JP5573946B2 - p型拡散層形成組成物、p型拡散層の製造方法、及び太陽電池素子の製造方法 - Google Patents
p型拡散層形成組成物、p型拡散層の製造方法、及び太陽電池素子の製造方法 Download PDFInfo
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- JP5573946B2 JP5573946B2 JP2012511720A JP2012511720A JP5573946B2 JP 5573946 B2 JP5573946 B2 JP 5573946B2 JP 2012511720 A JP2012511720 A JP 2012511720A JP 2012511720 A JP2012511720 A JP 2012511720A JP 5573946 B2 JP5573946 B2 JP 5573946B2
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- diffusion layer
- type diffusion
- forming composition
- layer forming
- ether
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Classifications
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
- H01L21/2251—Diffusion into or out of group IV semiconductors
- H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
- H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
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- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
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- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
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- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
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- H01L31/1864—Annealing
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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、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、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、基板に一様にn型拡散層を形成する。この従来の方法では、混合ガスを用いてリンの拡散を行うため、表面のみならず、側面、裏面にもn型拡散層が形成される。そのため、側面のn型拡散層を除去するためのサイドエッチングを行う。また、裏面のn型拡散層はp+型拡散層へ変換する必要があり、裏面にアルミペーストを印刷し、これを焼成して、n型拡散層をp+型拡散層にするのと同時に、オーミックコンタクトを得ている。
本発明は、以上の従来の問題点に鑑みなされたものであり、シリコン基板を用いた太陽電池素子の製造工程において、シリコン基板中の内部応力、基板の反りの発生を抑制しつつp型拡散層を形成することが可能なp型拡散層形成組成物であって、これにより得られたp型拡散層を有する基板においてキャリアのライフタイムが大きく低下しないp型拡散層形成組成物、p型拡散層の製造方法、及び太陽電池素子の製造方法の提供を課題とする。
<1> アクセプタ元素を含みライフタイムキラー元素の総量が1000ppm以下であるガラス粉末と、分散媒と、を含有するp型拡散層形成組成物であって、p型拡散層形成組成物中におけるライフタイムキラー元素の総量は、1100ppm以下であるp型拡散層形成組成物。
尚、本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
また、本明細書において「〜」は、その前後に記載される数値をそれぞれ最小値および最大値として含む範囲を示すものとする。
さらに本明細書において組成物中の各成分の量について言及する場合、組成物中に各成分に該当する物質が複数存在する場合には、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
ここで、p型拡散層形成組成物とはアクセプタ元素を含有し、例えば、シリコン基板に塗布した後に熱拡散処理(焼成)することでこのアクセプタ元素を熱拡散させてp型拡散層を形成することが可能な材料をいう。本発明のp型拡散層形成組成物を用いることで、p+型拡散層形成工程とオーミックコンタクト形成工程とを分離でき、オーミックコンタクト形成のための電極材の選択肢が広がるとともに、電極の構造の選択肢も広がる。例えば銀等の低抵抗材を電極に用いれば薄い膜厚で低抵抗が達成できる。また、電極も全面に形成する必要はなく、櫛型等の形状のように部分的に形成してもよい。以上のように薄膜あるいは櫛型形状等の部分的形状にすることで、シリコン基板中の内部応力、基板の反りの発生を抑えながらp型拡散層を形成することが可能となる。
さらにガラス粉末中のアクセプタ成分は焼成中でも揮散しにくいため、揮散ガスの発生によって所望の領域以外にまでp型拡散層が形成されるということが抑制される。この理由として、アクセプタ成分がガラス粉末中の元素と結合しているか、又はガラス中に取り込まれているため、揮散しにくいものと考えられる。
アクセプタ元素とは、シリコン基板中にドーピングさせることによってp型拡散層を形成することが可能な元素である。アクセプタ元素としては第13族の元素が使用でき、例えばB(ほう素)、Al(アルミニウム)及びGa(ガリウム)等が挙げられる。
ガラス成分物質としては、SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、V2O5、SnO、ZrO2、MoO3、La2O3、Nb2O5、Ta2O5、Y2O3、TiO2、GeO2、TeO2及びLu2O3等が挙げられ、SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、SnO、ZrO2、及びMoO3から選択される少なくとも1種を用いることが好ましい。
また、Al2O3−B2O3系、Ga2O3−B2O3系等のように、2種類以上のアクセプタ元素含有物質を含むガラス粉末でもよい。
上記では1成分ガラスあるいは2成分を含む複合ガラスを例示したが、B2O3−SiO2−Na2O系、B2O3−SiO2−CeO2系等のように、3成分以上の物質を含むガラス粉末でもよい。
ライフタイムキラー元素として、Fe、Cu,Ni、Mn、Cr、W及びAuが挙げられる。これらの元素量はICP質量分析装置、ICP発光分析装置、原子吸光分析装置で分析できる。また、キャリアのライフタイムはマイクロ波光導電減衰法(μ−PCD法)により測定できる。
ガラス粉末の粒径は、50μm以下であることが望ましい。50μm以下の粒径を有するガラス粉末を用いた場合には、平滑な塗膜が得られやすい。更に、ガラス粉末の粒径は10μm以下であることがより望ましい。なお、下限は特に制限されないが、0.01μm以上であることが好ましい。
ここで、ガラスの粒径は、平均粒子径を表し、レーザー散乱回折法粒度分布測定装置等により測定することができる。
最初に原料を秤量し、るつぼに充填する。るつぼの材質としては白金、白金−ロジウム、イリジウム、アルミナ、石英、炭素等が挙げられるが、溶融温度、雰囲気、溶融物質との反応性等を考慮して適宜選ばれる。
次に、電気炉でガラス組成に応じた温度で加熱し融液とする。このとき融液が均一となるよう攪拌することが望ましい。
続いて得られた融液をジルコニア基板やカーボン基板等の上に流し出して融液をガラス化する。
最後にガラスを粉砕し粉末状とする。粉砕にはジェットミル、ビーズミル、ボールミル等公知の方法が適用できる。
分散媒とは、組成物中において上記ガラス粉末を分散させる媒体である。具体的に分散媒としては、バインダーや溶剤などが採用される。
p型拡散層形成組成物とした場合、基板への塗布性の観点から、α−テルピネオール、ジエチレングリコールモノ−n−ブチルエーテル、酢酸2−(2−ブトキシエトキシ)エチルが好ましい溶剤として挙げられる。
p型拡散層形成組成物の粘度は、塗布性を考慮して、10mPa・S以上1000000mPa・S以下であることが好ましく、50mPa・S以上500000mPa・S以下であることがより好ましい。
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表面のダメージ層を20質量%苛性ソーダで除去する。次いで1質量%苛性ソーダと10質量%イソプロピルアルコールの混合液によりエッチングを行い、テクスチャー構造を形成する。太陽電池素子は、受光面(表面)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。
上記p型拡散層形成組成物の塗布量としては特に制限はない。例えば、ガラス粉末量として0.01g/m2〜100g/m2とすることができ、0.1g/m2〜10g/m2であることが好ましい。
熱拡散処理時間は、p型拡散層形成組成物に含まれるアクセプタ元素の含有率などに応じて適宜選択することができる。例えば、1分間〜60分間とすることができ、5分間〜30分間であることがより好ましい。
この内部応力は、結晶の結晶粒界に損傷を与え、電力損失が大きくなるという課題があった。また、反りは、モジュール工程における太陽電池素子の搬送や、タブ線と呼ばれる銅線との接続において、太陽電池素子を破損させ易くしていた。近年では、スライス加工技術の向上から、シリコン基板の厚みが薄型化されつつあり、更に太陽電池素子が割れ易い傾向にある。
より具体的には、上記混合ガス流量比NH3/SiH4が0.05〜1.0、反応室の圧力が0.1〜2Torr、成膜時の温度が300〜550℃、プラズマの放電のための周波数が100kHz以上の条件下で形成される。
このような表面電極は、例えば、上述の金属ペーストのスクリーン印刷、又は電極材料のメッキ、高真空中における電子ビーム加熱による電極材料の蒸着などの手段により形成することができる。バスバー電極とフィンガー電極とからなる表面電極は受光面側の電極として一般的に用いられていて周知であり、受光面側のバスバー電極及びフィンガー電極の公知の形成手段を適用することができる。
n型拡散層の形成にn型拡散層形成組成物を用いる方法では、まず、p型半導体基板の表面である受光面にn型拡散層形成組成物を塗布し、裏面に本発明のp型拡散層形成組成物を塗布し、600〜1200℃で熱拡散処理する。この熱拡散処理により、表面ではp型半導体基板中へドナー元素が拡散してn型拡散層が形成され、裏面ではアクセプタ元素が拡散してp+型拡散層が形成される。この工程以外は上記方法と同様の工程により、太陽電池素子が作製される。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
粒子形状が略球状で、平均粒子径が3.3μmのSiO2−B2O3系ガラス(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素980ppm)粉末20gとエチルセルロース3g、酢酸2−(2−ブトキシエトキシ)エチル77gとを自動乳鉢混練装置を用いて混合してペースト化し、p型拡散層形成組成物を調製した。
使用したガラス粉末をSiO2−B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素530ppm、略球状、平均粒子径3.8μm)に代えた以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p型拡散層形成組成物を塗布した側の表面のシート抵抗は82Ω/□であり、B(ほう素)が拡散しp型拡散層が形成されていた。裏面のシート抵抗は1000000Ω/□以上で測定不能であり、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは82%であった。更に、基板の反りは発生していなかった。
使用したガラス粉末をSiO2−B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素470ppm、略球状、平均粒子径3.3μm)に代えた以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p型拡散層形成組成物を塗布した側の表面のシート抵抗は78Ω/□であり、B(ほう素)が拡散しp型拡散層が形成されていた。裏面のシート抵抗は1000000Ω/□以上で測定不能であり、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは87%であった。更に、基板の反りは発生していなかった。
使用したガラス粉末をSiO2−B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素120ppm、略球状、平均粒子径3.7μm)に代えた以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p型拡散層形成組成物を塗布した側の表面のシート抵抗は81Ω/□であり、B(ほう素)が拡散しp型拡散層が形成されていた。裏面のシート抵抗は1000000Ω/□以上で測定不能であり、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは91%であった。更に、基板の反りは発生していなかった。
使用したガラス粉末をSiO2−B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素85ppm、略球状、平均粒子径3.5μm)に代えた以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p型拡散層形成組成物を塗布した側の表面のシート抵抗は80Ω/□であり、B(ほう素)が拡散しp型拡散層が形成されていた。裏面のシート抵抗は1000000Ω/□以上で測定不能であり、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは95%であった。更に、基板の反りは発生していなかった。
使用したガラス粉末をSiO2−B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素20ppm、略球状、平均粒子径3.2μm)とした以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p型拡散層形成組成物を塗布した側の表面のシート抵抗は85Ω/□であり、B(ほう素)が拡散しp型拡散層が形成されていた。裏面のシート抵抗は1000000Ω/□以上で測定不能であり、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは98%であった。更に、基板の反りは発生していなかった。
使用したガラス粉末をSiO2−B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素8ppm、略球状、平均粒子径3.5μm)とした以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p型拡散層形成組成物を塗布した側の表面のシート抵抗は81Ω/□であり、B(ほう素)が拡散しp型拡散層が形成されていた。裏面のシート抵抗は1000000Ω/□以上で測定不能であり、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは100%であった。更に、基板の反りは発生していなかった。
粒子形状が略球状で、平均粒子径が3.3μmのSiO2−B2O3系ガラス(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素1180ppm)粉末20gとエチルセルロース3g、酢酸2−(2−ブトキシエトキシ)エチル77gを混合してペースト化し、p型拡散層形成組成物を調製した。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
Claims (6)
- アクセプタ元素を含み、ライフタイムキラー元素の総量が1000ppm以下であるガラス粉末と、分散媒と、を含有するp型拡散層形成組成物であって、p型拡散層形成組成物中におけるライフタイムキラー元素の総量は、1100ppm以下であるp型拡散層形成組成物。
- 前記アクセプタ元素が、B(ほう素)、Al(アルミニウム)及びGa(ガリウム)か
ら選択される少なくとも1種である請求項1に記載のp型拡散層形成組成物。 - 前記アクセプタ元素を含むガラス粉末が、B2O3、Al2O3及びGa2O3から選択される少なくとも1種のアクセプタ元素含有物質と、SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、SnO、ZrO2、及びMoO3から選択される少なくとも1種のガラス成分物質と、を含有する請求項1又は請求項2に記載のp型拡散層形成組成物。
- 前記ライフタイムキラー元素が、Fe(鉄)、Cu(銅)、Ni(ニッケル)、Mn(マンガン)、Cr(クロム)、W(タングステン)及びAu(金)から選択される少なくとも1種である請求項1〜請求項3のいずれか1項に記載のp型拡散層形成組成物。
- 請求項1〜請求項4のいずれか1項に記載のp型拡散層形成組成物を塗布する工程と、熱拡散処理を施す工程と、を有するp型拡散層の製造方法。
- 半導体基板上に、請求項1〜請求項4のいずれか1項に記載のp型拡散層形成組成物を塗布する工程と、
熱拡散処理を施してp型拡散層を形成する工程と、
形成された前記p型拡散層上に電極を形成する工程と、
を有する太陽電池素子の製造方法。
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2011
- 2011-04-22 TW TW103124862A patent/TWI548102B/zh not_active IP Right Cessation
- 2011-04-22 KR KR1020127028224A patent/KR101868163B1/ko active IP Right Grant
- 2011-04-22 WO PCT/JP2011/059970 patent/WO2011132778A1/ja active Application Filing
- 2011-04-22 EP EP15168121.0A patent/EP2930740A1/en not_active Withdrawn
- 2011-04-22 US US13/642,526 patent/US20130071968A1/en not_active Abandoned
- 2011-04-22 JP JP2012511720A patent/JP5573946B2/ja not_active Expired - Fee Related
- 2011-04-22 TW TW100114099A patent/TWI495118B/zh not_active IP Right Cessation
- 2011-04-22 EP EP11772109.2A patent/EP2562793B1/en not_active Not-in-force
- 2011-04-22 CN CN201180020188.0A patent/CN102859659B/zh not_active Expired - Fee Related
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2013
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- 2014-02-26 JP JP2014035733A patent/JP2014099660A/ja active Pending
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Also Published As
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US20150214418A1 (en) | 2015-07-30 |
TWI495118B (zh) | 2015-08-01 |
EP2562793B1 (en) | 2017-08-30 |
US20140065761A1 (en) | 2014-03-06 |
EP2562793A4 (en) | 2013-09-11 |
JPWO2011132778A1 (ja) | 2013-07-18 |
US20130071968A1 (en) | 2013-03-21 |
CN102859659A (zh) | 2013-01-02 |
WO2011132778A1 (ja) | 2011-10-27 |
KR20130098142A (ko) | 2013-09-04 |
CN102859659B (zh) | 2017-07-28 |
JP2014099660A (ja) | 2014-05-29 |
US9520529B2 (en) | 2016-12-13 |
KR101868163B1 (ko) | 2018-06-15 |
EP2930740A1 (en) | 2015-10-14 |
TW201138128A (en) | 2011-11-01 |
TW201448237A (zh) | 2014-12-16 |
TWI548102B (zh) | 2016-09-01 |
EP2562793A1 (en) | 2013-02-27 |
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