JP2003069056A - Paste composition and solar battery using the same - Google Patents
Paste composition and solar battery using the sameInfo
- Publication number
- JP2003069056A JP2003069056A JP2001251166A JP2001251166A JP2003069056A JP 2003069056 A JP2003069056 A JP 2003069056A JP 2001251166 A JP2001251166 A JP 2001251166A JP 2001251166 A JP2001251166 A JP 2001251166A JP 2003069056 A JP2003069056 A JP 2003069056A
- Authority
- JP
- Japan
- Prior art keywords
- paste composition
- mass
- boron
- semiconductor substrate
- boron compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000004065 semiconductor Substances 0.000 claims abstract description 25
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011521 glass Substances 0.000 claims abstract description 18
- 229910052796 boron Inorganic materials 0.000 claims description 22
- 238000010304 firing Methods 0.000 claims description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001649 bromium compounds Chemical class 0.000 claims description 2
- 150000004673 fluoride salts Chemical class 0.000 claims description 2
- 150000004694 iodide salts Chemical class 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- -1 oxides Chemical class 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 239000000463 material Substances 0.000 description 10
- 238000007650 screen-printing Methods 0.000 description 6
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
- H01L21/2225—Diffusion sources
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、一般的にはペー
スト組成物およびそれを用いた太陽電池に関し、特定的
には、結晶系シリコン太陽電池を構成するｐ型シリコン
半導体基板の上に電極を形成する際に用いられるペース
ト組成物、およびそれを用いた太陽電池に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to a paste composition and a solar cell using the paste composition, and more specifically, to an electrode on a p-type silicon semiconductor substrate that constitutes a crystalline silicon solar cell. The present invention relates to a paste composition used for forming and a solar cell using the paste composition.
【０００２】[0002]
【従来の技術】ｐ型シリコン半導体基板の上に電極が形
成された電子部品として、太陽電池が知られている。図
１に示すように、太陽電池は、厚みが３００〜４００μ
ｍのｐ型シリコン半導体基板１を用いて構成される。ｐ
型シリコン半導体基板１の受光面側には、厚みが０．３
〜０．５μｍのｎ型不純物層２と、その上に反射防止膜
３とグリッド電極４が形成されている。2. Description of the Related Art Solar cells are known as electronic components in which electrodes are formed on a p-type silicon semiconductor substrate. As shown in FIG. 1, the solar cell has a thickness of 300 to 400 μm.
m p-type silicon semiconductor substrate 1 is used. p
The type silicon semiconductor substrate 1 has a thickness of 0.3 on the light receiving surface side.
An n-type impurity layer 2 having a thickness of 0.5 μm, an antireflection film 3 and a grid electrode 4 are formed thereon.
【０００３】また、ｐ型シリコン半導体基板１の裏面側
には、裏面電極層５が形成されている。裏面電極層５
は、アルミニウム粉末、ガラスフリットおよび有機質ビ
ヒクルからなるペースト組成物をスクリーン印刷等によ
って塗布し、乾燥した後、６６０℃（アルミニウムの融
点）以上の温度にて焼成することによって形成されてい
る。この焼成の際にアルミニウムがｐ型シリコン半導体
基板１の内部に拡散することにより、裏面電極層５とｐ
型シリコン半導体基板１との間にＡｌ−Ｓｉ合金層６が
形成されると同時に、アルミニウム原子の拡散による拡
散層としてｐ+層７が形成される。このｐ+層７の存在に
より、生成キャリアの収集効率が向上するＢＳＦ（Back
Surface Field)効果が得られる。実際の裏面電極は、
焼成後の裏面電極層５、Ａｌ−Ｓｉ合金層６およびｐ+
層７の三層をそのままで使用する場合と、電気抵抗を低
減させるために、焼成後の裏面電極層５、または焼成後
の裏面電極層５とＡｌ−Ｓｉ合金層６を化学的方法等に
よって除去した後、銀や銅からなる電極層を形成して使
用する場合がある。いずれの場合においても、ｐ+層７
がＢＳＦ効果を発揮する。A back electrode layer 5 is formed on the back side of the p-type silicon semiconductor substrate 1. Back electrode layer 5
Is formed by applying a paste composition composed of aluminum powder, glass frit and an organic vehicle by screen printing or the like, drying and firing at a temperature of 660 ° C. (melting point of aluminum) or higher. During this firing, aluminum diffuses into the p-type silicon semiconductor substrate 1 so that the back electrode layer 5 and p
At the same time as the Al—Si alloy layer 6 is formed between the type silicon semiconductor substrate 1 and the p + layer 7 as a diffusion layer by diffusion of aluminum atoms. Due to the presence of the p + layer 7, the BSF (Back
Surface Field) effect is obtained. The actual back electrode is
Back electrode layer 5, Al-Si alloy layer 6 and p + after firing
When the three layers of the layer 7 are used as they are, or in order to reduce the electric resistance, the back electrode layer 5 after firing, or the back electrode layer 5 after firing and the Al—Si alloy layer 6 are formed by a chemical method or the like. After the removal, an electrode layer made of silver or copper may be formed and used. In either case, p + layer 7
Exhibits the BSF effect.
【０００４】[0004]
【発明が解決しようとする課題】近年、太陽電池の出力
を向上させることが強く要求されている。太陽電池の出
力の向上を図るための一つの対策として、ＢＳＦ効果の
向上や電極の電気抵抗の低減が望まれている。この目的
のために、上記のｐ+層を形成するために用いられるペ
ースト組成物について種々検討されている。In recent years, there has been a strong demand for improving the output of solar cells. As one measure for improving the output of the solar cell, improvement of BSF effect and reduction of electric resistance of electrodes are desired. For this purpose, various studies have been made on the paste composition used for forming the p + layer.
【０００５】たとえば、特開２０００−９０７３４号公
報には、アルミニウム粉末、ガラスフリット、有機質ビ
ヒクルに加えて、さらにアルミニウム含有有機化合物を
含有する導電性ペーストが開示されている。また、特開
平８−１４８４４７号公報には、ペースト全体に対する
配合比率が６０〜９０ｗｔ％の範囲内にある固形分と、
１０〜４０ｗｔ％の範囲内にある有機質ビヒクルからな
り、かつ、固形分は、固形分全体に対する配合比率が８
５〜９８．５ｗｔ％の範囲内にある銀粉末と、０．５〜
１０ｗｔ％の範囲内にあるアルミニウム粉末と、１〜１
０ｗｔ％の範囲内にあるガラスフリットを含んだもので
あることを特徴とした導電性ペーストが開示されてい
る。しかしながら、これらの公報で開示されたペースト
を用いても、太陽電池の出力のさらなる向上という要求
を充分満足するほど、ＢＳＦ効果の向上や電極の電気抵
抗の低減を達成できていないのが現状である。For example, Japanese Unexamined Patent Publication No. 2000-90734 discloses a conductive paste containing an aluminum powder, a glass frit, an organic vehicle, and an aluminum-containing organic compound. Further, in Japanese Patent Application Laid-Open No. 8-148447, solid contents having a mixing ratio of 60 to 90 wt% with respect to the entire paste,
It is composed of an organic vehicle within the range of 10 to 40 wt%, and the solid content is 8 in the total solid content.
Silver powder in the range of 5 to 98.5 wt% and 0.5 to
Aluminum powder in the range of 10 wt%, 1-1
A conductive paste characterized by containing a glass frit in the range of 0 wt% is disclosed. However, even if the pastes disclosed in these publications are used, the BSF effect cannot be improved and the electrical resistance of the electrode cannot be reduced enough to satisfy the demand for further improvement of the output of the solar cell. is there.
【０００６】そこで、この発明の目的は、ＢＳＦ効果を
さらに向上させることが可能なペースト組成物と、その
組成物を用いて形成された電極を備えた太陽電池を提供
することである。[0006] Therefore, an object of the present invention is to provide a paste composition capable of further improving the BSF effect, and a solar cell provided with an electrode formed by using the composition.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、鋭意研究
を重ねた結果、特定の組成を有するペースト組成物を使
用することにより、上記の目的を達成できることを見出
した。この知見に基づいて、本発明に従ったペースト組
成物は、次のような特徴を備えている。As a result of intensive studies, the present inventors have found that the above object can be achieved by using a paste composition having a specific composition. Based on this finding, the paste composition according to the present invention has the following features.
【０００８】この発明に従ったペースト組成物は、ｐ型
シリコン半導体基板の上に電極を形成するためのペース
ト組成物であって、アルミニウム粉末と、有機質ビヒク
ルと、ガラスフリットと、ホウ素粉末、無機ホウ素化合
物および有機ホウ素化合物からなる群から選ばれた少な
くとも１種とを含む。A paste composition according to the present invention is a paste composition for forming an electrode on a p-type silicon semiconductor substrate, which is an aluminum powder, an organic vehicle, a glass frit, a boron powder, an inorganic material. At least one selected from the group consisting of boron compounds and organic boron compounds.
【０００９】好ましくは、この発明のペースト組成物
は、ホウ素粉末、無機ホウ素化合物および有機ホウ素化
合物からなる群から選ばれた少なくとも１種を、ホウ素
換算で０．０１質量％以上５．０質量％以下含む。Preferably, the paste composition of the present invention comprises at least 0.01% by mass and 5.0% by mass in terms of boron of at least one selected from the group consisting of boron powder, inorganic boron compounds and organic boron compounds. Including:
【００１０】さらに好ましくは、この発明のペースト組
成物は、アルミニウム粉末を６０質量％以上７５質量％
以下、ガラスフリットを０．３質量％以上５．０質量％
以下、有機質ビヒクルを２０質量％以上３０質量％以
下、ホウ素粉末、無機ホウ素化合物および有機ホウ素化
合物からなる群から選ばれた少なくとも１種を、ホウ素
換算で０．０１質量％以上５．０質量％以下含む。More preferably, the paste composition of the present invention contains 60% by mass or more and 75% by mass or more of aluminum powder.
Below, 0.3 mass% to 5.0 mass% of glass frit
Hereinafter, at least one selected from the group consisting of an organic vehicle of 20% by mass or more and 30% by mass or less, a boron powder, an inorganic boron compound and an organic boron compound is 0.01% by mass or more and 5.0% by mass in terms of boron. Including:
【００１１】この発明のペースト組成物において、無機
ホウ素化合物は、炭化物、酸化物、塩化物、臭化物、ヨ
ウ化物、弗化物、窒化物およびホウ酸から選ばれた少な
くとも１種であるのが好ましい。In the paste composition of the present invention, the inorganic boron compound is preferably at least one selected from carbide, oxide, chloride, bromide, iodide, fluoride, nitride and boric acid.
【００１２】また、この発明のペースト組成物におい
て、有機ホウ素化合物は、トリメトキシボロン、トリエ
トキシボロン、トリプロポキシボロンおよびトリプトキ
シボロンからなる群から選ばれた少なくとも１種である
のが好ましい。In the paste composition of the present invention, the organoboron compound is preferably at least one selected from the group consisting of trimethoxyboron, triethoxyboron, tripropoxyboron and tryptoxyboron.
【００１３】この発明に従った太陽電池は、上述の特徴
を有するペースト組成物をｐ型シリコン半導体基板の上
に塗布した後、焼成することにより形成した電極を備え
る。A solar cell according to the present invention includes an electrode formed by applying a paste composition having the above-mentioned characteristics onto a p-type silicon semiconductor substrate and then firing the applied paste composition.
【００１４】[0014]
【発明の実施の形態】この発明のペースト組成物は、ア
ルミニウム粉末、ガラスフリット、有機質ビヒクルに加
えて、さらに、ホウ素粉末、無機ホウ素化合物および有
機ホウ素化合物からなる群より選ばれた少なくとも１種
のホウ素含有物を含有することを特徴としている。従来
の組成にホウ素含有物を加えることにより、ＢＳＦ効果
をさらに向上させることが可能な電極形成材料としての
ペースト組成物が得られる。BEST MODE FOR CARRYING OUT THE INVENTION In addition to aluminum powder, glass frit and organic vehicle, the paste composition of the present invention further comprises at least one selected from the group consisting of boron powder, inorganic boron compounds and organic boron compounds. It is characterized by containing a boron-containing material. By adding a boron-containing material to the conventional composition, a paste composition as an electrode forming material capable of further improving the BSF effect can be obtained.
【００１５】上記のホウ素含有物を含有させることによ
り、ＢＳＦ効果が向上する理由は明らかではないが、次
のように推測される。ホウ素原子の存在によって、ペー
ストの焼成時にアルミニウム原子がｐ型シリコン半導体
基板の表面から内部に拡散しやすくなるので、ＢＳＦ効
果が向上する。あるいは、ペーストの焼成時にホウ素原
子そのものがｐ型シリコン半導体基板の内部に拡散する
ことによって、ＢＳＦ効果が向上する。The reason why the BSF effect is improved by including the above-mentioned boron-containing substance is not clear, but it is presumed as follows. The presence of boron atoms facilitates the diffusion of aluminum atoms from the surface of the p-type silicon semiconductor substrate to the inside during firing of the paste, thus improving the BSF effect. Alternatively, the BSF effect is improved by diffusing boron atoms themselves into the p-type silicon semiconductor substrate during firing of the paste.
【００１６】本発明のペースト組成物に含められる無機
ホウ素化合物としては、炭化物、酸化物、塩化物、臭化
物、ヨウ化物、弗化物、窒化物またはホウ酸が挙げられ
るが、これらの化合物に限定されるものではない。ま
た、本発明のペースト組成物に含められる有機ホウ素化
合物としては、トリメトキシボロン、トリエトキシボロ
ン、トリプロポキシボロンまたはトリプトキシボロンが
挙げられるが、これらの化合物に限定されるものではな
い。The inorganic boron compounds included in the paste composition of the present invention include, but are not limited to, carbides, oxides, chlorides, bromides, iodides, fluorides, nitrides or boric acid. Not something. Examples of the organoboron compound included in the paste composition of the present invention include, but are not limited to, trimethoxyboron, triethoxyboron, tripropoxyboron, and tryptoxyboron.
【００１７】本発明のペースト組成物に含められるホウ
素粉末、無機ホウ素化合物および有機ホウ素化合物から
なる群より選ばれた少なくとも１種のホウ素含有物の含
有量は、ホウ素換算で０．０１質量％以上５．０質量％
以下であることが好ましい。ホウ素含有物の含有量が
０．０１質量％未満では、ＢＳＦ効果を高めるほどの充
分な添加効果を得ることができない。ホウ素含有物の含
有量が５．０質量％を超えると、スクリーン印刷等にお
けるペーストの塗布性が低下する。The content of at least one boron-containing substance selected from the group consisting of a boron powder, an inorganic boron compound and an organic boron compound contained in the paste composition of the present invention is 0.01% by mass or more in terms of boron. 5.0 mass%
The following is preferable. If the content of the boron-containing substance is less than 0.01% by mass, a sufficient addition effect to enhance the BSF effect cannot be obtained. When the content of the boron-containing substance exceeds 5.0% by mass, the applicability of the paste in screen printing or the like deteriorates.
【００１８】また、本発明のペースト組成物に含められ
るアルミニウム粉末の含有量は、６０質量％以上７５質
量％以下であることが好ましい。アルミニウム粉末の含
有量が６０質量％未満では、焼成後の裏面電極の電気抵
抗が高くなり、太陽電池の特性低下を招くおそれがあ
る。アルミニウム粉末の含有量が７５質量％を超える
と、スクリーン印刷等におけるペーストの塗布性が低下
する。The content of the aluminum powder contained in the paste composition of the present invention is preferably 60% by mass or more and 75% by mass or less. When the content of the aluminum powder is less than 60% by mass, the electric resistance of the back electrode after firing becomes high, which may cause deterioration of the characteristics of the solar cell. When the content of the aluminum powder exceeds 75% by mass, the applicability of the paste in screen printing or the like deteriorates.
【００１９】さらに、本発明のペースト組成物に含めら
れるガラスフリットの含有量は、０．３質量％以上５．
０質量％以下であることが好ましい。ガラスフリット
は、焼成後の裏面電極とｐ型シリコン半導体基板との密
着性を向上させるために添加されているものである。ガ
ラスフリットの含有量が０．３質量％未満では、焼成後
の裏面電極の接着強度が低下する。ガラスフリットの含
有量が５．０質量％を超えれば、ガラスの偏析が生じる
おそれがある。Further, the content of the glass frit contained in the paste composition of the present invention is 0.3% by mass or more.
It is preferably 0% by mass or less. The glass frit is added to improve the adhesion between the back electrode after firing and the p-type silicon semiconductor substrate. When the content of the glass frit is less than 0.3% by mass, the adhesive strength of the back electrode after firing is lowered. If the content of the glass frit exceeds 5.0% by mass, segregation of glass may occur.
【００２０】本発明のペースト組成物に含まれるガラス
フリットとしては、ＳｉＯ2-Ｂｉ2Ｏ3−ＰｂＯ系の他
に、Ｂ2Ｏ3−ＳｉＯ2−Ｂｉ2Ｏ3系、Ｂ2Ｏ3−ＳｉＯ2−
ＺｎＯ系、Ｂ2Ｏ3−ＳｉＯ2−ＰｂＯ系等のホウ素を含
んだものも挙げられる。しかし、本発明のペースト組成
物では、ガラスフリット中のホウ素の有無にかかわら
ず、上記のホウ素含有物を含有させることによって、Ｂ
ＳＦ効果を確実に向上させることができる。As the glass frit contained in the paste composition of the present invention, in addition to SiO 2 -Bi 2 O 3 -PbO type, B 2 O 3 -SiO 2 -Bi 2 O 3 type, B 2 O 3 -type. SiO 2 −
Examples thereof include those containing boron such as ZnO type and B 2 O 3 —SiO 2 —PbO type. However, in the paste composition of the present invention, by incorporating the above-mentioned boron-containing material in the glass frit with or without boron, B
The SF effect can be surely improved.
【００２１】本発明のペースト組成物に含められる有機
質ビヒクルとしては、エチルセルロース、アクリル樹
脂、アルキッド樹脂等を溶剤に溶解したものが使用され
る。有機質ビヒクルの含有量は２０質量％以上３０質量
％以下であることが好ましい。有機質ビヒクルの含有量
が２０質量％未満では、ペーストの印刷性が低下する。
有機質ビヒクルの含有量が３０質量％を超えれば、焼成
後の裏面電極の密度が低下し、電極の電気抵抗が増大す
る。As the organic vehicle contained in the paste composition of the present invention, ethyl cellulose, acrylic resin, alkyd resin or the like dissolved in a solvent is used. The content of the organic vehicle is preferably 20% by mass or more and 30% by mass or less. If the content of the organic vehicle is less than 20% by mass, the printability of the paste will deteriorate.
When the content of the organic vehicle exceeds 30% by mass, the density of the back surface electrode after firing is decreased and the electric resistance of the electrode is increased.
【００２２】[0022]
【実施例】以下、本発明の一つの実施例について説明す
る。EXAMPLE One example of the present invention will be described below.
【００２３】まず、アルミニウム粉末を６０〜７５質量
％、ガラスフリットを０．３〜５．０質量％、有機質ビ
ヒクルを２０〜３０質量％の範囲内で含有するととも
に、ホウ素粉末、無機ホウ素化合物または有機ホウ素化
合物のホウ素（Ｂ）含有物を表１に示す割合（ホウ素
（Ｂ）換算添加量）で含有する各種のペースト組成物を
作製した。First, the aluminum powder is contained in the range of 60 to 75% by mass, the glass frit is contained in the range of 0.3 to 5.0% by mass, the organic vehicle is contained in the range of 20 to 30% by mass, and the boron powder, the inorganic boron compound or Various paste compositions containing the boron (B) -containing material of the organic boron compound in the proportions (boron (B) -equivalent addition amount) shown in Table 1 were prepared.
【００２４】具体的には、エチルセルロースをグリコー
ルエーテル系有機溶剤に溶解した有機質ビヒクルに、ア
ルミニウム粉末とＢ2Ｏ3−ＳｉＯ2−ＰｂＯ系のガラス
フリットを加え、さらに表１に示す各種のホウ素含有物
を加えて、周知の混合機にて混合し、ペースト組成物を
得た。Specifically, aluminum powder and a B 2 O 3 --SiO 2 --PbO glass frit are added to an organic vehicle obtained by dissolving ethyl cellulose in a glycol ether organic solvent, and various boron-containing materials shown in Table 1 are added. Then, the mixture was mixed with a well-known mixer to obtain a paste composition.
【００２５】ここで、アルミニウム粉末は、ｐ型シリコ
ン半導体基板との反応性の確保、塗布性、および塗布膜
の均一性の点から、平均粒径２〜２０μｍの球形、また
は球形に近い形状を有する粒子からなる粉末を用いるの
が好ましい。上記のペースト組成物の作製で用いたアル
ミニウム（Ａｌ）粉末の平均粒径を表１に示す。Here, the aluminum powder has a spherical shape with an average particle diameter of 2 to 20 μm, or a shape close to a spherical shape, from the viewpoint of ensuring the reactivity with the p-type silicon semiconductor substrate, the coating property, and the uniformity of the coating film. It is preferable to use a powder consisting of the particles having. Table 1 shows the average particle size of the aluminum (Al) powder used in the preparation of the above paste composition.
【００２６】表１に示すホウ素（Ｂ）含有物として、ホ
ウ素（Ｂ）粉末は試薬の２５０メッシュ通過品、ホウ酸
は試薬の２５０メッシュ通過品、酸化ホウ素は試薬の２
５０メッシュ通過品、炭化ホウ素は共立マテリアル株式
会社製のＢ４Ｃ−Ｊ５、トリエトキシボロンは試薬を用
いた。As the boron (B) -containing material shown in Table 1, boron (B) powder is a reagent of 250 mesh passing product, boric acid is a reagent of 250 mesh passing product, and boron oxide is a reagent of 2 mesh.
50 mesh passed product, B4C-J5 manufactured by Kyoritsu Material Co., Ltd. was used for boron carbide, and a reagent was used for triethoxyboron.
【００２７】上記の各種のペースト組成物を厚みが３０
０μｍ、大きさが２インチ（５０．８ｍｍ）×２インチ
（５０．８ｍｍ）のｐ型シリコン半導体基板に１８０メ
ッシュのスクリーン印刷版を用いて塗布・印刷し、乾燥
させた。The various paste compositions described above were used in a thickness of 30.
A p-type silicon semiconductor substrate having a size of 0 μm and a size of 2 inches (50.8 mm) × 2 inches (50.8 mm) was applied / printed using a 180 mesh screen printing plate and dried.
【００２８】塗布量は、焼成後の電極の厚みが４０〜６
０μｍになるように設定した。スクリーン印刷の評価
は、シリコン（Ｓｉ）基板に１００％印刷できれば○、
スクリーン印刷版にペースト組成物が残留し、シリコン
基板への印刷面積が１００％未満から９５％の範囲であ
れば△、９５％未満であれば×とした。この評価は表１
のスクリーン印刷性で示している。The coating amount is such that the thickness of the electrode after firing is 40 to 6
It was set to be 0 μm. The evaluation of screen printing is ○ if 100% can be printed on a silicon (Si) substrate,
When the paste composition remained on the screen printing plate and the printing area on the silicon substrate was in the range of less than 100% to 95%, it was evaluated as Δ, and when it was less than 95%, it was evaluated as x. This evaluation is shown in Table 1.
The screen printability is shown.
【００２９】ペーストが印刷されたｐ型シリコン半導体
基板を乾燥した後、赤外線焼成炉にて、空気雰囲気で４
００℃／分の加熱速度で加熱し、７１０〜７２０℃の温
度で３０秒間保持する条件で焼成した。焼成後、冷却す
ることにより、図１に示すようにｐ型シリコン半導体基
板１に裏面電極層５を形成した構造を得た。After drying the p-type silicon semiconductor substrate on which the paste is printed, the p-type silicon semiconductor substrate is dried in an infrared baking furnace in an air atmosphere for 4 hours.
Firing was performed under the conditions of heating at a heating rate of 00 ° C./min and holding at a temperature of 710 to 720 ° C. for 30 seconds. After firing, it was cooled to obtain a structure in which the back electrode layer 5 was formed on the p-type silicon semiconductor substrate 1 as shown in FIG.
【００３０】その後、裏面電極層を形成したｐ型シリコ
ン半導体基板を塩酸水溶液に浸漬することによって、裏
面電極層５とＡｌ−Ｓｉ合金層６を溶解除去した後、ｐ
+層７が形成されたｐ型シリコン半導体基板の表面抵抗
を、４探針式表面抵抗測定器にて測定した。ｐ+層７の
表面抵抗とＢＳＦ効果との間には相関関係があり、その
表面抵抗が小さいほど、ＢＳＦ効果が高いとされてい
る。シリコン（Ｓｉ）基板のｐ+層の表面抵抗を表１に
示す。After that, the p-type silicon semiconductor substrate having the back electrode layer formed thereon is dipped in a hydrochloric acid aqueous solution to dissolve and remove the back electrode layer 5 and the Al--Si alloy layer 6, and then p
The surface resistance of the p-type silicon semiconductor substrate on which the + layer 7 was formed was measured by a 4-probe surface resistance measuring instrument. There is a correlation between the surface resistance of the p + layer 7 and the BSF effect, and it is said that the smaller the surface resistance, the higher the BSF effect. Table 1 shows the surface resistance of the p + layer of the silicon (Si) substrate.
【００３１】[0031]
【表１】 [Table 1]
【００３２】表１に示す結果から、アルミニウム粉末の
平均粒径に関係なく、無添加の従来例においては焼成後
のｐ+層の表面抵抗が１２．０Ω□以上であったのに対
して、ホウ素含有物を０．０１質量％以上添加した場合
にはｐ+層の表面抵抗を１０．０Ω□以下まで低減させ
ることができる。また、ホウ素含有物は、ホウ素粉末、
ホウ酸、酸化ホウ素またはトリエトキシボロンのいずれ
の形態で添加しても上記の効果を達成できることがわか
る。From the results shown in Table 1, the surface resistance of the p + layer after firing was 12.0 Ω □ or more in the conventional example without addition, irrespective of the average particle size of the aluminum powder. When 0.01 mass% or more of the boron-containing material is added, the surface resistance of the p + layer can be reduced to 10.0 Ω □ or less. Further, the boron-containing material is boron powder,
It can be seen that the above effect can be achieved by adding any one of boric acid, boron oxide and triethoxyboron.
【００３３】以上に開示された実施の形態や実施例はす
べての点で例示であって制限的なものではないと考慮さ
れるべきである。本発明の範囲は、以上の実施の形態や
実施例ではなく、特許請求の範囲によって示され、特許
請求の範囲と均等の意味および範囲内でのすべての修正
や変形を含むものと意図される。It should be considered that the embodiments and examples disclosed above are illustrative in all points and not restrictive. The scope of the present invention is shown not by the above-described embodiments and examples but by the scope of the claims, and is intended to include meanings equivalent to the scope of the claims and all modifications and variations within the scope. .
【００３４】[0034]
【発明の効果】以上のように、この発明によれば、ホウ
素含有物を含む本発明のペースト組成物を塗布したｐ型
シリコン半導体基板を焼成することにより、ｐ+層の表
面抵抗を低減させることができるので、ＢＳＦ効果をよ
り一層高めることができ、結果として太陽電池の出力を
向上させることができる。As described above, according to the present invention, the surface resistance of the p + layer is reduced by baking the p-type silicon semiconductor substrate coated with the paste composition of the present invention containing the boron-containing material. Therefore, the BSF effect can be further enhanced, and as a result, the output of the solar cell can be improved.
【図１】 この発明が適用される太陽電池の断面構造を
模式的に示す図である。FIG. 1 is a diagram schematically showing a cross-sectional structure of a solar cell to which the present invention is applied.
１：ｐ型シリコン半導体基板、２：ｎ型不純物層、３：
反射防止膜、４：グリッド電極、５：裏面電極層、６：
Ａｌ−Ｓｉ合金層、７：ｐ+層。1: p-type silicon semiconductor substrate, 2: n-type impurity layer, 3:
Antireflection film, 4: Grid electrode, 5: Back electrode layer, 6:
Al-Si alloy layer, 7: p + layer.
Claims (6)
成するためのペースト組成物であって、 アルミニウム粉末と、有機質ビヒクルと、ガラスフリッ
トと、ホウ素粉末、無機ホウ素化合物および有機ホウ素
化合物からなる群から選ばれた少なくとも１種とを含
む、ペースト組成物。1. A paste composition for forming an electrode on a p-type silicon semiconductor substrate, comprising an aluminum powder, an organic vehicle, a glass frit, a boron powder, an inorganic boron compound and an organic boron compound. A paste composition comprising at least one selected from the group.
機ホウ素化合物からなる群から選ばれた少なくとも１種
を、ホウ素換算で０．０１質量％以上５．０質量％以下
含む、請求項１に記載のペースト組成物。2. The method according to claim 1, wherein the content of at least one selected from the group consisting of boron powder, an inorganic boron compound and an organic boron compound is 0.01 mass% or more and 5.0 mass% or less in terms of boron. Paste composition.
質量％以下、ガラスフリットを０．３質量％以上５．０
質量％以下、有機質ビヒクルを２０質量％以上３０質量
％以下、ホウ素粉末、無機ホウ素化合物および有機ホウ
素化合物からなる群から選ばれた少なくとも１種を、ホ
ウ素換算で０．０１質量％以上５．０質量％以下含む、
請求項１に記載のペースト組成物。3. Aluminum powder in an amount of 60% by mass or more and 75
Mass% or less, glass frit 0.3 mass% or more 5.0
At least one selected from the group consisting of mass% or less, organic vehicle of 20 mass% or more and 30 mass% or less, boron powder, inorganic boron compound and organic boron compound is 0.01 mass% or more and 5.0 in terms of boron. Including less than or equal to mass%,
The paste composition according to claim 1.
物、塩化物、臭化物、ヨウ化物、弗化物、窒化物および
ホウ酸から選ばれた少なくとも１種である、請求項１か
ら請求項３までのいずれか１項に記載のペースト組成
物。4. The inorganic boron compound is at least one selected from carbides, oxides, chlorides, bromides, iodides, fluorides, nitrides and boric acid. The paste composition according to any one of 1.
ボロン、トリエトキシボロン、トリプロポキシボロンお
よびトリプトキシボロンからなる群から選ばれた少なく
とも１種である、請求項１から請求項３までのいずれか
１項に記載のペースト組成物。5. The organic boron compound according to claim 1, wherein the organoboron compound is at least one selected from the group consisting of trimethoxyboron, triethoxyboron, tripropoxyboron, and tryptoxyboron. The paste composition according to item 1.
項に記載のペースト組成物をｐ型シリコン半導体基板の
上に塗布した後、焼成することにより形成した電極を備
えた、太陽電池。6. Any one of claims 1 to 5
A solar cell comprising an electrode formed by applying the paste composition according to the item 1 above on a p-type silicon semiconductor substrate and then firing the applied paste composition.
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|---|---|---|---|
| JP2001251166A JP4726354B2 (en) | 2001-08-22 | 2001-08-22 | Paste composition and solar cell using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001251166A JP4726354B2 (en) | 2001-08-22 | 2001-08-22 | Paste composition and solar cell using the same |
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|---|---|
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ID=19079853
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