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WO2017109835A1 - Solar cell manufacturing method - Google Patents

Solar cell manufacturing method Download PDF

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Publication number
WO2017109835A1
WO2017109835A1 PCT/JP2015/085706 JP2015085706W WO2017109835A1 WO 2017109835 A1 WO2017109835 A1 WO 2017109835A1 JP 2015085706 W JP2015085706 W JP 2015085706W WO 2017109835 A1 WO2017109835 A1 WO 2017109835A1
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type
type side
diffusion layer
paste
forming
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French (fr)
Japanese (ja)
Inventor
隼人 幸畑
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Mitsubishi Electric Corp
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Mitsubishi Electric Corp
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Priority to JP2017557536A priority Critical patent/JP6509376B2/en
Priority to PCT/JP2015/085706 priority patent/WO2017109835A1/en
Priority to TW105139420A priority patent/TWI622182B/en
Publication of WO2017109835A1 publication Critical patent/WO2017109835A1/en
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/14—Photovoltaic cells having only PN homojunction potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells

Definitions

  • the present invention relates to a method for manufacturing a solar cell that converts light energy into electric power.
  • Patent Document 1 In order to convert light energy into electric power with high efficiency, a double-sided light-receiving solar cell having an n-type silicon wafer is proposed in Patent Document 1.
  • the emitter In a solar cell having an n-type silicon wafer, the emitter is a p-type diffusion layer.
  • the concentration of impurities in the p-type diffusion layer is 5 ⁇ 10 19 (atoms / cm 3 ) or less.
  • the p-type side electrode that is in contact with the p-type diffusion layer is formed of an alloy of silver and aluminum. It's not easy. If the contact between the p-type diffusion layer and the p-type side electrode is insufficient, the conversion efficiency decreases.
  • the present invention has been made in view of the above, and an object of the present invention is to obtain a method for manufacturing a solar cell in which the contact between the p-type diffusion layer having a low impurity concentration and the p-type side electrode is high.
  • the present invention includes a step of forming a p-type diffusion layer on one side of an n-type silicon wafer, and silver on the outside of the p-type diffusion layer.
  • the present invention there is an effect that it is possible to obtain a method for manufacturing a solar cell with high contact between the p-type diffusion layer having a low impurity concentration and the p-type side electrode.
  • FIG. 1 The flowchart which shows the outline of the procedure of the manufacturing method of the solar cell of Embodiment 1.
  • FIG. The figure which shows the relationship between time at the time of performing a baking process, and baking temperature
  • FIG. 1 is a flowchart showing an outline of the procedure of the method for manufacturing the solar cell of the first embodiment.
  • an n-type silicon wafer is prepared (S1).
  • a p-type diffusion layer is formed on one side of the silicon wafer (S2).
  • a doping paste containing n-type component impurities is pasted by printing (S3).
  • the p-type diffusion layer is covered with a protective film.
  • the silicon wafer is heated to diffuse the n-type component impurities contained in the doping paste to the other surface side of the silicon wafer. Thereby, an n-type diffusion layer is formed on the other surface side of the silicon wafer (S4).
  • the p-type diffusion layer is covered with the p-type side passivation film, and the n-type diffusion layer is covered with the n-type side passivation film (S5).
  • a p-type side paste for forming a p-type side electrode is provided on the p-type side passivation film by printing, and an n-type side for forming an n-type side electrode on the n-type side passivation film.
  • a paste is provided by printing (S6).
  • the p-type side paste and the n-type side paste are baked (S7), and the p-type side electrode is formed from the p-type side paste and the n-type side electrode is formed from the n-type side paste.
  • FIG. 2 is a diagram for explaining the manufacturing method of solar cell 20 of Embodiment 1 in more detail. Furthermore, FIG. 2 has shown the cross section of the thing in the middle of manufacture of the solar cell 20 about each of several processes in the manufacturing method of the solar cell 20, or the cross section of the thing after completion
  • an n-type silicon wafer 1 is prepared.
  • irregularities are formed on both surfaces of the silicon wafer 1.
  • the silicon wafer 1 is etched with a solution composed of an alkaline solution and an additive.
  • an alkaline solution is a potassium hydroxide solution or a sodium hydroxide solution.
  • An example of an additive is isopropyl alcohol. Note that in FIG. 2A, the unevenness is not shown for easy explanation.
  • a p-type diffusion layer 2 is formed on one side of the silicon wafer 1.
  • the p-type diffusion layer 2 is formed by any one of the vapor phase diffusion method, the solid phase diffusion method, and the ion implantation method.
  • a pn junction is formed.
  • the impurity concentration in the p-type diffusion layer 2 is 5 ⁇ 10 19 (atoms / cm 3 ) or less.
  • the lower limit of the impurity concentration in the p-type diffusion layer 2 is 1 ⁇ 10 18 (atoms / cm 3 ).
  • An example of the impurity in the p-type diffusion layer 2 is a boron atom.
  • the surface of the silicon wafer 1 where the p-type diffusion layer 2 is not formed that is, the other surface of the silicon wafer 1 contains n-type component impurities.
  • the doping paste 3 is pasted by printing.
  • An example of an n-type component impurity is a phosphorus atom.
  • the p-type diffusion layer 2 is covered with a protective film. Note that in FIG. 2C, a protective film is not shown for easy explanation.
  • the silicon wafer 1 is put into a thermal diffusion furnace, the silicon wafer 1 is heated while introducing an impurity gas into the thermal diffusion furnace, and the n-type component impurities contained in the doping paste 3 are removed from the other surface of the silicon wafer 1.
  • the n-type diffusion layer 4 is formed on the other surface side of the silicon wafer 1.
  • the portion of the n-type diffusion layer 4 that has been in contact with the doping paste 3 is a high-concentration n-type diffusion layer 5 in which the concentration of the impurity of the n-type component is higher than the periphery of the portion.
  • the n-type diffusion layer 4 may be formed by a method other than the method using the doping paste 3.
  • An example of the impurity in the n-type diffusion layer 4 is a phosphorus atom.
  • the p-type diffusion layer 2 is covered with the p-type side passivation film 6 and the n-type diffusion layer 4 is covered with the n-type side passivation film 7.
  • the p-type side passivation film 6 is a film made of aluminum oxide, silicon dioxide, or silicon nitride.
  • a p-type side paste 8 made of silver and aluminum is formed on the side opposite to the side where the p-type diffusion layer 2 is located with reference to the p-type side passivation film 6. Is provided by printing. That is, the p-type side paste 8 composed of silver and aluminum is provided outside the p-type diffusion layer 2.
  • an n-type side paste 9 made of silver is provided by printing on the side opposite to the side where the n-type diffusion layer 4 is located with respect to the n-type side passivation film 7. That is, the n-type side paste 9 made of silver is provided outside the n-type diffusion layer 4.
  • the firing object 10 is fired to form the p-type side electrode 11 from the p-type side paste 8 and the n-type side electrode 12 from the n-type side paste 9 as shown in FIG. To do.
  • the manufacture of the solar cell 20 ends.
  • the temperature is within a range from 550 ° C to 700 ° C.
  • the p-type side paste 8 and the n-type side paste 9 are fired over a period of 20 seconds or more at a temperature within a range of 20 ° C. above and below the reference temperature from either reference.
  • the p-type side paste 8 and the n-type side paste 9 are baked at a constant temperature in the range of 550 ° C. to 700 ° C. for a period of 20 seconds or longer.
  • the constant temperature is a temperature within a band of 20 ° C. above and below the reference from any temperature.
  • the p-type side electrode 11 in contact with the p-type diffusion layer 2 is formed from the p-type side paste 8.
  • the p-type side paste 8 is baked at a constant temperature within a range from 550 ° C. to 700 ° C. over a period of 20 seconds or longer as described above.
  • the period during which the temperature is maintained is 60 seconds or less.
  • the firing object 10 is heated so that the temperature of the firing object 10 exceeds 700 ° C. That is, the firing object 10 is fired to form the n-type side electrode 12 at a temperature higher than the temperature at which the p-type side electrode 11 is formed from the p-type side paste 8. Thereby, the n-type side electrode 12 in contact with the n-type diffusion layer 4 is formed from the n-type side paste 9.
  • the highest temperature when firing the firing object 10 is a temperature for forming the n-type side electrode 12 made of silver, and is 800 ° C., for example.
  • FIG. 3 is a diagram showing the relationship between the time for performing the firing step and the firing temperature.
  • the firing step is a step of firing the firing object 10.
  • the firing temperature is the temperature of the firing object 10 when firing the firing object 10.
  • Step P for forming the p-type side electrode 11 is performed before Step N for forming the n-type side electrode 12.
  • the firing object 10 is fired at a constant temperature within a range from 550 ° C. to 700 ° C. over a period X of 20 seconds or longer.
  • the contact property between the p-type side electrode 11 constituted by silver and aluminum and the p-type diffusion layer 2 can be enhanced.
  • the conventional baking temperature is 750 ° C. to 850 ° C. and relatively high, but the baking temperature in the first embodiment is 550 ° C. to 700 ° C.
  • the temperature is in the range up to.
  • the p-type side paste 8 does not contain aluminum, the contact between the p-type diffusion layer 2 and the p-type side electrode 11 may be insufficient.
  • the p-type side paste 8 containing aluminum is baked at a constant temperature in the range of 550 ° C. to 700 ° C., aluminum reacts with silicon in the p-type diffusion layer 2 to cause aluminum atoms and silicon atoms to react. By bonding, it is considered that the contact property between the p-type diffusion layer 2 and the p-type side electrode 11 is enhanced.
  • the p-type side paste 8 is formed by baking the p-type side paste 8
  • the p-type side paste 8 is rapidly heated using a heater. Therefore, aluminum contained in the p-type side paste 8 and silicon in the p-type diffusion layer 2 are used. Does not react sufficiently, and the bonding force between aluminum atoms and silicon atoms is weak.
  • the p-type side paste 8 is baked over a period X of 20 seconds or more at a constant temperature in the range of 550 ° C. to 700 ° C. Therefore, it is considered that the bonding force between the aluminum atom and the silicon atom is increased, and as a result, the contact property between the p-type diffusion layer 2 and the p-type side electrode 11 is increased.
  • the firing object 10 is arranged so that the n-type side paste 9 is positioned closer to the heater than the p-type side paste 8.
  • FIG. 4 is a cross-sectional view of a firing apparatus 40 for firing the firing object 10.
  • the baking apparatus 40 includes a chamber 41 and a heater 42, and the heater 42 is provided on a wall surface vertically above the chamber 41.
  • the firing object 10 is arranged so that the p-type side paste 8 is positioned vertically below the n-type side paste 9.
  • the influence of the heat from the heater 42 on the p-type side passivation film 6 can be reduced, and as a result, the possibility that the p-type side passivation film 6 is damaged can be reduced.
  • the p-type side paste 8 is baked at a constant temperature in the range of 550 ° C. to 700 ° C. for a period of 20 seconds or longer.
  • the constant temperature is a temperature within a band of 20 ° C. above and below the reference from any temperature.
  • the p-type side paste 8 when the firing object 10 is fired using the heater 42, the p-type side paste 8 is positioned farther from the heater 42 than the n-type side paste 9.
  • the heater 42 when the heater 42 is provided on the vertically upper wall surface inside the chamber 41, the p-type paste 8 is positioned vertically below the n-type paste 9. Thereby, the possibility that the p-type side passivation film 6 is damaged can be reduced.
  • the configuration described in the above embodiment shows an example of the contents of the present invention, and can be combined with another known technique, and can be combined with other configurations without departing from the gist of the present invention. It is also possible to omit or change the part.

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  • Photovoltaic Devices (AREA)

Abstract

A solar cell manufacturing method of the present invention includes: a step for forming a p-type diffusion layer on one surface side of an n-type silicon wafer; a step for providing, on the outer side of the p-type diffusion layer, a p-type side paste configured from silver and aluminum; and a step for firing the p-type side paste for a period X equal to or longer than 20 seconds at a temperature, which is within a range of 550-700°C, and is within a zone 20°C above and below a temperature set as reference, and forming a p-type side electrode using the p-type side paste, said p-type side electrode being in contact with the p-type diffusion layer.

Description

太陽電池の製造方法Manufacturing method of solar cell

　本発明は、光エネルギを電力に変換する太陽電池の製造方法に関する。 The present invention relates to a method for manufacturing a solar cell that converts light energy into electric power.

　光エネルギを電力に高効率で変換するために、ｎ型のシリコンウェハを有する両面受光型太陽電池が特許文献１において提案されている。ｎ型のシリコンウェハを有する太陽電池では、エミッタはｐ型拡散層である。 In order to convert light energy into electric power with high efficiency, a double-sided light-receiving solar cell having an n-type silicon wafer is proposed in Patent Document 1. In a solar cell having an n-type silicon wafer, the emitter is a p-type diffusion layer.

国際公開第２０１４／０９８０１６号International Publication No. 2014/098016

　ｎ型のシリコンウェハを有する太陽電池では、光エネルギから電力への変換効率を上げるために、エミッタであるｐ型拡散層における不純物の濃度を低くすることが重要である。具体的には、変換効率を上げるために、ｐ型拡散層における不純物の濃度を５×１０１９（ａｔｏｍｓ／ｃｍ３）以下にすることが重要である。ｐ型拡散層と接触するｐ型側電極は銀とアルミニウムとの合金によって形成されるが、上記のような不純物の濃度が低いｐ型拡散層とｐ型側電極とを良好に接触させることは容易ではない。ｐ型拡散層とｐ型側電極との接触が不十分であると、変換効率は低下する。 In a solar cell having an n-type silicon wafer, it is important to reduce the concentration of impurities in the p-type diffusion layer as an emitter in order to increase the conversion efficiency from light energy to electric power. Specifically, in order to increase the conversion efficiency, it is important that the impurity concentration in the p-type diffusion layer is 5 × 10 19 (atoms / cm 3 ) or less. The p-type side electrode that is in contact with the p-type diffusion layer is formed of an alloy of silver and aluminum. It's not easy. If the contact between the p-type diffusion layer and the p-type side electrode is insufficient, the conversion efficiency decreases.

　本発明は、上記に鑑みてなされたものであって、不純物の濃度が低いｐ型拡散層とｐ型側電極との接触性が高い太陽電池の製造方法を得ることを目的とする。 The present invention has been made in view of the above, and an object of the present invention is to obtain a method for manufacturing a solar cell in which the contact between the p-type diffusion layer having a low impurity concentration and the p-type side electrode is high.

　上述した課題を解決し、目的を達成するために、本発明は、ｎ型のシリコンウェハの一方の面の側にｐ型拡散層を形成するステップと、前記ｐ型拡散層の外側に銀とアルミニウムとによって構成されるｐ型側ペーストを設けるステップと、５５０℃から７００℃までの範囲内の温度であって、いずれかの温度を基準として前記基準から上下２０℃の帯域内の温度で２０秒以上の期間にわたって前記ｐ型側ペーストを焼成し、前記ｐ型側ペーストから、前記ｐ型拡散層に接するｐ型側電極を形成するステップとを含むことを特徴とする。 In order to solve the above-described problems and achieve the object, the present invention includes a step of forming a p-type diffusion layer on one side of an n-type silicon wafer, and silver on the outside of the p-type diffusion layer. A step of providing a p-type side paste composed of aluminum, and a temperature within a range from 550 ° C. to 700 ° C., with a temperature within a range of 20 ° C. above and below the reference 20 ° C. Firing the p-type side paste over a period of seconds or more, and forming a p-type side electrode in contact with the p-type diffusion layer from the p-type side paste.

　本発明によれば、不純物の濃度が低いｐ型拡散層とｐ型側電極との接触性が高い太陽電池の製造方法を得ることができるという効果を奏する。 According to the present invention, there is an effect that it is possible to obtain a method for manufacturing a solar cell with high contact between the p-type diffusion layer having a low impurity concentration and the p-type side electrode.

実施の形態１の太陽電池の製造方法の手順の概略を示すフローチャートThe flowchart which shows the outline of the procedure of the manufacturing method of the solar cell of Embodiment 1. 実施の形態１の太陽電池の製造方法をより詳細に説明するための図The figure for demonstrating in more detail the manufacturing method of the solar cell of Embodiment 1. FIG. 焼成工程を実行する際の時間と焼成温度との関係を示す図The figure which shows the relationship between time at the time of performing a baking process, and baking temperature 焼成対象物を焼成するための焼成装置の断面図Cross-sectional view of a firing apparatus for firing an object to be fired

　以下に、本発明の実施の形態にかかる太陽電池の製造方法を図面に基づいて詳細に説明する。なお、この実施の形態によりこの発明が限定されるものではない。 Hereinafter, a method for manufacturing a solar cell according to an embodiment of the present invention will be described in detail with reference to the drawings. Note that the present invention is not limited to the embodiments.

実施の形態１．
　図１は、実施の形態１の太陽電池の製造方法の手順の概略を示すフローチャートである。図１に示す通り、まず、ｎ型のシリコンウェハを用意する（Ｓ１）。次に、シリコンウェハの一方の面の側にｐ型拡散層を形成する（Ｓ２）。次に、シリコンウェハの他方の面に、ｎ型拡散層を形成することを目的として、ｎ型の成分の不純物を含むドーピングペーストを印刷によってペーストする（Ｓ３）。その後、ｐ型拡散層を保護フィルムによって覆う。次に、シリコンウェハを加熱し、ドーピングペーストに含まれるｎ型の成分の不純物をシリコンウェハの他方の面の側に拡散させる。それにより、シリコンウェハの他方の面の側にｎ型拡散層を形成する（Ｓ４）。 Embodiment 1 FIG.
FIG. 1 is a flowchart showing an outline of the procedure of the method for manufacturing the solar cell of the first embodiment. As shown in FIG. 1, first, an n-type silicon wafer is prepared (S1). Next, a p-type diffusion layer is formed on one side of the silicon wafer (S2). Next, for the purpose of forming an n-type diffusion layer on the other surface of the silicon wafer, a doping paste containing n-type component impurities is pasted by printing (S3). Thereafter, the p-type diffusion layer is covered with a protective film. Next, the silicon wafer is heated to diffuse the n-type component impurities contained in the doping paste to the other surface side of the silicon wafer. Thereby, an n-type diffusion layer is formed on the other surface side of the silicon wafer (S4).

　次に、ｐ型拡散層をｐ型側パッシベーション膜で覆うと共に、ｎ型拡散層をｎ型側パッシベーション膜で覆う（Ｓ５）。次に、ｐ型側パッシベーション膜の上にｐ型側電極を形成するためのｐ型側ペーストを印刷によって設けると共に、ｎ型側パッシベーション膜の上にｎ型側電極を形成するためのｎ型側ペーストを印刷によって設ける（Ｓ６）。最後に、ｐ型側ペースト及びｎ型側ペーストを焼成し（Ｓ７）、ｐ型側ペーストからｐ型側電極を形成すると共に、ｎ型側ペーストからｎ型側電極を形成する。 Next, the p-type diffusion layer is covered with the p-type side passivation film, and the n-type diffusion layer is covered with the n-type side passivation film (S5). Next, a p-type side paste for forming a p-type side electrode is provided on the p-type side passivation film by printing, and an n-type side for forming an n-type side electrode on the n-type side passivation film. A paste is provided by printing (S6). Finally, the p-type side paste and the n-type side paste are baked (S7), and the p-type side electrode is formed from the p-type side paste and the n-type side electrode is formed from the n-type side paste.

　図１を用いて実施の形態１の太陽電池の製造方法の手順の概略を説明したが、図２を用いて実施の形態１の太陽電池の製造方法をより詳細に説明する。図２は、実施の形態１の太陽電池２０の製造方法をより詳細に説明するための図である。更に言うと、図２は、太陽電池２０の製造方法における複数の工程のそれぞれについての太陽電池２０の製造途中の物の断面又は製造終了後の物の断面を示している。 Although the outline of the procedure of the manufacturing method of the solar cell of Embodiment 1 was demonstrated using FIG. 1, the manufacturing method of the solar cell of Embodiment 1 is demonstrated in detail using FIG. FIG. 2 is a diagram for explaining the manufacturing method of solar cell 20 of Embodiment 1 in more detail. Furthermore, FIG. 2 has shown the cross section of the thing in the middle of manufacture of the solar cell 20 about each of several processes in the manufacturing method of the solar cell 20, or the cross section of the thing after completion | finish of manufacture.

　まず、図２（Ａ）に示すように、ｎ型のシリコンウェハ１を用意する。次に、シリコンウェハ１に入射する光の反射率を低減するために、シリコンウェハ１の両方の表面に凹凸を形成する。具体的には、アルカリ溶液と添加物とによって構成される溶液によりシリコンウェハ１をエッチングする。それにより、シリコンウェハ１の両方の表面にランダムピラミッド構造の凹凸を形成する。アルカリ溶液の一例は、水酸化カリウム溶液又は水酸化ナトリウム溶液である。添加物の一例は、イソプロピルアルコールである。なお、図２（Ａ）では説明を簡単に行うために凹凸は示されていない。 First, as shown in FIG. 2A, an n-type silicon wafer 1 is prepared. Next, in order to reduce the reflectance of light incident on the silicon wafer 1, irregularities are formed on both surfaces of the silicon wafer 1. Specifically, the silicon wafer 1 is etched with a solution composed of an alkaline solution and an additive. Thereby, irregularities having a random pyramid structure are formed on both surfaces of the silicon wafer 1. An example of the alkaline solution is a potassium hydroxide solution or a sodium hydroxide solution. An example of an additive is isopropyl alcohol. Note that in FIG. 2A, the unevenness is not shown for easy explanation.

　次に、図２（Ｂ）に示すように、シリコンウェハ１の一方の面の側にｐ型拡散層２を形成する。気相拡散法、固相拡散法及びイオン注入法のいずれかによって、ｐ型拡散層２を形成する。ｐ型拡散層２を形成することにより、ｐｎ接合が形成される。光エネルギから電力への高い変換効率を得るために、ｐ型拡散層２における不純物の濃度は５×１０１９（ａｔｏｍｓ／ｃｍ３）以下である。ｐ型拡散層２における不純物の濃度の下限は１×１０１８（ａｔｏｍｓ／ｃｍ３）である。ｐ型拡散層２における不純物の一例は、ボロン原子である。 Next, as shown in FIG. 2B, a p-type diffusion layer 2 is formed on one side of the silicon wafer 1. The p-type diffusion layer 2 is formed by any one of the vapor phase diffusion method, the solid phase diffusion method, and the ion implantation method. By forming the p-type diffusion layer 2, a pn junction is formed. In order to obtain a high conversion efficiency from light energy to electric power, the impurity concentration in the p-type diffusion layer 2 is 5 × 10 19 (atoms / cm 3 ) or less. The lower limit of the impurity concentration in the p-type diffusion layer 2 is 1 × 10 18 (atoms / cm 3 ). An example of the impurity in the p-type diffusion layer 2 is a boron atom.

　次に、図２（Ｃ）に示すように、シリコンウェハ１のｐ型拡散層２が形成されていない側の面に、すなわちシリコンウェハ１の他方の面に、ｎ型の成分の不純物を含むドーピングペースト３を印刷によってペーストする。ｎ型の成分の不純物の一例は、リン原子である。その後、ｐ型拡散層２を保護フィルムによって覆う。なお、図２（Ｃ）では説明を簡単に行うために保護フィルムは示されていない。 Next, as shown in FIG. 2C, the surface of the silicon wafer 1 where the p-type diffusion layer 2 is not formed, that is, the other surface of the silicon wafer 1 contains n-type component impurities. The doping paste 3 is pasted by printing. An example of an n-type component impurity is a phosphorus atom. Thereafter, the p-type diffusion layer 2 is covered with a protective film. Note that in FIG. 2C, a protective film is not shown for easy explanation.

　そして、シリコンウェハ１を熱拡散炉に入れ、不純物ガスを熱拡散炉に導入しながらシリコンウェハ１を加熱し、ドーピングペースト３に含まれるｎ型の成分の不純物をシリコンウェハ１の他方の面の側で拡散させる。それにより、図２（Ｄ）に示すように、シリコンウェハ１の他方の面の側に、ｎ型拡散層４が形成される。ｎ型拡散層４のうちのドーピングペースト３と接触していた部位は、その部位の周辺よりもｎ型の成分の不純物の濃度が高い高濃度ｎ型拡散層５である。なお、ｎ型拡散層４は、ドーピングペースト３を用いる方法以外の方法によって形成されてもよい。ｎ型拡散層４における不純物の一例は、リン原子である。 Then, the silicon wafer 1 is put into a thermal diffusion furnace, the silicon wafer 1 is heated while introducing an impurity gas into the thermal diffusion furnace, and the n-type component impurities contained in the doping paste 3 are removed from the other surface of the silicon wafer 1. Spread on the side. Thereby, as shown in FIG. 2D, the n-type diffusion layer 4 is formed on the other surface side of the silicon wafer 1. The portion of the n-type diffusion layer 4 that has been in contact with the doping paste 3 is a high-concentration n-type diffusion layer 5 in which the concentration of the impurity of the n-type component is higher than the periphery of the portion. The n-type diffusion layer 4 may be formed by a method other than the method using the doping paste 3. An example of the impurity in the n-type diffusion layer 4 is a phosphorus atom.

　次に、図２（Ｅ）に示すように、ｐ型拡散層２をｐ型側パッシベーション膜６で覆うと共に、ｎ型拡散層４をｎ型側パッシベーション膜７で覆う。ｐ型側パッシベーション膜６は、酸化アルミニウム、二酸化ケイ素又は窒化シリコンによって構成される膜である。 Next, as shown in FIG. 2E, the p-type diffusion layer 2 is covered with the p-type side passivation film 6 and the n-type diffusion layer 4 is covered with the n-type side passivation film 7. The p-type side passivation film 6 is a film made of aluminum oxide, silicon dioxide, or silicon nitride.

　次に、図２（Ｆ）に示すように、ｐ型側パッシベーション膜６を基準としてｐ型拡散層２が位置する側と反対の側に、銀とアルミニウムとによって構成されるｐ型側ペースト８を印刷によって設ける。つまり、ｐ型拡散層２の外側に銀とアルミニウムとによって構成されるｐ型側ペースト８を設ける。加えて、ｎ型側パッシベーション膜７を基準としてｎ型拡散層４が位置する側と反対の側に、銀によって構成されるｎ型側ペースト９を印刷によって設ける。つまり、ｎ型拡散層４の外側に銀によって構成されるｎ型側ペースト９を設ける。説明を簡単に行うために、図２（Ｆ）に示すｐ型側ペースト８及びｎ型側ペースト９が設けられたシリコンウェハ１を「焼成対象物１０」と定義する。 Next, as shown in FIG. 2 (F), a p-type side paste 8 made of silver and aluminum is formed on the side opposite to the side where the p-type diffusion layer 2 is located with reference to the p-type side passivation film 6. Is provided by printing. That is, the p-type side paste 8 composed of silver and aluminum is provided outside the p-type diffusion layer 2. In addition, an n-type side paste 9 made of silver is provided by printing on the side opposite to the side where the n-type diffusion layer 4 is located with respect to the n-type side passivation film 7. That is, the n-type side paste 9 made of silver is provided outside the n-type diffusion layer 4. In order to simplify the explanation, the silicon wafer 1 provided with the p-type side paste 8 and the n-type side paste 9 shown in FIG.

　次に、焼成対象物１０を焼成し、図２（Ｇ）に示すように、ｐ型側ペースト８からｐ型側電極１１を形成すると共に、ｎ型側ペースト９からｎ型側電極１２を形成する。それにより、太陽電池２０の製造は終了する。焼成対象物１０を焼成する際、銀とアルミニウムとによって構成されるｐ型側電極１１とシリコンウェハ１とを良好に接触させるために、まず、５５０℃から７００℃までの範囲内の温度であって、いずれかの温度を基準として基準から上下２０℃の帯域内の温度で２０秒以上の期間にわたってｐ型側ペースト８及びｎ型側ペースト９を焼成する。 Next, the firing object 10 is fired to form the p-type side electrode 11 from the p-type side paste 8 and the n-type side electrode 12 from the n-type side paste 9 as shown in FIG. To do. Thereby, the manufacture of the solar cell 20 ends. When firing the object 10 to be fired, in order to bring the p-type side electrode 11 composed of silver and aluminum into good contact with the silicon wafer 1, first, the temperature is within a range from 550 ° C to 700 ° C. Then, the p-type side paste 8 and the n-type side paste 9 are fired over a period of 20 seconds or more at a temperature within a range of 20 ° C. above and below the reference temperature from either reference.

　つまり、５５０℃から７００℃までの範囲内の一定の温度で２０秒以上の期間にわたってｐ型側ペースト８及びｎ型側ペースト９を焼成する。一定の温度は、いずれかの温度を基準として基準から上下２０℃の帯域内の温度である。それにより、ｐ型側ペースト８から、ｐ型拡散層２に接するｐ型側電極１１を形成する。なお、ｐ型側電極１１を形成するために行う焼成では、上述の通り２０秒以上の期間にわたって５５０℃から７００℃までの範囲内の一定の温度でｐ型側ペースト８を焼成するが、一定の温度を保つ期間は６０秒以下である。 That is, the p-type side paste 8 and the n-type side paste 9 are baked at a constant temperature in the range of 550 ° C. to 700 ° C. for a period of 20 seconds or longer. The constant temperature is a temperature within a band of 20 ° C. above and below the reference from any temperature. Thereby, the p-type side electrode 11 in contact with the p-type diffusion layer 2 is formed from the p-type side paste 8. In the baking performed to form the p-type side electrode 11, the p-type side paste 8 is baked at a constant temperature within a range from 550 ° C. to 700 ° C. over a period of 20 seconds or longer as described above. The period during which the temperature is maintained is 60 seconds or less.

　その後、焼成対象物１０の温度が７００℃を超える温度となるように焼成対象物１０を加熱する。すなわち、ｐ型側ペースト８からｐ型側電極１１を形成する際の温度より高い温度で、ｎ型側電極１２を形成するために焼成対象物１０を焼成する。それにより、ｎ型側ペースト９から、ｎ型拡散層４に接するｎ型側電極１２を形成する。焼成対象物１０を焼成する際の最高の温度は、銀によって構成されるｎ型側電極１２を形成するための温度であって、例えば８００℃である。 Thereafter, the firing object 10 is heated so that the temperature of the firing object 10 exceeds 700 ° C. That is, the firing object 10 is fired to form the n-type side electrode 12 at a temperature higher than the temperature at which the p-type side electrode 11 is formed from the p-type side paste 8. Thereby, the n-type side electrode 12 in contact with the n-type diffusion layer 4 is formed from the n-type side paste 9. The highest temperature when firing the firing object 10 is a temperature for forming the n-type side electrode 12 made of silver, and is 800 ° C., for example.

　図３は、焼成工程を実行する際の時間と焼成温度との関係を示す図である。焼成工程は、焼成対象物１０を焼成する工程である。焼成温度は、焼成対象物１０を焼成する際の焼成対象物１０の温度である。図３に示すように、ｐ型側電極１１を形成するステップＰを、ｎ型側電極１２を形成するステップＮよりも前に行う。ｐ型側電極１１を形成するステップＰでは、５５０℃から７００℃までの範囲内の一定の温度で２０秒以上の期間Ｘにわたって焼成対象物１０を焼成する。それにより、銀とアルミニウムとによって構成されるｐ型側電極１１とｐ型拡散層２との接触性を高めることができる。 FIG. 3 is a diagram showing the relationship between the time for performing the firing step and the firing temperature. The firing step is a step of firing the firing object 10. The firing temperature is the temperature of the firing object 10 when firing the firing object 10. As shown in FIG. 3, Step P for forming the p-type side electrode 11 is performed before Step N for forming the n-type side electrode 12. In Step P for forming the p-type side electrode 11, the firing object 10 is fired at a constant temperature within a range from 550 ° C. to 700 ° C. over a period X of 20 seconds or longer. Thereby, the contact property between the p-type side electrode 11 constituted by silver and aluminum and the p-type diffusion layer 2 can be enhanced.

　ｐ型側ペースト８を焼成してｐ型側電極１１を形成する場合、従来の焼成温度は７５０℃から８５０℃であって比較的高いが、実施の形態１における焼成温度は５５０℃から７００℃までの範囲の温度である。ｐ型側ペースト８がアルミニウムを含まない場合、ｐ型拡散層２とｐ型側電極１１との接触は不十分である場合がある。５５０℃から７００℃までの範囲内の一定の温度でアルミニウムを含むｐ型側ペースト８を焼成する場合、アルミニウムとｐ型拡散層２のうちのシリコンとが反応してアルミニウム原子とシリコン原子とが結合することによって、ｐ型拡散層２とｐ型側電極１１との接触性が高くなると考えられる。 When the p-type side electrode 8 is formed by baking the p-type side paste 8, the conventional baking temperature is 750 ° C. to 850 ° C. and relatively high, but the baking temperature in the first embodiment is 550 ° C. to 700 ° C. The temperature is in the range up to. When the p-type side paste 8 does not contain aluminum, the contact between the p-type diffusion layer 2 and the p-type side electrode 11 may be insufficient. When the p-type side paste 8 containing aluminum is baked at a constant temperature in the range of 550 ° C. to 700 ° C., aluminum reacts with silicon in the p-type diffusion layer 2 to cause aluminum atoms and silicon atoms to react. By bonding, it is considered that the contact property between the p-type diffusion layer 2 and the p-type side electrode 11 is enhanced.

　ｐ型側ペースト８を焼成してｐ型側電極１１を形成する場合、従来ではヒータを用いて急速に加熱するので、ｐ型側ペースト８に含まれるアルミニウムとｐ型拡散層２のうちのシリコンとが十分に反応せず、そのためアルミニウム原子とシリコン原子との結合力が弱い。それに対し、実施の形態１では、５５０℃から７００℃までの範囲内の一定の温度で２０秒以上の期間Ｘにわたってｐ型側ペースト８を焼成する。そのため、アルミニウム原子とシリコン原子との結合力が高くなり、ひいてはｐ型拡散層２とｐ型側電極１１との接触性が高くなると考えられる。 When the p-type side electrode 8 is formed by baking the p-type side paste 8, conventionally, the p-type side paste 8 is rapidly heated using a heater. Therefore, aluminum contained in the p-type side paste 8 and silicon in the p-type diffusion layer 2 are used. Does not react sufficiently, and the bonding force between aluminum atoms and silicon atoms is weak. On the other hand, in the first embodiment, the p-type side paste 8 is baked over a period X of 20 seconds or more at a constant temperature in the range of 550 ° C. to 700 ° C. Therefore, it is considered that the bonding force between the aluminum atom and the silicon atom is increased, and as a result, the contact property between the p-type diffusion layer 2 and the p-type side electrode 11 is increased.

　ヒータを用いてｐ型側ペースト８を焼成する場合、ｐ型側ペースト８がヒータの近くに位置するとｐ型側ペースト８を焼成するためのヒータからの熱によってｐ型側パッシベーション膜６が損傷する可能性がある。そのため、ヒータを用いて焼成対象物１０を焼成する場合、ｐ型側ペースト８よりもｎ型側ペースト９がヒータに近く位置するように焼成対象物１０を配置する。 When baking the p-type side paste 8 using a heater, if the p-type side paste 8 is positioned near the heater, the p-type side passivation film 6 is damaged by heat from the heater for baking the p-type side paste 8. there is a possibility. Therefore, when firing the firing object 10 using a heater, the firing object 10 is arranged so that the n-type side paste 9 is positioned closer to the heater than the p-type side paste 8.

　図４は、焼成対象物１０を焼成するための焼成装置４０の断面図である。図４に示す通り、焼成装置４０はチャンバ４１とヒータ４２とを有しており、ヒータ４２はチャンバ４１の内部の鉛直上方の壁面に設けられている。図４の焼成装置４０を用いて焼成対象物１０を焼成する場合、ｐ型側ペースト８がｎ型側ペースト９よりも鉛直下方に位置するように焼成対象物１０を配置する。それにより、ヒータ４２からの熱のｐ型側パッシベーション膜６への影響を小さくすることができ、ひいてはｐ型側パッシベーション膜６が損傷する可能性を低下させることができる。 FIG. 4 is a cross-sectional view of a firing apparatus 40 for firing the firing object 10. As shown in FIG. 4, the baking apparatus 40 includes a chamber 41 and a heater 42, and the heater 42 is provided on a wall surface vertically above the chamber 41. When firing the firing object 10 using the firing apparatus 40 of FIG. 4, the firing object 10 is arranged so that the p-type side paste 8 is positioned vertically below the n-type side paste 9. Thereby, the influence of the heat from the heater 42 on the p-type side passivation film 6 can be reduced, and as a result, the possibility that the p-type side passivation film 6 is damaged can be reduced.

　上述の通り、実施の形態１では、５５０℃から７００℃までの範囲内の一定の温度で２０秒以上の期間にわたってｐ型側ペースト８を焼成する。一定の温度は、いずれかの温度を基準として基準から上下２０℃の帯域内の温度である。それにより、ｐ型側ペースト８から形成されるｐ型側電極１１とｐ型拡散層２との接触性を高めることができる。その結果、光エネルギから電力への変換効率を高くすることができる。 As described above, in Embodiment 1, the p-type side paste 8 is baked at a constant temperature in the range of 550 ° C. to 700 ° C. for a period of 20 seconds or longer. The constant temperature is a temperature within a band of 20 ° C. above and below the reference from any temperature. Thereby, the contact property between the p-type side electrode 11 formed from the p-type side paste 8 and the p-type diffusion layer 2 can be enhanced. As a result, the conversion efficiency from light energy to electric power can be increased.

　加えて、実施の形態１では、ヒータ４２を用いて焼成対象物１０を焼成する場合、ｐ型側ペースト８をｎ型側ペースト９よりもヒータ４２から離して位置させる。例えば、ヒータ４２がチャンバ４１の内部の鉛直上方の壁面に設けられている場合、ｐ型側ペースト８をｎ型側ペースト９よりも鉛直下方に位置させる。それにより、ｐ型側パッシベーション膜６が損傷する可能性を低下させることができる。 In addition, in the first embodiment, when the firing object 10 is fired using the heater 42, the p-type side paste 8 is positioned farther from the heater 42 than the n-type side paste 9. For example, when the heater 42 is provided on the vertically upper wall surface inside the chamber 41, the p-type paste 8 is positioned vertically below the n-type paste 9. Thereby, the possibility that the p-type side passivation film 6 is damaged can be reduced.

　以上の実施の形態に示した構成は、本発明の内容の一例を示すものであり、別の公知の技術と組み合わせることも可能であるし、本発明の要旨を逸脱しない範囲で、構成の一部を省略又は変更することも可能である。 The configuration described in the above embodiment shows an example of the contents of the present invention, and can be combined with another known technique, and can be combined with other configurations without departing from the gist of the present invention. It is also possible to omit or change the part.

　１　シリコンウェハ、２　ｐ型拡散層、３　ドーピングペースト、４　ｎ型拡散層、５　高濃度ｎ型拡散層、６　ｐ型側パッシベーション膜、７　ｎ型側パッシベーション膜、８　ｐ型側ペースト、９　ｎ型側ペースト、１０　焼成対象物、１１　ｐ型側電極、１２　ｎ型側電極、２０　太陽電池、４０　焼成装置、４１　チャンバ、４２　ヒータ。 1 silicon wafer, 2 p-type diffusion layer, 3 doping paste, 4 n-type diffusion layer, 5 high-concentration n-type diffusion layer, 6 p-type side passivation film, 7 n-type side passivation film, 8 p-type side paste, 9 n Mold side paste, 10 firing object, 11 p-type side electrode, 12 n-type side electrode, 20 solar cell, 40 firing device, 41 chamber, 42 heater.

Claims (3)

　ｎ型のシリコンウェハの一方の面の側にｐ型拡散層を形成するステップと、
　前記ｐ型拡散層の外側に銀とアルミニウムとによって構成されるｐ型側ペーストを設けるステップと、
　５５０℃から７００℃までの範囲内の温度であって、いずれかの温度を基準として前記基準から上下２０℃の帯域内の温度で２０秒以上の期間にわたって前記ｐ型側ペーストを焼成し、前記ｐ型側ペーストから、前記ｐ型拡散層に接するｐ型側電極を形成するステップと
　を含むことを特徴とする太陽電池の製造方法。 forming a p-type diffusion layer on one side of an n-type silicon wafer;
Providing a p-type side paste composed of silver and aluminum outside the p-type diffusion layer;
The p-type side paste is baked over a period of 20 seconds or more at a temperature within a range of 20 ° C. above and below the reference from any one of the temperatures within a range from 550 ° C. to 700 ° C., forming a p-type side electrode in contact with the p-type diffusion layer from a p-type side paste. 　前記ｐ型側電極を形成するステップにおいて、前記ｐ型側ペーストをヒータによって焼成する場合、前記ｐ型側ペーストを、前記ｎ型のシリコンウェハの他方の面の側に設けられるｎ型側ペーストよりも前記ヒータから離して位置させることを特徴とする請求項１に記載の太陽電池の製造方法。 In the step of forming the p-type side electrode, when the p-type side paste is baked by a heater, the p-type side paste is more than an n-type side paste provided on the other surface side of the n-type silicon wafer. The solar cell manufacturing method according to claim 1, wherein the solar cell is positioned away from the heater. 　前記ｐ型拡散層を形成するステップの後かつ前記ｐ型側電極を形成するステップの前に行うステップであって、前記ｎ型のシリコンウェハの他方の面の側にｎ型拡散層を形成するステップと、
　前記ｎ型拡散層を形成するステップの後かつ前記ｐ型側電極を形成するステップの前に行うステップであって、前記ｎ型拡散層の外側に銀によって構成されるｎ型側ペーストを設けるステップと、
　前記ｐ型側電極を形成するステップの後に行うステップであって、前記ｎ型側ペーストを焼成し、前記ｎ型側ペーストから、前記ｎ型拡散層に接するｎ型側電極を形成するステップとを更に含み、
　前記ｎ型側電極を形成するステップにおける前記ｎ型側ペーストを焼成する温度は、前記ｐ型側電極を形成するステップにおける前記ｐ型側ペーストを焼成する温度よりも高い
　ことを特徴とする請求項１又は請求項２に記載の太陽電池の製造方法。 A step performed after the step of forming the p-type diffusion layer and before the step of forming the p-type side electrode, and forming the n-type diffusion layer on the other surface side of the n-type silicon wafer. Steps,
A step performed after the step of forming the n-type diffusion layer and before the step of forming the p-type side electrode, and a step of providing an n-type side paste made of silver outside the n-type diffusion layer When,
Performing after the step of forming the p-type side electrode, firing the n-type side paste, and forming an n-type side electrode in contact with the n-type diffusion layer from the n-type side paste; In addition,
The temperature for firing the n-type side paste in the step of forming the n-type side electrode is higher than the temperature for firing the p-type side paste in the step of forming the p-type side electrode. The manufacturing method of the solar cell of Claim 1 or Claim 2.
PCT/JP2015/085706 2015-12-21 2015-12-21 Solar cell manufacturing method Ceased WO2017109835A1 (en)

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