JP5903848B2 - Glass substrate with antireflection film - Google Patents
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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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Description
本発明は、反射防止膜付きガラス基材に関する。さらには、この反射防止膜付きガラス基材を利用した薄膜太陽電池に関する。 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.
ガラスやプラスチック等の基材の表面に、薄膜を形成し、新たな機能を付与する種々の表面処理技術が開発されており、表面にシリコンアルコキシドを用いて形成したシリカ薄膜からなる反射防止膜が報告されている（特許文献１）。 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).
ここで、反射防止性の高い反射防止膜を有する基材が求められている用途に、薄膜太陽電池が挙げられる。図１に、反射防止膜付き基材を使用する薄膜太陽電池の断面の模式図の一例を示す。図１は、スーパーストレート型薄膜太陽電池の例である。薄膜太陽電池１０は、反射防止膜１１、ガラス基材１２、透明電極層１３、光電変換層１４、透明導電膜１５、導電性反射膜１６の順に備えており、反射防止膜１１側から太陽光が入射する。ここで、ガラス基材１２の太陽光の入射面で、太陽光が反射すると、光電変換層１４に到達する太陽光が減少し、薄膜太陽電池の変換効率を低下させてしまう。このため、ガラス基材１２の太陽光の入射面上に、反射防止性の高い反射防止膜１１を形成し、光電変換層１４に入射する太陽光の透過量を増加させる必要がある。 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.
現在、最も使用されているソーダ石灰ガラス等の汎用ガラスは、Ｎａ、Ｃａを含有している。ここで、薄膜太陽電池は、外気に曝される環境で使用されるため、薄膜太陽電池のガラス基材に用いられる反射防止膜には、外気の温度差や天候による高温かつ高湿度下での耐久性が必須である。薄膜太陽電池が、このような環境下で長期に曝されると、下地のガラス基材から、Ｎａ、Ｃａ等のアルカリ成分が、反射防止膜表面に拡散する傾向があり、反射防止膜表面を白濁化させ、可視光透過率を下げてしまい、薄膜太陽電池の変換効率を低下させる問題があった。 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.
よって、薄膜太陽電池のガラス基材には、反射防止膜機能を付与させることにより、入射する太陽光の透過量を増加させると同時に、高温高湿下でのアルカリ成分の反射防止膜表面への拡散を抑える機能を持つことが求められる。 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.
しかしながら、上記表面にシリコンアルコキシドを用いて形成したシリカ薄膜からなる反射防止膜は、下地のガラス基材から、Ｎａ、Ｃａ等の成分が、反射防止膜表面に拡散し、反射防止膜表面を白濁化させてしまうため、薄膜太陽電池等の外気にさらされる環境での使用に適していない、という問題がある。 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.
本発明は、上記問題や要求を解決したものである。本発明は、Ｎａ、Ｃａを含有するソーダ石灰ガラス等の汎用ガラスを、高耐久性の反射防止膜付きガラス基材として利用することを目的とする。すなわち、反射防止機能を付与することにより、入射光の透過量を増加させると同時に、高温高湿下でのガラス基材中のＮａやＣａの反射防止膜表面への拡散を抑え、反射防止膜の白濁を抑制する反射防止膜付きガラス基材を提供することを目的とする。 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.
本発明は、以下に示す構成によって上記課題を解決した反射防止膜付きガラス基材、およびこの反射防止膜付きガラス基材を用いる薄膜太陽電池に関する。
（１）表面に、反射防止膜を備えるガラス基材であって、
ガラス基材は、ＮａおよびＣａからなる群より選択される少なくとも１種のアルカリ金属を含有し；
反射防止膜は、ＳｉＯ２を含有し、屈折率が１．３５〜１．５０であり；かつ
ガラス基材表面と反射防止膜との界面に、透過電子顕微鏡付属のエネルギー分散型Ｘ線分光分析装置による定量分析で、Ｓｉ、ＰおよびＯの合計１００原子％に対して、Ｐを１〜１２原子％含有する拡散抑制膜を備える、
ことを特徴とする、反射防止膜付きガラス基材。
（２）反射防止膜が、コロイダルシリカ粒子を含有する、上記（１）記載の反射防止膜付きガラス基材。
（３）上記（１）または（２）記載の反射防止膜付きガラス基材を備える、薄膜太陽電池。
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.
本発明（１）によれば、従来、高温高湿下では、ガラス基材中のＮａ、Ｃａが、反射防止膜表面に拡散し、反射防止膜表面を白濁化させてしまうため使用することができなかったＮａ、Ｃａを含有するソーダ石灰ガラス等の汎用ガラスを、高耐久性の反射防止膜付きガラス基材として利用することができる。具体的には、反射防止膜により入射光の透過量を増加させると同時に、拡散抑制膜により高温高湿下でのガラス基材中のＮａやＣａの表面拡散を抑え、反射防止膜の白濁を抑制するガラス基材を提供することができる。ここで、拡散抑制膜に含有されるＰは、ＮａやＣａを、リン酸ナトリウム（ＮａＰＯ３、Ｎａ４Ｐ２Ｏ７、Ｎａ３ＰＯ４等）、リン酸カルシウム（Ｃａ（ＰＯ３）２、Ｃａ２Ｐ２Ｏ７、Ｃａ３（ＰＯ４）２等）等のリン酸塩化合物として取り込み、ＮａやＣａの反射防止膜への拡散を抑制する、と考えられる。本発明（２）によれば、反射防止膜の硬度が高くなり、反射防止膜の耐久性が高いガラス基材を提供することができる。本発明（３）によれば、入射光の透過量が多いため、光電変換効率が高く、反射防止膜表面への高温高湿下での反射防止膜の白濁を抑えられるため、高温高湿下でも光電変換効率が低下しない薄膜太陽電池を提供することができる。 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.
以下、本発明を実施形態に基づいて具体的に説明する。なお、％は特に示さない限り、また数値固有の場合を除いて質量％である。 Hereinafter, the present invention will be specifically described based on embodiments. Unless otherwise indicated, “%” means “% by mass” unless otherwise specified.
本発明の反射防止膜付きガラス基材は、表面に、反射防止膜を備えるガラス基材であって、
ガラス基材は、ＮａおよびＣａからなる群より選択される少なくとも１種のアルカリ金属を含み；
反射防止膜は、ＳｉＯ２を含有し、屈折率が１．３５〜１．５０であり；かつ
ガラス基材表面と反射防止膜との界面に、透過電子顕微鏡付属のエネルギー分散型Ｘ線分光分析装置による定量分析で、Ｓｉ、ＰおよびＯの合計１００原子％に対して、Ｐを１〜１２原子％含有する拡散抑制膜を備える、
ことを特徴とする。
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.
図２に、本発明の反射防止膜付きガラス基材の断面の一例を示す。反射防止膜付きガラス基材１は、表面に、反射防止膜３を備えるガラス基材２であって、ガラス基材２表面と反射防止膜３の間に、Ｐを１〜１２原子％含有する拡散抑制膜４を備える。 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.
まず、Ｐを１〜１２原子％含有する拡散抑制膜について説明する。拡散抑制膜は、ガラス基材表面と反射防止膜との界面に存在し、透過電子顕微鏡付属のエネルギー分散型Ｘ線分光分析装置による定量分析で、Ｓｉ、ＰおよびＯの合計１００原子％に対して、Ｐを１〜１２原子％含有する。１原子％未満では、Ｐ添加の効果が十分ではなく、１２原子％を超えると、入射光の透過率が低下する。Ｐは、ＮａやＣａを、リン酸ナトリウム（ＮａＰＯ３、Ｎａ４Ｐ２Ｏ７、Ｎａ３ＰＯ４等）、リン酸カルシウム（Ｃａ（ＰＯ３）２、Ｃａ２Ｐ２Ｏ７、Ｃａ３（ＰＯ４）２等）等のリン酸塩化合物として取り込み、ＮａやＣａの反射防止膜への拡散を抑制する、と考えられる。ここで、Ｓｉ、ＰおよびＯの定量分析は、日本電子（株）製電界放射型透過電子顕微鏡（型番：ＪＥＭ−２０１０Ｆ）に付属のエネルギー分散型Ｘ線分光分析装置（ＥＤＳ）により、加速電圧：２００ｋＶ、プローブ径：１ｎｍの測定条件で行い、５回測定での平均値とする。図３に、反射防止膜付きガラス基材の断面の透過電子顕微鏡写真の一例を示す。図３の「×」は、定量分析を行ったポイントを示し、「×」の右の数字はポイントを示す。ポイント１〜３は、反射防止膜の分析ポイント、ポイント４は、拡散抑制膜の分析ポイント、ポイント５〜７は、ガラス基材の分析ポイントである。次に、表１に、ポイント１〜７の定量分析結果（単位：原子％）を示す。表１からわかるように、Ｓｉ、ＰおよびＯの合計１００原子％に対して、反射防止膜中のポイント１〜３では、Ｐが０．１〜０．５原子％、ガラス基材中のポイント５〜７では、Ｐが０原子％であったのに対し、拡散抑制膜中のポイント４では、５．１原子％と、１〜１２原子％であった。 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%.
また、拡散抑制膜は、厚さが３〜１０ｎｍであると好ましく、厚さが３ｎｍ未満では、高温高湿下でのガラス基材中のＮａ、Ｃａの表面拡散を十分に抑制できない場合があり、厚さが１０ｎｍを超えると、光の干渉が起こり、反射防止性が低下し易い。 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.
次に、ガラス基材は、ＮａおよびＣａからなる群より選択される少なくとも１種のアルカリ金属を含み、Ｎａは、ガラス基材：１００質量部に対して、１．０質量部以上であると、Ｃａは、ガラス基材：１００質量部に対して、０．５質量部以上であると、ガラス基材の入手の容易さ、コストの観点から適しており、また、本発明の効果を発揮するために適している。なお、Ｎａは、ガラス基材：１００質量部に対して、２０質量部以下、Ｃａは、ガラス基材：１００質量部に対して、１５質量部以下であると、ガラス基材の入手の容易さ、コストおよびガラスの耐久性の観点から、好ましい。ここで、Ｎａ、Ｃａの定量分析は、以下のように行う。まず、（株）リガク製波長分散型蛍光Ｘ線分析装置（型番：ＺＳＸ−ＰｒｉｍｕｓＩＩ）で、検出可能な元素を確認する。次に、検出された各元素について定量分析を行い、ＳｉはＳｉＯ２、ＮａはＮａ２Ｏ、ＣａはＣａＯであるとして、これら以外の元素については、自然界に最も多く存在する酸化物であるとして、計算する。ガラス基材としては、入手の容易さ、コストの観点から、ソーダ石灰ガラスが好ましい。 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.
反射防止膜は、ＳｉＯ２を含有し、ＳｉＯ２は、屈折率の観点から、反射防止膜：１００質量部に対して、９５〜１００質量部であると好ましい。ここで、ＳｉＯ２の定量分析は、オージェ電子分光分析装置（ＰｈｙｓｉｃａｌＥｌｅｃｔｒｏｎｉｃｓ製、型番：ＰＨＩ７００）で行う。なお、ＳｉＯ２以外に反射防止膜に含有される成分としては、リン酸等のリン含有化合物が挙げられる。 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.
反射防止膜の屈折率は、反射防止性の観点から、１．３５〜１．５０である。ここで、屈折率は、分光エリプソメトリー装置（Ｊ．Ａ．Ｗｏｏｌｌａｍ Ｊａｐａｎ（株）製、型番：Ｍ−２０００）を用いて測定し、解析した光学定数における６３３ｎｍの値とする。また、反射防止膜の透過率は、９０％以上であると好ましい。なお、反射防止膜付きガラス基材の透過率は、９２％以上であると、入射光の透過量が十分であり、好ましい。ここで、透過率は、分光光度計（日立ハイテクノロジーズ（株）製、型番：Ｕ−４１００）を用いて測定し、太陽電池用途において、透過率が重要となる３４０〜７５０ｎｍの範囲のうち、中央値となる５５０ｎｍの透過率％Ｔの値で評価する。 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.
反射防止膜の好ましい厚さは、ガラス基材の屈折率により変化するが、例えば、ガラス基材の屈折率が１．４５程度の場合には、７０〜１３０ｎｍである。ここで、膜厚は、日立ハイテクノロジーズ（株）製走査型電子顕微鏡（型番：Ｓ−４３００、ＳＵ−８０００）による断面観察により測定する。 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.
次に、反射防止膜は、コロイダルシリカ粒子を含有すると、反射防止膜の硬度が向上するため、好ましい。コロイダルシリカ粒子としては、球状コロイダルシリカ粒子、異方性コロイダルシリカ粒子が挙げられる。 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.
球状コロイダルシリカ粒子は、平均粒径：６〜４０ｎｍであると好ましく、６〜３０ｎｍであると、より好ましい。平均粒径が、６ｎｍより小さいと粒子の安定性に欠けるため二次凝集を引き起こしやすく反射防止膜用組成物の作製が困難であり、４０ｎｍより大きいと反射防止膜の平坦性を阻害するため適さないからである。ここで、平均粒径は、ＱＵＡＮＴＡＣＨＲＯＭＥ社製 ＡＵＴＯＳＯＲＢ−１を用いた比表面積測定から、球状コロイダルシリカ粒子が真球であると仮定して換算する。 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.
異方性コロイダルシリカ粒子は、平均粒径：５〜５０ｎｍであると好ましく、１２〜４０ｎｍであると、より好ましい。平均粒径が、５ｎｍより小さいと粒子の安定性に欠けるため二次凝集を引き起こしやすく反射防止膜作製が困難であり、５０ｎｍより大きいと反射防止膜の平坦性を阻害するため適さないからである。ここで、異方性コロイダルシリカ粒子の平均粒径とは、堀場製作所（株）製レーザー回折／散乱式粒度分布測定装置（型番：ＬＡ−９５０）にて測定し、粒子径基準を個数として演算した５０％平均粒子径（Ｄ５０）をいう。なお、異方性形状であるか、球状であるかは、上記走査型電子顕微鏡で観察した像で、識別したアスペクト比（長径／短径）が１．５以上のものを異方性形状と識別する。また、異方性コロイダルシリカ粒子の平均粒径とは、異方性コロイダルシリカ粒子の直径（長径）の平均値をいう。異方性コロイダルシリカ粒子のアスペクト比（長径／短径）は１．５〜５の範囲であることが好ましい。短径は１〜３４ｎｍの範囲であることが好ましい。 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.
〔反射防止膜付きガラス基材の製造方法〕
本発明の反射防止膜付きガラス基材は、ＮａおよびＣａからなる群より選択される少なくとも１種のアルカリ金属を含有するガラス基材上に、シリコンアルコキシド、またはこの加水分解物もしくはこの脱水物と、Ｐ含有化合物と、分散媒とを含む反射防止膜用組成物を、湿式塗工法により塗布した後、焼成することにより製造することができる。ガラス基材については、上述のとおりである。
[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.
反射防止膜用組成物は、シリコンアルコキシド、またはこの加水分解物もしくはこの脱水物と、Ｐ含有化合物と、分散媒とを含む。 The composition for antireflection films contains silicon alkoxide, or a hydrolyzate or dehydrated product thereof, a P-containing compound, and a dispersion medium.
シリコンアルコキシドとしては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、トリメチルメトキシシラン等が挙げられ、反応制御のし易さ、反射防止膜とした際の膜硬さの観点からテトラエトキシシランが好ましい。シリコンアルコキシド、またはこの加水分解物もしくはこの脱水物は、反射防止膜用組成物：１００質量部に対して、シリコンアルコキシドとして５〜２０質量部であると、反射防止膜の硬さの観点から好ましい。 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. .
Ｐ含有化合物としては、オルトリン酸（Ｈ３ＰＯ４）、ピロリン酸（Ｈ４Ｐ２Ｏ７）等が挙げられ、入手し易さの観点から、オルトリン酸が好ましい。Ｐ含有化合物は、シリコンアルコキシドの加水分解反応性および拡散抑制膜形成の観点から、反射防止膜用組成物：１００質量部に対して、０．０５〜３質量部であると好ましく、０．１〜１．５質量部であると、より好ましい。 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.
分散媒は、全ての分散媒１００質量％に対して、１質量％以上の水と、２質量％以上の水と相溶する溶剤、例えば、アルコール類とを含有することが好適である。例えば、分散媒が水およびアルコール類のみからなる場合、水を２質量％含有するときはアルコール類を９８質量％含有し、アルコール類を２質量％含有するときは水を９８質量％含有する。水の含有量が１質量％未満、またはアルコール類の含有量が２質量％未満では、導電性反射膜用組成物を湿式塗工法により塗工して得られた膜を低温で焼結し難くなり、また、焼成後の導電性反射膜の導電性と反射率が低下してしまうからである。アルコール類としては、メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、グリセロール、エリトリトール等が挙げられ、これらを混合して用いてもよい。分散媒の含有量は、良好な成膜性を得るために、反射防止膜用組成物：１００質量部に対して、６０〜９９質量部であると好ましい。 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.
コロイダルシリカ粒子は、反射防止膜用組成物：１００質量部に対して、５〜１５質量部であると好ましい。 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.
反射防止膜用組成物は、所望の成分を、常法により、ペイントシェーカー、ボールミル、サンドミル、セントリミル、三本ロール等によって混合し、透光性バインダー、場合により透明導電性粒子等を分散させ、製造することができる。無論、通常の攪拌操作によって製造することもできる。 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.
湿式塗工法としては、スプレーコーティング法、ディスペンサーコーティング法、スピンコーティング法、ナイフコーティング法、スリットコーティング法、インクジェットコーティング法、スクリーン印刷法、オフセット印刷法、またはダイコーティング法のいずれかであることが好ましいが、これに限られるものではなく、あらゆる方法を利用できる。 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.
ガラス基材上に、反射防止膜用組成物を、湿式塗工法により塗布した後、塗膜を有するガラス基材を焼成する焼成条件は、大気中または窒素やアルゴンなどの不活性ガス雰囲気中で、１５０〜５００℃で、３０〜６０分が好ましい。 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.
塗膜を有するガラス基材の焼成温度を１５０〜５００℃の範囲としたのは、１５０℃未満では、反射防止膜に、硬化不足の不具合が生じるからである。また、５００℃を越えると、低温プロセスという生産上のメリットを生かせない、すなわち、製造コストが増大し、生産性が低下してしまう。 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.
塗膜を有する基材の焼成時間を３０〜６０分間の範囲としたのは、焼成時間が３０分未満では、反射防止膜に焼成が十分でない不具合が生じるからである。焼成時間が６０分を越えると、必要以上に製造コストが増大して生産性が低下してしまうためである。 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.
拡散抑制膜形成のメカニズムは、反射防止膜用組成物の塗膜を焼成するときに、反射防止膜用組成物中のＰ含有化合物が、ガラス基材中のＮａやＣａと反応し、ガラス基材と反射防止膜との界面に、拡散抑制膜を形成する、と考えられる。詳細には、拡散抑制膜に含有されるＰは、ＮａやＣａを、リン酸ナトリウム（ＮａＰＯ３、Ｎａ４Ｐ２Ｏ７、Ｎａ３ＰＯ４等）、リン酸カルシウム（Ｃａ（ＰＯ３）２、Ｃａ２Ｐ２Ｏ７、Ｃａ３（ＰＯ４）２等）等のリン酸塩化合物として取り込み、ＮａやＣａの反射防止膜への拡散を抑制する、と考えられる。 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.
以上により、本発明の反射防止膜付きガラス基材を形成することができる。このように、反射防止膜と拡散抑制膜の形成に湿式塗工法を使用することにより、真空蒸着法やスパッタ法などの真空プロセスを可能な限り排除できるため、より安価に反射防止膜付きガラス基材を製造することができる。 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.
〔反射防止膜付きガラス基材の応用〕
次に、反射防止膜付きガラス基材の応用について説明する。図４に、本発明の反射防止膜付きガラス基材を使用する薄膜太陽電池の断面の模式図の一例を示す。図４は、スーパーストレート型薄膜太陽電池の例である。薄膜太陽電池２０は、反射防止膜２１、拡散抑制膜２１Ａ、ガラス基材２２、透明電極層２３、光電変換層２４、透明導電膜２５、導電性反射膜２６の順に備えており、反射防止膜２１側から太陽光が入射する。この薄膜太陽電池２０は、反射防止膜２１を備えるので、入射した太陽光の光電変換層２４への透過量が多く、高温高湿下で長時間使用しても、拡散抑制膜２１Ａにより、ガラス基材２２中のＮａやＣａの反射防止膜２１表面への拡散を抑え、反射防止膜２１の白濁を抑制するため、高温高湿下でも光電変換効率が低下しない薄膜太陽電池を提供することができる。
[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.
この薄膜太陽電池２０を製造する方法としては、光電変換層２４等を形成する前に、予め、反射防止膜２１、拡散抑制膜２１Ａを形成する方が、反射防止膜用組成物の塗膜焼成時での光電変換層２４の劣化を避けることができるため、好ましい。しかしながら、光電変換層２２〜導電性反射膜２６が形成されたガラス基板２２上に、反射防止膜２１、拡散抑制膜２１Ａを形成することもできる。この場合には、反射防止膜用組成物の塗膜焼成温度が、好ましくは１３０〜４００℃、より好ましくは１５０〜３５０℃である。アモルファスシリコン、微結晶シリコン、またはこれらを用いたハイブリッド型シリコン太陽電池は比較的熱に弱く、焼成工程によって変換効率が低下するからである。 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.
以下に、実施例により、本発明を詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
表２〜４で示す組成（数値は、質量部を示す）になるように、合計が６０ｇで、１００ｃｍ３のガラス瓶中に入れ、直径：０．３ｍｍのジルコニアビーズ（ミクロハイカ、昭和シェル石油製）：１００ｇを用いて、ペイントシェーカーで６時間分散することにより、実施例１〜２１、比較例２〜３で使用する反射防止（以下、ＡＲという）膜用組成物を作製した。ＡＲ膜用組成物の作製に使用するＡＲ膜用組成物原料は、以下のようにして作製した。
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膜用組成物原料１〕
５００ｃｍ３のガラス製の４つ口フラスコを用い、１４０ｇのテトラエトキシシランと、１４０ｇのエチルアルコールを加え、攪拌しながら、１．５ｇの８５％リン酸を１２０ｇの純水に溶解した溶液を、一度に加え、その後５０℃で３時間反応させることにより作製した。
[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膜用組成物原料２〕
５００ｃｍ３のガラス製の４つ口フラスコを用い、１１５ｇのテトラエトキシシランと、１７５ｇのエチルアルコールを加え、攪拌しながら、１．０ｇの８５％リン酸を１１０ｇの純水に溶解した溶液を、一度に加え、その後５０℃で３時間反応させることにより作製した。
[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膜用組成物原料３〕
５００ｃｍ３のガラス製の４つ口フラスコを用い、１３０ｇのテトラエトキシシランと、１４５ｇのエチルアルコールを加え、攪拌しながら、４．５ｇの８５％リン酸を１２５ｇの純水に溶解した溶液を、一度に加え、その後４５℃で３時間反応させることにより作製した。
[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膜用組成物原料４〕
５００ｃｍ３のガラス製の４つ口フラスコを用い、１２５ｇのテトラエトキシシランと、１６０ｇのエチルアルコールを加え、攪拌しながら、２．１ｇの８５％リン酸を１１５ｇの純水に溶解した溶液を、一度に加え、その後６０℃で２時間反応させることにより作製した。
[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膜用組成物原料５〕
５００ｃｍ３のガラス製の４つ口フラスコを用い、１４５ｇのテトラエトキシシランと、１４０ｇのエチルアルコールを加え、攪拌しながら、０．５ｇの８５％リン酸を１１５ｇの純水に溶解した溶液を、一度に加え、その後５５℃で３時間反応させることにより作製した。
[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膜用組成物原料６〕
５００ｃｍ３のガラス製の４つ口フラスコを用い、１４０ｇのトリメチルメトキシシランと、１４０ｇのメチルアルコールを加え、攪拌しながら、２．０ｇの８５％リン酸を１２０ｇの純水に溶解した溶液を、一度に加え、その後５０℃で３時間反応させることにより作製した。
[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膜用組成物原料７〕
５００ｃｍ３のガラス製の４つ口フラスコを用い、１４０ｇのテトラエトキシシランと、１４０ｇのエチルアルコールを加え、攪拌しながら、１．５ｇの６０％硝酸を１２０ｇの純水に溶解した溶液を、一度に加え、その後５０℃で３時間反応させることにより作製した。
[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膜用組成物原料８〕
５００ｃｍ３のガラス製の４つ口フラスコを用い、１４０ｇのテトラエトキシシランと、１４０ｇのエチルアルコールを加え、攪拌しながら、１．５ｇの３５％塩酸を１２０ｇの純水に溶解した溶液を、一度に加え、その後５０℃で３時間反応させることにより作製した。
[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.
〔混合溶媒〕
混合溶媒１には、イソプロパノール、エタノール及びＮ，Ｎ−ジメチルホルムアミドの混合液（質量比４：２：１）を、混合溶媒２には、エタノール、ブタノールの混合液（質量比９８：２）を用いた。
[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.
〔実施例１〜２１〕
実施例１では、ＡＲ膜用組成物原料１を、分散媒となるＩＰＡで希釈混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。
[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.
実施例２では、ＡＲ膜用組成物原料２を、分散媒となるエタノールで希釈混合した。さらに、平均粒径４０ｎｍの日産化学工業（株）製異方性コロイダルシリカ粒子（製品名：ＳＴ−ＯＵＰ）を、全体の１０質量％の比率で添加し、混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例３では、ＡＲ膜用組成物原料４を、分散媒となるＩＰＡで希釈混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例４では、ＡＲ膜用組成物原料６を、分散媒となるエタノールで希釈混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例５では、ＡＲ膜用組成物原料３を、分散媒となる混合溶媒１で希釈混合した。さらに、平均粒径１２ｎｍの日産化学工業（株）製異方性コロイダルシリカ粒子（製品名：ＩＰＡ−ＳＴ−ＵＰ）を、全体の１０質量％の比率で添加し、混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例６では、ＡＲ膜用組成物原料５を、分散媒となるエタノールで希釈混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例７では、ＡＲ膜用組成物原料６を、分散媒となるエタノールで希釈混合した。さらに、平均粒径１２ｎｍの日産化学工業（株）製異方性コロイダルシリカ粒子（製品名：ＩＰＡ−ＳＴ−ＵＰ）を、全体の１５質量％の比率で添加し、混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例８では、ＡＲ膜用組成物原料１を、分散媒となる混合溶媒２で希釈混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例９では、ＡＲ膜用組成物原料４を、分散媒となる混合溶媒１で希釈混合した。さらに平均粒径３０ｎｍの日産化学工業（株）製異方性コロイダルシリカ粒子（製品名：ＳＴ−ＯＵＰ）を、全体の５質量％の比率で混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例１０では、ＡＲ膜用組成物原料５を、分散媒となる混合溶媒２で希釈混合した。さらに平均粒径１０ｎｍの日産化学工業（株）製球状コロイダルシリカ粒子（製品名：ＳＴ−Ｏ）を、全体の１０質量％の比率で混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例１１では、ＡＲ膜用組成物原料３を、分散媒となる混合溶媒２で希釈混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例１２では、ＡＲ膜用組成物原料１を、分散媒となるエタノールで希釈混合した。さらに平均粒径６ｎｍの日産化学工業（株）製球状コロイダルシリカ粒子（製品名：ＳＴ−ＯＸＳ）を、全体の１０質量％の比率で混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例１３では、ＡＲ膜用組成物原料２を、分散媒となるＩＰＡで希釈混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例１４では、ＡＲ膜用組成物原料６を、分散媒となるブタノールで希釈混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例１５では、ＡＲ膜用組成物原料４を、分散媒となるＩＰＡで希釈混合した。さらに平均粒径１０ｎｍの日産化学工業（株）製球状コロイダルシリカ粒子（製品名：ＩＰＡ−ＳＴ）を、全体の１５質量％の比率で混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例１６では、ＡＲ膜用組成物原料６を、分散媒となる混合溶媒２で希釈混合した。さらに平均粒径１０ｎｍの日産化学工業（株）製球状コロイダルシリカ粒子（製品名：ＩＰＡ−ＳＴ）を、全体の１０質量％の比率で混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例１７では、ＡＲ膜用組成物原料５を、分散媒となる混合溶媒１で希釈混合した。さらに平均粒径４０ｎｍの日産化学工業（株）製異方性コロイダルシリカ粒子（製品名：ＳＴ−ＯＵＰ）を、全体の１５質量％の比率で混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例１８では、ＡＲ膜用組成物原料６を、分散媒となるＩＰＡで希釈混合した。さらに平均粒径６ｎｍの日産化学工業（株）製球状コロイダルシリカ粒子（製品名：ＳＴ−ＯＸＳ）を、全体の１０質量％の比率で混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例１９では、ＡＲ膜用組成物原料５を、分散媒となる混合溶媒１で希釈混合した。さらに平均粒径３０ｎｍの日産化学工業（株）製異方性コロイダルシリカ粒子（製品名：ＳＴ−ＯＵＰ）を、全体の１０質量％の比率で混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例２０では、ＡＲ膜用組成物原料１を、分散媒となるＩＰＡで希釈混合した。さらに平均粒径４５ｎｍの日産化学工業（株）製異方性コロイダルシリカ粒子（製品名：ＩＰＡ−ＳＴ−Ｌ）を、全体の１５質量％の比率で混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
実施例２１では、ＡＲ膜用組成物原料１を、分散媒となるＩＰＡで希釈混合した。さらに平均粒径３０ｎｍの日産化学工業（株）製異方性コロイダルシリカ粒子（製品名：ＳＴ−ＯＵＰ）を、全体の４０質量％の比率で混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を製造した。 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.
〔比較例１〜３〕
比較例１では、ＡＲ膜用組成物を成膜しない、ガラス単体の評価を実施した。
[Comparative Examples 1-3]
In Comparative Example 1, an evaluation was made on a single glass without forming the AR film composition.
比較例２では、ＡＲ膜用組成物原料７を、分散媒となるＩＰＡで希釈混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を作製した。 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.
比較例３では、ＡＲ膜用組成物原料８を、分散媒となるＩＰＡで希釈混合し、ＡＲ膜用組成物を作製した。屈折率が１．５５のガラス基板に対して、ＡＲ膜用組成物を、湿式塗工法により成膜後、ＡＲ塗膜を２００℃で３０分焼成することにより、ＡＲ膜付きガラス基材を作製した。 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.
〔ガラス基材のＮａ、Ｃａ含有量の測定〕
Ｎａ、Ｃａの定量分析は、以下のように行った。まず、（株）リガク製波長分散型蛍光Ｘ線分析装置（型番：ＺＳＸ−ＰｒｉｍｕｓＩＩ）で、検出可能な元素を確認した。次に、検出された各元素について定量分析を行い、ＳｉはＳｉＯ２、ＮａはＮａ２Ｏ、ＣａはＣａＯ、ＫはＫ２Ｏ、ＡｌはＡｌ２Ｏ３、ＦｅはＦｅ２Ｏ３、ＢはＢ２Ｏ３、ＰｂはＰｂＯ、ＴｉはＴｉＯ２、ＺｎはＺｎＯ、ＳｂはＳｂ２Ｏ３、ＢａはＢａＯ、ＭｎはＭｎＯ、ＳｒはＳｒＯであるとして、これら以外の元素については、自然界に最も多く存在する酸化物であるとして、計算した。表２〜４に、これらの結果を示す。
[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.
〔拡散抑制膜中のＰの分析〕
ガラス基材、拡散抑制膜、反射防止膜の界面部分を含む断面を観察用に加工し、日本電子（株）製電界放射型透過電子顕微鏡（型番：ＪＥＭ−２０１０Ｆ）により、拡散抑制膜を観察した。同時に、拡散抑制膜中のＰの定量分析を、日本電子（株）製電界放射型透過電子顕微鏡（型番：ＪＥＭ−２０１０Ｆ）に付属のエネルギー分散型Ｘ線分光分析装置により、加速電圧：２００ｋＶ、プローブ径：１ｎｍの測定条件で行い、５回測定での平均値から求めた。表２〜４に、これらの結果を示す。
[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.
〔拡散抑制膜とＡＲ膜の膜厚の測定〕
拡散抑制膜の膜厚を、日本電子製電界放射型透過電子顕微鏡（型番：ＪＥＭ−２０１０Ｆ）による断面観察により測定した。また、ＡＲ膜の膜厚を、日立ハイテクノロジーズ（株）製走査型電子顕微鏡（型番：Ｓ−４３００、ＳＵ−８０００）による断面観察により測定した。表２〜４に、これらの結果を示す。
[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.
〔ＡＲ膜の屈折率、初期透過率の評価〕
ＡＲ膜の屈折率は、分光エリプソメトリー装置（Ｊ．Ａ．Ｗｏｏｌｌａｍ Ｊａｐａｎ（株）製 Ｍ−２０００）を用いて測定し、解析した光学定数における６３３ｎｍの値とした。また、ＡＲ膜付きガラス基材の初期透過率は、日立ハイテクノロジーズ（株）製分光光度計（型番：Ｕ−４１００）を用いて測定し、太陽電池用途において、透過率が重要となる３４０〜７５０ｎｍの範囲のうち、中央値となる５５０ｎｍの透過率（単位：％）の値で評価した。表２〜４に、これらの結果を示す。
[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.
〔高温高湿試験後の透過率〕
また、太陽電池の寿命評価方法としてＪＩＳ Ｃ ８９３８に規定されている高温高湿試験として８５℃かつ８５％ＲＨの温湿度条件下に一定保持したエスペック（株）製恒温恒湿機（型番：ＰＬ−１ＫＰ）中に、１０００時間サンプルを保持した後、恒温恒湿機から出して室温に戻したサンプルの透過率を、上述の分光光度計で測定した。また、（高温高湿試験後の透過率）／（初期透過率）を算出した。また、表２〜４に、これらの結果を示す。なお、表２〜４には、（高温高湿試験後の透過率）／（初期透過率）は、高温高湿試験後／初期と記載した。
[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.
〔ＡＲ膜の硬度〕
ＡＲ膜の硬度を、塗膜の一般評価法としてＪＩＳ Ｋ ５６００に規定されている引っかき硬度（鉛筆法）試験として、コーティングテスター工業製手動式鉛筆引っかき試験器を用いて、荷重７５０ｇ、角度４５°で三菱鉛筆製引っかき試験用えんぴつで測定した。表２〜４に、これらの結果を示す。
[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.
表２〜４からわかるように、実施例１〜１９では、ＡＲ膜の屈折率が１．３５〜１．５０で、拡散抑制膜中にＰが１〜１２原子％で、拡散抑制膜の厚さが３〜１０ｎｍであり、ＡＲ膜の透過率が９２．５％以上と高く、高温高湿試験後の透過率も高く、初期の９９．１〜９９．９％であった。これに対して、比較例１では反射防止膜を形成していないため、初期の透過率が９１％と低く、高温高湿試験後の透過率が８８％と大きく低下した。ＡＲ膜用組成物原料にＰ含有化合物を含まない比較例２及び３では、拡散抑制膜が確認できず、高温高湿試験後の透過率が、初期透過率に比べて、大きく低下した。なお、コロイダルシリカ粒子の粒径が大きい実施例２０と、コロイダルシリカ粒子の含有量が多い実施例２１は、反射防止膜の膜厚が平坦とならずに、初期の透過率が実施例１〜１９より低く、反射防止膜の硬度も低かった。 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.
１ 反射防止膜付きガラス基材
２ ガラス基材
３ 反射防止膜
４ 拡散抑制膜
１０、２０ 薄膜太陽電池
１１、２１ 反射防止膜
２１Ａ 拡散抑制膜
１２、２２ ガラス基材
１３、２３ 透明電極層
１４、２４ 光電変換層
１５、２５ 透明導電膜
１６、２６ 導電性反射膜
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)
ガラス基材は、ＮａおよびＣａからなる群より選択される少なくとも１種のアルカリ金属を含有し；
反射防止膜は、ＳｉＯ２を含有し、屈折率が１．３５〜１．５０であり、厚さが７０〜１３０ｎｍであり；かつ
ガラス基材表面と反射防止膜との界面に、透過電子顕微鏡付属のエネルギー分散型Ｘ線分光分析装置による定量分析で、Ｓｉ、ＰおよびＯの合計１００原子％に対して、Ｐを１〜１２原子％含有し、厚さが３〜１０ｎｍである拡散抑制膜を備える、
ことを特徴とする、反射防止膜付きガラス基材。 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
A thin film solar cell comprising the glass substrate with an antireflection film according to claim 1.
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