JP2014118620A - Ferritic stainless steel plate for solar cell member and its manufacturing method - Google Patents
Ferritic stainless steel plate for solar cell member and its manufacturing method Download PDFInfo
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- Y—GENERAL 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
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- Y02E10/50—Photovoltaic [PV] energy
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Abstract
Description
本発明は、太陽電池セルや太陽電池モジュールを構成する部品、例えば基板やバックシート等の素材に好適な、太陽電池部材用フェライト系ステンレス鋼板およびその製造方法に関する。 The present invention relates to a ferritic stainless steel sheet for solar cell members and a method for producing the same suitable for materials constituting solar cells and solar cell modules, such as substrates and backsheets.
近年、新エネルギー源として太陽光を利用した発電システムが注目されており、単結晶Si、多結晶Siを構成層とする結晶系Si太陽電池が実用化され、電力供給用太陽光発電システムとして重要な役割を担っている。しかし、結晶系Si太陽電池は、その製造にバルク結晶を製造するプロセスを要するため、大量の原料を使用し、結晶成長に長時間かかり、しかも製造プロセスが複雑であり且つ多大なエネルギーを必要とすることから、製造コストが極めて高い。 In recent years, a power generation system using sunlight has attracted attention as a new energy source. Crystalline Si solar cells composed of single crystal Si and polycrystal Si have been put into practical use and are important as a solar power generation system for power supply. Have a role to play. However, since a crystalline Si solar cell requires a process for producing a bulk crystal, its production requires a large amount of raw materials, takes a long time for crystal growth, is complicated in production process, and requires a lot of energy. Therefore, the manufacturing cost is extremely high.
このような背景下、Si使用量を大幅に低減した薄膜系Si太陽電池や、Siを全く使用しない化合物薄膜系、有機薄膜系、色素増感型、更には量子ドット型等の新しい太陽電池が盛んに研究開発され、実用化が開始されている。これらの太陽電池はいずれも薄膜系太陽電池であり、基板上に、非晶質Siや化合物半導体を成膜して薄膜状の光吸収層を形成することにより製造される。したがって、結晶系Si太陽電池よりも製造工程が単純であり、且つ、製造時間の短縮化が可能である。また、薄膜（光吸収層）の厚さは数十nm〜数μmであることから、結晶系Si太陽電池に比べて使用原料の大幅な削減が可能である。 Against this backdrop, there are new thin-film Si solar cells that significantly reduce the amount of Si used, as well as new solar cells such as compound thin-film systems, organic thin-film systems, dye-sensitized types, and quantum dot types that do not use Si at all. It has been actively researched and developed and has been put into practical use. Each of these solar cells is a thin film solar cell, and is manufactured by forming a thin light absorption layer on a substrate by depositing amorphous Si or a compound semiconductor. Therefore, the manufacturing process is simpler than that of the crystalline Si solar cell, and the manufacturing time can be shortened. In addition, since the thickness of the thin film (light absorption layer) is several tens of nm to several μm, it is possible to significantly reduce the amount of raw materials used compared to crystalline Si solar cells.
以上の理由により、薄膜系太陽電池は製造コストが低く、量産性が高いため、次世代太陽電池として大いに期待されている。特に、光吸収層としてCu(In1-XGaX)Se2（以下、CIGSと略す場合もある）を使用した化合物薄膜系太陽電池であるCIGS太陽電池は、薄膜系太陽電池のなかでも光電変換効率が高く、製造コストも安価であることから、注目度が高い。 For the above reasons, thin film solar cells are highly expected as next-generation solar cells because of low production costs and high mass productivity. In particular, CIGS solar cells, which are compound thin-film solar cells that use Cu (In 1-X Ga X ) Se 2 (hereinafter sometimes abbreviated as CIGS) as the light absorption layer, are among the thin-film solar cells. The degree of attention is high because of its high conversion efficiency and low manufacturing costs.
薄膜系太陽電池の基板には、主にソーダライムガラス等のガラス板、ステンレス箔、ポリイミド等の合成樹脂膜が使用されている。これらのうち、ガラス板は可撓性がないため、コイルの状態で連続的に処理するロール・ツー・ロール法が適用できず、量産化や低コスト化に不利である。また、合成樹脂膜は耐熱性に劣るため、太陽電池セル製造工程における高温プロセスに耐えられないといった欠点を有する。 For the substrate of the thin film solar cell, a glass plate such as soda lime glass, a synthetic resin film such as stainless steel foil and polyimide is mainly used. Among these, since the glass plate is not flexible, the roll-to-roll method of continuously processing in a coil state cannot be applied, which is disadvantageous for mass production and cost reduction. In addition, since the synthetic resin film is inferior in heat resistance, it has a drawback that it cannot withstand a high temperature process in the solar cell manufacturing process.
これらに対し、ステンレス箔は、可撓性および耐熱性に優れている。したがって、量産化や低コスト化に有利なロール・ツー・ロール法が適用でき、しかも太陽電池セル製造工程における高温プロセスに耐え得る耐熱性を有するため、太陽電池セル生産効率の向上や、軽量で可撓性を有する薄膜系太陽電池の製造が可能となる。 On the other hand, the stainless steel foil is excellent in flexibility and heat resistance. Therefore, the roll-to-roll method, which is advantageous for mass production and cost reduction, can be applied, and it has heat resistance that can withstand high temperature processes in the solar cell manufacturing process. A thin film solar cell having flexibility can be manufactured.
また、ステンレス箔は優れた可撓性を有するので、これを基板とした薄膜系太陽電池は曲面への施工も可能となり、いわゆるフレキシブル太陽電池として太陽電池の更なる用途展開が期待できる。特に、ステンレス鋼のなかでもフェライト系ステンレス鋼は、線熱膨張係数の値がCIGSと同程度であることから、薄膜系太陽電池の基板用素材やバックシート用素材としての適用が積極的に検討されている。 In addition, since the stainless steel foil has excellent flexibility, a thin film solar cell using the stainless steel foil as a substrate can be applied to a curved surface, and further application development of the solar cell can be expected as a so-called flexible solar cell. In particular, ferritic stainless steel among stainless steels has the same linear thermal expansion coefficient as CIGS, so it is actively considered for use as a substrate material or backsheet material for thin-film solar cells. Has been.
図１はCIGS系太陽電池セルの一般的な構造を例示したもの（断面図）である。図１に示すように、CIGS系太陽電池セル10は、基板1に、例えばMo層からなる裏面電極層2を成膜したのち、CIGS系光吸収層3を成膜し、更にCdS等のバッファ層4a、ZnO等の高抵抗バッファ層4b、透明導電層5を順次成膜し、裏面電極層2および透明導電層5にグリッド電極6を設けることにより製造される。
FIG. 1 illustrates a general structure of a CIGS solar cell (cross-sectional view). As shown in FIG. 1, a CIGS
また、太陽電池モジュール100は、図２に示すように、受光面に強化ガラス、フッ素樹脂等の素材からなる透明のバリアフィルム20、裏面にステンレス鋼板、樹脂等からなるバックシート30を配置し、バリアフィルム20とバックシート30との間に複数の太陽電池セル10を配列し、各セル同士のグリッド電極（図省略）をコネクタ40で接続し、EVA等の樹脂50を充填することにより製造される。
In addition, as shown in FIG. 2, the
ここで、基板および裏面電極層の上層に光吸収層を成膜する際、その成膜温度は光吸収層を構成する材料の種類に依存するが、例えばCIGS層の場合450〜650℃となる。そのため、基板としてステンレス箔を用いる場合、光吸収層を成膜する際の高温プロセスを経ることで基板が変形する問題がある。そして、その変形量が大きくなると光吸収層が基板から剥離し易くなり、光吸収層の剥離は生産性の低下や光電変換効率の低下を招く。したがって、薄膜系太陽電池技術においては、光吸収層の成膜プロセスなどの高温プロセス時に基板の変形を抑制することも重要課題とされている。 Here, when forming the light absorption layer on the upper layer of the substrate and the back electrode layer, the film formation temperature depends on the type of material constituting the light absorption layer, but is, for example, 450 to 650 ° C. in the case of the CIGS layer. . Therefore, when a stainless steel foil is used as the substrate, there is a problem that the substrate is deformed through a high temperature process when forming the light absorption layer. When the amount of deformation increases, the light absorbing layer is easily peeled from the substrate, and peeling of the light absorbing layer causes a decrease in productivity and a decrease in photoelectric conversion efficiency. Therefore, in the thin film solar cell technology, it is also important to suppress the deformation of the substrate during a high temperature process such as a film forming process of the light absorption layer.
上記課題を有利に解決するものとして、特許文献１には、CIGS太陽電池基板用のステンレス材に関し、Cr含有量が7〜40質量％である冷間圧延後のステンレス材に、N2ガス等の不活性ガス雰囲気中において250〜1050℃の温度に数秒間保持する熱処理（予備熱処理）を施す技術が提案されている。
そして、特許文献１で提案された技術によると、例えば光吸収層成膜時のような450〜650℃の高温プロセスにおいても、ステンレス材（基板）の変形を抑制し、Mo層からなる裏面電極や光吸収層であるCIGS薄膜の基板からの剥離を抑制することができる。
Patent Document 1 discloses a stainless steel material for a CIGS solar cell substrate as an object to advantageously solve the above-mentioned problems. For example, N 2 gas or the like is applied to a stainless steel material after cold rolling with a Cr content of 7 to 40% by mass. There has been proposed a technique of performing a heat treatment (preliminary heat treatment) that is maintained at a temperature of 250 to 1050 ° C. for several seconds in an inert gas atmosphere.
According to the technique proposed in Patent Document 1, for example, even in a high-temperature process at 450 to 650 ° C. such as when forming a light absorption layer, the deformation of the stainless material (substrate) is suppressed, and the back electrode made of the Mo layer And the CIGS thin film, which is a light absorption layer, can be prevented from peeling from the substrate.
特許文献１にも記載されているように、光吸収層（CIGS層）の成膜に先立ち、冷間圧延後のステンレス材（基板）に250〜1050℃の温度で熱処理を施すことで、光吸収層成膜プロセスなどの高温プロセスにおいてステンレス材が変形する現象を抑制し、延いては光吸収層が基板から剥離する現象を抑制することができる。
以上のような効果が得られる理由については、必ずしも明確ではないが、本発明者ら次のように考えている。
As described in Patent Document 1, prior to the film formation of the light absorption layer (CIGS layer), the stainless steel (substrate) after the cold rolling is heat treated at a temperature of 250 to 1050 ° C. It is possible to suppress a phenomenon in which the stainless material is deformed in a high-temperature process such as an absorption layer forming process, and to suppress a phenomenon in which the light absorption layer is peeled off from the substrate.
The reason why the above effect is obtained is not necessarily clear, but the present inventors consider as follows.
ステンレス鋼板の製造工程で、冷間圧延を繰り返すことによって、ステンレス鋼板に加工ひずみが導入される。このように加工ひずみが導入されたステンレス鋼板を太陽電池用基板とし、光吸収層を成膜する目的で高温加熱処理を施すと、ステンレス鋼板の加工ひずみが解放されて、ステンレス鋼板が変形し、裏面電極や光吸収層が基板から剥離する。しかし、予めステンレス鋼板に熱処理を施すことによって、冷間圧延時に導入された加工ひずみを低減することができる。そのため、熱処理後に光吸収層を成膜することで、基板であるステンレス鋼板の変形が抑制され、結果として基板からの光吸収層の剥離が抑制されるものと推測される。 By repeating cold rolling in the manufacturing process of the stainless steel plate, processing strain is introduced into the stainless steel plate. The stainless steel plate introduced with processing strain in this way is used as a solar cell substrate, and when heat treatment is performed for the purpose of forming a light absorption layer, the processing strain of the stainless steel plate is released, and the stainless steel plate is deformed, The back electrode and the light absorption layer are peeled off from the substrate. However, by subjecting the stainless steel plate to heat treatment in advance, it is possible to reduce processing strain introduced during cold rolling. Therefore, it is presumed that by forming the light absorption layer after the heat treatment, deformation of the stainless steel plate as the substrate is suppressed, and as a result, peeling of the light absorption layer from the substrate is suppressed.
以上のように、光吸収層（CIGS層）の成膜に先立ち、冷間圧延後のステンレス材（基板）に250〜1050℃の温度で熱処理を施すことで、光吸収層の成膜時においてステンレス材の加工ひずみが解放する現象を抑制し、延いてはステンレス材の変形を抑制することができる。 As described above, prior to film formation of the light absorption layer (CIGS layer), the stainless steel material (substrate) after cold rolling is subjected to heat treatment at a temperature of 250 to 1050 ° C. The phenomenon that the processing strain of the stainless steel material is released can be suppressed, and the deformation of the stainless steel material can be suppressed.
しかしながら、特許文献１で提案された技術では、特にフェライト系ステンレス鋼板の熱処理を580〜720℃の温度範囲で実施した場合、ステンレス鋼板の耐食性が劣化する場合があることが判明した。太陽電池の基板となるステンレス鋼板の耐食性が劣化すると、太陽電池の光電変換効率が低下し、更には太陽電池モジュール使用期間も低下する。 However, with the technique proposed in Patent Document 1, it has been found that the corrosion resistance of the stainless steel sheet may deteriorate, particularly when the heat treatment of the ferritic stainless steel sheet is performed in the temperature range of 580 to 720 ° C. When the corrosion resistance of the stainless steel plate serving as the substrate of the solar cell is deteriorated, the photoelectric conversion efficiency of the solar cell is lowered, and further, the use period of the solar cell module is also lowered.
以上のように、特許文献１で提案された技術では、熱処理温度として580〜720℃の温度域を選択した場合、基板から光吸収層が剥離する問題は解消し得るものの、基板の耐食性の劣化が問題となる。それゆえ、種々の光吸収層（CIGS層）の成膜温度やステンレス鋼板に要求される硬さに応じて熱処理温度を選択することができず、改善の余地があった。 As described above, in the technique proposed in Patent Document 1, when the temperature range of 580 to 720 ° C. is selected as the heat treatment temperature, the problem that the light absorption layer peels off from the substrate can be solved, but the corrosion resistance of the substrate is deteriorated. Is a problem. Therefore, the heat treatment temperature cannot be selected according to the film forming temperature of various light absorption layers (CIGS layer) and the hardness required for the stainless steel plate, and there is room for improvement.
本発明は、上記の問題を有利に解決するもので、太陽電池セル製造時の高温プロセスにおいて基板から光吸収層が剥離する現象を抑制できることはいうまでもなく、太陽電池モジュールの長時間使用に耐え得る優れた耐食性を有する太陽電池部材用フェライト系ステンレス鋼板およびその製造方法を提供することを目的とする。 The present invention advantageously solves the above-described problem, and it is needless to say that the phenomenon that the light absorption layer is peeled off from the substrate in a high temperature process at the time of manufacturing the solar battery cell can be suppressed. It aims at providing the ferritic stainless steel plate for solar cell members which has the outstanding corrosion resistance which can endure, and its manufacturing method.
本発明者らは、上記課題を解決すべく、熱処理を施したフェライト系ステンレス鋼板に関し、その耐食性に影響を及ぼす各種要因について鋭意検討した。まず、本発明者らは、Cr含有量が11〜30質量％であるフェライト系ステンレス鋼からなる冷延鋼板を用意し、特許文献１で提案された技術にしたがい不活性ガス雰囲気中250〜1050℃の種々の熱処理温度で冷延ままの鋼板に熱処理を施した。 In order to solve the above-mentioned problems, the present inventors diligently studied various factors affecting the corrosion resistance of a heat treated ferritic stainless steel sheet. First, the present inventors prepared a cold-rolled steel plate made of a ferritic stainless steel having a Cr content of 11 to 30% by mass, and in an inert gas atmosphere according to the technique proposed in Patent Document 1, The steel sheet as cold-rolled was subjected to heat treatment at various heat treatment temperatures of ° C.
熱処理後の鋼板の表層部を観察したところ、鋼板の最表層部には数nm〜数百nm程度の薄いCr酸化皮膜が観察され、この酸化皮膜直下に鋼板母材と比較してCr濃度が低下した領域が観察された。なお、加熱（熱処理）による酸化皮膜形成に伴い鋼板表層のCrが消費されるが、Crの酸化反応が速いため、鋼板母材から鋼板表層へのCrの拡散が間に合わず、酸化皮膜直下にCr濃度が低下した領域が生じるものと推測される。 When the surface layer part of the steel sheet after heat treatment was observed, a thin Cr oxide film of several nm to several hundred nm was observed on the outermost layer part of the steel sheet, and the Cr concentration was directly below this oxide film compared with the steel sheet base metal. A reduced area was observed. In addition, although Cr on the steel sheet surface layer is consumed with the formation of the oxide film by heating (heat treatment), the Cr oxidation reaction is fast, so the diffusion of Cr from the steel sheet base material to the steel sheet surface layer is not in time, and Cr immediately below the oxide film. It is presumed that a region where the concentration is lowered is generated.
そこで、酸化皮膜直下層のCr濃度を分析した結果、熱処理温度が580℃以上になると、酸化皮膜直下のCr濃度が母材のCr濃度よりも大幅に低下することが明らかになり、この酸化皮膜直下のCr濃度低下が耐食性劣化の原因であることを本発明者らは突き止めた。また、特にCr含有量が18質量％以下のフェライト系ステンレス鋼板においては、酸化皮膜直下のCr濃度が極めて低くなり、耐食性が劣化し易いことを見出した。 Therefore, as a result of analyzing the Cr concentration immediately below the oxide film, it became clear that when the heat treatment temperature is 580 ° C or higher, the Cr concentration immediately below the oxide film is significantly lower than the Cr concentration of the base metal. The present inventors have found that a decrease in the Cr concentration directly below is the cause of corrosion resistance deterioration. In addition, it has been found that particularly in a ferritic stainless steel sheet having a Cr content of 18% by mass or less, the Cr concentration immediately below the oxide film becomes extremely low, and the corrosion resistance tends to deteriorate.
これらの事項を踏まえ、熱処理後の鋼板について、表層部のCr濃度分布を測定するとともに、耐食性評価を行った。その結果、Cr含有量が18質量％以下のフェライト系ステンレス鋼板であっても、Cr含有量が14質量％以上であり、且つ、鋼板表層の酸化皮膜中のCr濃度と酸化皮膜直下のCr濃度が以下の(1)式を満足すれば、太陽電池を構成する部品の素材に要求される耐食性を十分に満足するフェライト系ステンレス鋼板が得られることを知見した。 Based on these matters, the Cr concentration distribution in the surface layer portion of the heat-treated steel sheet was measured and the corrosion resistance was evaluated. As a result, even if it is a ferritic stainless steel sheet with a Cr content of 18% by mass or less, the Cr content is 14% by mass or more, and the Cr concentration in the oxide film on the surface layer of the steel sheet and the Cr concentration just below the oxide film However, it has been found that if the following expression (1) is satisfied, a ferritic stainless steel sheet that sufficiently satisfies the corrosion resistance required for the material of the components constituting the solar cell can be obtained.
（酸化皮膜中のCr濃度（質量％））＋3×（酸化皮膜直下のCr濃度（質量％））
＞62（質量％）… (1)
すなわち、酸化皮膜直下のCr濃度を低下させないようにすることで優れた耐食性を維持できることは勿論のこと、酸化皮膜直下のCr濃度が低い場合であっても、酸化皮膜中のCr濃度を上記(1)式を満たすように制御することで、優れた耐食性を維持できることを見出した。
(Cr concentration in oxide film (mass%)) + 3 x (Cr concentration directly under oxide film (mass%))
> 62 (mass%) ... (1)
In other words, by keeping the Cr concentration just below the oxide film from being lowered, it is possible to maintain excellent corrosion resistance, and even when the Cr concentration just below the oxide film is low, the Cr concentration in the oxide film is the above ( It has been found that excellent corrosion resistance can be maintained by controlling to satisfy formula (1).
更に、本発明者らは、Cr含有量が質量％で14％以上18％以下である冷間圧延フェライト系ステンレス鋼板について、上記(1)式を満足し、太陽電池モジュールの長時間使用に耐え得る十分な耐食性を備えたステンレス鋼板とするための熱処理条件について模索した。その結果、熱処理温度が580℃以上720℃以下の場合であっても、不活性ガス雰囲気中で熱処理を行い、雰囲気ガスの露点および熱処理時間を最適化することで、上記(1)式を満足し、所望の耐食性を備えたフェライト系ステンレス鋼板が得られることを知見した。 Furthermore, the inventors of the present invention have satisfied the above formula (1) for a cold rolled ferritic stainless steel sheet having a Cr content of 14% or more and 18% or less by mass, and can withstand long-term use of the solar cell module. We searched for heat treatment conditions to obtain a stainless steel plate with sufficient corrosion resistance. As a result, even when the heat treatment temperature is 580 ° C or more and 720 ° C or less, the heat treatment is performed in an inert gas atmosphere, and the above formula (1) is satisfied by optimizing the dew point of the atmosphere gas and the heat treatment time. It was found that a ferritic stainless steel sheet having desired corrosion resistance can be obtained.
先述のとおり、冷間圧延ステンレス鋼板に580℃以上720℃以下の熱処理を施すと、冷間圧延時に導入された加工ひずみが低減するため、その後450〜650℃の高温に加熱してもステンレス鋼板の変形が効果的に抑制される。したがって、上記の如く熱処理条件を最適化することで、太陽電池セル製造時の高温プロレスで問題とされていた変形を抑制することが可能であり、且つ、太陽電池モジュールの長時間使用に耐え得る耐食性を備えた太陽電池部材用フェライト系ステンレス鋼板が得られることを知見した。 As mentioned above, when cold-rolled stainless steel sheet is subjected to heat treatment at 580 ° C or higher and 720 ° C or lower, the processing strain introduced during cold rolling is reduced. Is effectively suppressed. Therefore, by optimizing the heat treatment conditions as described above, it is possible to suppress deformation, which has been a problem in high temperature professional wrestling during the manufacture of solar cells, and can withstand long-term use of solar cell modules. It discovered that the ferritic stainless steel plate for solar cell members provided with corrosion resistance was obtained.
本発明は、上記の知見に立脚するものであり、その要旨構成は次のとおりである。
［１］ 質量％でCr：14％以上18％以下を含有し、鋼板表層部の酸化皮膜中のCr濃度と、前記酸化皮膜直下のCr濃度が、下記(1)式を満足することを特徴とする太陽電池部材用フェライト系ステンレス鋼板。
記
（酸化皮膜中のCr濃度（質量％））＋3×（酸化皮膜直下のCr濃度（質量％））
＞62（質量％）… (1)
The present invention is based on the above findings, and the gist of the present invention is as follows.
[1] Contains Cr: 14% or more and 18% or less by mass%, and the Cr concentration in the oxide film on the surface layer of the steel sheet and the Cr concentration immediately below the oxide film satisfy the following formula (1): A ferritic stainless steel sheet for solar cell members.
(Cr concentration in oxide film (mass%)) + 3 x (Cr concentration directly under oxide film (mass%))
> 62 (mass%) ... (1)
［２］ 前記［１］の太陽電池部材用フェライト系ステンレス鋼板の製造方法において、質量％でCr：14％以上18％以下を含有するフェライト系ステンレス鋼板に、最終の冷間圧延を施した後、露点−70℃以上−40℃以下に調整した不活性ガス雰囲気中において、580℃以上720℃以下の温度域に加熱し、該温度域における滞留時間を5秒以上とする熱処理を施すことを特徴とする太陽電池部材用フェライト系ステンレス鋼板の製造方法。 [2] In the method for producing a ferritic stainless steel sheet for solar cell members according to [1], after the final cold rolling is performed on a ferritic stainless steel sheet containing Cr: 14% to 18% by mass%. In an inert gas atmosphere adjusted to a dew point of −70 ° C. or more and −40 ° C. or less, heating to a temperature range of 580 ° C. or more and 720 ° C. or less, and performing a heat treatment with a residence time in the temperature range of 5 seconds or more. A method for producing a ferritic stainless steel sheet for a solar cell member.
本発明によれば、太陽電池セル製造時の高温プロセスにおける変形量が極めて小さく、しかも耐食性に優れたフェライト系ステンレス鋼板が得られる。したがって、本発明のフェライト系ステンレス鋼板を太陽電池基板に用いることにより、基板に光吸収層を成膜する際、成膜温度を450〜650℃の高温にした場合であっても基板の変形を抑制することができ、延いては基板から光吸収層が剥離する問題を解消して光電変換効率の高い太陽電池が得られる。 ADVANTAGE OF THE INVENTION According to this invention, the deformation amount in the high temperature process at the time of photovoltaic cell manufacture is very small, and also the ferritic stainless steel plate excellent in corrosion resistance is obtained. Therefore, by using the ferritic stainless steel plate of the present invention for the solar cell substrate, when the light absorption layer is formed on the substrate, the substrate can be deformed even when the film forming temperature is set to 450 to 650 ° C. Thus, the problem of the light absorption layer peeling off from the substrate can be solved, and a solar cell with high photoelectric conversion efficiency can be obtained.
また、本発明のフェライト系ステンレス鋼板は、優れた耐食性を有することから、太陽電池の基板のみならずバックシート等に適用することで、太陽電池モジュールの信頼性向上と長寿命化を図ることができ、産業上格段の効果を奏する。更に、本発明によると、太陽電池モジュールを構成する複数種の部品（例えば基板とバックシート）を、同一の鋼種を用いて製造することができるため、太陽電池の製造コストを削減することが可能となり、且つ、太陽電池の生産性を高めることが可能となる。 Moreover, since the ferritic stainless steel sheet of the present invention has excellent corrosion resistance, it can be applied not only to the solar cell substrate but also to the back sheet, etc., thereby improving the reliability and extending the life of the solar cell module. Yes, and it has a remarkable industrial effect. Furthermore, according to the present invention, it is possible to manufacture a plurality of types of components (for example, a substrate and a back sheet) constituting the solar cell module using the same steel type, so that the manufacturing cost of the solar cell can be reduced. In addition, the productivity of the solar cell can be increased.
以下、本発明について詳細に説明する。
本発明の太陽電池部材用フェライト系ステンレス鋼板は、質量％でCr：14％以上18％以下を含有し、鋼板表層部の酸化皮膜中のCr濃度と、前記酸化皮膜直下のCr濃度が、以下の(1)式を満足することを特徴とする。
（酸化皮膜中のCr濃度（質量％））＋3×（酸化皮膜直下のCr濃度（質量％））
＞62（質量％）… (1)
Hereinafter, the present invention will be described in detail.
The ferritic stainless steel sheet for solar cell members of the present invention contains Cr: 14% or more and 18% or less by mass%, and the Cr concentration in the oxide film on the surface layer of the steel sheet and the Cr concentration directly below the oxide film are as follows: It satisfies the following formula (1).
(Cr concentration in oxide film (mass%)) + 3 x (Cr concentration directly under oxide film (mass%))
> 62 (mass%) ... (1)
Cr：14％以上18％以下
本発明の太陽電池部材用フェライト系ステンレス鋼板は、Crを質量％で14％以上18％以下含有する。
Crは、ステンレス鋼板に耐食性を付与するうえで必須の元素である。Cr含有量が質量％で14％未満では、太陽電池モジュールの長時間使用に耐え得る耐食性を確保することができない。そのため、基板やバックシートに適用した場合、太陽電池モジュールの長期使用時に基板等の腐食が問題となる。また、基本的にCr含有量が高いほど耐食性は向上し、Cr含有量が18％を超えるフェライト系ステンレス鋼板では、580℃以上720℃以下の範囲で熱処理を施した場合でも、酸化皮膜直下のCr濃度低下に起因する耐食性劣化は起こり難い。したがって、本発明では、熱処理による耐食性の劣化が生じ易いフェライト系ステンレス鋼板、すなわちCr含有量が質量％で18％以下のフェライト系ステンレス鋼板を対象とする。
Cr: 14% or more and 18% or less The ferritic stainless steel sheet for solar cell members of the present invention contains 14% or more and 18% or less by mass of Cr.
Cr is an essential element for imparting corrosion resistance to the stainless steel plate. When the Cr content is less than 14% by mass, the corrosion resistance that can withstand long-term use of the solar cell module cannot be ensured. Therefore, when applied to a substrate or a back sheet, corrosion of the substrate or the like becomes a problem during long-term use of the solar cell module. In addition, the higher the Cr content, the better the corrosion resistance. For ferritic stainless steel sheets with a Cr content exceeding 18%, even when heat treatment is performed in the range of 580 ° C or more and 720 ° C or less, it is directly under the oxide film. Corrosion resistance deterioration due to Cr concentration decrease is unlikely to occur. Therefore, the present invention is directed to a ferritic stainless steel plate that is susceptible to deterioration of corrosion resistance due to heat treatment, that is, a ferritic stainless steel plate having a Cr content of 18% or less by mass.
（酸化皮膜中のCr濃度（質量％））＋3×（酸化皮膜直下のCr濃度（質量％））
＞62（質量％）… (1)
フェライト系ステンレス鋼板に、580℃以上の高温熱処理を施すと、鋼板最表層にCrの酸化皮膜が形成され、酸化皮膜直下に鋼板母材と比較してCr濃度が低下した領域が形成される。そして、上記熱処理後のフェライト系ステンレス鋼板の板厚方向のCr濃度分布は、図３（ａ）に例示するような分布となる。図３（ａ）に示すように、熱処理後のフェライト系ステンレス鋼板では、酸化皮膜において鋼板母材よりもCr濃度が高くなる。一方、酸化皮膜直下ではCr濃度が大幅に低下し、この酸化皮膜直下におけるCr濃度の低下がフェライト系ステンレス鋼板の耐食性劣化の主たる原因となる。
(Cr concentration in oxide film (mass%)) + 3 x (Cr concentration directly under oxide film (mass%))
> 62 (mass%) ... (1)
When a high-temperature heat treatment at 580 ° C. or higher is applied to a ferritic stainless steel sheet, a Cr oxide film is formed on the outermost layer of the steel sheet, and a region having a lower Cr concentration than the steel sheet base material is formed immediately below the oxide film. And the Cr concentration distribution of the thickness direction of the ferritic stainless steel plate after the said heat processing becomes distribution as illustrated to Fig.3 (a). As shown to Fig.3 (a), in the ferritic stainless steel plate after heat processing, Cr density | concentration becomes higher than a steel plate base material in an oxide film. On the other hand, the Cr concentration is greatly reduced immediately below the oxide film, and the decrease in the Cr concentration immediately below the oxide film is a main cause of deterioration of the corrosion resistance of the ferritic stainless steel sheet.
そこで、本発明では、酸化皮膜直下におけるCr濃度の低下を抑制すること、或いは、酸化皮膜のCr濃度を高めて酸化皮膜直下におけるCr濃度低下分を補うことで、フェライト系ステンレス鋼板の耐食性を確保する。酸化皮膜中のCr濃度と酸化皮膜直下のCr濃度が前記(1)式を満たさない場合、十分な耐食性を得ることができない。したがって、本発明では、酸化皮膜中のCr濃度（質量％）と3×（酸化皮膜直下のCr濃度（質量％））の合計が62質量％超となるように制御する。 Therefore, in the present invention, the corrosion resistance of the ferritic stainless steel sheet is ensured by suppressing the decrease in Cr concentration immediately below the oxide film, or by increasing the Cr concentration of the oxide film to compensate for the decrease in Cr concentration immediately below the oxide film. To do. If the Cr concentration in the oxide film and the Cr concentration immediately below the oxide film do not satisfy the above formula (1), sufficient corrosion resistance cannot be obtained. Therefore, in the present invention, the total of the Cr concentration (mass%) in the oxide film and 3 × (Cr concentration (mass%) immediately below the oxide film) is controlled to be over 62 mass%.
なお、鋼板表層の板厚方向のCr濃度分布は、オージェ電子分光法（AES）を用いて測定することができる。
図３（ｂ）に、AESを用いて熱処理後のフェライト系ステンレス鋼板の板厚方向のCr濃度分布を測定した一例を示す。
本発明では、AESを用いて熱処理後のフェライト系ステンレス鋼板の最表面から深さ（板厚方向）90nmまでの領域のCr濃度分布とO（酸素）濃度分布を測定する。そして、本発明では、前記領域のうちO（酸素）濃度が1mass％以上である領域におけるCr濃度の最大値を「酸化皮膜中のCr濃度」とする。また、本発明では、フェライト系ステンレス鋼板の最表面から深さ（板厚方向）90nmまでの領域のうち、前記最大値が測定された位置よりも板厚中央側の領域におけるCr濃度の最小値を「酸化皮膜直下のCr濃度」とする。
The Cr concentration distribution in the thickness direction of the steel sheet surface layer can be measured using Auger electron spectroscopy (AES).
FIG. 3 (b) shows an example in which the Cr concentration distribution in the thickness direction of the ferritic stainless steel sheet after heat treatment is measured using AES.
In the present invention, the Cr concentration distribution and the O (oxygen) concentration distribution in the region from the outermost surface of the ferritic stainless steel sheet after heat treatment to the depth (plate thickness direction) of 90 nm are measured using AES. In the present invention, the maximum value of Cr concentration in a region where the O (oxygen) concentration is 1 mass% or more in the region is defined as “Cr concentration in oxide film”. In the present invention, the minimum value of the Cr concentration in the region on the center side of the plate thickness from the position where the maximum value is measured in the region from the outermost surface of the ferritic stainless steel plate to the depth (plate thickness direction) of 90 nm. Is the “Cr concentration directly under the oxide film”.
以上のように、Cr含有量が質量％で14％以上18％以下であるようなフェライト系ステンレス鋼板に高温熱処理を施すと、鋼板表面に酸化皮膜が形成されることに伴い酸化皮膜直下のCr濃度が低下し、太陽電池に要求される耐食性を維持できなくなるおそれがある。しかしながら、本発明によると、フェライト系ステンレス鋼板の表層部Cr濃度分布を、上記(1)式を満足するように制御することで、耐食性の問題を効果的に解消することができる。それゆえ、本発明によると、例えばSUS430のように汎用性の高い鋼材を太陽電池用部材として積極的に使用することができ、太陽電池の低コスト化が期待できる。 As described above, when a high temperature heat treatment is applied to a ferritic stainless steel sheet having a Cr content of 14% or more and 18% or less by mass, an oxide film is formed on the surface of the steel sheet and Cr immediately below the oxide film is formed. There is a possibility that the concentration decreases and the corrosion resistance required for the solar cell cannot be maintained. However, according to the present invention, the corrosion resistance problem can be effectively solved by controlling the surface layer Cr concentration distribution of the ferritic stainless steel sheet so as to satisfy the above formula (1). Therefore, according to the present invention, a highly versatile steel material such as SUS430 can be actively used as a solar cell member, and the cost reduction of the solar cell can be expected.
なお、本発明の太陽電池部材用フェライト系ステンレス鋼板について、特に好適な成分組成を示すと次のとおりである。以下の成分を表す「％」は、特に断らない限り質量％を意味するものとする。 In addition, it is as follows when the especially suitable component composition is shown about the ferritic stainless steel plate for solar cell members of this invention. “%” Representing the following components means mass% unless otherwise specified.
C：0.12％以下
Cは、鋼中のCrと結合してステンレス鋼板の耐食性の低下をもたらすため、その含有量が低いほど望ましい。但し、C含有量が0.12％以下であれば耐食性を著しく低下させることはないため、C含有量は0.12％以下が好ましい。より好ましくは0.045％以下である。
C: 0.12% or less
C is combined with Cr in the steel to cause a decrease in the corrosion resistance of the stainless steel plate, so the lower the content, the better. However, if the C content is 0.12% or less, the corrosion resistance will not be remarkably lowered. Therefore, the C content is preferably 0.12% or less. More preferably, it is 0.045% or less.
Si：2.5％以下
Siは、脱酸に用いる元素であるが、過剰に含有されるとステンレス鋼板の延性の低下をもたらす場合がある。したがって、Si含有量は2.5％以下が好ましい。より好ましくは1.0％以下である。
Si: 2.5% or less
Si is an element used for deoxidation, but if contained excessively, the ductility of the stainless steel plate may be lowered. Therefore, the Si content is preferably 2.5% or less. More preferably, it is 1.0% or less.
Mn：1.0％以下
Mnは、鋼中のSと結合してMnSを形成し、ステンレス鋼板の耐食性を低下させる場合がある。したがって、Mn含有量は1.0％以下が好ましい。より好ましくは0.8％以下である。
Mn: 1.0% or less
Mn may combine with S in the steel to form MnS, which may reduce the corrosion resistance of the stainless steel plate. Therefore, the Mn content is preferably 1.0% or less. More preferably, it is 0.8% or less.
S：0.030％以下
上述のとおり、Sは、Mnと結合してMnSを形成し、ステンレス鋼板の耐食性を低下させる。したがって、S含有量は0.030％以下が好ましい。より好ましくは0.008％以下である。
S: 0.030% or less As described above, S combines with Mn to form MnS, thereby reducing the corrosion resistance of the stainless steel plate. Therefore, the S content is preferably 0.030% or less. More preferably, it is 0.008% or less.
P：0.050％以下
Pは、ステンレス鋼板の延性の低下をもたらすため、低いほど望ましいが、その含有量が0.050％以下であれば延性を著しく低下させることはない。したがって、P含有量は0.050％以下が好ましい。より好ましくは0.040％以下である。
P: 0.050% or less
P lowers the ductility of the stainless steel plate, so it is preferable to be lower. However, if its content is 0.050% or less, the ductility is not significantly reduced. Therefore, the P content is preferably 0.050% or less. More preferably, it is 0.040% or less.
Cr：14％以上18％以下
先述のとおり、Crはステンレス鋼板の耐食性を確保するうえで必須の元素であり、本発明ではCｒ含有量を14％以上18％以下とする。好ましくは15％以上17％以下である。
Cr: 14% or more and 18% or less As described above, Cr is an essential element for securing the corrosion resistance of the stainless steel sheet, and in the present invention, the Cr content is set to 14% or more and 18% or less. Preferably they are 15% or more and 17% or less.
N：0.06％以下
Nは、鋼中のCrと結合して、ステンレス鋼板の耐食性の低下をもたらす。そのため、N含有量は低いほど望ましいが、0.06％以下であれば耐食性を著しく低下させることはない。したがって、N含有量は0.06％以下が好ましい。より好ましくは0.015％以下である。
N: 0.06% or less
N combines with Cr in the steel to cause a reduction in the corrosion resistance of the stainless steel plate. Therefore, the lower the N content, the better. However, if it is 0.06% or less, the corrosion resistance will not be significantly reduced. Therefore, the N content is preferably 0.06% or less. More preferably, it is 0.015% or less.
以上が本発明の太陽電池部材用フェライト系ステンレス鋼板の特に好適な基本成分であるが、本発明では上記基本成分に加えて、必要に応じて次の元素を適宜含有させることができる。 The above is a particularly preferable basic component of the ferritic stainless steel sheet for solar cell members of the present invention. In the present invention, the following elements can be appropriately contained as required in addition to the above basic components.
Al：0.20％以下
Alは、脱酸に用いられる元素であり、脱酸効果を得るためにはAl含有量を0.001％以上とすることが好ましい。但し、Al含有量が過剰になると、ステンレス鋼板の延性の低下をもたらす場合がある。したがって、Al含有量は0.20％以下が好ましい。より好ましくは0.15％以下である。
Al: 0.20% or less
Al is an element used for deoxidation, and in order to obtain a deoxidation effect, the Al content is preferably 0.001% or more. However, when the Al content is excessive, the ductility of the stainless steel plate may be reduced. Therefore, the Al content is preferably 0.20% or less. More preferably, it is 0.15% or less.
なお、残部はFeおよび不可避的不純物である。不可避的不純物のうち、O（酸素）の含有量は、0.02％以下であることが好ましい。 The balance is Fe and inevitable impurities. Among inevitable impurities, the content of O (oxygen) is preferably 0.02% or less.
本発明の太陽電池部材用フェライト系ステンレス鋼板は、太陽電池セルの基板や、太陽電池モジュールのバックシート等、太陽電池を構成する部品の素材に適用されるものであることから、その板厚は20μm以上400μm以下とすることが好ましい。特に、CIGS系太陽電池をはじめとする薄膜系太陽電池セルの基板や薄膜系太陽電池モジュールのバックシートに適用する場合には、板厚を20μm以上120μm以下とすることが好ましい。また、30μm以上80μm以下とすることがより好ましい。 Since the ferritic stainless steel sheet for solar cell members of the present invention is applied to a material for components constituting a solar battery, such as a substrate of a solar battery cell or a back sheet of a solar battery module, its thickness is The thickness is preferably 20 μm or more and 400 μm or less. In particular, when applied to substrates of thin film solar cells such as CIGS solar cells and back sheets of thin film solar cell modules, the plate thickness is preferably 20 μm or more and 120 μm or less. Further, it is more preferably 30 μm or more and 80 μm or less.
次に、本発明の太陽電池部材用フェライト系ステンレス鋼板の製造方法について説明する。
本発明の太陽電池部材用フェライト系ステンレス鋼板の製造方法は、質量％でCr：14％以上18％以下を含有するフェライト系ステンレス鋼板に、最終の冷間圧延を施した後、露点−70℃以上−40℃以下に調整した不活性ガス雰囲気中において、580℃以上720℃以下の温度域に加熱し、該温度域における滞留時間を5秒以上とする熱処理を施すことを特徴とする。
Next, the manufacturing method of the ferritic stainless steel plate for solar cell members of this invention is demonstrated.
The method for producing a ferritic stainless steel sheet for solar cell members according to the present invention comprises a ferritic stainless steel sheet containing Cr: 14% or more and 18% or less by mass%, and after the final cold rolling, a dew point of -70 ° C. In an inert gas atmosphere adjusted to −40 ° C. or lower, heating is performed in a temperature range of 580 ° C. or higher and 720 ° C. or lower, and heat treatment is performed so that the residence time in the temperature range is 5 seconds or longer.
本発明の製造方法で用いるフェライト系ステンレス鋼板は、質量％でCr：14％以上18％以下を含有するフェライト系ステンレス鋼板である以上その種類は問わない。例えば、前記の好適な成分組成を有するSUS430のフェライト系ステンレス鋼板を用いることもできるし、高強度化を目的としてNb等を添加したフェライト系ステンレス鋼板を用いてもよい。 The ferritic stainless steel plate used in the production method of the present invention is not limited as long as it is a ferritic stainless steel plate containing Cr: 14% to 18% by mass. For example, a SUS430 ferritic stainless steel plate having the above-mentioned preferred component composition may be used, or a ferritic stainless steel plate to which Nb or the like is added may be used for the purpose of increasing the strength.
また、これらのフェライト系ステンレス鋼板（熱処理を施す前のステンレス鋼板）の製造方法については、その製造条件等に特段の制限はなく、従来公知の方法に従えばよい。すなわち、連続鋳造法や、造塊−分塊圧延法、薄スラブ連鋳法等、公知の鋳造方法により鋳造されたスラブに、熱間圧延を施して熱延板とし、該熱延板に、必要に応じて酸洗、焼鈍を施したのち、冷間圧延（圧下率：50％以上90％以下程度）を施すことにより製造され、最終の冷間圧延までの製造方法は特に限定されない。 Moreover, about the manufacturing method of these ferritic stainless steel plates (stainless steel plate before heat-processing), there are no special restrictions in the manufacturing conditions etc., What is necessary is just to follow a conventionally well-known method. That is, a slab cast by a known casting method such as a continuous casting method, an ingot-bundling rolling method, a thin slab continuous casting method, etc. is hot-rolled into a hot-rolled plate, After performing pickling and annealing as necessary, it is manufactured by cold rolling (rolling ratio: about 50% or more and about 90% or less), and the manufacturing method until the final cold rolling is not particularly limited.
なお、最終の冷間圧延後のフェライト系ステンレス鋼板の板厚は、20μm以上400μm以下とすることが好ましい。また、太陽電池部材用フェライト系ステンレス鋼板を薄膜系太陽電池セルの基板や薄膜系太陽電池モジュールのバックシートに適用する場合には、板厚を20μm以上120μm以下とすることが好ましい。また、30μm以上80μm以下とすることがより好ましい。 The thickness of the ferritic stainless steel sheet after the final cold rolling is preferably 20 μm or more and 400 μm or less. Moreover, when applying the ferritic stainless steel plate for solar cell members to a substrate of a thin film solar cell or a back sheet of a thin film solar cell module, the plate thickness is preferably 20 μm or more and 120 μm or less. Further, it is more preferably 30 μm or more and 80 μm or less.
本発明では、上記のようにして得られた冷間圧延後のフェライト系ステンレス鋼板に、580℃以上720℃以下の温度域に加熱する熱処理を施す。この熱処理は、ステンレス鋼板表層の過度の酸化を抑制するために、不活性ガス雰囲気中で行う。不活性ガスの種類は特に限定されず、窒素ガス、水素ガス、アルゴンガス、アンモニア分解ガス（75体積％水素と25体積％窒素の混合ガス）、HNガス（5体積％水素と95体積％窒素の混合ガス）などの還元性あるいは不活性ガスが例示される。 In the present invention, the ferritic stainless steel sheet after cold rolling obtained as described above is subjected to a heat treatment for heating to a temperature range of 580 ° C. or more and 720 ° C. or less. This heat treatment is performed in an inert gas atmosphere in order to suppress excessive oxidation of the surface layer of the stainless steel plate. The type of the inert gas is not particularly limited, and nitrogen gas, hydrogen gas, argon gas, ammonia decomposition gas (mixed gas of 75 volume% hydrogen and 25 volume% nitrogen), HN gas (5 volume% hydrogen and 95 volume% nitrogen) And reducing or inert gases such as mixed gas).
上記熱処理をステンレス鋼板に施すことにより、冷間圧延時に導入された加工ひずみが低減する結果、太陽電池セル製造時の高温プロレスで問題とされていたステンレス鋼板の変形を抑制することができる。
しかしながら、上記熱処理では、必ずしも前記(1)式を満足して太陽電池モジュールの長時間使用に耐え得る十分な耐食性を備えたフェライト系ステンレス鋼板は得られない。
フェライト系ステンレス鋼板表層の酸化皮膜中Cr濃度と、酸化皮膜直下のCr濃度を、前記(1)式を満足するように制御し、所望の耐食性を付与するためには、上記熱処理を施す際に雰囲気ガスの露点と熱処理時間を最適化することが必須となる。
By applying the heat treatment to the stainless steel plate, the processing strain introduced at the time of cold rolling is reduced. As a result, deformation of the stainless steel plate, which has been a problem in high temperature professional wrestling at the time of solar cell manufacturing, can be suppressed.
However, in the above heat treatment, a ferritic stainless steel sheet having sufficient corrosion resistance that can withstand long-term use of the solar cell module that satisfies the formula (1) cannot be obtained.
In order to provide the desired corrosion resistance by controlling the Cr concentration in the oxide film on the surface of the ferritic stainless steel sheet and the Cr concentration immediately below the oxide film so as to satisfy the above formula (1), the above heat treatment is performed. It is essential to optimize the dew point of the atmospheric gas and the heat treatment time.
露点：−40℃以下−70℃以上
雰囲気ガスの露点が−40℃を超えると、熱処理炉内の酸素分圧が上昇して、フェライト系ステンレス鋼板中に含有されるCrが過度に酸化され易くなり、耐食性が劣化する。一方、雰囲気ガスの露点が−70℃を下回ると、露点を安定して制御することが困難となる。したがって、雰囲気ガスの露点を−40℃以下−70℃以上とすることが極めて重要である。なお、好ましくは−50℃以下−70℃以上である。
Dew point: -40 ° C or lower -70 ° C or higher If the dew point of the atmospheric gas exceeds -40 ° C, the oxygen partial pressure in the heat treatment furnace rises and Cr contained in the ferritic stainless steel sheet is easily oxidized. As a result, the corrosion resistance deteriorates. On the other hand, when the dew point of the atmospheric gas is lower than -70 ° C, it becomes difficult to stably control the dew point. Therefore, it is extremely important that the dew point of the atmospheric gas is −40 ° C. or lower and −70 ° C. or higher. The temperature is preferably −50 ° C. or lower and −70 ° C. or higher.
580℃以上720℃以下の温度域における滞留時間：5秒以上
フェライト系ステンレス鋼板を高温に加熱すると、鋼板表層にCrの酸化皮膜が形成される。そして、この酸化皮膜の形成に伴い、酸化皮膜直下にはCr濃度が低下した領域が形成される。ここで、580℃以上720℃以下の温度域における滞留時間が5秒未満であると、鋼板母材からのCrの拡散が間に合わず、酸化皮膜直下のCr濃度が低下するうえ、酸化皮膜中にも十分なCr量を取り込むことができない。すなわち、上記滞留時間が5秒未満であると、Cr濃度を前記(1)式を満足するように制御することができず、フェライト系ステンレス鋼板の耐食性が劣化する。
Residence time in a temperature range of 580 ° C. or more and 720 ° C. or less: 5 seconds or more When a ferritic stainless steel plate is heated to a high temperature, a Cr oxide film is formed on the surface layer of the steel plate. Along with the formation of this oxide film, a region having a reduced Cr concentration is formed immediately below the oxide film. Here, if the residence time in the temperature range of 580 ° C. or more and 720 ° C. or less is less than 5 seconds, the diffusion of Cr from the steel plate base material will not be in time, and the Cr concentration immediately below the oxide film will decrease, and in the oxide film However, a sufficient amount of Cr cannot be taken in. That is, if the residence time is less than 5 seconds, the Cr concentration cannot be controlled so as to satisfy the formula (1), and the corrosion resistance of the ferritic stainless steel sheet is deteriorated.
以上の理由により、本発明では、580℃以上720℃以下の温度域における滞留時間を5秒以上とする必要がある。なお、上記滞留時間の上限に特に制限はないが、上記滞留時間が長くなり過ぎるとステンレス鋼板が変形するおそれがあるので、10分以下とすることが好ましい。また、3分以下とすることがより好ましく、30秒以下とすることがより一層好ましい。 For the above reasons, in the present invention, the residence time in the temperature range from 580 ° C. to 720 ° C. needs to be 5 seconds or more. In addition, there is no restriction | limiting in particular in the upper limit of the said residence time, However, Since there exists a possibility that a stainless steel plate may deform | transform if the said residence time becomes long too much, it is preferable to set it as 10 minutes or less. Further, it is more preferably 3 minutes or less, and even more preferably 30 seconds or less.
なお、先述のとおり、不活性ガスの種類は限定されないが、窒素ガスと水素ガスの混合ガスを使用することが好ましい。また、その混合比率は、水素を75±5体積％（残部は窒素）とすることが好ましい。このような混合ガスを用いると、フェライト系ステンレス鋼板の耐食性がより一層向上する。 As described above, the type of inert gas is not limited, but it is preferable to use a mixed gas of nitrogen gas and hydrogen gas. The mixing ratio is preferably 75 ± 5% by volume of hydrogen (the balance being nitrogen). When such a mixed gas is used, the corrosion resistance of the ferritic stainless steel sheet is further improved.
太陽電池製造時や太陽電池使用時において、太陽電池基板から光吸収層が剥離し易くなると、太陽電池の生産性や光電変換効率の低下を招く。したがって、太陽電池の基板には、太陽電池セル製造時の高温プロセスにおいて、光吸収層が基板から剥離しないことが要求される。また、太陽電池セルや太陽電池モジュールを構成する部品（基板、バックシート等）には、優れた耐食性が要求される。そこで、これらの要求特性に鑑み、太陽電池部材用フェライト系ステンレス鋼板の試料を作製し、鋼板表層部におけるCr濃度を測定するとともに、上記の特性を評価するための各種試験を実施した。試料の作製方法、Cr濃度の測定方法、各種試験・評価方法は次のとおりである。 If the light absorption layer is easily peeled from the solar cell substrate during solar cell production or when the solar cell is used, productivity of the solar cell and photoelectric conversion efficiency are reduced. Therefore, it is required for the substrate of the solar battery that the light absorption layer does not peel from the substrate in a high-temperature process when manufacturing the solar battery cell. Moreover, the components (a board | substrate, a back sheet, etc.) which comprise a photovoltaic cell or a photovoltaic module are required to have excellent corrosion resistance. In view of these required characteristics, a sample of a ferritic stainless steel sheet for solar cell members was prepared, and the Cr concentration in the surface layer portion of the steel sheet was measured, and various tests for evaluating the above characteristics were performed. The sample preparation method, Cr concentration measurement method, and various tests and evaluation methods are as follows.
（１）試料の作製方法
表１に示す化学成分を有する板厚：0.3mmのフェライト系ステンレス冷延鋼板に、光輝焼鈍を施したのち、20段ゼンジミア冷間圧延機により冷間圧延を施し、板厚：0.05mmの鋼板とした。
上記により得られた板厚：0.05mmの鋼板に、脱脂後、不活性ガス雰囲気中で加熱する熱処理を施し、太陽電池部材用フェライト系ステンレス鋼板の試料を製造した。表２に、上記熱処理に用いた不活性ガスの種類、雰囲気ガスの露点、鋼板の最高到達温度、580℃以上720℃以下の温度域における鋼板の滞留時間を示す。
なお、一部の鋼板については、熱処理を施さず、冷間圧延ままの鋼板（板厚：0.05mm）を太陽電池部材用フェライト系ステンレス鋼板の試料とした。
(1) Sample preparation method Thickness of 0.3 mm ferritic stainless steel cold rolled steel sheet with chemical components shown in Table 1 was bright annealed and then cold rolled with a 20-stage Sendzimir cold rolling mill. Plate thickness: 0.05 mm steel plate.
A steel plate having a thickness of 0.05 mm obtained as described above was subjected to heat treatment after degreasing and heated in an inert gas atmosphere to produce a ferritic stainless steel plate sample for solar cell members. Table 2 shows the type of inert gas used in the heat treatment, the dew point of the atmospheric gas, the maximum temperature reached by the steel sheet, and the residence time of the steel sheet in the temperature range of 580 ° C to 720 ° C.
In addition, about some steel plates, it did not heat-process and the steel plate (plate thickness: 0.05mm) as it was cold-rolled was used as the sample of the ferritic stainless steel plate for solar cell members.
（２）鋼板表層Cr濃度の測定
上記（１）により作製された各種試料について、試料の最表層部に形成された酸化皮膜中のCr濃度および酸化皮膜直下のCr濃度を求めた。
酸化皮膜中のCr濃度および酸化皮膜直下のCr濃度は、AES測定とイオンスパッタリングとを併用し、鋼板（試料）の板厚深さ方向のCr濃度分布（最表面から深さ90nmまでの領域におけるCr濃度分布）を測定することにより求めた。
AES測定には走査型オージェ電子分光分析装置（PHI SAM-660）を用い、AES測定における電子銃の加速電圧は5kV、試料電流量は0.1μAとし、イオン銃の加速電圧は3kV、スパッタレートは3nm/min（SiO2実測値）とし、板厚方向の膜厚に換算した。
得られたオージェ電子スペクトルから、O（酸素）、Fe、Cr、Mn、Si各元素のオージェピーク高さ（微分スペクトルでのピーク間の高さ）を読み取り、各元素のオージェピークに対する相対感度係数とから、Crの相対濃度を算出した。
鋼板（試料）の最表面から深さ90nmまでの領域（但し、酸素濃度が1mass％以上である領域）におけるCr濃度の最高値を「酸化皮膜中のCr濃度」として求めた。一方、鋼板（試料）の最表面から深さ90nmまでの領域のうち前記最高値が測定された位置よりも板厚中央側の領域におけるCr濃度の最小値を「酸化皮膜直下のCr濃度」として求めた。
(2) Measurement of steel sheet surface layer Cr concentration For the various samples prepared in the above (1), the Cr concentration in the oxide film formed on the outermost layer part of the sample and the Cr concentration directly under the oxide film were determined.
The Cr concentration in the oxide film and the Cr concentration immediately below the oxide film are obtained by using both AES measurement and ion sputtering, and the Cr concentration distribution in the thickness direction of the steel sheet (sample) (in the region from the outermost surface to a depth of 90 nm) (Cr concentration distribution) was measured.
Scanning Auger Electron Spectrometer (PHI SAM-660) is used for AES measurement. In AES measurement, the acceleration voltage of the electron gun is 5 kV, the sample current is 0.1 μA, the acceleration voltage of the ion gun is 3 kV, and the sputtering rate is It was set to 3 nm / min (measured value of SiO 2 ) and converted to the film thickness in the plate thickness direction.
From the obtained Auger electron spectrum, read the Auger peak height (height between peaks in the differential spectrum) of each element of O (oxygen), Fe, Cr, Mn, and Si, and the relative sensitivity coefficient for the Auger peak of each element From these, the relative concentration of Cr was calculated.
The maximum value of Cr concentration in the region from the outermost surface of the steel plate (sample) to a depth of 90 nm (where the oxygen concentration is 1 mass% or more) was determined as “Cr concentration in oxide film”. On the other hand, the minimum value of Cr concentration in the region on the center side of the plate thickness from the position where the maximum value was measured in the region from the outermost surface of the steel plate (sample) to the depth of 90 nm is referred to as “Cr concentration directly under the oxide film” Asked.
（３）耐食性試験
上記（１）により作製された各種試料について、太陽電池モジュールの環境劣化、耐久性評価試験として一般に用いられているIEC61646およびJIS C 8917の規定に準拠した高温高湿試験方法を実施し、耐食性を評価した。
具体的には、端面を耐水テープでシールした試料を、温度：85℃、湿度：85％の恒温恒湿槽内に1000時間保持する高温高湿試験を実施した。そして、試験後の試料表面の発銹状態を目視観察することにより耐食性を評価した。発銹が観察されない場合を耐食性良好（○）と評価し、発銹が観察される場合を耐食性不良（×）と評価した。
(3) Corrosion resistance test A high temperature and high humidity test method based on the IEC61646 and JIS C 8917 standards generally used for environmental degradation and durability evaluation tests of solar cell modules for various samples prepared in (1) above. Implemented and evaluated the corrosion resistance.
Specifically, a high-temperature and high-humidity test was performed in which a sample whose end face was sealed with water-resistant tape was held in a constant temperature and humidity chamber at a temperature of 85 ° C. and a humidity of 85% for 1000 hours. Then, the corrosion resistance was evaluated by visually observing the rusting state of the sample surface after the test. The case where no wrinkle was observed was evaluated as good corrosion resistance (O), and the case where wrinkle was observed was evaluated as poor corrosion resistance (x).
（４）太陽電池モジュール製造時の高温プロセスにおける光吸収層の基板からの耐剥離性試験
上記（１）により作製された各種試料を基板とし、該基板上に、スパッタリング法を用いてMo層からなる裏面電極（厚さ1μm）を成膜した。次いで、Mo層からなる裏面電極上に、多元蒸着法を用いてCu(In1-XGaX)Se2からなる光吸収層（厚さ2μm）を成膜した。なお、光吸収層の成膜温度は650℃とした。
光吸収層を成膜した直後の試料を目視および光学顕微鏡（倍率：1000倍）を用いて観察し、裏面電極および光吸収層の剥離の有無を確認した。基板である試料から裏面電極および光吸収層が剥離していない場合を耐剥離性良好（○）と評価し、基板である試料から裏面電極および光吸収層が剥離している場合を耐剥離性不良（×）と評価した。
(4) Peeling resistance test of light absorption layer from substrate in high-temperature process at the time of manufacturing solar cell module Various samples prepared by (1) above are used as a substrate, and a Mo layer is formed on the substrate by sputtering. A back electrode (thickness: 1 μm) was formed. Next, a light absorption layer (thickness: 2 μm) made of Cu (In 1-X Ga x ) Se 2 was formed on the back electrode made of the Mo layer by multi-source deposition. The film forming temperature of the light absorption layer was 650 ° C.
The sample immediately after forming the light absorption layer was observed visually and using an optical microscope (magnification: 1000 times), and the presence or absence of peeling of the back electrode and the light absorption layer was confirmed. When the back electrode and the light absorption layer are not peeled from the substrate sample, the peel resistance is evaluated as good (◯), and when the back electrode and the light absorption layer are peeled from the substrate sample, the peel resistance is evaluated. It was evaluated as defective (x).
得られた結果を表３に示す。また、上記（２）により求めた各種試料の酸化皮膜中のCr濃度および酸化皮膜直下のCr濃度と、上記（３）による各種試料の耐食性評価との関係を、図４に示す。 The obtained results are shown in Table 3. FIG. 4 shows the relationship between the Cr concentration in the oxide film of the various samples obtained in (2) and the Cr concentration immediately below the oxide film, and the corrosion resistance evaluation of the various samples in (3).
表３および図４より、次の事項が明らかである。
（ａ）熱処理を施さない冷間圧延ままの鋼板であるNo.0の試料では、該試料を基板として光吸収層を成膜した場合、基板から光吸収層が剥離した。これに対し、冷間圧延後の鋼板に熱処理を施したNo.1〜16の試料では、それぞれの試料を基板として光吸収層を成膜した場合に、光吸収層の基板からの剥離は認められない。
（ｂ）冷間圧延後の鋼板に熱処理を施した試料のうち、露点−40〜−70℃の雰囲気ガス中、580℃以上720℃以下の温度域での滞留時間を5秒以上とする熱処理を施したNo.2〜4、およびNo.7〜16の試料は、前記(1)式を満足し、優れた耐食性を有する。一方、580℃以上720℃以下の温度域での滞留時間が4秒以下であるNo.1、5、6の試料は、(1)式を満足せず、良好な耐食性が得られていない。
From Table 3 and FIG. 4, the following matters are clear.
(A) In the sample No. 0 that is a cold-rolled steel sheet not subjected to heat treatment, when the light absorption layer was formed using the sample as a substrate, the light absorption layer was peeled off from the substrate. On the other hand, in the samples Nos. 1 to 16 where the steel sheets after cold rolling were heat-treated, when the light absorption layer was formed using each sample as a substrate, peeling of the light absorption layer from the substrate was recognized. I can't.
(B) Among the samples subjected to the heat treatment on the steel sheet after the cold rolling, the heat treatment in which the residence time in the temperature range of 580 ° C. or more and 720 ° C. or less is 5 seconds or more in the atmospheric gas having a dew point of −40 to −70 ° C. The samples No. 2 to 4 and No. 7 to 16 subjected to No. 2 satisfy the above formula (1) and have excellent corrosion resistance. On the other hand, the samples No. 1, 5, and 6 in which the residence time in the temperature range of 580 ° C. or more and 720 ° C. or less is 4 seconds or less do not satisfy the formula (1), and good corrosion resistance is not obtained.
なお、上記実施例において試料の耐剥離性を評価する際、各種試料を基板としてスパッタリング法により裏面電極を成膜し、多元蒸着法により光吸収層を成膜した。しかし、本発明においては、これら以外の方法により裏面電極や光吸収層を成膜した場合であっても上記実施例（発明例）と同様の効果を発現する。 When evaluating the peel resistance of the samples in the above examples, a back electrode was formed by sputtering using various samples as a substrate, and a light absorption layer was formed by multi-source deposition. However, in the present invention, even when the back electrode or the light absorption layer is formed by a method other than these, the same effects as in the above-described embodiment (invention example) are exhibited.
本発明によれば、安価で、大量生産が可能なフェライト系ステンレス鋼板を太陽電池基板に適用した場合であっても、基板上に形成される光吸収層の剥離を抑制することができる。また、本発明によれば、フェライト系ステンレス鋼板に高温熱処理を施した場合であっても、ステンレス鋼が有する優れた耐食性を維持することができるため、安価で、大量生産が可能なフェライト系ステンレス鋼板を太陽電池の基板やバックシートに適用することができる。それゆえ、太陽電池モジュールの製造コスト削減に寄与するだけでなく、光電変換効率の向上も期待され、産業上格段の効果を奏する。 ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where the ferritic stainless steel plate which is cheap and can be mass-produced is applied to a solar cell substrate, peeling of the light absorption layer formed on a board | substrate can be suppressed. In addition, according to the present invention, even when a high temperature heat treatment is performed on a ferritic stainless steel sheet, the excellent corrosion resistance of the stainless steel can be maintained, so that it is inexpensive and can be mass-produced. A steel plate can be applied to a solar cell substrate or backsheet. Therefore, not only contributes to the reduction of the manufacturing cost of the solar cell module, but also an improvement in photoelectric conversion efficiency is expected, and there is a remarkable industrial effect.
1 … 基板
2 … 裏面電極層
3 … 光吸収層
4a … バッファ層
4b … 高抵抗バッファ層
5 … 透明導電層
6 … グリッド電極
10 … 薄膜系太陽電池セル
20 … バリアフィルム
30 … バックシート
40 … コネクタ
50 … 樹脂
100 … 薄膜系太陽電池モジュール
1… Board
2… Back electrode layer
3… Light absorption layer
4a… Buffer layer
4b… High resistance buffer layer
5… Transparent conductive layer
6… Grid electrode
10… Thin film solar cells
20… Barrier film
30… Back seat
40… Connector
50… Resin
100… Thin film solar cell module
Claims (2)
記
（酸化皮膜中のCr濃度（質量％））＋3×（酸化皮膜直下のCr濃度（質量％））
＞62（質量％）… (1) Cr containing 14% or more and 18% or less by mass%, and the Cr concentration in the oxide film on the surface layer of the steel sheet and the Cr concentration immediately below the oxide film satisfy the following formula (1): Ferritic stainless steel sheet for battery members.
(Cr concentration in oxide film (mass%)) + 3 x (Cr concentration directly under oxide film (mass%))
> 62 (mass%) ... (1)
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| JP7527819B2 (en) | 2020-03-23 | 2024-08-05 | 日鉄ステンレス株式会社 | Ferritic stainless steel sheet, its manufacturing method and substrate |
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| JP7527819B2 (en) | 2020-03-23 | 2024-08-05 | 日鉄ステンレス株式会社 | Ferritic stainless steel sheet, its manufacturing method and substrate |
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