to 50 nm, and is 0.5 to 30 nm. It is more preferable that the thickness is 0.5 nm or more and 15 nm or less.

  The surface roughness (Ra) is the surface roughness (Ra) in the surface shape observed by AFM, and can be measured by a measuring method based on JIS B 0601 (1994).

  Thus, when the surface roughness (Ra) of the surface on which the conductive thin film is laminated of the glass substrate on which the undercoat layer containing silicon oxide is laminated satisfies the above range, the glass substrate is electrically conductive at high temperatures. Even in an actual use environment in which a voltage is applied to the thin film, it is preferable because peeling of the conductive thin film can be suppressed.

  The haze of the glass substrate having an undercoat layer containing silicon oxide is 3% or less, more preferably 1% or less, and particularly preferably 0.8% or less.

  The haze indicates the ratio of the amount of scattered transmitted light out of the light (total transmitted light amount) transmitted to the opposite surface when light is applied to the glass substrate, and is based on a method in accordance with JIS K 7136. Can be measured.

  That is, when the haze is in the above range, the degree of scattering of the light transmitted through the glass substrate is small, which means that the glass substrate having the undercoat layer is transparent and has no haze.

  Thus, of the light transmitted through the glass substrate having an undercoat layer containing silicon oxide, the fine irregularities to such an extent that the ratio of the amount of scattered transmitted light hardly increases, and the underside of the glass substrate having an undercoat layer containing silicon oxide By providing it on the upper surface of the coat layer, it can be preferably used for various applications such as a glass substrate for solar cells, a glass substrate for display, a low emission glass substrate, and a low emission glass substrate for construction which are required to be transparent.

And as a glass substrate with a conductive thin film of this embodiment, the surface on the side where the conductive thin film is laminated of the glass substrate with the undercoat layer containing silicon oxide laminated on the surface of the glass substrate is fluorinated. It is preferable that the etching process is performed with hydrogen. Thereby, it can be easily set as the glass substrate which has the undercoat layer containing the silicon oxide which has the said characteristic. This will be described below.
<Etching treatment of undercoat layer containing silicon oxide>
In the glass substrate with a conductive thin film of this embodiment, as an etching process using hydrogen fluoride, for example, by blowing a gas containing hydrogen fluoride under normal pressure on the sheet-like glass being conveyed. It can be carried out.

  At this time, the sheet-like glass being conveyed is blown with a gas containing hydrogen fluoride under normal pressure, and at least the gas containing the hydrogen fluoride of the sheet-like glass is blown. It is preferable that the portion to be attached is 300 ° C. or higher, and the time for blowing the gas containing hydrogen fluoride to the treated portion of the sheet-like glass is 1 second or longer and 2 minutes or shorter.

  Here, the sheet-like glass in the present embodiment is a glass substrate in which an undercoat layer containing silicon oxide is formed on the surface of a glass substrate manufactured through a cooling process, a cutting process, and the like after the molding process, a manufacturing process In this embodiment, any form may be used including an undercoat layer containing silicon oxide formed on the surface of the glass ribbon not subjected to the cutting step after the molding step. In the case of a glass ribbon, a glass substrate having a desired size can be obtained by performing a cutting process after the etching process.

  In the first embodiment, as described above, when using a sheet-like glass in which an undercoat layer containing silicon oxide is formed on the surface of the glass ribbon in the glass substrate manufacturing process, energy required for heating is used. From the viewpoint of manufacturing cost and the like.

  There are no particular limitations on the more specific conditions for etching the upper surface of the undercoat layer containing silicon oxide with hydrogen fluoride. However, in 1st Embodiment, it can carry out preferably on the conditions similar to what was described as an etching process by the hydrogen fluoride about the glass substrate surface.

  In addition, when conveying sheet-like glass as demonstrated in 1st Embodiment, sheet-like glass can be conveyed with a roller etc. At this time, at least the surface of the undercoat layer containing silicon oxide of the sheet-like glass may be treated with hydrogen fluoride, but the surface not provided with the undercoat layer is also treated with a gas containing hydrogen fluoride. Processing may be performed.

  Further, as already described in the first embodiment, the surface that is in contact with the conveying means such as a roller and the surface that is not in contact can be treated with a gas containing hydrogen fluoride. It is preferable to perform processing on a surface that is not in contact with a roller or the like. For this reason, in this embodiment, when conveying the sheet-like glass, the surface on which the undercoat layer containing silicon oxide is formed is conveyed so that it does not come into contact with a roller or the like, and the surface is treated with hydrogen fluoride. Preferably it is done.

  And fine unevenness | corrugation can be formed on this undercoat layer by performing the etching process by hydrogen fluoride about the sheet-like glass (in which the undercoat layer containing a silicon oxide was formed). By forming such irregularities, the adhesion (peeling resistance) between the undercoat layer and the conductive thin film can be increased, and the occurrence of peeling of the conductive thin film can be suppressed.

  This is because the adhesive strength of the conductive thin film to the undercoat layer can be increased by providing the fine irregularities on the surface of the undercoat layer containing silicon oxide.

  In addition, even when other undercoat layers and other layers described later are formed on the undercoat layer containing silicon oxide subjected to the etching treatment as described above, it is formed on the undercoat layer containing silicon oxide. The irregularities thus transferred are transferred to the surface of an undercoat layer or the like laminated thereon. For this reason, peeling resistance with a conductive thin film can be improved similarly.

In general, in a glass substrate with a conductive thin film, peeling is likely to occur between the undercoat layer and the conductive thin film. By adopting the above-described configuration, adhesion between the undercoat layer and the conductive thin film is achieved. The strength can be increased and the peel resistance of these layers can be increased. In particular, the conductive thin film is easily peeled off in an environment where a voltage is applied. However, the above configuration makes it possible to suppress the peeling of the conductive thin film even in such an environment.
<Other layers>
Also in this embodiment, in addition to the glass substrate, the undercoat layer, and the conductive thin film described above, the following layers listed as other layers in the first embodiment can be arbitrarily provided.

A TiO ₂ film, a SnO ₂ film, or the like can be provided between the glass substrate and the undercoat layer containing silicon oxide.

Further, a mixed oxide or multilayer film of SiO ₂ and SnO ₂ can be provided between the undercoat layer containing silicon oxide and the conductive thin film.

  An antireflection film or the like can be provided on the surface of the glass substrate opposite to the surface on which the conductive thin film is formed.

  The film itself provided between the glass substrate and the conductive thin film may have alkali barrier performance.

  Even when the above-described layer is provided, it is possible to suppress the peeling of the conductive thin film due to the unevenness formed on the surface of the undercoat layer.

  As mentioned above, although the glass substrate with a conductive thin film of this embodiment was described, it is preferable that the glass substrate with a conductive thin film of this embodiment has a temperature at which film peeling occurs in a DHB test is 150 ° C. or higher, and is 165 ° C. or higher. More preferably.

  The DHB test can be performed by the same procedure as the method described in the first embodiment.

According to the study of the inventors of the present invention, when the temperature at which film peeling occurs in the DHB test is equal to or higher than the above temperature, even in an application used under a severe use environment such as a solar cell, for a sufficient period of time. It can be set as the glass substrate with an electroconductive thin film which film peeling does not generate | occur | produce easily.
[Third Embodiment]
In this embodiment, the thin film solar cell using the glass substrate with a conductive thin film described in the first or second embodiment, that is, the glass substrate with a conductive thin film described in the first or second embodiment is used. The example used as the glass substrate for thin film solar cells is demonstrated.

  FIG. 2 is a cross-sectional view showing an example of a thin film solar cell. In the thin film solar cell 20, a thin film solar cell element 21 is formed on one surface of a glass substrate 11 via an undercoat layer 12. As described above, an antireflection film (not shown) or the like may be provided on the other surface of the glass substrate 11.

  The thin film solar cell element 21 includes a transparent electrode layer (conductive thin film) 22, a photoelectric conversion layer 23 (power generation layer), and a back electrode layer 24 in order from the glass substrate 11 side.

  The transparent electrode layer 22 is a layer made of the conductive thin film 13 described above.

  The photoelectric conversion layer 23 is a layer made of a thin film semiconductor. Examples of the thin film semiconductor include an amorphous silicon semiconductor, a microcrystalline silicon semiconductor, a compound semiconductor (such as a chalcopyrite semiconductor and a CdTe semiconductor), and an organic semiconductor.

Examples of the material of the back electrode layer 24 include materials that do not transmit light (such as silver and aluminum) and materials that transmit light (such as ITO, SnO ₂ , and ZnO).

  Thus, the glass substrate with a conductive thin film described in the first or second embodiment can be suitably used for a glass substrate for a thin film solar cell. And the glass substrate with a conductive thin film described in the first or second embodiment has a fine, moderately fine surface roughness of the glass substrate and a small haze. For this reason, it is excellent in transparency, and it can suppress generation | occurrence | production of the film peeling of an electroconductive thin film also in the actual use environment where the voltage was applied to the electroconductive thin film at high temperature. Therefore, a thin film solar cell using the glass substrate with a conductive thin film can be made highly durable.

  The thin film solar cell of this embodiment can be suitably applied to all thin film solar cells in which a transparent conductive film (conductive thin film) is provided on a glass plate such as a thin film silicon solar cell and a CdTe thin film solar cell.

Specific examples will be described below, but the present invention is not limited to these examples.
(1) Evaluation method The characteristic evaluation method of the glass substrate with a conductive thin film obtained in the following examples and comparative examples will be described below.
(DHB test)
The DHB test in the present invention was performed according to the following procedure.

  (1) The sample was placed between two electrodes. The side where the conductive thin film was not formed (the glass substrate surface) was brought into contact with the copper electrode (anode) covered with aluminum, and the side of the conductive thin film was brought into contact with the graphite electrode (cathode). After heating to the set temperature, the voltage was maintained at 500 V and the voltage application time was maintained for 15 minutes.

  (2) After cooling to room temperature, the conductive thin film side of the sample was exposed to an atmosphere with a relative humidity of 100% for 1 hour to cause aggregation on the conductive thin film side. The aggregation temperature and water temperature were 55 ° C., and the vaporization temperature was 50 ° C. ± 2 ° C.

  (3) It was confirmed whether or not peeling of the conductive thin film occurred on the surface of the sample on the conductive thin film side. The presence or absence of peeling was defined as peeling when the area of the peeled portion that could be visually confirmed in the sample exceeded 10%.

(4) Prepare a plurality of other samples prepared under the same conditions, and perform the test three times for each set temperature (three samples each). The temperature at which the conductive thin film of the sample is peeled off is T _max (° C.) It was.

In the step (1), the heating temperature, that is, the set temperature, is set to every 15 ° C. in the range of 120 ° C. to 225 ° C., and samples are prepared and measured for each set temperature. In addition, the DHB temperature was set to “above 225 ° C.” for samples in which peeling did not occur even at 225 ° C.
(Surface roughness Ra)
About the surface which performed the etching process of the glass substrate after an etching process, surface roughness (Ra) was measured based on JISB0601.

Specifically, using a scanning probe microscope (manufactured by SII Nano Technology, model number SPI3800N), the observation layer in the obtained glass substrate is 2 μm square, the number of acquired data is 1024 × 1024, and in DFM mode. The surface roughness (Ra) at the time of observation was measured.
(Haze)
Haze was measured according to JIS K 7136.

Specifically, it was carried out with a C light source using a haze meter (manufactured by Suga Test Instruments Co., Ltd., model number HZ-2).
(2) Experimental procedure [Example 1]
A gas containing hydrogen fluoride was brought into contact with the surface of a 4 mm-thick soda lime silicate glass substrate using a double-flow injector 30 used in the atmospheric pressure CVD method as shown in the schematic diagram of FIG. Simply referred to as “HF processing”).

As specific conditions, from a central slit 31 shown in FIG. 3, a gas mixed with 3.70 SLM of hydrogen fluoride (liter of gas in a standard state per liter per minute) and 41.3 SLM of nitrogen is heated to 150 ° C. to obtain a flow rate. It sprayed toward the glass substrate at 34 cm / s. At the same time, 17.5 g / min of H ₂ O and 75.2 SLM of N ₂ were similarly heated to 150 ° C. and sprayed toward the glass substrate from the outer slit 32, and the glass substrate was etched.

The concentration of hydrogen fluoride with respect to the whole gas was 2.6% by volume, and the molar ratio of water and hydrogen fluoride was [H ₂ O (mol)] / [HF (mol)] = 5.9. The gas flows on the glass substrate 33 through the flow path 34, and the exhaust slit 35 blows and exhausts twice the gas flow rate.

  The glass substrate was heated to 550 ° C. and conveyed in the direction of arrow A in the figure. The temperature of the glass substrate was measured by installing a radiation thermometer immediately before blowing the gas. The etching time (time for blowing a gas containing hydrogen fluoride to the treated portion of the glass substrate) was as short as about 20 seconds.

  After the etching treatment, the surface roughness (Ra) of the glass substrate on which the etching treatment was performed was 5.7 nm, and haze was 0.06%.

The surface of the glass substrate heated to 580 ° C. (the surface subjected to the etching process) is formed by CVD with an TiO ₂ film having a thickness of 8 nm, an alkali barrier film (undercoat layer) made of SiO _{2 having} a thickness of 25 nm and a thickness of 550 nm A transparent conductive film (conductive thin film) made of SnO ₂ was formed. About the obtained glass substrate with a transparent conductive film, it used for the DHB test. The results are shown in Table 1.
[Example 2]
From a central slit 31 shown in FIG. 3, a gas obtained by mixing 1.85 SLM of hydrogen fluoride (liters per minute in a standard state gas) and 43.15 SLM of nitrogen is heated to 150 ° C. and applied to a glass substrate at a flow rate of 34 cm / s. I sprayed it. At the same time, 17.5 g / min of H ₂ O and 75.2 SLM of N ₂ were similarly heated to 150 ° C. and sprayed toward the glass substrate from the outer slit 32, and the glass substrate was etched.

The concentration of hydrogen fluoride with respect to the entire gas was 1.3% by volume and [H ₂ O (mol)] / [HF (mol)] = 11.8.

  The other points were the same as in Example 1.

  After the etching process, the surface roughness (Ra) of the glass substrate on which the etching process was performed was 8.3 nm, and the haze was 0.03%.

Furthermore, the transparent conductive film etc. were formed into a film similarly to Example 1, and it used for the DHB test about the obtained glass substrate with a transparent conductive film. The results are shown in Table 1.
[Example 3]
From a central slit 31 shown in FIG. 3, a gas obtained by mixing 3.70 SLM of hydrogen fluoride (liters of gas per minute in a standard state) and nitrogen 41.3 SLM is heated to 150 ° C. and applied to a glass substrate at a flow rate of 34 cm / s. I sprayed it. At the same time, N ₂ 97SLM was similarly heated to 150 ° C. from the outer slit 32 and sprayed toward the glass substrate to perform an etching process on the glass substrate.

The concentration of hydrogen fluoride relative to the entire gas was 2.6% by volume and [H ₂ O (mol)] / [HF (mol)] = 0. The glass substrate was conveyed and etched. The etching time was as short as about 10 seconds.

  The other points were the same as in Example 1.

  After the etching process, the surface roughness (Ra) of the glass substrate on which the etching process was performed was 4.0 nm, and the haze was 0.05%.

Furthermore, the transparent conductive film etc. were formed into a film similarly to Example 1, and it used for the DHB test about the obtained glass substrate with a transparent conductive film. The results are shown in Table 1.
[Example 4]
From a central slit 31 shown in FIG. 3, a gas obtained by mixing 3.70 SLM of hydrogen fluoride (liters of gas per minute in a standard state) and nitrogen 41.3 SLM is heated to 150 ° C. and applied to a glass substrate at a flow rate of 34 cm / s. I sprayed it. At the same time, 63.0 g / min of H ₂ O and 18.6 SLM of N ₂ were similarly heated to 150 ° C. and sprayed toward the glass substrate from the outer slit 32, and the glass substrate was etched.

The concentration of hydrogen fluoride with respect to the entire gas was 2.6% by volume and [H ₂ O (mol)] / [HF (mol)] = 21.2. The glass substrate was heated to 600 ° C. during the etching process. The other points were the same as in Example 1.

  After the etching process, the surface roughness (Ra) of the glass substrate on which the etching process was performed was 7.0 nm, and the haze was 0.03%.

Furthermore, the transparent conductive film etc. were formed into a film similarly to Example 1, and it used for the DHB test about the obtained glass substrate with a transparent conductive film. The results are shown in Table 1.
[Example 5]
An alkali barrier film (undercoat layer) made of 8 nm thick TiO ₂ film and 25 nm thick SiO ₂ was formed on the surface of a 4 mm thick soda lime silicate glass substrate heated to 580 ° C. by the CVD method.

The glass substrate with an undercoat layer heated to 595 ° C. was mixed with 1.50 SLM of hydrogen fluoride (liter per minute as a gas in a standard state) and 58.5 SLM of nitrogen from the central slit 31 shown in FIG. The gas was heated to 150 ° C. and sprayed toward the glass substrate at a flow rate of 34 cm / s. At the same time, 20 g / min of H ₂ O and 205 SLM of N ₂ were similarly heated to 150 ° C. and sprayed toward the glass substrate from the outer slit 32, and the glass substrate was etched.

The concentration of hydrogen fluoride with respect to the entire gas was 0.5% by volume and [H ₂ O (mol)] / [HF (mol)] = 16.6. The glass substrate was conveyed and etched. The etching time was as short as about 7.5 seconds.

  After the etching treatment, the surface roughness (Ra) of the glass substrate (undercoat layer) on the surface subjected to the etching treatment was 0.6 nm and haze was 0.25%.

Furthermore, the transparent conductive film etc. were formed into a film similarly to Example 1, and it used for the DHB test about the obtained glass substrate with a transparent conductive film. The results are shown in Table 1.
[Comparative Example 1]
From the central slit 31 shown in FIG. 3, a gas in which hydrogen fluoride 0SLM (liters per minute in a standard state) and nitrogen 45SLM are mixed is heated to 150 ° C. and blown toward the glass substrate at a flow rate of 34 cm / s. It was. At the same time, 52.5 g / min of H ₂ O and 31.7 SLM of N ₂ were similarly heated to 150 ° C. and sprayed toward the glass substrate from the outer slit 2 to treat the glass substrate. The concentration of hydrogen fluoride relative to the entire gas was 0% by volume.

  The other points were the same as in Example 1.

  After the etching treatment, the surface roughness (Ra) of the glass substrate on which the etching treatment was performed was 0.4 nm, and haze was 0.04%.

Furthermore, the transparent conductive film etc. were formed into a film similarly to Example 1, and it used for the DHB test about the obtained glass substrate with a transparent conductive film. The results are shown in Table 1.
[Comparative Example 2]
A transparent conductive film or the like was formed on an untreated glass substrate (soda lime silicate glass substrate having a thickness of 4 mm) in the same manner as in Example 1 and subjected to a DHB test. The results are shown in Table 1.

  The haze and surface roughness (Ra) were measured on the surface of the untreated glass substrate on which the undercoat layer and the conductive thin film were formed. The surface roughness (Ra) of the glass substrate was 0.3 nm, and the haze = It was 0.06%.

  According to the results of the above Examples and Comparative Examples, in the glass substrates with conductive thin films of Examples 1 to 5 subjected to the etching treatment with hydrogen fluoride, the result of the DHB test was 150 ° C. or more, and the actual It was confirmed that the glass substrate with the conductive thin film sufficiently suppressed the occurrence of peeling of the conductive thin film even under the usage environment.

  On the other hand, in the glass substrate with the conductive thin film of Comparative Examples 1 and 2 in which the etching treatment with hydrogen fluoride is not performed, the result of the DHB test is less than 150 ° C., and the film peeling durability of the conductive thin film is It was not enough.

以上、導電性薄膜付きガラス基板、薄膜太陽電池、低放射ガラス基板、導電性薄膜付きガラス基板の製造方法を実施形態および実施例等で説明したが、本発明は上記実施形態および実施例等に限定されない。特許請求の範囲に記載された本発明の要旨の範囲内において、種々の変形、変更が可能である。

As mentioned above, although the manufacturing method of the glass substrate with an electroconductive thin film, a thin film solar cell, a low radiation glass substrate, and the glass substrate with an electroconductive thin film was demonstrated by embodiment and an Example, this invention is based on the said embodiment, an Example, etc. It is not limited. Various modifications and changes are possible within the scope of the gist of the present invention described in the claims.

  This application claims priority based on Japanese Patent Application No. 2012-229515 filed with the Japan Patent Office on October 17, 2012. The entire contents of Japanese Patent Application No. 2012-229515 are incorporated herein by reference. Incorporate.

DESCRIPTION OF SYMBOLS 10 Glass substrate with conductive thin film 11 Glass substrate 12 Undercoat layers 13 and 22 Conductive thin film (top coat layer)

Claims (2)

An undercoat layer and then a conductive thin film are laminated on the surface of the glass substrate,
In the method for producing a glass substrate with a conductive thin film, the surface of the glass substrate on which the undercoat layer and the conductive thin film are laminated is etched with hydrogen fluoride.
Etching treatment with hydrogen fluoride
A gas containing hydrogen fluoride having a hydrogen fluoride concentration of 0.1% by volume or more and 10% by volume or less is applied to a sheet-like glass being conveyed at a temperature of 300 ° C. or more and 1 second or more and 2 minutes under normal pressure. The manufacturing method of the glass substrate with a conductive thin film characterized by performing by spraying below. An undercoat layer containing silicon oxide and then a conductive thin film are laminated on the surface of the glass substrate,
The glass substrate with undercoat layer containing silicon oxide, the surface of the side where the conductive thin film is laminated in the method for producing a conductive thin film-coated glass substrate etching process Ru is a by hydrogen fluoride,
Etching treatment with hydrogen fluoride
A gas containing hydrogen fluoride having a hydrogen fluoride concentration of 0.1% by volume or more and 10% by volume or less is usually applied to a sheet-like glass on which an undercoat layer containing silicon oxide is formed. A method for producing a glass substrate with a conductive thin film, which is performed by spraying at 300 ° C. or higher for 1 second or more and 2 minutes or less.

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