JPH06204512A - Electrode paste for semiconductor substrate - Google Patents
Electrode paste for semiconductor substrateInfo
- Publication number
- JPH06204512A JPH06204512A JP5001006A JP100693A JPH06204512A JP H06204512 A JPH06204512 A JP H06204512A JP 5001006 A JP5001006 A JP 5001006A JP 100693 A JP100693 A JP 100693A JP H06204512 A JPH06204512 A JP H06204512A
- Authority
- JP
- Japan
- Prior art keywords
- phosphorus
- electrode
- semiconductor substrate
- pts
- electrode paste
- 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.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 44
- 239000004065 semiconductor Substances 0.000 title claims abstract description 31
- 239000002003 electrode paste Substances 0.000 title claims abstract description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 43
- 239000011574 phosphorus Substances 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 3
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910000679 solder Inorganic materials 0.000 abstract description 13
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract 2
- 238000002360 preparation method Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 239000010703 silicon Substances 0.000 description 15
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- -1 oxyacid Chemical compound 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- YOMVJXWHNWGAMU-UHFFFAOYSA-N [Ag]#P Chemical compound [Ag]#P YOMVJXWHNWGAMU-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は半導体基板上に形成され
る電極ペーストに関し、特に太陽電池などの半導体基板
上にスクリーン印刷により形成される電極ペーストに関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode paste formed on a semiconductor substrate, and more particularly to an electrode paste formed by screen printing on a semiconductor substrate such as a solar cell.
【０００２】[0002]
【従来の技術および発明が解決しようとする課題】近
年、自然との調和を保ちつつ産業の発達を図るという観
点から環境問題がクローズアップされ、クリーンなエネ
ルギーに対する要求が強まっており、その中の１つの手
段として太陽電池に対する関心が高まっている。ところ
で、太陽電池の基本は約１００年前にセレン光電池ある
い亜酸化銅光電池に始まったが、変換効率が１〜１．５
％と低いため、実用化には至らなかった。その後半導体
工学の発展により、特に１９５４年単結晶Ｓｉを用いた
大面積ｐｎ接合作製技術の確立により、変換効率が６％
ほどになり、現在の太陽電池の変換効率としては、１０
〜１５％程度のものが得られている。この太陽電池の実
用化にあたっての課題は、係る変換効率の向上を図りつ
つ製造コストを低減することにある。そのため、電極形
成についても、高生産性で自動連続化が可能であるとい
うことから、受光面電極、裏面電極ともに、従来の真空
蒸着に代わって低コストの印刷法が採用されている。こ
の印刷法による電極形成のために用いられる導電ペース
ト（以下「電極ペースト」という）には、半導体基板と
の密着性が良いこと、接触抵抗が小さいこと（オーミッ
ク接触をすること）、電極ペーストの抵抗値が低いこと
などの特性が要求されており、次のような電極ペースト
が公知である。2. Description of the Related Art Recently, environmental problems have been highlighted from the viewpoint of industrial development while maintaining harmony with nature, and the demand for clean energy is increasing. There is growing interest in solar cells as one means. By the way, the basics of solar cells began about 100 years ago with selenium photovoltaic cells or cuprous oxide photovoltaic cells, but the conversion efficiency is 1 to 1.5.
%, So low that it could not be put to practical use. After that, due to the development of semiconductor engineering, especially in 1954, the conversion efficiency was 6% due to the establishment of large area pn junction fabrication technology using single crystal Si.
The current solar cell conversion efficiency is 10
Approximately 15% is obtained. The problem in putting this solar cell to practical use is to reduce the manufacturing cost while improving the conversion efficiency. Therefore, as for the electrode formation, since it is possible to achieve high productivity and automatic continuation, a low-cost printing method is adopted for both the light-receiving surface electrode and the back surface electrode instead of the conventional vacuum deposition. The conductive paste (hereinafter referred to as "electrode paste") used for forming electrodes by this printing method has good adhesiveness with a semiconductor substrate, low contact resistance (makes ohmic contact), Properties such as low resistance are required, and the following electrode pastes are known.
【０００３】まず、特開昭５４−２６６７６号公報に
は、「Ａｇペースト中にＡｌまたはＴｉを加えた電極材
料をシリコン基板上に印刷し、これをＮ2 雰囲気中で低
温焼成し、もって電極とシリコン基板との接触抵抗が低
い半導体装置を製造せんとする方法およびその半導体装
置に関する発明」が開示されている（以下「従来技術
Ｉ」という）。また、特開昭５９−３３８６７号公報に
は、「Ａｇペースト中に稀土類元素を加えた電極材料を
シリコン基板上に印刷焼成し、焼成時に半導体表面に形
成される酸化ケイ素を稀土類元素によって還元し、もっ
て電極とシリコン基板との接触抵抗の低い電極材料を得
んとする発明」が開示されている（以下「従来技術II」
という）。First, JP-A-54-26676 discloses that "an electrode material obtained by adding Al or Ti to an Ag paste is printed on a silicon substrate, and this is baked at a low temperature in an N 2 atmosphere to obtain an electrode. A method for manufacturing a semiconductor device having a low contact resistance with a silicon substrate and an invention relating to the semiconductor device "are disclosed (hereinafter referred to as" prior art I "). Further, JP-A-59-33867 discloses that "an electrode material obtained by adding a rare earth element to an Ag paste is printed and fired on a silicon substrate, and silicon oxide formed on a semiconductor surface at the time of firing is changed by the rare earth element. "Invention in which an electrode material having a reduced contact resistance between the electrode and the silicon substrate is obtained" is disclosed (hereinafter referred to as "prior art II").
That).
【０００４】このように、シリコン基板と電極とのオー
ミック接触をできるだけ形成し、変換効率の向上を図る
ための各種の提案がされている。しかしながら、従来技
術にあっては焼成後の半導体基板と電極との間の接着強
度は必ずしも十分でなく、特に過酷な環境下で用いられ
る太陽電池においては、初期の強度が高くとも経時的に
劣化し、電極の剥がれに至ることがあった。また、太陽
電池の変換効率を左右する重要な要素として、半導体基
板と電極間の接触抵抗があるが、基板と電極間の密着性
が十分でない場合、両者の接触不良による接触抵抗の増
大や整流性接触の発現により変換効率が低くなる。例え
ば、従来技術Ｉに係る方法で作製された太陽電池の変換
効率は最大１２％であり、実用的に十分でなく、その接
触抵抗も１０-2〜１０-3Ω−cmの範囲にあり、それほど
低いとは言えない。また、従来技術IIの電極材料をその
電極とする太陽電池の接触抵抗は０．０３〜０．３４Ω
−cmの範囲にあり、従来技術Ｉよりさらに高くなってい
る。As described above, various proposals have been made for improving the conversion efficiency by forming ohmic contact between the silicon substrate and the electrode as much as possible. However, in the conventional technique, the adhesive strength between the semiconductor substrate and the electrode after firing is not always sufficient, and in a solar cell used in a particularly harsh environment, even if the initial strength is high, it deteriorates with time. However, the electrodes may come off. In addition, the contact resistance between the semiconductor substrate and the electrode is an important factor that affects the conversion efficiency of the solar cell, but if the adhesion between the substrate and the electrode is not sufficient, increase in contact resistance or rectification due to poor contact between the two The conversion efficiency decreases due to the occurrence of sexual contact. For example, the conversion efficiency of the solar cell manufactured by the method according to the conventional technique I is 12% at maximum, which is not practically sufficient, and the contact resistance thereof is in the range of 10 -2 to 10 -3 Ω-cm. Not so low. Further, the contact resistance of a solar cell using the electrode material of Conventional Technique II as its electrode is 0.03 to 0.34 Ω.
It is in the range of −cm, which is higher than that of the prior art I.
【０００５】本発明は従来の技術の有するこのような問
題点に鑑みてなされたものであって、その目的は、半導
体基板との密着性が良好で、接触抵抗が十分に小さい半
導体基板用電極ペーストを提供することにある。The present invention has been made in view of the above problems of the prior art, and an object thereof is an electrode for a semiconductor substrate which has good adhesion to the semiconductor substrate and has a sufficiently small contact resistance. To provide the paste.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に本発明は、銀粉末１００重量部とリン及び／またはリ
ンを含む化合物０．１〜３．０重量部と有機ビヒクル１
５〜４０重量部を有することを特徴とする半導体基板用
電極ペーストを第一の発明とし、上記第一の発明におい
て、リンを含む化合物が酸化リン、酸素酸、リン酸塩、
リン化物およびリンの有機化合物のうち１種以上のもの
からなることを特徴とする半導体基板用電極ペーストを
第二の発明とし、上記第二の発明において、リン酸塩が
リン酸アンモニウムであることを特徴とする半導体基板
用電極ペーストを第三の発明とし、上記第二の発明にお
いて、リン化物が、ＡｓＰ、ＢＰ、Ｃ3 Ｐ、ＳｉＰ、Ｓ
ｎＰ3 、Ｓｎ3 Ｐ4 、Ｓｎ4 Ｐ3 、ＴｉＰ、ＺｒＰ2 お
よびＺｒＰのうち１種以上のものからなることを特徴と
する半導体基板用電極ペーストを第四の発明とし、上記
第二の発明において、リンの有機化合物がリン酸エステ
ルであることを特徴とする半導体基板用電極ペーストを
第五の発明とする。To achieve the above object, the present invention provides 100 parts by weight of silver powder, 0.1 to 3.0 parts by weight of phosphorus and / or a compound containing phosphorus, and organic vehicle 1.
The electrode paste for a semiconductor substrate is characterized by having 5 to 40 parts by weight, and the compound containing phosphorus is phosphorus oxide, oxyacid, phosphate,
A second invention is an electrode paste for a semiconductor substrate, which comprises one or more of a phosphide and an organic compound of phosphorus, and in the above second invention, the phosphate is ammonium phosphate. A semiconductor substrate electrode paste characterized by the above-mentioned is a third invention, and in the second invention, the phosphide is AsP, BP, C 3 P, SiP, S.
A fourth invention is an electrode paste for a semiconductor substrate, which comprises at least one of nP 3 , Sn 3 P 4 , Sn 4 P 3 , TiP, ZrP 2 and ZrP. In the fifth invention, the electrode paste for a semiconductor substrate is characterized in that the organic compound of phosphorus is a phosphoric acid ester.
【０００７】銀粉末ならびに有機ビヒクルは、一般の電
極ペースト材料に用いられているものが使用できる。例
えば、銀粉末の粒径は１０μｍ以下で、その形状は球
状、フレーク状等のいかなるものでも使用できる。有機
ビヒクルとしては、例えばセルロース系やアクリレート
系の樹脂をターピネオール、ブチルカルビトール、セル
ソルブ等の溶剤に溶解したものを使用することができ
る。As the silver powder and the organic vehicle, those used in general electrode paste materials can be used. For example, the particle size of the silver powder is 10 μm or less, and any shape such as spherical or flake can be used. As the organic vehicle, for example, a cellulose-based or acrylate-based resin dissolved in a solvent such as terpineol, butyl carbitol, or cellosolve can be used.
【０００８】リンについては、黄リン、紫リン、黒リン
等の同素体の他、無定形の赤リン、紅リンなどを使用す
ることもできる。また、酸化リンとしては、Ｐ2 Ｏ5 、
Ｐ2Ｏ4 等を使用することができ、酸素酸としてはＨ3
ＰＯ2 、Ｈ3 ＰＯ3 等を使用することができる。そし
て、リン酸塩、リン化物およびリンの有機化合物として
は上記各物質を使用することができる。これらリンおよ
びリンを含む化合物を銀ペーストに添加することによ
り、半導体基板との接着強度を増大することができる
が、これらの中でも後記する理由によりリン酸エステル
の添加が効果的である。Regarding phosphorus, in addition to allotropes such as yellow phosphorus, purple phosphorus and black phosphorus, amorphous red phosphorus, red phosphorus and the like can be used. Further, as phosphorus oxide, P 2 O 5 ,
P 2 O 4 or the like can be used, and H 3 is used as the oxygen acid.
PO 2 , H 3 PO 3, etc. can be used. Each of the above substances can be used as the phosphate, the phosphide, and the organic compound of phosphorus. By adding these phosphorus and a compound containing phosphorus to the silver paste, the adhesive strength with the semiconductor substrate can be increased. Among these, the addition of phosphoric acid ester is effective for the reasons described below.
【０００９】リンまたはリンを含む化合物が室温で固体
の場合、これらは粉末状のものを用いることができる
が、その粒径は１０μｍ以下であることが好ましい。と
いうのは、半導体基板に電極を焼付ける際の焼成条件
は、ハイブリッドＩＣの導電回路や電子部品の電極等を
焼付ける際の焼成条件に比して著しく時間が短いので、
リンまたはリンを含む化合物の粉末の粒径が大きいと、
焼成後接合に寄与せず未反応のまま導体中に残存するも
のが多くなり、半田濡れ性を劣化させるからである。When phosphorus or a compound containing phosphorus is solid at room temperature, powdery ones can be used, but the particle size is preferably 10 μm or less. This is because the baking conditions for baking the electrodes on the semiconductor substrate are significantly shorter than the baking conditions for baking the conductive circuit of the hybrid IC and the electrodes of the electronic parts.
When the particle size of the powder of phosphorus or a compound containing phosphorus is large,
This is because, after firing, a large amount of unreacted material remains in the conductor without contributing to bonding and deteriorates solder wettability.
【００１０】リンおよび／またはリンを含む化合物が電
極ペーストに含まれているので、リンとシリコンと直接
の反応によりシリコン基板と電極ペーストとの密着性は
確保されている。従って、接着性確保のために必ずしも
ガラス粉末を添加する必要はない。しかし、一定の接着
強度を確保しようとすれば、リンおよび／またはリンを
含む化合物の添加量を多くしなければならず、半田濡れ
性が悪くなることがある。そこで、ガラス粉末を併用し
てリンおよび／またはリンを含む化合物の添加量が過多
にならないようにするのが好ましい。なお、銀１００重
量部に対するガラス粉末の添加量は１０重量部以下に抑
えるのが好ましい。１０重量部超配合すると、電極膜の
半田濡れ性が著しく劣化するからである。Since phosphorus and / or a compound containing phosphorus is contained in the electrode paste, the adhesion between the silicon substrate and the electrode paste is secured by the direct reaction between phosphorus and silicon. Therefore, it is not always necessary to add the glass powder to secure the adhesiveness. However, in order to secure a certain adhesive strength, it is necessary to increase the amount of phosphorus and / or a compound containing phosphorus added, and the solder wettability may deteriorate. Therefore, it is preferable to use glass powder in combination to prevent an excessive amount of phosphorus and / or a compound containing phosphorus from being added. The amount of glass powder added is preferably 10 parts by weight or less with respect to 100 parts by weight of silver. This is because when the content exceeds 10 parts by weight, the solder wettability of the electrode film is significantly deteriorated.
【００１１】[0011]
【作用】銀１００重量部に対するリンおよび／またはリ
ンを含む化合物が０．１重量部未満では電極の基板に対
する接着強度が十分でなく、一方、その添加量が３重量
部を超えると、電極の半田濡れ性が著しく悪くなる。ま
た、銀１００重量部に対する有機ビヒクルの配合量が１
５重量部未満ではペースト化が容易でなく、一方、その
配合量が４０重量部を超えると焼成後の電極の抵抗が高
くなりすぎる。If the amount of phosphorus and / or the compound containing phosphorus is less than 0.1 part by weight based on 100 parts by weight of silver, the adhesive strength of the electrode to the substrate is not sufficient. Solder wettability deteriorates significantly. Moreover, the compounding amount of the organic vehicle with respect to 100 parts by weight of silver is 1
If the amount is less than 5 parts by weight, it is not easy to form a paste, while if the amount is more than 40 parts by weight, the resistance of the electrode after firing becomes too high.
【００１２】リンを含む化合物としてリン酸エステルは
それ自体分散剤や減粘剤としても作用するものが多く、
ペースト中の銀粉やその他の固形分を分散させる効果
や、高固形分のペーストの粘度を低くし、スクリーン印
刷に適した粘度を与える効果が期待できる。すなわち、
太陽電池の電極の膜厚を厚くすることで電気抵抗を低く
しようとした場合、そのためにペースト中の固形分（銀
粉）を増しても、これに伴う粘度の増大はリン酸エステ
ルの添加により抑制され、印刷不良を避けることができ
る。As the phosphorus-containing compound, many phosphoric acid esters themselves also act as a dispersant and a thickener,
The effect of dispersing silver powder and other solids in the paste and the effect of lowering the viscosity of the paste with a high solid content and giving a viscosity suitable for screen printing can be expected. That is,
If you try to lower the electric resistance by increasing the thickness of the solar cell electrode, even if you increase the solid content (silver powder) in the paste for that reason, the accompanying increase in viscosity is suppressed by the addition of phosphate ester. As a result, defective printing can be avoided.
【００１３】[0013]
【実施例】以下に本発明の実施例について説明するが、
本発明はこれら実施例に限定されるものではない。平均
粒径０．８μｍからなる銀粉末１００重量部に対し、以
下の表１に示す配合のリンおよび／またはリンを含む化
合物、ガラス粉末および有機ビヒクルを添加・混合し、
この混合物をアルミナ３本ロールミルを通過させてペー
スト化した。なお、有機ビヒクルとしては、エチルセル
ロース７重量部をターピネオールに溶解したものを用
い、ガラス粉末としてはホウ珪酸鉛系のものを用いた。EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to these examples. To 100 parts by weight of silver powder having an average particle size of 0.8 μm, phosphorus and / or a compound containing phosphorus having a composition shown in Table 1 below, glass powder and an organic vehicle were added and mixed,
This mixture was passed through a three-roll alumina mill to form a paste. The organic vehicle used was 7 parts by weight of ethyl cellulose dissolved in terpineol, and the glass powder used was a lead borosilicate type.
【００１４】次いで、このようにして得た銀−リン系電
極ペースト３を、図１に示すｐｎ接合のシリコン基板の
ｎ型シリコン基板２面上に塗布し、一方、ｐ型シリコン
基板１面上には銀−アルミニウム電極ペースト４を塗布
し、７００℃で１分間焼付けた。なお、リンはｎ型半導
体を形成する代表的なドーパントであり、また、電極の
焼付け温度（７００℃）は、拡散法によりｐ型薄層とｎ
型薄層を接合する際の処理温度（約９００℃）に比して
十分低いので、電極焼成時のリンの拡散は問題にならな
い。Next, the silver-phosphorus-based electrode paste 3 thus obtained is applied to the n-type silicon substrate 2 surface of the pn-junction silicon substrate shown in FIG. 1, while the p-type silicon substrate 1 surface is applied. Was coated with silver-aluminum electrode paste 4 and baked at 700 ° C. for 1 minute. Phosphorus is a typical dopant that forms an n-type semiconductor, and the baking temperature (700 ° C.) of the electrode is the same as the p-type thin layer and n
Since it is sufficiently lower than the processing temperature (about 900 ° C.) for joining the mold thin layers, the diffusion of phosphorus at the time of firing the electrode is not a problem.
【００１５】そして、このようにして作製した太陽電池
の電流−電圧特性から、『シリコン基板と電極との接触
抵抗』と『フィルファクター』を求め、次に説明する方
法で『半田濡れ性』と『接着強度』を調査した。その結
果を以下の表２に示す。Then, "contact resistance between silicon substrate and electrode" and "fill factor" were obtained from the current-voltage characteristics of the solar cell thus manufactured, and "solder wettability" was determined by the method described below. "Adhesive strength" was investigated. The results are shown in Table 2 below.
【００１６】半田濡れ性＝６２Ｓｎ／３６Ｐｂ／２Ａｇ
からなる半田を用い、その半田の２２０℃静止浴中に上
記太陽電池を１０秒間浸漬後引き上げて、十分に導体表
面が半田に濡れている場合を○、ピンホールが認められ
た場合を×とした。Solder wettability = 62Sn / 36Pb / 2Ag
When the above-mentioned solar cell was immersed in a 220 ° C static bath of the solder for 10 seconds and then pulled up, the conductor surface was sufficiently wet with the solder, and the case where pinholes were observed was marked with x. did.
【００１７】接着強度＝直径０．６mmのワイヤーを上記
半田にて上記太陽電池の電極（２mm□）上に固定し、そ
のピール強度を測定した。その値が０．５ｋｇ以上が合
格である。Adhesive strength = A wire having a diameter of 0.6 mm was fixed on the electrode (2 mm □) of the solar cell with the solder, and the peel strength was measured. A value of 0.5 kg or more is acceptable.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】表２に明らかなように、本実施例に係る電
極材料には適量のリンまたはリンを含む化合物が添加さ
れているので、シリコン基板との接触抵抗が極めて低
く、半田濡れ性が良好で、接着強度が高い。しかし、比
較例１は、リンの添加量が少なすぎるので、シリコン基
板と電極との接触抵抗が高く、接着強度が低い。また、
比較例２はリンの添加量が多過ぎるので、接触抵抗が高
く、半田濡れ性が不良で、接着強度の測定さえできなか
った。As is apparent from Table 2, since the electrode material according to this embodiment contains an appropriate amount of phosphorus or a compound containing phosphorus, the contact resistance with the silicon substrate is extremely low and the solder wettability is good. Therefore, the adhesive strength is high. However, in Comparative Example 1, since the amount of phosphorus added is too small, the contact resistance between the silicon substrate and the electrode is high, and the adhesive strength is low. Also,
In Comparative Example 2, since the amount of phosphorus added was too large, the contact resistance was high, the solder wettability was poor, and even the adhesive strength could not be measured.
【００２１】[0021]
【発明の効果】以上説明したように、本発明によれば、
基板と電極との接触抵抗が十分に低く、半田濡れ性が良
好で、接着強度が高い電極ペーストを提供することがで
き、半導体基板用電極材料として極めて好適に用いるこ
とができる。As described above, according to the present invention,
It is possible to provide an electrode paste having a sufficiently low contact resistance between a substrate and an electrode, good solder wettability, and high adhesive strength, and it can be used very suitably as an electrode material for a semiconductor substrate.
【図１】ｐｎ接合太陽電池の断面図である。FIG. 1 is a cross-sectional view of a pn junction solar cell.
１…ｐ型シリコン基板 ２…ｎ型シリコン基板 ３…銀−リン系電極ペースト ４…銀−アルミニウム電極ペースト DESCRIPTION OF SYMBOLS 1 ... p-type silicon substrate 2 ... n-type silicon substrate 3 ... silver-phosphorus electrode paste 4 ... silver-aluminum electrode paste
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０５Ｋ 1/09 Ａ 6921−4Ｅ Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location H05K 1/09 A 6921-4E
Claims (5)
リンを含む化合物０．１〜３．０重量部と有機ビヒクル
１５〜４０重量部を有することを特徴とする半導体基板
用電極ペースト。1. An electrode paste for a semiconductor substrate comprising 100 parts by weight of silver powder, 0.1 to 3.0 parts by weight of phosphorus and / or a compound containing phosphorus, and 15 to 40 parts by weight of an organic vehicle.
リン酸塩、リン化物およびリンの有機化合物のうち１種
以上のものからなることを特徴とする請求項１記載の半
導体基板用電極ペースト。2. The compound containing phosphorus is phosphorus oxide, oxygen acid,
The electrode paste for a semiconductor substrate according to claim 1, comprising one or more kinds of a phosphate, a phosphide and an organic compound of phosphorus.
とを特徴とする請求項２記載の半導体基板用電極ペース
ト。3. The electrode paste for a semiconductor substrate according to claim 2, wherein the phosphate is ammonium phosphate.
ｉＰ、ＳｎＰ3 、Ｓｎ3 Ｐ4 、Ｓｎ4 Ｐ3 、ＴｉＰ、Ｚ
ｒＰ2 およびＺｒＰのうち１種以上のものからなること
を特徴とする請求項２記載の半導体基板用電極ペース
ト。4. The phosphide is AsP, BP, C 3 P, S.
iP, SnP 3 , Sn 3 P 4 , Sn 4 P 3 , TiP, Z
The electrode paste for a semiconductor substrate according to claim 2, comprising at least one of rP 2 and ZrP.
ることを特徴とする請求項２記載の半導体基板用電極ペ
ースト。5. The electrode paste for a semiconductor substrate according to claim 2, wherein the organic compound of phosphorus is a phosphoric acid ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5001006A JPH06204512A (en) | 1993-01-07 | 1993-01-07 | Electrode paste for semiconductor substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5001006A JPH06204512A (en) | 1993-01-07 | 1993-01-07 | Electrode paste for semiconductor substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06204512A true JPH06204512A (en) | 1994-07-22 |
Family
ID=11489499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5001006A Pending JPH06204512A (en) | 1993-01-07 | 1993-01-07 | Electrode paste for semiconductor substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06204512A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006156522A (en) * | 2004-11-26 | 2006-06-15 | Kyocera Corp | Wiring board and its manufacturing method |
| JP2008010527A (en) * | 2006-06-28 | 2008-01-17 | Sharp Corp | Conductive paste for solar cell electrode |
| DE112006002451T5 (en) | 2005-09-16 | 2008-07-10 | Murata Manufacturing Co., Ltd., Nagaokakyo | Ceramic multilayer substrate and method of making the same |
| JP2010150473A (en) * | 2008-12-26 | 2010-07-08 | Dai Ichi Kogyo Seiyaku Co Ltd | Polyurethane resin composition and polyurethane resin |
| WO2011090211A1 (en) * | 2010-01-25 | 2011-07-28 | 日立化成工業株式会社 | Paste composition for electrode, and solar cell |
| JP2013008759A (en) * | 2011-06-23 | 2013-01-10 | Toyo Aluminium Kk | Paste composition, manufacturing method of solar cell element, and solar cell element |
| JP2017171934A (en) * | 2008-01-30 | 2017-09-28 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Conductive ink |
| CN111285339A (en) * | 2020-03-15 | 2020-06-16 | 湖北中科墨磷科技有限公司 | Sn (tin)3P4Preparation method of induced two-dimensional black phosphorus crystal |
-
1993
- 1993-01-07 JP JP5001006A patent/JPH06204512A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006156522A (en) * | 2004-11-26 | 2006-06-15 | Kyocera Corp | Wiring board and its manufacturing method |
| DE112006002451T5 (en) | 2005-09-16 | 2008-07-10 | Murata Manufacturing Co., Ltd., Nagaokakyo | Ceramic multilayer substrate and method of making the same |
| US7691469B2 (en) | 2005-09-16 | 2010-04-06 | Murata Manufacturing Co., Ltd. | Ceramic multilayer substrate and method for manufacturing the same |
| DE112006002451B4 (en) * | 2005-09-16 | 2016-08-18 | Murata Manufacturing Co., Ltd. | Ceramic multilayer substrate, ceramic multilayer module, and method of making the same |
| JP2008010527A (en) * | 2006-06-28 | 2008-01-17 | Sharp Corp | Conductive paste for solar cell electrode |
| JP2017171934A (en) * | 2008-01-30 | 2017-09-28 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Conductive ink |
| JP2010150473A (en) * | 2008-12-26 | 2010-07-08 | Dai Ichi Kogyo Seiyaku Co Ltd | Polyurethane resin composition and polyurethane resin |
| WO2011090211A1 (en) * | 2010-01-25 | 2011-07-28 | 日立化成工業株式会社 | Paste composition for electrode, and solar cell |
| JP2011171270A (en) * | 2010-01-25 | 2011-09-01 | Hitachi Chem Co Ltd | Paste composition for electrode, and solar cell |
| JP2013008759A (en) * | 2011-06-23 | 2013-01-10 | Toyo Aluminium Kk | Paste composition, manufacturing method of solar cell element, and solar cell element |
| CN111285339A (en) * | 2020-03-15 | 2020-06-16 | 湖北中科墨磷科技有限公司 | Sn (tin)3P4Preparation method of induced two-dimensional black phosphorus crystal |
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