JP5903848B2 - Glass substrate with antireflection film - Google Patents

Glass substrate with antireflection film Download PDF

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JP5903848B2
JP5903848B2 JP2011258310A JP2011258310A JP5903848B2 JP 5903848 B2 JP5903848 B2 JP 5903848B2 JP 2011258310 A JP2011258310 A JP 2011258310A JP 2011258310 A JP2011258310 A JP 2011258310A JP 5903848 B2 JP5903848 B2 JP 5903848B2
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film
glass substrate
antireflection film
ar
antireflection
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JP2013113941A (en
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怜子 日向野
怜子 日向野
礼子 泉
礼子 泉
芳昌 林
芳昌 林
山崎 和彦
和彦 山崎
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三菱マテリアル株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/54Material technologies
    • Y02E10/549Material technologies organic PV cells

Description

  The present invention relates to a glass substrate with an antireflection film. Furthermore, it is related with the thin film solar cell using this glass substrate with an antireflection film.

  Various surface treatment technologies have been developed to form a thin film on the surface of a substrate such as glass or plastic and to add a new function. An antireflection film made of a silica thin film formed using silicon alkoxide on the surface has been developed. It has been reported (Patent Document 1).

  Here, a thin film solar cell is mentioned as the use for which the base material which has an antireflection film with high antireflection property is calculated | required. In FIG. 1, an example of the schematic diagram of the cross section of the thin film solar cell which uses the base material with an antireflection film is shown. FIG. 1 is an example of a super straight type thin film solar cell. The thin film solar cell 10 includes an antireflection film 11, a glass substrate 12, a transparent electrode layer 13, a photoelectric conversion layer 14, a transparent conductive film 15, and a conductive reflection film 16 in this order, and sunlight from the antireflection film 11 side. Is incident. Here, when sunlight reflects on the sunlight incident surface of the glass substrate 12, the sunlight reaching the photoelectric conversion layer 14 is reduced, and the conversion efficiency of the thin-film solar cell is lowered. For this reason, it is necessary to form the antireflection film 11 having high antireflection properties on the sunlight incident surface of the glass substrate 12 to increase the amount of sunlight transmitted to the photoelectric conversion layer 14.

  Currently, general-purpose glass such as soda-lime glass most used contains Na and Ca. Here, since the thin film solar cell is used in an environment exposed to the outside air, the antireflection film used for the glass substrate of the thin film solar cell has a high temperature and high humidity due to the temperature difference of the outside air or the weather. Durability is essential. When a thin-film solar cell is exposed to such an environment for a long time, alkali components such as Na and Ca tend to diffuse from the underlying glass substrate to the antireflection film surface. There has been a problem that it becomes white turbid, lowers the visible light transmittance, and lowers the conversion efficiency of the thin-film solar cell.

  Therefore, the glass substrate of the thin film solar cell is given an antireflection film function to increase the amount of incident sunlight, and at the same time, the alkali component on the antireflection film surface under high temperature and high humidity. It is required to have a function to suppress diffusion.

  However, the antireflection film comprising a silica thin film formed on the surface using silicon alkoxide has components such as Na and Ca diffused from the underlying glass substrate to the antireflection film surface, and the antireflection film surface becomes cloudy. Therefore, there is a problem that it is not suitable for use in an environment exposed to the outside air such as a thin film solar cell.

Japanese Patent Laid-Open No. 2002-161262

  The present invention solves the above problems and requirements. An object of the present invention is to use general-purpose glass such as soda-lime glass containing Na and Ca as a highly durable glass substrate with an antireflection film. That is, by adding an antireflection function, the amount of incident light transmitted is increased, and at the same time, the diffusion of Na and Ca in the glass substrate under high temperature and high humidity to the antireflection film surface is suppressed, and the antireflection film An object of the present invention is to provide a glass substrate with an antireflection film that suppresses white turbidity.

The present invention relates to a glass substrate with an antireflection film that solves the above-described problems with the following configuration, and a thin film solar cell using the glass substrate with an antireflection film.
(1) A glass substrate provided with an antireflection film on the surface,
The glass substrate contains at least one alkali metal selected from the group consisting of Na and Ca;
The antireflection film contains SiO 2 and has a refractive index of 1.35 to 1.50; and energy dispersive X-ray spectroscopic analysis attached to a transmission electron microscope at the interface between the glass substrate surface and the antireflection film In a quantitative analysis by an apparatus, a diffusion suppression film containing 1 to 12 atomic% of P with respect to a total of 100 atomic% of Si, P and O is provided.
A glass substrate with an antireflection film, characterized in that
(2) The glass substrate with an antireflection film according to the above (1), wherein the antireflection film contains colloidal silica particles.
(3) A thin film solar cell comprising the glass substrate with an antireflection film as described in (1) or (2) above.

According to the present invention (1), conventionally, under high temperature and high humidity, Na and Ca in the glass base material diffuse into the surface of the antireflection film and cause the antireflection film surface to become cloudy. General-purpose glass such as soda-lime glass containing Na and Ca that could not be used can be used as a highly durable glass substrate with an antireflection film. Specifically, at the same time as increasing the amount of incident light transmitted by the antireflection film, the diffusion suppression film suppresses the surface diffusion of Na and Ca in the glass substrate under high temperature and high humidity, thereby reducing the cloudiness of the antireflection film. An inhibitory glass substrate can be provided. Here, P contained in the diffusion suppressing film is Na or Ca, such as sodium phosphate (NaPO 3 , Na 4 P 2 O 7 , Na 3 PO 4, etc.), calcium phosphate (Ca (PO 3 ) 2 , Ca 2. P 2 O 7, Ca 3 ( PO 4) 2 , etc.) incorporation as phosphate compounds such as, for suppressing the diffusion of the anti-reflection film of Na and Ca, is considered. According to this invention (2), the hardness of an antireflection film becomes high and the glass base material with high durability of an antireflection film can be provided. According to the present invention (3), since the amount of incident light transmitted is large, the photoelectric conversion efficiency is high, and the white turbidity of the antireflection film under high temperature and high humidity on the surface of the antireflection film can be suppressed. However, a thin film solar cell in which the photoelectric conversion efficiency does not decrease can be provided.

It is an example of the schematic diagram of the cross section of the thin film solar cell which uses a base material with an antireflection film. It is an example of the cross section of the glass base material with an antireflection film of this invention. It is an example of the transmission electron micrograph of the cross section of the glass base material with an antireflection film of this invention. It is an example of the schematic diagram of the cross section of the thin film solar cell which uses the glass base material with an antireflection film of this invention.

  Hereinafter, the present invention will be specifically described based on embodiments. Unless otherwise indicated, “%” means “% by mass” unless otherwise specified.

The glass substrate with an antireflection film of the present invention is a glass substrate provided with an antireflection film on the surface,
The glass substrate comprises at least one alkali metal selected from the group consisting of Na and Ca;
The antireflection film contains SiO 2 and has a refractive index of 1.35 to 1.50; and energy dispersive X-ray spectroscopic analysis attached to a transmission electron microscope at the interface between the glass substrate surface and the antireflection film In a quantitative analysis by an apparatus, a diffusion suppression film containing 1 to 12 atomic% of P with respect to a total of 100 atomic% of Si, P and O is provided.
It is characterized by that.

  In FIG. 2, an example of the cross section of the glass base material with an antireflection film of this invention is shown. The glass substrate 1 with an antireflection film is a glass substrate 2 provided with an antireflection film 3 on the surface, and contains 1 to 12 atomic% of P between the surface of the glass substrate 2 and the antireflection film 3. A diffusion suppression film 4 is provided.

First, a diffusion suppressing film containing 1 to 12 atomic% of P will be described. The diffusion suppressing film is present at the interface between the glass substrate surface and the antireflection film, and is quantitatively analyzed by an energy dispersive X-ray spectrometer attached to the transmission electron microscope with respect to a total of 100 atomic% of Si, P and O. And P is contained in 1 to 12 atomic%. If it is less than 1 atomic%, the effect of P addition is not sufficient, and if it exceeds 12 atomic%, the transmittance of incident light decreases. P represents Na or Ca, such as sodium phosphate (NaPO 3 , Na 4 P 2 O 7 , Na 3 PO 4, etc.), calcium phosphate (Ca (PO 3 ) 2 , Ca 2 P 2 O 7 , Ca 3 (PO 4 2 ) and the like, and is considered to suppress diffusion of Na and Ca into the antireflection film. Here, the quantitative analysis of Si, P, and O was performed using an energy dispersive X-ray spectrometer (EDS) attached to a field emission transmission electron microscope (model number: JEM-2010F) manufactured by JEOL Ltd. : 200 kV, probe diameter: 1 nm, and the average value of five measurements. In FIG. 3, an example of the transmission electron micrograph of the cross section of the glass base material with an antireflection film is shown. “X” in FIG. 3 indicates a point where the quantitative analysis is performed, and the number on the right side of “X” indicates the point. Points 1 to 3 are analysis points of the antireflection film, point 4 is an analysis point of the diffusion suppressing film, and points 5 to 7 are analysis points of the glass substrate. Next, Table 1 shows the results of quantitative analysis of points 1 to 7 (unit: atomic%). As can be seen from Table 1, with respect to the total of 100 atomic% of Si, P and O, in points 1 to 3 in the antireflection film, P is 0.1 to 0.5 atomic%, and the point in the glass substrate In 5-7, P was 0 atomic%, whereas at point 4 in the diffusion suppressing film, 5.1 atomic% and 1-12 atomic%.

  In addition, the diffusion suppressing film preferably has a thickness of 3 to 10 nm. If the thickness is less than 3 nm, surface diffusion of Na and Ca in the glass substrate under high temperature and high humidity may not be sufficiently suppressed. If the thickness exceeds 10 nm, light interference occurs and the antireflection property tends to decrease.

Next, the glass substrate contains at least one alkali metal selected from the group consisting of Na and Ca, and Na is 1.0 part by mass or more with respect to 100 parts by mass of the glass substrate. , Ca is 0.5 parts by mass or more with respect to 100 parts by mass of the glass base material, which is suitable from the viewpoint of availability of the glass base material and cost, and also exhibits the effects of the present invention. Suitable for In addition, Na is 20 mass parts or less with respect to 100 mass parts of glass base materials, and Ca is 15 mass parts or less with respect to 100 mass parts of glass substrate materials. From the viewpoint of cost and durability of the glass, it is preferable. Here, the quantitative analysis of Na and Ca is performed as follows. First, a detectable element is confirmed with a wavelength dispersive X-ray fluorescence analyzer (model number: ZSX-Primus II) manufactured by Rigaku Corporation. Next, each detected element is quantitatively analyzed. Si is SiO 2 , Na is Na 2 O, and Ca is CaO, and other elements are assumed to be the most abundant oxides in nature. ,calculate. As the glass substrate, soda lime glass is preferable from the viewpoint of availability and cost.

Antireflection film containing SiO 2, SiO 2, from the viewpoint of refractive index, antireflection film: preferably per 100 parts by mass, if it is 95 to 100 parts by mass. Here, the quantitative analysis of SiO 2 is performed with an Auger electron spectroscopy analyzer (manufactured by Physical Electronics, model number: PHI700). In addition to SiO 2 , examples of components contained in the antireflection film include phosphorus-containing compounds such as phosphoric acid.

  The refractive index of the antireflection film is 1.35 to 1.50 from the viewpoint of antireflection properties. Here, the refractive index is measured using a spectroscopic ellipsometer (manufactured by JA Woollam Japan, model number: M-2000), and is set to a value of 633 nm in the analyzed optical constant. The transmittance of the antireflection film is preferably 90% or more. The transmittance of the glass substrate with an antireflection film is preferably 92% or more because the amount of incident light transmitted is sufficient. Here, the transmittance is measured using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, model number: U-4100), and in the range of 340 to 750 nm in which the transmittance is important in solar cell applications, Evaluation is made by the value of transmittance% T at 550 nm, which is the median value.

  The preferred thickness of the antireflection film varies depending on the refractive index of the glass substrate. For example, when the refractive index of the glass substrate is about 1.45, it is 70 to 130 nm. Here, the film thickness is measured by cross-sectional observation with a scanning electron microscope (model number: S-4300, SU-8000) manufactured by Hitachi High-Technologies Corporation.

  Next, it is preferable that the antireflection film contains colloidal silica particles because the hardness of the antireflection film is improved. Examples of the colloidal silica particles include spherical colloidal silica particles and anisotropic colloidal silica particles.

  Spherical colloidal silica particles preferably have an average particle size of 6 to 40 nm, and more preferably 6 to 30 nm. If the average particle size is smaller than 6 nm, the stability of the particles is lacking, so that it is easy to cause secondary aggregation, making it difficult to produce a composition for an antireflective film. Because there is no. Here, the average particle diameter is converted from the specific surface area measurement using AUTOSORB-1 manufactured by QUANTACHROME, assuming that the spherical colloidal silica particles are true spheres.

The anisotropic colloidal silica particles preferably have an average particle size of 5 to 50 nm, and more preferably 12 to 40 nm. If the average particle size is less than 5 nm, the stability of the particles is insufficient, and therefore secondary aggregation is likely to occur, making it difficult to produce an antireflection film. If the average particle size is more than 50 nm, the flatness of the antireflection film is hindered. . Here, the average particle size of the anisotropic colloidal silica particles is measured with a laser diffraction / scattering particle size distribution measuring device (model number: LA-950) manufactured by Horiba, Ltd., and the particle size reference is calculated as the number. Of 50% average particle diameter (D 50 ). Whether the shape is anisotropic or spherical is an image observed with the above-mentioned scanning electron microscope, and the identified aspect ratio (major axis / minor axis) is 1.5 or more. Identify. Moreover, the average particle diameter of anisotropic colloidal silica particles means the average value of the diameter (major axis) of anisotropic colloidal silica particles. The aspect ratio (major axis / minor axis) of the anisotropic colloidal silica particles is preferably in the range of 1.5 to 5. The minor axis is preferably in the range of 1 to 34 nm.

[Method for producing glass substrate with antireflection film]
The glass substrate with an antireflection film of the present invention comprises a silicon alkoxide, a hydrolyzate, or a dehydrated product on a glass substrate containing at least one alkali metal selected from the group consisting of Na and Ca. The composition for an antireflection film containing a P-containing compound and a dispersion medium can be produced by applying the composition by a wet coating method and then baking the composition. The glass substrate is as described above.

  The composition for antireflection films contains silicon alkoxide, or a hydrolyzate or dehydrated product thereof, a P-containing compound, and a dispersion medium.

  Examples of silicon alkoxides include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, trimethylmethoxysilane, and the like. From the viewpoint of ease of reaction control and film hardness when used as an antireflection film. Ethoxysilane is preferred. Silicon alkoxide, or its hydrolyzate or this dehydrated product is preferably 5 to 20 parts by mass as silicon alkoxide with respect to 100 parts by mass of the composition for antireflection film from the viewpoint of the hardness of the antireflection film. .

Examples of the P-containing compound include orthophosphoric acid (H 3 PO 4 ) and pyrophosphoric acid (H 4 P 2 O 7 ), and orthophosphoric acid is preferable from the viewpoint of availability. The P-containing compound is preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the composition for an antireflection film, from the viewpoint of hydrolysis reactivity of silicon alkoxide and formation of a diffusion suppressing film, It is more preferable in it being -1.5 mass parts.

  The dispersion medium preferably contains 1% by mass or more of water and 2% by mass or more of a solvent compatible with water, for example, alcohols, with respect to 100% by mass of all the dispersion media. For example, when the dispersion medium is composed of only water and alcohols, it contains 98% by mass of alcohol when it contains 2% by mass of water, and 98% by mass of water when it contains 2% by mass of alcohol. When the water content is less than 1% by mass or the alcohol content is less than 2% by mass, it is difficult to sinter the film obtained by applying the conductive reflective film composition by a wet coating method at a low temperature. Moreover, it is because the electroconductivity and reflectivity of the electroconductive reflective film after firing are reduced. Examples of alcohols include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, erythritol, and the like. In order to obtain good film formability, the content of the dispersion medium is preferably 60 to 99 parts by mass with respect to 100 parts by mass of the composition for an antireflection film.

  The colloidal silica particles are preferably 5 to 15 parts by mass relative to 100 parts by mass of the composition for an antireflection film.

  The composition for an antireflection film is prepared by mixing desired components with a paint shaker, a ball mill, a sand mill, a centrimill, a three roll, etc., by a conventional method, and dispersing a translucent binder, optionally transparent conductive particles, Can be manufactured. Of course, it can also be produced by a normal stirring operation.

  The wet coating method is preferably any one of a spray coating method, a dispenser coating method, a spin coating method, a knife coating method, a slit coating method, an inkjet coating method, a screen printing method, an offset printing method, or a die coating method. However, the present invention is not limited to this, and any method can be used.

  After applying the composition for an antireflection film on a glass substrate by a wet coating method, the baking conditions for baking the glass substrate having a coating film are in the atmosphere or an inert gas atmosphere such as nitrogen or argon. 150 to 500 ° C., preferably 30 to 60 minutes.

  The reason why the firing temperature of the glass substrate having the coating film is in the range of 150 to 500 ° C. is that when it is less than 150 ° C., the antireflection film has a problem of insufficient curing. On the other hand, if the temperature exceeds 500 ° C., the production merit of the low temperature process cannot be utilized, that is, the manufacturing cost increases and the productivity decreases.

  The reason why the firing time of the substrate having the coating film is set in the range of 30 to 60 minutes is that when the firing time is less than 30 minutes, the antireflection film is not sufficiently fired. This is because if the firing time exceeds 60 minutes, the production cost is increased more than necessary and the productivity is lowered.

When the coating film of the composition for antireflection film is baked, the P-containing compound in the composition for antireflection film reacts with Na or Ca in the glass substrate to form a glass substrate. It is considered that a diffusion suppression film is formed at the interface between the material and the antireflection film. In detail, P contained in the diffusion suppressing film is composed of Na or Ca, sodium phosphate (NaPO 3 , Na 4 P 2 O 7 , Na 3 PO 4, etc.), calcium phosphate (Ca (PO 3 ) 2 , Ca 2 P 2 O 7 , Ca 3 (PO 4 ) 2, etc.) and the like, and is considered to suppress diffusion of Na and Ca to the antireflection film.

  By the above, the glass base material with an antireflection film of the present invention can be formed. In this way, by using a wet coating method to form the antireflection film and the diffusion suppression film, vacuum processes such as vacuum deposition and sputtering can be eliminated as much as possible. The material can be manufactured.

[Application of glass substrate with antireflection film]
Next, application of the glass substrate with an antireflection film will be described. In FIG. 4, an example of the schematic diagram of the cross section of the thin film solar cell which uses the glass base material with an antireflection film of this invention is shown. FIG. 4 is an example of a super straight type thin film solar cell. The thin film solar cell 20 includes an antireflection film 21, a diffusion suppression film 21A, a glass substrate 22, a transparent electrode layer 23, a photoelectric conversion layer 24, a transparent conductive film 25, and a conductive reflection film 26 in this order. Sunlight enters from the 21 side. Since the thin-film solar cell 20 includes the antireflection film 21, the amount of incident sunlight transmitted through the photoelectric conversion layer 24 is large. To suppress the diffusion of Na and Ca in the base material 22 to the surface of the antireflection film 21 and to suppress the white turbidity of the antireflection film 21, it is possible to provide a thin film solar cell in which the photoelectric conversion efficiency does not decrease even under high temperature and high humidity. it can.

  As a method for producing the thin-film solar cell 20, it is preferable to form the antireflection film 21 and the diffusion suppression film 21A in advance before forming the photoelectric conversion layer 24 and the like, and to bak the coating film of the composition for antireflection film. It is preferable because deterioration of the photoelectric conversion layer 24 over time can be avoided. However, the antireflection film 21 and the diffusion suppression film 21A can also be formed on the glass substrate 22 on which the photoelectric conversion layer 22 to the conductive reflection film 26 are formed. In this case, the coating film baking temperature of the composition for an antireflection film is preferably 130 to 400 ° C, more preferably 150 to 350 ° C. This is because amorphous silicon, microcrystalline silicon, or a hybrid silicon solar cell using these is relatively weak against heat, and conversion efficiency is lowered by the firing process.

  Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

Zirconia beads (microhaika, manufactured by Showa Shell Sekiyu KK) with a total diameter of 60 g and placed in a 100 cm 3 glass bottle so as to have the compositions shown in Tables 2 to 4 (the numerical values indicate parts by mass). : The composition for anti-reflective (henceforth AR) film | membrane used by Examples 1-21 and Comparative Examples 2-3 was produced by disperse | distributing for 6 hours with a paint shaker using 100g. The AR film composition raw material used for the production of the AR film composition was produced as follows.

[AR film composition raw material 1]
Using a 500 cm 3 glass four-necked flask, 140 g of tetraethoxysilane and 140 g of ethyl alcohol were added, and a solution of 1.5 g of 85% phosphoric acid dissolved in 120 g of pure water was stirred. It was prepared by adding all at once and then reacting at 50 ° C. for 3 hours.

[AR film composition raw material 2]
Using a 500 cm 3 glass four-necked flask, 115 g of tetraethoxysilane and 175 g of ethyl alcohol were added, and a solution of 1.0 g of 85% phosphoric acid dissolved in 110 g of pure water was stirred. It was prepared by adding all at once and then reacting at 50 ° C. for 3 hours.

[AR film composition raw material 3]
Using a 500 cm 3 glass four-necked flask, adding 130 g of tetraethoxysilane and 145 g of ethyl alcohol, stirring, a solution of 4.5 g of 85% phosphoric acid dissolved in 125 g of pure water, It was prepared by adding all at once and then reacting at 45 ° C. for 3 hours.

[AR film composition raw material 4]
Using a 500 cm 3 glass four-necked flask, 125 g of tetraethoxysilane and 160 g of ethyl alcohol were added, and while stirring, a solution of 2.1 g of 85% phosphoric acid dissolved in 115 g of pure water, It was prepared by adding at once and then reacting at 60 ° C. for 2 hours.

[AR film composition raw material 5]
Using a 500 cm 3 glass four-necked flask, 145 g of tetraethoxysilane and 140 g of ethyl alcohol were added, and a solution of 0.5 g of 85% phosphoric acid dissolved in 115 g of pure water was stirred. It was prepared by adding all at once and then reacting at 55 ° C. for 3 hours.

[AR film composition raw material 6]
Using a 500 cm 3 glass four-necked flask, 140 g of trimethylmethoxysilane and 140 g of methyl alcohol were added, and a solution of 2.0 g of 85% phosphoric acid dissolved in 120 g of pure water was stirred. It was prepared by adding all at once and then reacting at 50 ° C. for 3 hours.

[AR film composition raw material 7]
Using a four-necked flask made of 500 cm 3 glass, add 140 g of tetraethoxysilane and 140 g of ethyl alcohol, and while stirring, add a solution of 1.5 g of 60% nitric acid in 120 g of pure water. And then reacted at 50 ° C. for 3 hours.

[AR film composition raw material 8]
Using a four-necked flask made of glass of 500 cm 3 , add 140 g of tetraethoxysilane and 140 g of ethyl alcohol, and stir a solution of 1.5 g of 35% hydrochloric acid in 120 g of pure water once. And then reacted at 50 ° C. for 3 hours.

[Mixed solvent]
The mixed solvent 1 is a mixture of isopropanol, ethanol and N, N-dimethylformamide (mass ratio 4: 2: 1), and the mixed solvent 2 is a mixture of ethanol and butanol (mass ratio 98: 2). Using.

[Examples 1 to 21]
In Example 1, AR film composition raw material 1 was diluted and mixed with IPA serving as a dispersion medium to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 2, AR film composition raw material 2 was diluted and mixed with ethanol as a dispersion medium. Furthermore, an anisotropic colloidal silica particle (product name: ST-OUP) manufactured by Nissan Chemical Industries, Ltd. having an average particle diameter of 40 nm was added at a ratio of 10% by mass, mixed, and an AR film composition was prepared. Produced. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 3, the AR film composition raw material 4 was diluted and mixed with IPA serving as a dispersion medium to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 4, the AR film composition raw material 6 was diluted and mixed with ethanol as a dispersion medium to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 5, the AR film composition raw material 3 was diluted and mixed with the mixed solvent 1 serving as a dispersion medium. Furthermore, an anisotropic colloidal silica particle (product name: IPA-ST-UP) manufactured by Nissan Chemical Industries, Ltd. having an average particle diameter of 12 nm was added and mixed at a ratio of 10% by mass, and the composition for AR film was added. A product was made. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 6, the AR film composition raw material 5 was diluted and mixed with ethanol as a dispersion medium to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 7, the AR film composition raw material 6 was diluted and mixed with ethanol as a dispersion medium. Furthermore, an anisotropic colloidal silica particle (product name: IPA-ST-UP) manufactured by Nissan Chemical Industries, Ltd. having an average particle diameter of 12 nm was added and mixed at a ratio of 15% by mass of the whole, and the composition for AR film was added. A product was made. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 8, the AR film composition raw material 1 was diluted and mixed with the mixed solvent 2 serving as a dispersion medium to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 9, the AR film composition raw material 4 was diluted and mixed with the mixed solvent 1 serving as a dispersion medium. Furthermore, an anisotropic colloidal silica particle (product name: ST-OUP) manufactured by Nissan Chemical Industries, Ltd. having an average particle size of 30 nm was mixed at a ratio of 5% by mass to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 10, the AR film composition raw material 5 was diluted and mixed with the mixed solvent 2 serving as a dispersion medium. Further, spherical colloidal silica particles (product name: ST-O) manufactured by Nissan Chemical Industries, Ltd. having an average particle size of 10 nm were mixed at a ratio of 10% by mass to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 11, the AR film composition raw material 3 was diluted and mixed with the mixed solvent 2 serving as a dispersion medium to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 12, the AR film composition raw material 1 was diluted and mixed with ethanol serving as a dispersion medium. Furthermore, spherical chemical colloidal silica particles (product name: ST-OXS) manufactured by Nissan Chemical Industries, Ltd. having an average particle diameter of 6 nm were mixed at a ratio of 10% by mass to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 13, AR film composition raw material 2 was diluted and mixed with IPA serving as a dispersion medium to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 14, the AR film composition raw material 6 was diluted and mixed with butanol as a dispersion medium to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 15, the AR film composition raw material 4 was diluted and mixed with IPA serving as a dispersion medium. Further, spherical colloidal silica particles (product name: IPA-ST) manufactured by Nissan Chemical Industries, Ltd. having an average particle diameter of 10 nm were mixed at a ratio of 15% by mass to produce an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 16, the AR film composition raw material 6 was diluted and mixed with the mixed solvent 2 serving as a dispersion medium. Further, spherical colloidal silica particles (product name: IPA-ST) manufactured by Nissan Chemical Industries, Ltd. having an average particle diameter of 10 nm were mixed at a ratio of 10% by mass to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 17, the AR film composition raw material 5 was diluted and mixed with the mixed solvent 1 serving as a dispersion medium. Furthermore, an anisotropic colloidal silica particle (product name: ST-OUP) manufactured by Nissan Chemical Industries, Ltd. having an average particle diameter of 40 nm was mixed at a ratio of 15% by mass to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 18, the AR film composition raw material 6 was diluted and mixed with IPA serving as a dispersion medium. Furthermore, spherical chemical colloidal silica particles (product name: ST-OXS) manufactured by Nissan Chemical Industries, Ltd. having an average particle diameter of 6 nm were mixed at a ratio of 10% by mass to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 19, the AR film composition raw material 5 was diluted and mixed with the mixed solvent 1 serving as a dispersion medium. Furthermore, an anisotropic colloidal silica particle (product name: ST-OUP) manufactured by Nissan Chemical Industries, Ltd. having an average particle size of 30 nm was mixed at a ratio of 10% by mass to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 20, AR film composition raw material 1 was diluted and mixed with IPA serving as a dispersion medium. Furthermore, an anisotropic colloidal silica particle (product name: IPA-ST-L) manufactured by Nissan Chemical Industries, Ltd. having an average particle diameter of 45 nm was mixed at a ratio of 15% by mass to prepare an AR film composition. . After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Example 21, AR film composition raw material 1 was diluted and mixed with IPA serving as a dispersion medium. Furthermore, an anisotropic colloidal silica particle (product name: ST-OUP) manufactured by Nissan Chemical Industries, Ltd. having an average particle size of 30 nm was mixed at a ratio of 40% by mass to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

[Comparative Examples 1-3]
In Comparative Example 1, an evaluation was made on a single glass without forming the AR film composition.

  In Comparative Example 2, AR film composition raw material 7 was diluted and mixed with IPA serving as a dispersion medium to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

  In Comparative Example 3, the AR film composition raw material 8 was diluted and mixed with IPA serving as a dispersion medium to prepare an AR film composition. After the AR film composition is formed on a glass substrate having a refractive index of 1.55 by a wet coating method, the AR coating film is baked at 200 ° C. for 30 minutes to produce a glass substrate with an AR film. did.

[Measurement of Na and Ca content of glass substrate]
The quantitative analysis of Na and Ca was performed as follows. First, detectable elements were confirmed with a wavelength dispersive X-ray fluorescence spectrometer (model number: ZSX-Primus II) manufactured by Rigaku Corporation. Next, each detected element is quantitatively analyzed. Si is SiO 2 , Na is Na 2 O, Ca is CaO, K is K 2 O, Al is Al 2 O 3 , Fe is Fe 2 O 3 , B Is B 2 O 3 , Pb is PbO, Ti is TiO 2 , Zn is ZnO, Sb is Sb 2 O 3 , Ba is BaO, Mn is MnO, and Sr is SrO. It was calculated as the most abundant oxide. Tables 2 to 4 show these results.

[Analysis of P in Diffusion Suppression Film]
The cross section including the interface part of the glass substrate, diffusion suppression film and antireflection film is processed for observation, and the diffusion suppression film is observed with a field emission transmission electron microscope (model number: JEM-2010F) manufactured by JEOL Ltd. did. At the same time, quantitative analysis of P in the diffusion suppression film was performed using an energy dispersive X-ray spectrometer attached to a field emission transmission electron microscope (model number: JEM-2010F) manufactured by JEOL Ltd., with an acceleration voltage of 200 kV, The measurement was performed under the measurement condition of probe diameter: 1 nm, and the average value was obtained from five measurements. Tables 2 to 4 show these results.

[Measurement of film thickness of diffusion suppression film and AR film]
The film thickness of the diffusion suppressing film was measured by cross-sectional observation with a field emission transmission electron microscope (model number: JEM-2010F) manufactured by JEOL. The film thickness of the AR film was measured by cross-sectional observation using a scanning electron microscope (model number: S-4300, SU-8000) manufactured by Hitachi High-Technologies Corporation. Tables 2 to 4 show these results.

[Evaluation of refractive index and initial transmittance of AR film]
The refractive index of the AR film was measured using a spectroscopic ellipsometer (JA Woollam Japan M-2000), and the value was 633 nm in the analyzed optical constant. Moreover, the initial transmittance of the glass substrate with an AR film is measured using a spectrophotometer (model number: U-4100) manufactured by Hitachi High-Technologies Corporation, and the transmittance is important for solar cell applications. In the range of 750 nm, the median value of 550 nm transmittance (unit:%) was evaluated. Tables 2 to 4 show these results.

[Transmittance after high temperature and high humidity test]
In addition, a constant temperature and humidity machine manufactured by ESPEC Co., Ltd. (model number: PL), which is maintained at a constant temperature and humidity of 85 ° C. and 85% RH as a high temperature and high humidity test specified in JIS C 8938 as a method for evaluating the life of solar cells. −1 KP), the sample was held for 1000 hours, and then the transmittance of the sample taken out of the thermo-hygrostat and returned to room temperature was measured with the above spectrophotometer. Further, (transmittance after high temperature and high humidity test) / (initial transmittance) was calculated. Tables 2 to 4 show these results. In Tables 2 to 4, (Transmittance after high-temperature and high-humidity test) / (Initial transmittance) is described as After high-temperature and high-humidity test / initial.

[Hardness of AR film]
The hardness of the AR film was determined as a scratch hardness (pencil method) test specified in JIS K 5600 as a general evaluation method of the coating film, using a manual pencil scratch tester manufactured by Coating Tester Industry, with a load of 750 g and an angle of 45 °. Measured with a pencil for pencil test made by Mitsubishi Pencil. Tables 2 to 4 show these results.

  As can be seen from Tables 2 to 4, in Examples 1 to 19, the refractive index of the AR film is 1.35 to 1.50, P is 1 to 12 atomic% in the diffusion suppression film, and the thickness of the diffusion suppression film is The transmittance of the AR film was as high as 92.5% or more, and the transmittance after the high-temperature and high-humidity test was also high, which was 99.1 to 99.9% in the initial stage. On the other hand, since the antireflection film was not formed in Comparative Example 1, the initial transmittance was as low as 91%, and the transmittance after the high temperature and high humidity test was greatly decreased to 88%. In Comparative Examples 2 and 3 in which the AR film composition raw material did not contain a P-containing compound, no diffusion suppression film could be confirmed, and the transmittance after the high-temperature and high-humidity test was greatly reduced compared to the initial transmittance. In Example 20 in which the particle size of the colloidal silica particles is large and in Example 21 in which the content of the colloidal silica particles is large, the film thickness of the antireflection film is not flat, and the initial transmittance is in Examples 1 to 2. It was lower than 19, and the hardness of the antireflection film was also low.

DESCRIPTION OF SYMBOLS 1 Glass base material with antireflection film 2 Glass base material 3 Antireflection film 4 Diffusion suppression film 10, 20 Thin film solar cell 11, 21 Antireflection film 21A Diffusion suppression film 12, 22 Glass base material 13, 23 Transparent electrode layer 14, 24 Photoelectric conversion layer 15, 25 Transparent conductive film 16, 26 Conductive reflective film

Claims (3)

  1. A glass substrate provided with an antireflection film on the surface,
    The glass substrate contains at least one alkali metal selected from the group consisting of Na and Ca;
    The antireflection film contains SiO 2, has a refractive index of 1.35 to 1.50, a thickness of 70 to 130 nm ; and a transmission electron microscope at the interface between the glass substrate surface and the antireflection film. Diffusion suppression film containing 1 to 12 atomic% of P and 3 to 10 nm in thickness with respect to a total of 100 atomic% of Si, P and O by quantitative analysis using the attached energy dispersive X-ray spectrometer Comprising
    A glass substrate with an antireflection film, characterized in that
  2.   The glass substrate with an antireflection film according to claim 1, wherein the antireflection film contains colloidal silica particles.
  3. A thin film solar cell comprising the glass substrate with an antireflection film according to claim 1.
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