JP6447493B2 - バリア層形成用組成物、バリア層付き半導体基板、太陽電池用基板の製造方法及び太陽電池素子の製造方法 - Google Patents
バリア層形成用組成物、バリア層付き半導体基板、太陽電池用基板の製造方法及び太陽電池素子の製造方法 Download PDFInfo
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Description
まず、光閉じ込め効果を促して高効率化を図るよう、受光面にテクスチャー構造を形成したp型シリコン基板を準備し、続いてオキシ塩化リン(POCl3)、窒素及び酸素の混合ガス雰囲気において800℃〜900℃で数十分の処理を行って、p型シリコン基板の表面に一様にn型拡散層を形成する。次いで、受光面に銀(Ag)等の電極ペースト、裏面側にアルミニウム(Al)等の電極ペーストを塗布した後、熱処理(焼成)することにより、太陽電池素子を得ていた。
また、特開2011−119341号公報に記載の、SiO2前駆体を含有するマスキングペーストを用いる方法では、0.1mPa・s〜30mPa・sの低粘度のペーストを想定しており、スクリーン印刷法での塗布が難しく、厚いマスク層を形成することが困難であった。そのため、この方法の場合、十分にドーパントの拡散を防止できないという問題があった。
<1> 下記一般式1で表される少なくとも一種のアルコキシシラン、ポリシラザン、及び前記アルコキシシランを加水分解し縮合重合させたシロキサン樹脂からなる群より選択される少なくとも一種のケイ素含有化合物と、有機バインダと、分散媒と、を含有し、25℃における粘度が1Pa・s〜100Pa・sである、バリア層形成用組成物。
前記半導体基板上に付与された、前記<1>〜<9>のいずれか一項に記載のバリア層形成用組成物の乾燥体であるバリア層と、
を有するバリア層付き半導体基板。
前記半導体基板上の前記バリア層が形成されていない部分に、ドナー元素又はアクセプター元素を拡散して、前記半導体基板内に部分的に拡散層を形成する工程と、を含む、太陽電池用基板の製造方法。
尚、本発明におけるバリア層は、半導体基板を平面図として観察したときに、全面に形成される場合のみならず、一部に形成される場合をも包含される。
本発明のバリア層形成用組成物は、下記一般式1で表される少なくとも一種のアルコキシシラン、ポリシラザン、及び前記アルコキシシランを加水分解し縮合重合させたシロキサン樹脂からなる群より選択される少なくとも一種のケイ素含有化合物と、有機バインダと、分散媒と、を含有する。そして、本発明のバリア層形成用組成物は、25℃における粘度が1Pa・s〜100Pa・sである。
SinOn−1(OC2H5)2(n+1) 一般式3
本発明のバリア層形成用組成物は分散媒を含有する。分散媒とは、組成物中において特定ケイ素含有化合物又は有機バインダを分散又は溶解させる媒体である。
本発明のバリア層形成用組成物は、有機バインダを含有する。有機バインダを含有することで、粘度を調節することができ、また、スクリーン印刷時の印刷線のダレを抑制することができる。
バリア層形成用組成物は、特定ケイ素含有化合物と、有機バインダと、分散媒と、に加え、必要に応じて、その他の成分として、増粘剤、湿潤剤、界面活性剤、無機粉末、チキソ剤等の各種添加剤を含有してもよい。
前述の有機バインダがチキソ剤の役割を兼ねていてもよく、このような材料としてエチルセルロースを挙げることができる。
本明細書において粘度とは、EMD型回転粘度計を25℃で1分間、所定の回毎分(min―1、1/60sec−1)で回転させたときの測定値に、所定の換算係数を乗じた値と定義する。換算係数は、回転数及び用いたコーンの種類によって異なる。本明細書では、25±1℃に保たれたバリア層形成用組成物について、コーン角度3゜、コーン半径14mmのコーンロータを装着したEMD型回転粘度計を用いて粘度が測定される。
本発明のバリア層付き半導体基板は、半導体基板と、前記半導体基板上に付与された前記バリア層形成用組成物の乾燥体であるバリア層と、を有する。半導体基板上にバリア層が設けられていることで、バリア層が設けられた領域以外の領域に選択的に不純物拡散層を形成することができる。
本発明の太陽電池用基板の製造方法は、前記バリア層形成用組成物を半導体基板上に付与してパターン状のバリア層を形成する工程と、前記半導体基板上の前記バリア層が形成されていない部分に、ドナー元素又はアクセプター元素を拡散して、前記半導体基板内に部分的に拡散層を形成する工程と、を含む。
また、本発明の太陽電池素子の製造方法は、上記製造方法により得られる太陽電池用基板の拡散層上に、電極を形成する工程を含む。
裏面電極型以外のその他の形式としては、選択エミッタ型及び両面受光型を例示することができる。選択エミッタ型の太陽電池用基板では、受光面側の電極直下に他の領域よりもドーパント濃度の高い拡散層が形成されている。この高濃度の拡散層の領域を形成するのに、本発明のバリア層形成用組成物を用いることができる。また、両面受光型の太陽電池素子では、両面に電極としてフィンガーバー及びバスバーが形成され、半導体基板の一方の面にはn+型拡散層、他方の面にはp+型拡散層が形成されている。このn+型拡散層及びp+型拡散層を位置選択的に形成するために、本発明のバリア層形成用組成物を用いることができる。
詳細には、インゴットからスライスした際に発生するシリコン基板表面のダメージ層を20質量%水酸化ナトリウム水溶液で除去する。次いで、1質量%水酸化ナトリウム水溶液と10質量%イソプロピルアルコールとを含む水溶液によりシリコン基板をエッチングし、n型半導体基板10にテクスチャー構造を形成する(図中ではテクスチャー構造の記載を省略する)。太陽電池素子は、n型半導体基板10の受光面側にテクスチャー構造を形成することにより、光閉じ込め効果が促され、高効率化が図られる。
太陽電池は、前記太陽電池素子の少なくとも一種を含み、太陽電池素子の電極上に配線材料が配置されて構成される。太陽電池は更に必要に応じて、配線材料を介して複数の太陽電池素子が連結され、更に封止材で封止されていてもよい。
前記配線材料及び封止材としては特に制限されず、当業界で通常用いられているものから適宜選択することができる。
(バリア層形成用組成物11の調製)
テルピネオール(日本テルペン化学株式会社「ターピネオール−LW」)8.5gにエチルセルロース(ダウケミカル社「エトセルSTD200」、(エトセル)は登録商標)1.5gを加え、150℃にて1時間溶解し、15質量%エチルセルロース/テルピネオール溶液を調製した。
エチルシリケート(多摩化学工業株式会社「シリケート40」、SiO2換算量:40%)1.5g(ケイ素化合物はSiO2換算で6質量%)、15質量%エチルセルロース/テルピネオール溶液4.3g(エチルセルロース:6.45質量%)、及びテルピネオール4.2g(テルピネオール:63.55質量%)をプラスチック製容器に入れた。これを自転・公転ミキサ(株式会社シンキー「AR−100」)を用い、10分間、混合し、バリア層形成用組成物11を調製した。
リン酸二水素アンモニウム(和光純薬工業株式会社)の20質量%水溶液を調製し、上澄みの飽和リン酸二水素アンモニウム水溶液をリン拡散液として用いた。
テクスチャー処理したn型シリコン基板(以下、「n型シリコン基板」ともいう)表面上に、スクリーン印刷(MT−320T、マイクロ・テック株式会社)によってバリア層形成用組成物11を塗布し、150℃のホットプレート上で5分間乾燥後、500℃のホットプレートで1分間乾燥させた。これをバリア層付き基板とする。
次いで、別のシリコン基板を用意し、リン拡散液を500min−1でスピンコート(ミカサ株式会社、MS−A100)し、200℃にて乾燥した。これを対向拡散用基板とする。
バリア層形成用組成物を塗布した部分の基板のシート抵抗は、三菱化学株式会社、Loresta−EP MCP−T360型低抵抗率計を用いて四探針法により測定した。バリア層形成用組成物11を塗布した部分のシート抵抗は190Ω/□であった。塗布しない部分のシート抵抗は40Ω/□であった。
表1及び2に示す組成のバリア層形成用組成物を調製し、実施例1と同様にして評価した。結果を表1及び2に示す。尚、表1及び2中に示した材料は、以下の通りである。尚、表中「−」は添加していないことを示す。
メチルシリケート:多摩化学工業株式会社、製品名「Mシリケート51、SiO2換算量:51質量%
ポリシラザン:AZエレクトロニックマテリアルズ社、製品名「NN110」(10質量%ポリシラザン/キシレン溶液)、SiO2換算量:約13.3質量%
ブチルカルビトールアセテート:和光純薬工業株式会社
酸化ケイ素:株式会社高純度化学研究所、製品名酸化ケイ素(平均粒子径:1μm)
Claims (13)
- ポリシラザンを含むケイ素含有化合物と、有機バインダと、分散媒とを含有し、25℃における粘度が1Pa・s〜100Pa・sである、バリア層形成用組成物。
- 前記ケイ素含有化合物の含有率が、SiO2換算で1質量%〜18質量%である、請求項1に記載のバリア層形成用組成物。
- 前記ケイ素含有化合物の含有率が、SiO2換算で5質量%〜16質量%である、請求項1に記載のバリア層形成用組成物。
- 前記ケイ素含有化合物の含有率が、SiO2換算で6質量%〜13質量%である、請求項1に記載のバリア層形成用組成物。
- 前記有機バインダが、セルロース誘導体、アクリル樹脂及びアルキド樹脂からなる群より選択される少なくとも一種を含む、請求項1〜請求項4のいずれか一項に記載のバリア層形成用組成物。
- 前記有機バインダが、エチルセルロースを含む、請求項1〜請求項5のいずれか一項に記載のバリア層形成用組成物。
- 前記分散媒が、水、アルコール溶剤、エーテル溶剤、グリコールモノエーテル溶剤及びテルペン溶剤からなる群より選択される少なくとも一種を含む、請求項1〜請求項6のいずれか一項に記載のバリア層形成用組成物。
- 前記分散媒が、テルピネオール、ブチルカルビトール及びブチルカルビトールアセテートからなる群より選択される少なくとも一種を含む、請求項1〜請求項6のいずれか一項に記載のバリア層形成用組成物。
- 25℃における粘度が、10Pa・s〜80Pa・sである、請求項1〜請求項8のいずれか一項に記載のバリア層形成用組成物。
- 半導体基板と、
前記半導体基板上に付与された、請求項1〜請求項9のいずれか一項に記載のバリア層形成用組成物の乾燥体であるバリア層と、
を有するバリア層付き半導体基板。 - 請求項1〜請求項9のいずれか一項に記載のバリア層形成用組成物を半導体基板上に付与してパターン状のバリア層を形成する工程と、
前記半導体基板上の前記バリア層が形成されていない部分に、ドナー元素又はアクセプター元素を拡散して、前記半導体基板内に部分的に拡散層を形成する工程と、
を含む、太陽電池用基板の製造方法。 - 前記バリア層形成用組成物を前記半導体基板に付与する方法が、スクリーン印刷法である、請求項11に記載の太陽電池用基板の製造方法。
- 請求項11又は請求項12に記載の製造方法により得られる太陽電池用基板の拡散層の上に、電極を形成する工程を含む、太陽電池素子の製造方法。
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WO2014126117A1 (ja) | 2014-08-21 |
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CN104969364A (zh) | 2015-10-07 |
KR20150117644A (ko) | 2015-10-20 |
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