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TW201135754A - Paste composition for electrode and photovoltaic cell - Google Patents

Paste composition for electrode and photovoltaic cell Download PDF

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Publication number
TW201135754A
TW201135754A TW100102724A TW100102724A TW201135754A TW 201135754 A TW201135754 A TW 201135754A TW 100102724 A TW100102724 A TW 100102724A TW 100102724 A TW100102724 A TW 100102724A TW 201135754 A TW201135754 A TW 201135754A
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TW
Taiwan
Prior art keywords
electrode
particles
mass
copper
silver
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TW100102724A
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Chinese (zh)
Inventor
Shuuichirou Adachi
Masato Yoshida
Takeshi Nojiri
Mitsunori Iwamuro
Keiko Kizawa
Takuya Aoyagi
Hiroki Yamamoto
Takashi Naito
Takahiko Kato
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Hitachi Chemical Co Ltd
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Publication of TW201135754A publication Critical patent/TW201135754A/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
    • H01L31/02245—Electrode arrangements specially adapted for back-contact solar cells for metallisation wrap-through [MWT] type solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • 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

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Conductive Materials (AREA)
  • Photovoltaic Devices (AREA)

Abstract

A paste composition for electrode is provided. The paste composition for electrode has a metal particle containing copper as a main composition, a glass particle containing diphosphorus pentaoxide and 5 oxidation 2 vanadium (V2O5), a solvent and a resist, wherein the containing ratio of the 5 oxidation 2 vanadium in this glass particle is equal to or greater than 1 mass%. Besides, a photovoltaic cell is provided, wherein the photovoltaic cell has an electrode formed by using the paste composition for electrode.

Description

201135754 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種電極用膏狀組合物及光伏電池。 【先前技術】 一般於光伏電池中設置有表面電極，該表面電極的配 線電阻或接觸電阻與同轉換效率相關的電壓損失有關聯， 另外，配線寬度或形狀會對太陽光的入射量產生影響（例 如’參照濱川圭弘著，「太陽光發電最新的技術與系統」， CMC 出版社，2001 年，p26-p27)。 光伏電池的表面電極通常是以如下方式形成。即，力 ，由使碟等在高溫下熱擴散於？型梦基板的受光面側㈣ f的η型半導體層上，利用網版印刷等塗佈導電性組^ =。t 電極的導電性組合物中包含導電㈣ 叔末、玻璃粒子、以及各種添加劑等。 種理:為電Ϊ金屬粉末，-般使用銀粉末，但因名 福-、右二研究使用銀粉末以外的金屬粉末。例如， 物Li二:曰光伏電池用電極的導電⑽ 揣-古本專_ 2006-313744號公報）。另外， 電:形子與銀以外的金屬粒子的 號公報）。 4照曰本專利特開2008-226816 —般用於電極形成的主 以及原料金屬本身價袼高，=於資源的問題、 因此期望美出一種替代含有銀 4 201135754201135754 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a paste composition for an electrode and a photovoltaic cell. [Prior Art] A surface electrode is generally provided in a photovoltaic cell, and the wiring resistance or contact resistance of the surface electrode is related to a voltage loss associated with conversion efficiency, and the width or shape of the wiring affects the incident amount of sunlight ( For example, 'Reference to Hiroshi Kawakawa, "The latest technology and system for solar power generation," CMC Press, 2001, p26-p27). The surface electrodes of photovoltaic cells are typically formed in the following manner. That is, the force is caused by the heat spread of the dish at a high temperature? On the n-type semiconductor layer of the light-receiving surface side (four) f of the type dream substrate, the conductivity group is coated by screen printing or the like. The conductive composition of the t electrode contains conductive (tetra) unterminated, glass particles, various additives, and the like. Seeds: For the electric metal powder, the silver powder is generally used, but the metal powder other than the silver powder is used for the research of the name - Fu and the second. For example, Li 2: Conductive electrode for photovoltaic cells (10) 揣-古本专 _ 2006-313744. In addition, electric: a bullet of a metal particle other than silver. 4 According to the patent application No. 2008-226816, the main electrode for electrode formation and the raw material metal itself are expensive, = the problem of resources, and therefore it is expected to be an alternative to containing silver 4 201135754

Kf^^/ΛΙ. 的導電性組麵（含有銀財）的錄材料 :列舉應用於半導體配線材料中的銅ί 不僅資源豆田，而且原料金屬成本亦為銀 钔 廉價。但是，銅是於勘。C以上的高溫下容易衰^之—而 例如’當日本專利特開纖_226816號 極形成用組合物含有銅作為導電性金屬時，的電 =成電極’需要於氮氣等的環境下進行== 【發明内容】 本發明的課題在於提供一種燒結時 制，可形成電阻率低的電極的電極用膏电人件至1抑 有使用該電極用膏狀組合―:及具 八本發明的第1型態是-種電極用膏狀ί:二 3 :以銅為主成分的金屬粒子、含有五氧化五2 :飢，述五氧化二飢的含有率為 下、、，口日日化起始溫度超過600它。 二ΐίΞ用J狀組合物較佳為更包含銀粒子。 U的第2 H —種光伏電池，其 =基板上的上述電極用膏狀組合物進行燒結所形成的電 [發明的效果] $據本發明，可提供—種燒結時的銅的氧 制’可形成電阻率低的電極的電極时狀組合物，以及具 201135754 有使用該電極用膏狀組合物所形成的電極的光伏電池。 *為讓本發明之上述和其他目的、特徵和優點能更明顯 易懂，下文特舉較佳實施例，並配合所附圖式，作詳細說 明如下。 【實施方式】 於本說明書中，「〜」表示分別包含其前後所記載的數 值作為最小值及最大值的範圍。 〈電極用膏狀組合物&gt; 本發明的電極用膏驗合物包含：至少—種以銅為主 为的金屬粒子、至少-種含有五氧化二磷及五氧化二飢 且上述五氧化二朗含有率為丨質量％以 至少-種溶劑、以及至少一種樹脂。 鄕子 、藉由為上述構成，燒結時的銅的氧化得到抑制， 成電阻率低的電極。 (金屬粒子） 本發明中的以銅為主成分的金屬粒子（以下，有時 6 201135754 、熔點等特性的觀點 以及Au #。其中’就調整耐氧化性 而言，較佳為含有Α1。 率例如於上述二=中所包含的其他原子的含有 加中’可設定為3質量％以下， 就对氧化性與低電阻率的觀點而言，較佳為！質量％以下。 缺對峨予吨恤的成分的金屬粒子較 ”、、…、差同時測定（Therm〇gravimetry-Differential Thennai Analysis ’ TG_DTA)中表示最大面積的放熱峰 (:hermicpeak)的波峰溫度為WC以上，更佳為·。C 〜800C，進一步更佳為35(rc〜75(rc。 藉由使用上述以被賦予财氧化性的銅為主成分的金屬 粒子’燒結時的金翻的氧化剌抑制，可形成低電阻率 的電極。再者，熱重熱差同時測定是於通常的大氣中，使 用熱重-熱差分析褒置（SII Nan〇Techn〇1〇gy公司製造， TG/DTA 62GG型）’以例如測定溫度範圍：室溫〜丨麵^、 升酿速度.40 C/分、大氣流量：2〇〇 mi/分的條件來進行。 作為上述熱重-熱差同時測定（TG-DTA)中表示最大 面積的放熱峰的波峰溫度為·。c以上的關為主成分的 金屬粒子’具體而言’例如可列舉：含有磷的銅合金粒子， 被覆銀的銅粒子，以及_選自由三魏合物、飽和脂肪 酸、不飽和脂肪酸、無機金屬化合物鹽、有機金屬化合物 鹽、聚苯胺（polyaniline)系樹脂、以及金屬烧氧化物 (alkoxuie)所組成的組群中的至少一種進行表面處理而成 的銅粒子，較佳為使用選自該些銅粒子中的至少一種。另 201135754 ^以^述含有銅的粒子可單獨使用—種，亦可組合使用兩 量為制，作為累積重 為 μ 卿〜10 μη；ϋ 二 mD5()%」）’ ΐ二=性更有效地提昇。另外，藉由為二二 ㈣丁眼3有銅的粒子彼此的接觸面積變大，電阻率更有 。再者，含有銅的粒子的粒徑是藉由MieiOtme ;度分布測定裝置(日機裝公司製造， 近似=，ίΐί有銅的粒子的形狀並無特別限制，可為 ^狀、扁平狀、塊狀、板狀、及鱗片狀等中的任一種 狀’柄氧化性與低電阻率軸 狀、扁平狀、·狀。 雜為近似球 鋼的電;物中所包含的上述含有 %。 更佳為74質量％〜88質量 另外’於本發明中，亦可组人 以外的導電性的粒子。 …使用上述含有銅的粒子 -含有磷的銅合金粒子_ 作為含有磷_合金，已知有被稱為磷銅釺料(⑺鱗 201135754 phosphorus brazing)(磷濃度· 材料。麟銅釺料亦可用作銅與麵的接合劑， =果可獲得電_低溫·柄可能，可朗製程成本 率，較金!^包含的鱗含有 到w 二率==: =而中，就輸性與低電阻率： 减，占而5 ’更佳為0.01質量％以上、8 f量％ 更佳為0.5質量％以上、7.8質量％以下，再進 質量％以上、7.5質量％以下。 為1 藉由含有磷的銅合金中所包含的碟含 以下，可達成更低的電阻率，且含有皮里/〇 優異。另外，藉㈣含有率為_ f 性 優異的耐氧化性。 上，可達成更 上述含有鱗的銅合金粒子是包含鋼與填的合金，但亦 可更包含其他原子。作為其他原子，例如可列舉：％、^、 K、Na、Li、Ba、Sr、Ca、Mg、Be、Zn、pb、cd、Ti v、Kf^^/ΛΙ. The conductive composition of the conductive group (including silver): Listed in the copper used in the semiconductor wiring material, not only the resources of the bean field, but also the cost of the raw metal is silver. However, copper is in exploration. When the composition for pole formation of the Japanese Patent Publication No. _226816 contains copper as a conductive metal, for example, when the composition of the electrode is formed into a conductive metal, it is necessary to carry out the reaction in the atmosphere of nitrogen or the like. [Explanation] An object of the present invention is to provide a paste-like electrode assembly for forming an electrode having a low electrical resistivity when the sintering is performed, and a paste-like combination using the electrode--and a first type having eight inventions The state is a kind of electrode paste type ί: 2 3: a metal particle containing copper as a main component, containing pentoxide 5: hunger, the content rate of pentoxide is lower, and the daily temperature of the mouth is daily More than 600 it. Preferably, the J-shaped composition further comprises silver particles. The second H-type photovoltaic cell of U, which is an electric charge formed by sintering the above-mentioned electrode paste composition on the substrate. [Effect of the invention] According to the present invention, it is possible to provide oxygen in the case of sintering. An electrode-time composition which can form an electrode having a low electrical resistivity, and a photovoltaic cell having an electrode formed using the paste composition for the electrode of 201135754. The above and other objects, features, and advantages of the present invention will become more apparent from the understanding of the appended claims appended claims [Embodiment] In the present specification, "~" means a range including the numerical values described before and after the minimum value and the maximum value. <Erasing Paste Composition> The electrode paste composition of the present invention comprises: at least one type of metal particles mainly composed of copper, at least one type containing phosphorus pentoxide and pentoxide and the above-mentioned pentoxide The lang content is 丨% by mass in at least one solvent, and at least one resin. In the above configuration, the enthalpy is suppressed by oxidation of copper during sintering, and the electrode has a low specific resistance. (Metal Particles) The metal particles containing copper as a main component in the present invention (hereinafter, 6 201135754, the viewpoint of characteristics such as melting point, and Au #. Among them, it is preferable to contain Α1 in terms of adjusting oxidation resistance. For example, from the viewpoint of oxidizing property and low electrical resistivity, it is preferably 3% by mass or less from the viewpoint of oxidizing property and low electrical resistivity in the case where the content of the other atoms contained in the above two is 3% by mass or less. The peak of the metal particles of the composition of the shirt is more than the above, and the peak of the exothermic peak (:hermicpeak) indicating the maximum area is WC or more, more preferably C. Further, it is preferable to form a low resistivity by suppressing ruthenium ruthenium during the sintering of the metal particles which are mainly composed of copper having a oxidizing property as a main component. In addition, the thermogravimetric difference is measured simultaneously in a normal atmosphere using a thermogravimetric-thermal differential analysis device (manufactured by SII Nan〇Techn〇1〇gy, TG/DTA 62GG type) to measure the temperature, for example. Range: room temperature ~ The surface of the exothermic peak indicating the maximum area in the thermogravimetry-thermal differential measurement (TG-DTA) is carried out under the conditions of the temperature of the surface, the growth rate of .40 C/min, and the atmospheric flow rate of 2 〇〇mi/min. The metal particles having a temperature of c· or more as a main component 'specifically' include, for example, copper alloy particles containing phosphorus, copper particles coated with silver, and _ selected from tri-ween, saturated fatty acid, and unsaturated. Preferably, the copper particles are surface-treated with at least one of a group consisting of a fatty acid, an inorganic metal compound salt, an organometallic compound salt, a polyaniline resin, and a metal oxide oxide (alkoxuie). It is selected from at least one of the copper particles. In addition, the particles containing copper may be used alone or in combination of two amounts, as the cumulative weight is μ qing ~ 10 μη; ϋ two mD5 ( )%")' ΐ2=Sexuality is more effectively improved. In addition, the contact area between the particles having copper in the two-two (four)-t-eye 3 is increased, and the resistivity is more. Further, the particles containing copper particles The path is by MieiOtme; Distribution measuring device (manufactured by Nikkiso Co., Ltd., approximate =, ίΐί) The shape of the copper-containing particles is not particularly limited, and may be any of a shape such as a shape, a flat shape, a block shape, a plate shape, and a scale shape. The oxidizing property and the low electrical resistivity are axial, flat, and the like. The miscellaneous is approximately the same as the steel of the ball steel; the content of the above contained in the material is more preferably 74% by mass to 88% by mass. Conductive particles other than the group. The use of the above-mentioned copper-containing particles - phosphorus-containing copper alloy particles _ as a phosphorus-containing alloy is known as a phosphorus-copper material ((7) scale 201135754 phosphorus brazing) (phosphorus concentration) · Materials. Lintong copper can also be used as a bonding agent for copper and noodles. = If you get electricity, you can get electricity. Low temperature and handle. It can be used to process the cost. It is more expensive than gold. The scale contained in the product contains the ratio of w to the second rate ==: = In terms of transmissibility and low resistivity: minus, accounting for 5' is preferably 0.01% by mass or more, and 8f is more preferably 0.5% by mass or more and 7.8% by mass or less, and further is more than 7% by mass or less. . When the content of the disk contained in the copper alloy containing phosphorus is 1 or less, a lower resistivity can be achieved and it is excellent in containing Piri/〇. Further, the (four) content rate is excellent in oxidation resistance of _f. Further, the above-mentioned scale-containing copper alloy particles may be alloys containing steel and filled, but may further contain other atoms. Examples of other atoms include, for example, %, ^, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, pb, cd, Ti v,

Sn、A卜&amp;、貨、_、耵、〇)、祕、以及如等。其中， 就調整耐氧化性、熔點等特性的觀點而言，較佳為包含A卜 另外’上述含有填的銅合金粒子中所包含的=原子 的含有率例如於上述含有磷的鋼合金粒子中，可設定為3 201135754 ，較佳為 質量％以下，就耐氧化性與低電阻率的觀點 1質量％以下。 ° 上述含有磷的銅合金粒子的粒徑並無特別限制 累積重量為50%時的粒徑（以下，有時略記為「D5〇 *、、 較佳為〇.4卿〜10 μΠ1，更佳為1卿〜7 μιη。藉由設上為 0.4 μΓη以上，财氧化性更有效地提昇。另外，藉由為ι〇二 以下，電極中的含有翻銅合金粒子彼此的接觸面 大’電阻率更有效地下降。 另外’上述含㈣的銅合金粒子的形狀並無特別限 制，可為近似球狀、扁平狀、塊狀、板狀、及鱗片狀等中 的任一種形狀，就耐氧化性與低電阻率的觀點而言，較佳 為近似球狀、扁平狀、或板狀。 含有磷的銅合金可藉由通常所使用的方法來製造。另 外，含有鱗的銅合金粒子可使用以達到所期望的麟含有率 的方式製備的含有磷的銅合金，利用製備金屬粉末的通常 的方法來製備，例如，可利用水霧化法並以常規方式來製 造。水霧化法於金屬便覽（丸善（股份）出版事業部）等 中有所記載。 具體而言’例如使含有磷的銅合金溶解’藉由喷嘴喷 霧將其粉末化後，對所獲得的粉末進行乾燥、分級，藉此 可$^造所期望的含有麟的銅合金粒子。另外，藉由適宜選 擇分級條件’可製造具有所期望的粒徑的含有鱗的銅合金 粒子。 作為本發明的電極用膏狀組合物中所包含的上述含有 201135754 =的銅i合金粒子的含量，例如可設定為7()質量％〜94 I ^ 就耐氧化性與低電阻率的觀點而言，較佳為72質量 〇 90質量〇/〇 ’更佳為74質量％〜88質量％。 卜於本發明中，上述含有填的銅合金粒子可單獨 .3人種亦可组合使用兩種以上。另外，亦可與含有填 98^°金粒子以外的表示最大面賴放鱗的波峰溫度為 以上的含有銅的粒子組合使用。 翻赴^ ’於本發明中，就耐氧化性與電極的低電阻率的 〇〇1哲i’較佳為於電極用膏狀組合物巾包含齡有率為 94曾二里/〇〜8質量％的含有磷的銅合金粒子70質量0/〇〜 i ’更料於f餘合財包含縣有率為 旦 7 $質量沁的含有磷的銅合金粒子74質量％〜88 質量％。 =外’於本發财，亦可組合使用上述含 金粒子以外的導電性的粒子。 -被覆銀的銅粒子_ 面的作^本發財的被覆賴絲子，只要是練子的表 銅备部分賴_齡子即可。藉錢用被覆銀的 的發明的電極用纽組合物帽包含的含有鋼 i子’可形成耐氧化性優異、電阻率⑽電極。進而， 下ί銀破覆銅粒子，被覆銀的鋼粒子與銀粒子的界面電 #Α I Φ可形成電阻率進一步下降的電極。進而，當水分 可^^狀組合物Μ，藉由使用被覆銀的鋼粒 凡仔如下效果：可抑制室溫下的銅的氧化，並可提 201135754 昇使用期限。 、作為上述被覆銀的銅粒子中的銀的被覆量（銀含有 率）’較佳為如熱重-熱差同時測定中表示最大面積的放熱 峰=波峰溫度達到28(rc以上的被覆量（銀含有率具體 而吕’於被覆銀的銅粒子的總質量中為丨質量％以上，但 就耐氧化性與電極的低電阻率的觀點而言，於被覆銀的銅 粒子的總質量中，較佳為！質量％〜88.質量％，更佳為3 質量。/。〜8G質量％，進而更佳為5 f量％〜75質量％。 另外，被覆銀的銅粒子的粒徑並無特別限制，作為累 積重量為50%時的粒徑（以下，有時略記為「d观」）， 較佳為G.4卿〜1G μηι，更佳為i叫〜7卿。藉由設定為 乂 μηι=上’耐氧化性更有效地提昇。另外，藉由為叫 以下’電極中的被覆銀的銅粒子彼此的接觸面 阻率更有效地下降。 ' % 上述被覆銀的銅粒子的職並無制限制，可 為近似球狀、扁平狀、塊狀、板狀、 ^ 了 球狀、爲平狀、或板狀。的觀點而§，較佳為近似 構成上述被覆銀的銅粒子 果的範圍内包含其他原子。作為m貝本發明的效 处、^、价、^、：為=子’例如可列舉： 以、丁卜 V、Sn、八卜 Zr、w、J g、恥、Zn、Pb、Sn, A Bu &amp;, goods, _, 耵, 〇), secret, and so on. In addition, from the viewpoint of adjusting properties such as oxidation resistance and melting point, it is preferable that the content ratio of the atom contained in the above-mentioned filled copper alloy particles is in the above-mentioned phosphorus-containing steel alloy particles. It can be set to 3 201135754, preferably not more than 5% by mass, and 1% by mass or less from the viewpoint of oxidation resistance and low electrical resistivity. The particle diameter of the phosphorus-containing copper alloy particles is not particularly limited to the particle diameter at which the cumulative weight is 50% (hereinafter, it may be abbreviated as "D5〇*, preferably 〇.4 qing to 10 μΠ1, more preferably It is 1 qing~7 μιη. By setting it to 0.4 μΓη or more, the oxidizing property is more effectively improved. In addition, by 〇2 or less, the contact surface of the copper-containing alloy particles in the electrode has a large 'resistivity. Further, the shape of the copper alloy particles containing the above (4) is not particularly limited, and may be any shape such as a spherical shape, a flat shape, a block shape, a plate shape, or a scale shape, and is resistant to oxidation. From the viewpoint of low resistivity, it is preferably approximately spherical, flat, or plate-shaped. The copper alloy containing phosphorus can be produced by a commonly used method. In addition, scale-containing copper alloy particles can be used. A phosphorus-containing copper alloy prepared in such a manner as to achieve a desired lin content is prepared by a usual method for preparing a metal powder, for example, by a water atomization method and in a conventional manner. (Maruzen (share It is described in the "Publication Division" and the like. Specifically, for example, "dissolving a copper alloy containing phosphorus" is powdered by a nozzle spray, and then the obtained powder is dried and classified, whereby A copper alloy particle containing a lining is desired. Further, the scaly-containing copper alloy particle having a desired particle diameter can be produced by appropriately selecting the classification condition. As the paste composition for an electrode of the present invention The content of the copper i alloy particles containing 201135754 = may be, for example, 7 ()% by mass to 94 I ^ . From the viewpoint of oxidation resistance and low electrical resistivity, it is preferably 72 mass 〇 90 mass 〇 / 〇 ' More preferably, it is 74% by mass to 88% by mass. In the present invention, the above-mentioned copper alloy particles may be used alone or in combination of two or more kinds, and may be used in combination with two or more kinds of gold particles. In addition, in the present invention, the copper-containing particles having the highest peak temperature and the peak temperature are used in combination. In the present invention, the oxidation resistance and the low resistivity of the electrode are preferably Paste composition for electrode paste The age-bearing rate is 94 Zeng Erli / 〇 ~ 8 mass% of phosphorus-containing copper alloy particles 70 mass 0 / 〇 ~ i 'More than f surplus wealth including county rate of Dan 7 $ quality 含有 containing phosphorus The amount of the copper alloy particles is 74% by mass to 88% by mass. The outer layer of the copper particles can be used in combination with the above-mentioned gold-containing particles. As long as the silk is prepared, it can be used as a table for the preparation of the copper. The iron-containing composition of the electrode assembly with the coated silver can be used to form an excellent resistance to oxidation and resistivity. (10) Electrode. Further, the copper particles are broken by the silver, and the interface electricity of the silver-coated steel particles and the silver particles #Α I Φ can form an electrode having a further decrease in electrical resistivity. Further, when the moisture can be used as a composition, By using silver coated steel particles, the following effects are obtained: the oxidation of copper at room temperature can be suppressed, and the service life of 201135754 liters can be raised. The coating amount (silver content) of silver in the silver-coated copper particles is preferably an exothermic peak indicating a maximum area in the simultaneous measurement of the thermogravimetry-heat difference = a peak temperature of 28 (rc or more) The silver content is specifically 5% by mass based on the total mass of the silver-coated copper particles, but in terms of oxidation resistance and low resistivity of the electrode, among the total mass of the silver-coated copper particles, Preferably, the mass % is 88% by mass, more preferably 3 mass% to 8 g mass%, more preferably 5 f% by mass to 75% by mass. Further, the particle size of the silver-coated copper particles is not In particular, the particle diameter when the cumulative weight is 50% (hereinafter sometimes abbreviated as "d") is preferably G.4 qing to 1G μηι, more preferably i is ～7 qing. By setting it as乂μηι=Upper oxidation resistance is more effectively improved. In addition, the contact resistance ratio of the silver-coated copper particles in the following 'electrode is more effectively lowered. ' % The above-mentioned silver-coated copper particles There is no restriction, it can be approximately spherical, flat, block, plate, ^ ball From the viewpoint of a flat shape or a plate shape, it is preferable to include other atoms in a range of approximately the copper particles constituting the silver-coated silver. The effect of the invention is as follows: ^, valence, ^,: For example, the = sub- can be listed as: Ding Bu V, Sn, Ba Bu Zr, w, J g, shame, Zn, Pb,

Au等。其中，就調整耐氧化性Nl、以及 觀點而言，較佳為包含&gt;屬粒子㈣點等特性的 12 201135754 右至上述被覆銀的銅粒子巾所包含的其他原子的含 =率=於上述被覆銀的銅粒子中，可奴為3質量％以 以下就耐祕性與低電阻率的觀點而言，較佳為^質量％ 相上频舰的絲？為11由雜覆&amp;述的含有 破的銅合金而成者亦較佳。藉此，耐氧化性進—步提耳， 所开)成的電極的電阻率進一步下降。 ，於被覆銀的銅粒子中的含有磷的銅合金的詳細情 :兄^、含義與已述的含_的銅合金相同，較佳 亦 相同。 作為上述被覆銀的銅粒子的製備方法，只要是可藉由 被覆銀銅粒子（錄為含有_銅合錄子）的表面^至 少一部分的製備方法’則並無特職制。例如可如下般製 備即將銅粉（或者含有磷的銅合金粉）分散於硫酸、 鹽酸、麟酸等酸性溶液中向該銅粉分散液中添加螯 合劑來製作銅粉⑽^所獲得的崎漿射添加銀離子 溶液，藉此可藉由取代反應而於銅粉表面上形成銀層。 上述螯合劑並無特別限制，例如可使用：乙二胺四乙 酸鹽、三亞乙基二胺（triethylenediamine)、二亞乙基三胺 五乙酸（diethylenetriaminepentaaceticadd)、亞胺二乙酸 (iminodiacetic acid)等。另外，作為銀離子溶液，例如可 使用硝酸銀溶液等。 作為本發明的電極用膏狀組合物中所包含的上述被覆 銀的銅粒子的含有率’另外’作為包含後述的銀粒子時的 13 201135754 一 ί · Vf L銀的銅粒子與銀粒子的總含有率，例如可設定為70 較二4暂質曰量％，就耐氧化性與低電阻率的觀點而言， r圭為72質量%〜90質量％，更佳為74質量%〜88質量 另外’於本發明中，上述被覆銀的鋼粒子可單獨使用 ::以：合ϊ用兩種以上。另外’亦可與被覆銀的銅 拉子以外的表不最大面積的放鱗的波峰溫度為28叱以 上的含有銅的粒子組合使用。 “ 中，就耐氧化性與電極的低電阻率的觀點而 a ’#乂佳為於電極用膏狀組合物中包含被覆銀的銅粒 ，質量中的銀含有率為i質量％〜88 f量％的被覆銀的銅 粒子70質量％〜94 #量％(當包含後述的銀粒子時為被覆 銀的銅粒子與銀粒子的總含有率），更佳為於電極用膏狀^ 合物中包含銀含有率為5質量％〜75質量％的被覆銀的銅 粒子74質量％〜88質量％(當包含後述的銀粒子時為被覆 銀的銅粒子與銀粒子的總含有率）。 進而，較佳為於電極用膏狀組合物中包含銀含有率為 1質量％〜88質量％、磷含有率為0.01質量％〜8質量％的 被覆銀的含有磷的銅合金粒子70質量％〜94質量％(包°含 後述的銀粒子時的被覆銀的含有磷的銅合金粒子與銀粒| 的總含有率），更佳為於電極用膏狀組合物中包含銀含有率 為5質量％〜75質量％、磷含有率為1質量％〜7 5質量％ 的被覆銀的含有磷的銅合金粒子74質量％〜88質量％(包 含後述的銀粒子時的被覆銀的含有磷的鋼合金粒子與銀粒 201135754 J / ^tuzpif 子的總含有率）。 亦可組合使用上述被覆銀的銅粒 另外，於本發明中 子以外的導電性的粒子 -經表面處理的銅粒子· 本發明中的含有銅的粒子為利用選自由三嗤化合物、 飽和脂肪酸、不飽和脂騎、無機金屬化合㈣、有機金 屬化合物鹽、聚苯㈣触、以及金狀氧化物所組成的 組群（以下’有時稱為「表面處理劑」）中的至少一種進行 表面處理而成的銅粒子亦較佳。藉由使用以表面處理劑的 至少-種進行表Φ處顧成的峰子作為 膏狀組合㈣所包含的含有_奸，可職 f、電阻率低的電極。進而’當水纽人至電刻膏狀組 。物中時’藉由使驗表面處理的練子，可獲得如下效 果.可抑制室溫下的銅的氧化，並可提昇使用期限。 另外，於本發明中，上述表面處理劑可單獨使用一種， 亦可纟且合使用兩種以上。 人於本發明中，經表面處理的銅粒子是利用選自由三唑 =合物、飽和脂肪酸、不飽和脂肪酸、無機金屬化合物鹽、 έ機金屬化合物鹽、聚苯胺系樹脂、以及金屬烷氧化物所 、、且成的組群中的至少一種進行了表面處理，但視需要亦可 併用其他表面處理劑。 Μ作為上述表面處理劑中的三唾化合物，例如可列舉： t幷—唑、二唑等。另外，作為上述表面處理劑中的飽和 知肪酸，例如可列舉：庚酸、辛酸、壬酸、癸酸、十一酸 15 201135754 ^ /HUZpif (undecanoic acid )、十二酸（laurostearic acid )、十三酸 (tridecylic acid)、十四酸、十五酸、硬脂酸、十九酸、花 生酸、二十二酸（benhenic acid)等。另外，作為上述表 面處理劑中的不飽和脂肪酸，例如可列舉：丙烯酸、曱基 丙烯酸、丁烯酸（crotonic acid )、異丁烯酸、十一稀酸 (undecylenic acid )、油酸、反油酸、鯨油酸（cet〇leic add )、 蕓苔酸（brassidic acid )、芥子酸、山梨酸、亞麻油酸（lin〇ldc acid )、次亞麻油酸（lin〇lenic acid )、花生油酸（咖咖如心 acid)等。 另外，作為上述表面處理劑中的無機金屬化合物鹽， 例如可列舉：矽酸鈉、錫酸鈉、硫酸錫、硫酸鋅、辞酸鈉、 瑣酸銼、鍅酸鈉、氧氣化鍅、硫酸鈦、氣化鈦、草酸鈦酸 鉀專。另外’作為上述表面處理劑中的有機金屬化合物鹽， 例如可列舉：硬脂酸鉛、乙酸鉛、四烷氧基鍅的對異丙笨 基，基（p-cumylphenyl)衍生物、四烷氧基鈦的對異丙苯 基苯基衍生物等。另外，作為上述表面處理射的金屬烧 氧化物’例如可列舉：鈦絲化物、雜氧化物、錯烧氧 化物、魏氧化物（silieGn alkGxide)、舰氧化物、 氣化物簟。 作為其他表面處理劑，例如可列舉十二烧基苯績酸 另外’當使用硬脂酸或硬脂酸錯作為表面處理劑時 ，由併用硬脂酸及硬麟錯的至少種與乙酸錯作為表 處，’耐氧化性進-步提昇，可形成電阻率更低的電才, 本务明中的經表面處理的鋼粒子只要銅粒子的表面 16 201135754 至^一部分被上述表面處理劑的至少—種被覆 ^表面處理的銅粒子中所包含的表面處理劑的含^為 為：二重_熱差同時測定中表示最大面積的放執d 二度達到28G°C以上的含量。具體 f峰 處理的銅粒子的質量中為_質量％以上，表面 ’更佳為於經表面處理的2 面處理的銅粒子二〜= 表面處理的銅粒子的銅亦可於無損本發明 的效果的乾圍内包含其他原子。作^月 --v-sn-A1-zr；；；r：8c：：rib, ί佳為包其含整耐氧化性、熔點等特性的觀點而言， 另外，上述經表面處理的銅粒子中所包含的其 的含有率例如於上述經表面處理的銅粒子中，可為 質量，以下’就耐氧化性與低電阻率的觀點而言叹較佳為 1質量％以下。 ^外’上述絲面處理的输子騎已述的含有構的 銅^進行表面處麵成者亦較佳H耐氧化性進一 步提昇，所形成的電極的電阻率進一步下降。 關於經表面處理的銅粒子中的含有磷的鋼合金的詳細 情況’其含義與已述的含有磷的銅合金相同，較佳的型離 亦相同。 〜 17 201135754 D / W^pif 制，作為c面處理的銅粒子的粒徑並無特別限 Α η ^ 川叩1更佳為1 μιη〜7 μιη。 此的接縮電巾的上賴表面處_銅粒子彼 此的接觸面積變大，餘錢有效地下降。 制，Ϊ:近ί:表:平處:子的形狀並編 氧化性與低電阻率的觀點而言，較佳 马近似球狀、扁平狀、或板狀。 鹿於用表面處理劑的銅粒子的表面處理方法，可對 户理勺表面處理劑而適宜選擇。例如，製備使表面 解於可溶解表面處理劑的溶劑中而成的表面處理 洛液’使銅粒子浸潰於該表面處理溶 此可利用該表面處理劑被覆銅粒子的表面的至分错 上述可溶解表面處理劑的溶劑可對應於表面處理劑而 =選擇。例t口可列舉：水、甲醇、乙醇、異丙醇等醇系 /合劑、乙二醇单乙喊（ethyleneglycolmonoethyletheI^ =醇系溶劑、二乙二醇單頂等卡必醇系溶劑、二乙二醇 ^ ϋ 6 iiil ( diethylene glycol monoethyl ether acetate) 專卡必醇乙酸酯系溶劑等。 具體而言，例如當使用苯幷三唑、三唑、十二烷基苯 ，作為表面處理劑時’可使用醇系溶劑來製備表面^理 溶液，然後對銅粒子進行表面處理。 18 201135754 乃夕卜 可使用醇“ 作為表面處理劑時， 表面處理溶液令的表面處理 :表面處理劑的種類或所期望的表面處^量^ 定為1質量％，質量％，較佳 面處==: =中所包含的上^ 定與錄子_㈣，例如可設 1 里。貝罝/〇,就耐氧化性與低電阻率的觀1¾ 而二交佳為72質量%〜9。質量%，更^ 88質量％。 只里/〇 另外於本發0种，上述經表面處理的銅粒子可單獨 $用種’亦可組合使用兩種以上。另外，亦可與經表面 处里的銅粒子以外的表示最大面積的放熱峰的 WC以上龄好組合制。 ^ _於本發明中，就耐氧化性與電極的低電阻率的觀點而 吕，較佳為於電極用膏狀組合物中包含以含有選自由三唑 化合物、飽和脂肪酸、不飽和脂肪酸、無機金屬化合物鹽、 有機金屬化合物鹽、聚笨胺系樹脂、以及金屬烷氧化物所 組成的組群中的至少一種0 01質量％〜10質量％的方式進 行了表面處理的銅粒子70質量〇/〇〜94質量％(當包含後述 的銀粒子時為經表面處理的銅粒子與銀粒子的總含有 率）’更佳為於電極用膏狀組合物中包含以含有選自由三唑 19 201135754 化合物、飽和脂肪酸、不飽和脂肪酸以及無機金屬化合物 鹽所組成的組群中的至少一種(U質量％〜8質量％的方式 進行了表面處理的銅粒子74質量％〜88質量％(當包含後 述的銀粒子時為經表面處理的銅粒子與銀粒子的總含有 率）。 進而，較佳為於電極用膏狀組合物中包含以含有選自 由三唑化合物、飽和脂肪酸、不飽和脂肪酸、無機金屬化 合物鹽、有機金屬化合物鹽、聚苯胺系樹脂、以及金屬烷 氧化物所組成的組群中的至少一種〇 〇1質量％〜1〇質量％ 的方式進行了表面處理，且磷含有率為8質量％以下的經 表面處理的含有磷的銅合金粒子7〇質量％〜94質量％(當 包含後述的銀粒子時為經表面處理的含有磷的銅合金粒子 與銀粒子的總含料），更佳為於電则纽組合物中包含 以含有選自由三唑化合物、飽和脂肪酸、不飽和脂肪酸以 及無機金屬化合物鹽所組成的組群中的至少一種〇1質量 /〇〜8負畺％的方式進行了表面處理，且罐含有率為^質量 °/〇〜7.5質量％的經表面處理的含有磷的銅合金粒子％質 量％〜88質量％ (當包含後述的銀粒子時為經表面處理的 含有填的銅合金粒子與銀粒子的總含有率）。 另外，於本發明中，亦可組合使用上述經表面處理的 鋼粒子以外的導電性的粒子。 (玻璃粒子） 一本發明的電極用膏狀組合物包含至少一種含有五氧化 一磷及五氧化二釩且上述五氧化二釩的含有率為丨質量％ 20 201135754 以上的玻璃粒子。藉由電姻纽組合物包含具有上述特 定組成的玻璃粒子，燒結貫穿（fire through)性提昇，並 以更低的電阻率形成電極射基板的歐姆接觸。 此處的燒結貫穿㈤e th_gh)性是指於電極形成溫 度下，上述玻璃粒子與作為抗反射膜的氮化矽膜進行反應 而將氮化销去除’形成電極财基板的歐姆接觸。 上述玻璃粒子是由含有五氧化m氧化二鈒的玻 璃_(P2〇5 V2〇5系玻璃）而成的。藉由含有五氧化二磷及 ^氧化二鈒，耐氧化性進—步提昇，所形成的電極的電阻 率進-步下降，進而’燒結貫穿性提昇。可認為其是由例 如以下原因所造成的：藉由更包含五氧化二鈒，玻璃的軟 化點下降。 旦Φ上述ΐ&quot;!粒子中的五氧化二朗含有率於玻璃的總質 =中為1質量％以上，但就耐氧化性與電極的低電阻率的 觀點而言，較佳為i質量％〜70質量％。 另外，五氧化二磷的含有率並無特別限制，但就耐氧 化性與電極的低電阻率的觀點而言，較佳為i質量％以 上，更佳為4質量。/。〜50質量％。 另外，上述五氧化二磷-五氧化二釩系玻璃（P205-V205 與玻，）視需要可更包含其他成分。作為其滅分，可列 二化鋇（Ba0 )、二氧化猛（施02 )、氡化納（Na20 )、 =钟（κ2ο)、二氧化結（Zr〇2)、三氧化鎮（w〇小氧 Te〇)、二氧化鉬（Mo〇3)、三氧化二銻（Sb203) 藉由更包含其他成分，可更高效地取入源自氮化石夕的 21 201135754 二氧化矽。另外，可使軟化·溶解溫度進一步下降❶進而， 可抑制與含有銅的粒子或視需要而包含的銀粒子的反應。 上述玻璃粒子就耐氧化性與電極的低電阻率的觀點而 吕，較佳為包含玻璃軟化點為600°c以下，結晶化起始溫 ，超過600。。的玻璃的玻璃粒子。再者，上述玻璃軟化點 是利用熱機械分析裝置（Thermo Mechanical Analyzer， T^IA)輯常的方絲測定，糾，上述結晶化起始溫度 是利用熱重-熱差分析裝置（ThermalAu et al. In addition, it is preferable to adjust the oxidation resistance N1 and, in view of the above, 12, 2011, 754 including the characteristics of the particles (four) and the content of the other atoms contained in the silver-coated copper particle towel In the case of the silver-coated copper particles, the usability is 3 mass% or less, and from the viewpoint of the durability and the low resistivity, it is preferably a mass% of the filaments of the frequency ship. It is also preferable that it is composed of a broken copper alloy as described above. Thereby, the resistivity of the electrode which is resistant to oxidation is further increased. The details of the phosphorus-containing copper alloy in the silver-coated copper particles are the same as those of the copper alloy containing _ described above, and are preferably the same. The method for preparing the silver-coated copper particles is not particularly limited as long as it is a method for preparing at least a part of the surface of the coated silver-copper particles (which is recorded as containing a copper-copper). For example, it is possible to prepare a slurry obtained by dissolving copper powder (or a copper alloy powder containing phosphorus) in an acidic solution such as sulfuric acid, hydrochloric acid or linonic acid, and adding a chelating agent to the copper powder dispersion to prepare a copper powder (10). A silver ion solution is added by injection, whereby a silver layer can be formed on the surface of the copper powder by a substitution reaction. The chelating agent is not particularly limited, and examples thereof include ethylenediaminetetraacetate, triethylenediamine, diethylenetriaminepentaaceticadd, and iminodiacetic acid. Further, as the silver ion solution, for example, a silver nitrate solution or the like can be used. The content rate of the silver-coated copper particles contained in the paste composition for an electrode of the present invention is 'in addition' as a total of copper particles and silver particles of 13 201135754 ί · Vf L silver when silver particles described later are contained. The content rate can be set, for example, to 70% by weight of the second temporary liquid. From the viewpoint of oxidation resistance and low electrical resistivity, r is 72% by mass to 90% by mass, more preferably 74% by mass to 88% by mass. Further, in the present invention, the silver-coated steel particles may be used singly or in combination of two or more kinds. Further, it is also possible to use a combination of copper-containing particles having a peak temperature other than the maximum surface area of the silver-coated copper ferrule having a peak temperature of 28 Å or more. "In view of the oxidation resistance and the low resistivity of the electrode, a '#乂" is a copper-coated copper particle in the paste composition for an electrode, and the silver content in the mass is i% by mass to 88 f. The amount of the silver-coated copper particles is 70% by mass to 94% by weight (the total content of the silver-coated copper particles and the silver particles when the silver particles described later are contained), and more preferably the paste for the electrode. The silver-containing copper particles having a silver content of 5 mass% to 75% by mass are 74% by mass to 88% by mass (when the silver particles described later are included, the total content of the silver-coated copper particles and the silver particles). It is preferable that the paste composition for an electrode contains 70% by mass of silver-containing phosphorus-containing copper alloy particles having a silver content of 1% by mass to 88% by mass and a phosphorus content of 0.01% by mass to 85% by mass. 94% by mass (the total content of the silver-containing copper alloy particles containing silver and the silver particles when the silver particles described later are contained), and more preferably the silver content is 5 mass in the paste composition for an electrode. %~75 mass%, phosphorus content: 1% by mass to 7.5 mass% of coated silver The phosphorus-containing copper alloy particles are 74% by mass to 88% by mass (the total content of the silver-containing steel alloy particles containing silver and the silver particles 201135754 J / ^tuzpif when the silver particles described later are included). Silver-coated copper particles In addition to the conductive particles other than the neutrons of the present invention - the surface-treated copper particles. The copper-containing particles in the present invention are selected from the group consisting of triterpenoids, saturated fatty acids, and unsaturated fats. Copper particles obtained by surface treatment of at least one of an inorganic metal compound (IV), an organometallic compound salt, a polyphenylene (tetra) contact, and a gold oxide group (hereinafter referred to as "surface treatment agent") Also preferred. By using at least one of the surface treatment agents, the peaks of the surface Φ are used as the paste-containing combination (4), and the electrode containing the traitor is a low-resistance electrode. Further, 'when the water is new to the electric paste group. When the material is treated, the following effects can be obtained. The oxidation of copper at room temperature can be suppressed, and the lifespan can be improved. Further, in the present invention, the surface treatment agent may be used singly or in combination of two or more. In the present invention, the surface-treated copper particles are selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organometallic compound salts, polyaniline resins, and metal alkoxides. At least one of the group and the group is subjected to surface treatment, but other surface treatment agents may be used in combination as needed. Μ As the trisal compound in the above surface treatment agent, for example, t-oxazole or diazole can be mentioned. Further, examples of the saturated fatty acid in the surface treatment agent include heptanoic acid, octanoic acid, citric acid, citric acid, and undecanoic acid 15 201135754 ^ /HUZpif (undecanoic acid ), and laurostearic acid. Tridecylic acid, tetradecanoic acid, pentadecanoic acid, stearic acid, nonadecanic acid, arachidic acid, benhenic acid, and the like. Further, examples of the unsaturated fatty acid in the surface treatment agent include acrylic acid, mercaptoacrylic acid, crotonic acid, methacrylic acid, undecylenic acid, oleic acid, and oleic acid. Cetyl acid (cet〇leic add), brassic acid, sinapic acid, sorbic acid, lin〇ldc acid, lin〇lenic acid, peanut oleic acid (caffeine) Heart acid) and so on. Further, examples of the inorganic metal compound salt in the surface treatment agent include sodium citrate, sodium stannate, tin sulfate, zinc sulfate, sodium decanoate, bismuth citrate, sodium citrate, cesium oxysulfide, and titanium sulphate. , gasification of titanium, potassium oxalate titanate. Further, as the organometallic compound salt in the above surface treatment agent, for example, lead stearate, lead acetate, tetrapropoxy fluorene, isopropylidene, p-cumylphenyl derivative, tetraalkoxy A p-cumyl phenyl derivative of a base titanium or the like. Further, examples of the metal oxide oxide emitted as the surface treatment include titanium wire, a hetero oxide, a misfired oxide, a sulphur oxide (silieGn alkGxide), a ship oxide, and a vapor enthalpy. As another surface treatment agent, for example, didecylbenzene acid can be cited. When 'stearic acid or stearic acid is used as a surface treatment agent, at least one of stearic acid and hard cymbal and acetic acid are used in combination. At the table, 'the oxidation resistance advances step by step, and the electricity with lower resistivity can be formed. The surface treated steel particles in the present invention are as long as the surface of the copper particles 16 201135754 to ^ part of the surface treatment agent The content of the surface treatment agent contained in the surface-treated copper particles is: the double-heat difference simultaneous measurement indicates that the maximum area of the release d is twice the amount of 28 G ° C or more. Specifically, the mass of the copper particles treated by the f-peak is _ mass% or more, and the surface 'better is the surface-treated copper particle of the two-side treatment ～= the copper of the surface-treated copper particles can also detract from the effect of the present invention. The inner circumference contains other atoms. ^^--v-sn-A1-zr;;;r:8c::rib, ί preferably in terms of its properties of oxidation resistance, melting point, etc., in addition, the above-mentioned surface-treated copper particles The content of the copper particles contained in the surface-treated copper particles may be mass, and the following is preferably 1% by mass or less from the viewpoint of oxidation resistance and low electrical resistivity. The outer surface of the above-mentioned silk-faced conveyor rides the already-formed copper, and the surface resistance is further improved. The oxidation resistance of the electrode is further improved, and the resistivity of the formed electrode is further lowered. The details of the phosphorus-containing steel alloy in the surface-treated copper particles are the same as those of the phosphorus-containing copper alloy described above, and the preferred forms are also the same. ~ 17 201135754 D / W^pif system, the particle size of the copper particles treated as c-plane is not particularly limited Α η ^ Chuanxi 1 is preferably 1 μιη to 7 μιη. At the surface of the upper surface of the shrinkable electric towel, the contact area of the copper particles becomes larger, and the remaining money is effectively lowered. System, Ϊ: Near ί: Table: flat: sub-shape and oxidizing and low resistivity, the horse is preferably spherical, flat, or plate-like. The surface treatment method of the copper particles of the deer using the surface treatment agent can be appropriately selected for the surface treatment agent of the household treatment spoon. For example, a surface treatment liquid solution prepared by dissolving a surface in a solvent capable of dissolving a surface treatment agent is prepared by impregnating the surface of the surface of the copper particles with the surface treatment agent. The solvent that can dissolve the surface treatment agent can be selected corresponding to the surface treatment agent. Examples of the t port include alcohol, a mixture of water, methanol, ethanol, and isopropanol, and a single ethylene glycol (ethyleneglycolmonoethylethe I^ = alcohol solvent, diethylene glycol monotop, etc., carbitol solvent, diethyl Diol ϋ 6 iiil (diethylene glycol monoethyl ether acetate), etc. Specifically, for example, when benzotriazole, triazole or dodecylbenzene is used as a surface treatment agent 'Aqueous solvent can be used to prepare the surface treatment solution, and then the copper particles are surface-treated. 18 201135754 The use of alcohol as a surface treatment agent, the surface treatment of the surface treatment agent: the type or surface treatment agent The desired surface is determined to be 1% by mass, % by mass, and the upper surface of the preferred surface ==: = is contained in the recording table _ (4), for example, 1 mile can be set. The oxidizing property and the low resistivity are both as good as 72% by mass to 9% by mass. More preferably, the mass% is more than 88% by mass. In addition to the present invention, the above-mentioned surface-treated copper particles can be used alone. The species can also be used in combination of two or more types. The WC of the largest area other than the copper particles in the surface is preferably combined with WC or higher. ^ _ In the present invention, the oxidation resistance and the low resistivity of the electrode are preferable, and it is preferably used for the electrode. The paste composition comprises at least one selected from the group consisting of a triazole compound, a saturated fatty acid, an unsaturated fatty acid, an inorganic metal compound salt, an organometallic compound salt, a polyamido resin, and a metal alkoxide. The amount of copper particles 70 surface-treated in a range of from 0.01% by mass to 10% by mass is 〇/〇 to 94% by mass (when the silver particles described later are included, the total content of the surface-treated copper particles and silver particles) More preferably, the paste composition for an electrode contains at least one selected from the group consisting of a compound of triazole 19 201135754, a saturated fatty acid, an unsaturated fatty acid, and an inorganic metal compound salt (U mass% to 8 mass) % of the surface-treated copper particles are 74% by mass to 88% by mass (when the silver particles described later are included, the total content of the surface-treated copper particles and silver particles is Further, it is preferable that the paste composition for an electrode contains a compound selected from the group consisting of a triazole compound, a saturated fatty acid, an unsaturated fatty acid, an inorganic metal compound salt, an organometallic compound salt, a polyaniline resin, and a metal alkane. Surface-treated phosphorus-containing copper alloy particles having a phosphorus content of 8% by mass or less and having a phosphorus content of at least 1% by mass to 1% by mass in the group consisting of oxides 5% by mass to 94% by mass (when the silver particles described later are contained, the total content of the surface-treated phosphorus-containing copper alloy particles and silver particles), more preferably contained in the electric stellate composition The surface treatment is carried out in such a manner that at least one of the group consisting of an azole compound, a saturated fatty acid, an unsaturated fatty acid, and an inorganic metal compound salt is 质量1 mass/〇8 畺% ,%, and the tank content rate is ^ mass ° / 〇 7.5 mass% of the surface-treated phosphorus-containing copper alloy particles % by mass to 88% by mass (surface-treated filled copper when containing silver particles described later) Gold particles and the total content of the silver particles). Further, in the present invention, conductive particles other than the surface-treated steel particles may be used in combination. (Glass Particles) The paste composition for an electrode of the present invention contains at least one kind of glass particles containing phosphorus pentoxide and vanadium pentoxide and having a content of vanadium pentoxide of 丨 mass % 20 201135754 or more. The electric wedding composition contains glass particles having the above specific composition, the fire through property is improved, and the ohmic contact of the electrode-projecting substrate is formed at a lower resistivity. Here, the sintering penetration (f) e th_gh) refers to an ohmic contact in which the glass particles are reacted with a tantalum nitride film as an antireflection film at the electrode formation temperature to remove the nitride pin to form an electrode substrate. The glass particles are made of glass _ (P2〇5 V2〇5-based glass) containing pentoxide oxide. By containing phosphorus pentoxide and bismuth oxide, the oxidation resistance is further improved, and the resistivity of the formed electrode is further lowered, and the sintering penetration is improved. It can be considered to be caused by, for example, the following reasons: by further containing antimony pentoxide, the softening point of the glass is lowered. The content of the pentoxide in the above-mentioned ΐ&quot;! particles is 1% by mass or more based on the total mass of the glass, but is preferably i% by mass in terms of oxidation resistance and low resistivity of the electrode. ~70% by mass. Further, the content of phosphorus pentoxide is not particularly limited, but from the viewpoint of oxidation resistance and low electrical resistivity of the electrode, it is preferably i mass% or more, more preferably 4 mass%. /. ~ 50% by mass. Further, the above phosphorus pentoxide-vanadium pentoxide-based glass (P205-V205 and glass) may further contain other components as needed. As its extinction, it can list bismuth (Ba0), bismuth (Shi 02), bismuth (Na20), = clock (κ2ο), dioxide (Zr〇2), and trioxide (w〇) Small oxygen (Te), molybdenum dioxide (Mo〇3), antimony trioxide (Sb203) By further containing other components, 21 201135754 cerium oxide derived from nitrite can be taken more efficiently. Further, the softening/dissolving temperature can be further lowered, and the reaction with the copper-containing particles or, if necessary, the silver particles can be suppressed. The glass particles preferably have a glass softening point of 600 ° C or less and a crystallization starting temperature of more than 600 from the viewpoint of oxidation resistance and low resistivity of the electrode. . Glass of glass particles. Further, the glass softening point is measured by a square wire which is often analyzed by a thermomechanical analyzer (T^IA), and the crystallization starting temperature is measured by a thermogravimetry-thermal difference analyzer (Thermal)

Gravimetry-Differential Thermal Analyzer，TG-DTA)以通 常的方法來測定。 本發明的電極用膏狀組合物除上述p2〇5_V2〇5系玻璃 以外’亦可更包含至少—種不含五氧化二顧五氧化二飢 的其他玻璃粒子。 ▲作為上述其他玻璃粒子，就可高效地取入二氧化石夕而 S ’可較佳地列舉由包含㈣朗所構成的柄粒子。作 為此種包含鉛的玻璃’例如可馨日本專利第娜〇〇64 ^ A報等中所錢的玻璃，於本發明中亦可較佳地使用 些玻璃。 眘^外^於本發财，騎細於魏㈣響，則使用 =上不切的無錯玻璃雜佳。作為無财璃，例如可 二：日本專利特開2006-313744號公報的段落編號_ 〜又洛編號0025中所記載的無錯玻璃、或者日本專利特開 09-188281號公報等中所記载的無錯玻璃，自該些盈私 玻璃中適宜選擇後應用於本發明中亦較佳。 、 22 201135754 她j為上述玻雜子的含有率，於電極时狀組合物的 :貝I中，較佳為0.1質量〇/〇〜10質量0/〇，更佳為0.5質量 質量％’進而更佳為1質量％〜7質量％。藉由以上 述範圍的含有率包含綱粒子，更有效地達成耐氧化性、 電極的低電阻率及低接觸電阻。 曰。於本發明中，較佳為含有包含乂2〇5的含有率為1質 里j以上的P2〇rV2〇5系玻璃的玻璃粒子0.1質量〇/〇〜10 質量/°，更佳為含有包含V2〇5的含有率為1質量❶/。〜70 。質量％的P2〇5_V2〇5系玻璃的玻璃粒子〇 5質量質量 /〇θ進而更佳為含有包含V2〇5的含有率為1質量％〜70 質量〇/❶的P2〇5-V2〇5系玻璃的玻璃粒子1質量％〜7質量％。 (溶劑及樹脂） 本發明的電極用膏狀組合物包含至少一種溶劑與至少 :種樹脂。藉此，可對應於賦予至雜板時的賦予方法將 發明的電極用膏狀組合物的液體物性（例如，黏度、表 面張力等）調整為所需的液體物性。 —上述'谷劑並無特別限制。例如可列舉：己烧、環己炫*、 2等H容劑；二氣乙稀、二氣乙烧、二氣苯等氯化烴 'W谷Μ，四氫吱喃、呋喃、四氫吡喃、吡喃、二噁烧 卞 ane) 1,3-—氧戊環、三Π山（tri〇xane)等環狀_系溶 ^ Ν’Ν&quot;Ί基胺、耶二f基乙醢胺料胺系溶 劑；二甲基亞碾、二乙基亞颯等亞砜系溶劑；丙酮、曱基 乙基酿I、一乙基g同、環己酮等酮系溶劑；乙醇、丙醇、 丁醇、二丙酮醇等醇系化合物；2,2,4-三曱基-1,3-戊二醇 23 201135754 單乙酸酯、2,2,4·三甲美·! 1丄、^ 基-1，3-戍二醢。。 ，·戊一醇單丙酸酯、2,2,4-三甲 酯、2,2,4-三乙、_2’2:t三甲基-1，3_戍二醇單異丁酸 醋、二乙二醇單丁喊乙酸、乙二醇單丁崎乙酸 纖劑、二乙二醇二乙㈣鱗的酉旨系溶劑；丁基溶 萜品醇、月桂心兀醇的鍵系溶劑；α_萜品烯、α_ 帖口·月桂油歸、別 ρ铺、松脂醇、香旱細m麟、α韻、 溶劑，以及該些的混合=羅勒婦、水芽稀等的㈣系 膏狀;土述f劑’就於嫩上形成電極用 ΪΠ醋=、嶋溶劑、多元醇的咖= 的至少-種。為選自多疋醇的醋系溶劑及_系溶劑中 用二ίΓ中’ 4溶劑可單獨使用一種’亦可組合使 樹庐另作為上述樹脂，只要是可藉由燒結而熱分解的 曰’、·可無特別限制地使用該技術領域中通常所使用的 地月旨j體而言，例如可列舉：甲基纖維素、乙基纖維素、 ^基纖維素、確化纖維素等纖維素系樹脂；聚乙稀醇類； ^乙稀。比略姻類；丙稀酸樹脂；乙酸乙婦醋-丙稀酸醋共 聚，，聚乙婦丁盤等的丁酸樹脂；齡改性醇酸樹脂、萬麻 /由月曰肪酸改性醇酸樹脂之類的醇酸樹脂；環氧樹脂；紛樹 脂；松香酯樹脂等。 作為本發明中的上述樹脂，就燒結時的消失性的觀點 24 201135754 3:承s為璉自纖維素系樹脂、丙烯酸樹脂中的至少-種’更佳為選自纖維素系樹脂中的至少一種。 於本發明申，上述樹脂可單獨传 絲 用兩種以上。 早職用—種，亦可組合使 脂的:==_用膏狀組合物中，上述溶劑與上述樹 脂的種類液;=與所使用的溶劑及樹 用資狀組合物如樹脂的總含量於電極 观U置中，杈佳為3質量％以上、29 9質 :二=5質量%以上、25質料™^ 住马7 $里％以上、2G質量％以下。 狀組與樹脂的總含量為上述範圍内，將電極用膏 、口賦予至矽基板時的賦予適應性變得良好，可更容 易地形成具有_望的寬纽S度的電極。 (命》粒子） 本毛a月的電極用貧狀組合物較佳為更包含至少一種銀 Ϊ率進藉耐氧化性進一步提昇，電極的電 ㈣1 牛 亦可獲得製成光伏電池模組時的 知接性提昇的效果。此種情關如可如下般考慮。 。—般於作為電極形成溫度區域的600。(:至900。〇的溫 域中，產生銀於銅中的少量的固溶、以及銅於銀中的 =的固溶’而在銅與銀的界面形成銅_銀固溶體的層（固 1域）。可認為當將含有銅的粒子與絲子的混合物加孰 至兩溫後’緩慢地冷輕室溫時，^產生固溶區域，但因 升&gt;成電極時以數秒自高溫域冷卻至常溫，故可認為高溫下 25 201135754 ======或:與銀的共晶組織 ^體層有助於電極形成溫度下的含有銅_子的耐氧化 開::固溶體層於wc至5〇〇。。以上的溫度下 2始形成。因此’可認為藉由將熱重·熱差 ==峰的波，溫度為28。。。以上的含有銅的： 子。銀粒子併用，可更有效地提昇含有鋼的粒 性，所形成的電極的電阻率進一步下降。 、氧化 構=述録子的銀村包含不可避統混 -v，、A1、zr、w，:、、T1gc= t發明巾的銀粒子的粒魏無翻關， _較佳為。.4 μιη以上、1〇、_二為 更佳為1 μιη以上、5 μηι以下。藉由定 耐氧化性更有效地提昇。另外帅以上’ :的銀粒子及含有銅的粒子等金二此：面二 大，電阻率更有效地下降。 面積鋟 於本發明的電極用膏狀組合物中，上 的粒徑(麵)與上述銀粒子的粒徑(晴：:,： 無特別限制，較佳為任一方的 關係並 的粒徑(麵)，更佳為任—方二 比為1〜1G。#此，電_電阻率更有效地下降。可= 26 201135754 其疋由例如以下原因所造成的：電極内的含有銅的粒子及 銀粒子等金屬粒子彼此的接觸面積變大。 另外’作為本發明的電極用膏狀組合物中的銀粒子的 含有率，就耐氧化性與電極的低電阻率的觀點而言，於電 極用膏狀組合物中，較佳為8.4質量％〜85 5質量i，更 為8.9質量％〜8〇 !質量％。 ^ ，於本發明中，就耐氧化性與電極的低電阻 ，點而言’將上述含有鋪粒子與域錄子的總量 =00質量。/。時的上述含有_粒子的含有率較佳為9質 。，以上88 f量％以下，更佳為Π質量％以上、7 〇以下。藉由上述含有銅的粒子的含有率 包含的五氧化，銀:反二 的粒子的含有率為88f#% 詞 子中所包含的銅愈石夕从接緒=^抑制含有鋼的粒 降。97札、絲板接觸，電極的接觸電阻進一步下 另外，於本發明的電極用膏狀組合物 :極的低電阻率、對於石夕 點二氧化生、 含有銅的粒子及上述銀粒子，上述 94質量％，更佳為％質量％〜8; 4^為:質量％〜 的粒子及上述銀粒子的總含量為7〇::猎由上述含有銅 用膏狀組合物時可容县’、、' 务里。以上，賦予電極 述含有銅的粒子及上述銀二的2為另外，藉由上 下，可更有效地—予電極用二二摩質= 27 ；3 201135754 J /厶jjif 生。 &quot;、个的要桠用骨狀組合物中，就耐氧化伯 =極的低電阻率的觀點而言，較佳為上述含有銅的粒子 1==:!含有率為70質量%〜94質量%，上述减 才子的3有率為（U質量0/〇〜1〇質量〇/〇，上述溶 的總含有率為3質量％〜29_9質量％，更佳為上述Gravimetry-Differential Thermal Analyzer (TG-DTA) was measured in the usual manner. The paste composition for an electrode of the present invention may further contain at least one other glass particle which does not contain pentoxide and pentoxide, in addition to the above-mentioned p2〇5_V2〇5-based glass. ▲ As the other glass particles, it is possible to efficiently take in the sulphur dioxide, and S ′ preferably includes stalk particles composed of (iv) lan. For this type of glass containing lead, for example, the glass of the Japanese Patent No. 64-A, etc., may be preferably used in the present invention. Be careful ^ outside ^ in this fortune, riding fine in Wei (four) ringing, then use = no mistakes on the wrong glass. For example, it is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 09-188281. The error-free glass is also preferably used in the present invention after being suitably selected from the above-mentioned profit-seeking glasses. 22 201135754 her j is the content of the above-mentioned glassy substance, in the electrode-time composition: in the shell I, preferably 0.1 mass 〇 / 〇 ~ 10 mass 0 / 〇, more preferably 0.5 mass% - and further More preferably, it is 1 mass% - 7 mass%. The content of the above-mentioned range includes the particles, and the oxidation resistance, the low resistivity of the electrode, and the low contact resistance are more effectively achieved. Hey. In the present invention, it is preferable that the glass particles containing P2〇rV2〇5-based glass having a content of 乂2〇5 and a content of j or more of 1 or more are 0.1 mass 〇/〇 10 10 mass/°, more preferably contained. The content of V2〇5 is 1 mass❶/. ~70. The mass % of P2〇5_V2〇5-glass glass particles 〇5 mass%/〇θ and more preferably P2〇5-V2〇5 containing V2〇5 content of 1% by mass to 70 mass 〇/❶. The glass particles of the glass are 1% by mass to 7% by mass. (Solvent and Resin) The paste composition for an electrode of the present invention contains at least one solvent and at least one kind of resin. Thereby, the liquid physical properties (e.g., viscosity, surface tension, and the like) of the paste composition for an electrode of the invention can be adjusted to a desired liquid physical property in accordance with the method of imparting the application to the miscellaneous sheet. - The above-mentioned 'treats are not particularly limited. For example, there may be mentioned H-capacitor such as hexane, cyclohexanol, and 2; chlorinated hydrocarbons such as diethylene glycol, dioxane, and benzene, and the chlorinated hydrocarbons such as tetrahydrofuran, furan, and tetrahydropyridinium.喃, pyran, dioxins 卞 ane) 1,3- oxolane, tri〇xane (tri〇xane), etc. ring _ system dissolve ^ Ν 'Ν &quot; mercaptoamine, yttrium amide Amine solvent; dimethyl sulfoxide, diethyl sulfoxide and other sulfoxide solvents; ketone solvents such as acetone, mercaptoethyl I, monoethyl g, cyclohexanone; ethanol, propanol, Alcoholic compounds such as butanol and diacetone alcohol; 2,2,4-trimethyl-1,3-pentanediol 23 201135754 Monoacetate, 2,2,4·Sanjiamei·! 1丄, ^ base - 1,3-戍 二醢. . , · pentanol monopropionate, 2,2,4-trimethyl ester, 2,2,4-triethyl, _2'2:t trimethyl-1,3_nonanediol monoisobutyric acid vinegar , diethylene glycol monobutyric acid, ethylene glycol monobutyric acid acetate, diethylene glycol diethylene (tetra) scales of the solvent; butyl soluble terpineol, laurel heart alcohol solvent; α_ Terpinene, α_ 贴口·laurel oil return, ρρ shop, rosin alcohol, fragrant dry fine m lin, alpha rhyme, solvent, and the mixture of these = basil, water bud, etc. (four) paste; soil The "agent" is used to form at least one type of vinegar = 嶋 嶋 、, 嶋 嶋 solvent, and polyol of the polyol. For the vinegar solvent selected from the group consisting of polyhydric alcohols and the solvent, the '4 solvent can be used alone' or the combination can be used as the above resin, as long as it is thermally decomposable by sintering. The meridian body which is generally used in the technical field can be used without particular limitation, and examples thereof include a cellulose system such as methyl cellulose, ethyl cellulose, cellulose, and cellulose. Resin; polyethylene glycol; ^ ethylene. Bismuth; acrylic acid resin; acetic acid ethyl vinegar-acrylic acid vinegar copolymerization, butyric acid resin, etc.; aged modified alkyd resin, wanma / modified by lunar acid An alkyd resin such as an alkyd resin; an epoxy resin; a resin; a rosin ester resin. The above-mentioned resin in the present invention is a viewpoint of the disappearance at the time of sintering. 24 201135754 3: The s is at least one type from the cellulose resin or the acrylic resin, and more preferably at least selected from the cellulose resin. One. In the present invention, the above resins may be used alone or in combination of two or more. For premature use, it is also possible to combine the fat: ==_ in the paste composition, the above solvent and the above type of resin; = and the solvent used and the total content of the tree-like composition such as resin In the case of the electrode U, it is preferably 3% by mass or more, 29 9 masses: two = 5% by mass or more, and 25 masses of TM^ are in the range of 7% by volume or more and 2% by mass or less. The total content of the resin group and the resin is within the above range, and the impartability for imparting the paste and the electrode to the ruthenium substrate is improved, and an electrode having a wide S degree can be more easily formed. (Life) particles) The poorly used composition of the electrode for a month is preferably further comprising at least one silver lanthanum. The oxidation resistance is further improved, and the electric (four) 1 ox of the electrode can also be obtained when the photovoltaic battery module is fabricated. The effect of improved connectivity. This kind of situation can be considered as follows. . - Generally, 600 is formed as a temperature region of the electrode. (: to 900. In the temperature range of 〇, a small amount of solid solution of silver in copper and a solid solution of copper in silver; and a layer of copper-silver solid solution formed at the interface between copper and silver ( Solid 1 domain). It can be considered that when the mixture of copper-containing particles and filaments is twisted to two temperatures, 'slowly cool and light room temperature, ^ produces a solid solution region, but because of the rise> into the electrode in seconds The high temperature region is cooled to normal temperature, so it can be considered that the high temperature is 25 201135754 ====== or: the eutectic structure with silver contributes to the oxidation resistance of the copper-containing electrode at the electrode formation temperature:: solid solution layer From wc to 5 〇〇. The above temperature is formed at 2°. Therefore, it can be considered that the temperature is 28 by the wave of thermogravimetry and heat difference == peak. The above copper-containing: sub-silver particles When used together, the graininess of the steel containing steel can be more effectively improved, and the resistivity of the formed electrode is further decreased. The oxidized structure = the silver village of the record contains the incompatible mixture -v, A1, zr, w,:, T1gc=t The silver particles of the invention towel have no turning, _ preferably. 4 μιη or more, 1 〇, _2 is more preferably 1 μιη or more, 5 μηι It is more effective to improve the oxidation resistance. In addition, the silver particles and the copper-containing particles are the same as the gold: the surface is two, and the resistivity is more effectively decreased. The area is different from the electrode paste of the present invention. In the composition, the particle diameter (surface) and the particle diameter of the silver particles (clear::, not particularly limited, preferably a particle diameter (surface) in any relationship, more preferably any The ratio is 1 to 1 G. In this case, the electric resistance decreases more effectively. It can be = 26 201135754 The following is caused by, for example, the contact area between the copper-containing particles in the electrode and the metal particles such as silver particles. Further, the content of the silver particles in the paste composition for an electrode of the present invention is preferably in the paste composition for an electrode from the viewpoint of oxidation resistance and low resistivity of the electrode. 8.4% by mass to 85 5 mass i, more 8.9% by mass to 8 〇!% by mass. ^ In the present invention, in terms of oxidation resistance and low resistance of the electrode, the point of the above-mentioned containing particles and domains is recorded. The total amount of sub-mass = 00 mass% / / The above-mentioned 88 f amount% or less, more preferably Π mass% or more and 7 〇 or less. The content of the above-mentioned copper-containing particles is pentoxide, and the content ratio of the silver: anti-two particles is 88f# The copper in the vocabulary contains the grain drop of the steel. The contact resistance of the electrode is further increased. In addition, the paste composition for the electrode of the present invention is extremely The low resistivity, the above-mentioned 94% by mass, more preferably the % by mass of the above-mentioned silver particles, and the above-mentioned silver particles, the particles of the above-mentioned silver particles, and the above-mentioned silver particles. The total content is 7〇:: When the above-mentioned paste composition containing copper is used, it can be filled into the county ', '. As described above, the electrode containing copper and the silver 2 are additionally provided, and by the top and bottom, it is more effective to use the second electrode as the second electrode = 27; 3 201135754 J /厶jjif. In the case of the bone-shaped composition, it is preferable that the content of the copper-containing particles 1 ==:! is 70% by mass to 94% from the viewpoint of resistance to oxidation of the electrode. % by mass, the ratio of the above-mentioned minus of 3 (U mass 0 / 〇 ~ 1 〇 mass 〇 / 〇, the total content of the above solution is 3% by mass to 29 9% by mass, more preferably the above

3 f銅的粒子及上述銀粒子的總含有率為72質量％〜9C 質量％，上述玻璃粒子的含有率為0.5質量％〜8質量％， 上述溶劑及上述樹脂的總含有料5 f#%〜Μ質量％， 進而更佳為上述含有_粒子及上述銀粒子輯含有0 二質量^〜88質量％，上述玻璃粒子的含有率為ι質量$ 質上述;谷劑及上述樹脂的總含有率為7質量％〜 2〇質量％。 (助熔劑） 電極用膏狀組合物可更包含至少一種助熔劑。藉由包 含j炫劑，耐氧化性進—步提昇，所形成的電極心阻率 =一步下降。義，亦可獲得電極㈣射基板的密接性 叔昇的效果。 作為本發明中的助熔劑，只要是可去除形成於含有銅 的，子的表面的氧化膜的助熔劑，則並無特別限制。具體 而言’例如可列舉脂肪酸、硼酸化合物、氟化物、以及石朋 氣化物等作為較佳的助熔劑。 匕充更具體而言，可列舉：十二酸、十四酸、棕櫚酸、硬 脂酸、山梨酸、硬炔酸、氧化硼、硼酸鉀、硼酸鈉、硼酸 28 201135754 ::氣it ^匕鈉，氟化鐘、酸性氟化鉀、酸性 氟化：二氟化鐘、氟化鉀、氟化鈉、氟化鐘等。 就電極材料燒結時的耐熱性（助熔劑於蜱 :邮揮發的特性)及補充含有銅的：二 胸酸物氣化卸作為特佳的糊 組合=:以，助_分別單獨使用-種 亦可 含量合物中的助'熔劑的 以及降低雷;H有銅的粒子的耐氧化性的觀點、 R&amp;安A: 。斗的燒結結束時助熔劑被去除的部分的空 為(U質量。/。〜5 合物的總質量中，較佳 而更佳為0.5質量I〜3°; = °‘3質量%〜4質量%’進 θ〇/ , 1 3.5質篁/〇,特佳為〇 7質量％〜 罝％，極佳為1質量％〜2.5質量％。 (其他成分） 外作 可列舉:塑化劑、分散劑、界面活性劑: 、、、金屬氧化物、陶竞、有機金屬化合物等。 χ 、電極用貧狀組合物的製造方法並益 制。可利用通常所估田认、#左业…将別限 子、玻璃粒子^ ==·混合方法對上述含有銅的粒 等進行分散.混合^此及視需要而包含的銀粒子 &lt;使用㈣^製造本發明的電極用纽組合物。 °用貧狀組合物的電極的製造方法&gt; 29 201135754 作為使用本發明的電極用膏狀組合 :後:二:極:膏狀組合物賦予至形成電== 展後進订燒結，藉此可於所期望的區域n ，上述電刻f餘合物，即使純时訂^ 2 虱1Μ進彳了燒結處理’亦可形成電阻率低的電極。’ 伏 狀的方式賦予至石夕基板上，乾燥後進 了 ^ =二，用膏狀組合物，即使於氧的存在下（例^ li订燒結處理，亦可形成電阻率低 2將電極用膏狀組合物塗佈於石夕基板上的方法例 . =p刷、噴墨法、及分配法等，就生產性的 觀點而5車父佳為利用網版印刷的塗佈。 =利用網版印刷塗佈本發明的電極用膏狀組合物時， 較佳為具有8G Pa.sMooo Pa.s的範_黏度。再者 ==合物的黏度是於坑下利用价⑻咖咖黏度 上iC電極用膏狀組合物的賦予量可對應於 小而適宜選擇。例如，可將電極用膏狀Μ合= 里5又疋為2 g/m2〜1〇 g/m2，較佳為4 g/m2〜8 g/m2。 另作為使用本發明的電極用膏狀組合物形成電極 時的熱處理條件（燒結條件），可應用該技術領域中通常所 使用的熱處理條件。 201135754 D/HVZpif 敖而5，熱處理溫度（燒結溫度）為8〇〇它〜9〇〇。〇， ΐ當使用本發㈣電極㈣狀組合物時，可應用更低的溫 又下的熱處理條件’例如’可形成於〜8赃的熱處 理溫度下具有良好的特性的電極。 另外，熱處理時間可對應於熱處理溫度等而適宜選 擇，例如可設定為i秒〜20秒。 &lt;光伏電池&gt; 本發明的光伏電池具有對被賦予至石夕基板上的上述電 極用；g狀組合物進行燒結而形成的電極。藉此，可獲得且 有良好的雜的級電池，且該紐電池的生產性優異Γ 以下，一面參照圖式一面說明本發明的光伏電池的具 體例，但本發明並不限定於此。 〜將表示具有代紐的光伏電池元件的—儀剖面圖、 受光面及背面的概要示於圖丨、圖2及圖3。 、通常，於光伏電池元件的半導體基板13〇中使用單晶 或夕aa Si等。s亥半導體基板13〇中含有硼等，而構成p型 半導體。受光面側為了抑制太陽光的反射，藉祕刻而形 ，有凹凸（紋理，未圖示）。於該受光面侧摻雜磷等，並以 次微米級的厚度設置有n型半導體的擴散層⑶，並且在 與P型塊狀部分的邊界形成有pn接合部。進而，於受光面 側，藉由蒸鍍法等在擴散層131上設置膜厚為1〇〇 nm&amp; 右的氮化矽等的抗反射層132。 、其次，對設置於受光面側的受光面電極133、以及形 成於背面的集電電極134及功率取出電極135進行說明。 31 201135754 欠光面電極133與功率取出電極135是由上述電極用膏狀 組合物形成。另外，集電電極m是由包含朗粉末的紹 ，極膏狀組合物形成。該些電極是利用網版印㈣將上述 膏狀組合物塗佈成所期望的圖紐，進行賴，然後於大 氣中以6G()°C〜85G°C左右進行燒結而形成。 於本發明中，藉由使用上述電極用膏狀組合物，即使 於比較低邮度Tit概結，村魏雜_ 率優異的電極。 此時’於受光面侧，形成受絲電極133❸上述電極 用《狀組合物巾所包含的玻触子魏反射層⑶進行反 應(/堯結貫穿），而使受光面電極133與擴散層131電性連 接（歐姆接觸）。 ^ 為光’藉由使用上述電極用膏狀組合物來形成 又先面電極133，-面含有銅作為導電性金屬，一面抑制 =氧化，而以良好的生產性形成低電阻率的受光面電極 133 〇 另外，於背面侧，當進行燒結時 的嫌膏狀組合物中的峨叫體基=的； 二而電^=成2散層136’#此可在半導體基板^ 出電極135之間獲得歐姆接觸。 另外，將作為本發明的其他型態的光伏電池元件的一 例的受光面及AA剖面構造的立辦岡, 極構造的平面圖⑻=V：_(a)、以及背面側電 如圖4(a)的立體圖所示，於包含P型半導體的石夕基 32 201135754 J /'tuz.pif 板的單元晶圓1上，藉由雷射鑽孔或麵刻等而形成有貫穿 j =侧及背面綱面的通孔。另外’於受光面侧形成有 射效率的紋理（未圖示）。進而，於受光面側形成 有利用η型化擴散處理所形成的n型半導體層3，且於n 型J導體層3上形成有抗反㈣（未圖示心是藉由與 先前的結晶Si型光伏電池單元相同的步驟來製造。 繼而藉由印刷法或喷墨法將本發g肖的電極用膏狀组 合物填充至先前卿成的通孔内部，進而，於受光面側同 樣地將本發明的電極用膏狀組合物印刷成栅狀，而形成如 下的組合物層’該組合物層形成通孔電極4及集電用栅電 極2。 此處，用於填充用與印刷用的膏較理想的是使用以黏 度為首的特性最適合於各個製程的組成的膏，亦可使用相 同組成的膏一次性地進行填充、印刷。 另一方面，於受光面的相反侧（背面側）形成用於防 止栽子複合的高濃度摻雜層5。此處，使用硼或鋁（A1) 作^形成高濃度摻雜層5的雜質元素來形成p+層。該高濃 $換雜層5例如可藉由於上述抗反射膜形成前的單元製造 步驟中實施將B作為擴散源的熱擴散處理來形成，或者當 使用A1時’可藉由於上述印刷步驟中將A1膏印刷在相反 面側來形成。 、其後’於650°C至850°C下進行燒結，被填充、印刷於 上述通孔内部與受光面側所形成的抗反射膜上的上述電極 用膏狀、纟且合物藉由燒結貫穿效果，而達成與下部η型層的 33 201135754 另外，於相反面侧，如由圖4 ( 本發明的電極用膏狀組合物分別於η側y ’面圖所示，將 狀’並進行燒結，藉此形成背面電極6、7P。貝均印刷成條 於本發明中，使用上述電極用膏狀 極4、集電用柵電極2、背面電極6及背^形成通孔電 面含有銅作為導電性金屬，— 57 ’藉此- 的生產性戦低電㈣的通孔化，而以優異 面電極6及背面電極7。 集電用柵電極2、背 再者’本發明的電極用膏狀組合 述的光伏電池電極的用途，例如，亦可較: 測器電路、半導趙元件的二;用:線電路、各種感 [實例] π定2 J由實例更具體地說明本發明，但本發明並不 =於_貫例。再者，只要料無特別說明 及％」為質量基準。 &lt;實例1&gt; (a)電極用膏狀纟且合物的製備 、製備包含氧化釩（V2〇5) 1〇份' 氧化磷（p2〇5) 29 6 伤氧化鋇（BaO) 10.4份、氧化鉬（M〇〇3) 1〇份、氧化 鶴（W〇3) 30伤、氧化鉀（κ2〇) 份的玻璃（以下，有 時略圮為「Κ41」）。所獲得的玻璃K41的軟化點為554。〇， 結晶化溫度超過600。〇。 34 201135754 使用所獲得的玻璃K41，獲得粒徑（D5〇%)為1.7 μιη 的玻璃粒子。 將銅粒子（三井金屬礦業股份有限公司製造，純度為 99.9%，粒徑（D50%)為丨5 μπ〇 39 2份、銀粒子（粒徑 (D50% )為3 μιη ’ Aldrich公司製造的高純度化學品）45 9 份、玻璃粒子（K41) 1.7份、以及含有4%的乙基纖維素 (EC)的丁基卡必醇乙酸酯（BCA)溶液132份加以混 合，然後於瑪瑶製乳蛛中 2〇分鐘，製成電極用膏狀組 合物1。 (b)光伏電池單元的製作 準備於受光面形成有η型半導體層、紋理及抗反射膜 (氮化矽膜）的膜厚為19〇 μιη的ρ型半導體基板，並切 成125 mm&gt;&lt;125 mm的大小。利用網版印刷法，將上述所 獲得的電極用膏狀組合物丨以成為如圖2所示的電極圖案 的方式印刷於其受光面。電極的圖案是由15〇㈣寬度的 手指線（Finger Une)與u mm寬度的匯流條（Busbar) 構成，且以使燒結後的膜厚達到2〇μιη的方式適宜調整印 刷條件（篩板的篩孔、印刷速度、印刷麼力）。將所獲得者 放入加熱至15(TC的供箱中15分鐘，藉自蒸散來去除溶劑。 、、’盧而同樣利用網版印刷將銘電極膏印刷於整個背 面。以使燒結後的膜厚達到40从瓜的方式適宜調整印刷條 件。將所獲得者放入加熱至15(rc的烘箱中15分鐘， 蒸散來去除溶劑。 繼而’於紅外線急速加熱爐内，在大氣環境下以85〇它 35 201135754 J / wzpif 進打2秒的加熱處理（燒結），製成形成有所期望的電極的 光伏電池單元1。 &lt;實例2〜實例 於貫例1中，將銅粒子的粒徑（D50%)及含量、銀 =子的粒僅（D5〇%)及含量、玻璃粒子的種類及含量、 含有4〇/❶的乙基纖維素（EC)的丁基卡必醇乙酸酯（bca) 溶液的含量如表i所示般變更，除此以外，以與實例i相 同的方式製成電極时狀組合物2〜電细纽組合物8。 _ =者，玻璃粒子（AY1)包含氧化釩（v2〇5) 45份、 (/205) 24 2份、氧化鎖（Ba〇) 2〇.8份、氧化錄 2 3 5伤、氧化鶴（w〇3) 5份，且粒經（D5〇%)為 1典7卿。另外，該玻璃的軟化點為492〇c，結晶化溫度超 客進而，分別使用所獲得的電極用膏狀組合物2〜電極 用膏狀組合物8，並將加熱處理的溫度及處理時間如表！ 更，除此以外，以與實例1相同的方式分別 也成有所财㈣極的絲電料元2〜光 〈比較例1&gt; 於貫例1令’使用包含銀粒子及錯玻璃粒子的市售 光伏電池用銀膏（杜邦股份有限公司製造，PV159)作為 =用膏狀組合物，除此以外，以與實例丨相同的方式製 成光伏電池單元C卜 表 &lt;比較例2&gt; 於製備實例1巾的電極时狀組合物時，不使用含有 36 201135754 U / -Ύν/^ρΐΙ 銅的粒子，並以成為表1所示的組成的方式變更各成分， 除此以外，以與實例1相同的方式製成電極用膏狀組合物 C2。 除使用不包含含有銅的粒子的電極用膏狀組合物C2 以外，以與實例1相同的方式製成光伏電池單元C2。 37 201135754 J-aCNOKeThe total content of the particles of 3 f copper and the silver particles is 72% by mass to 9% by mass, the content of the glass particles is 0.5% by mass to 8% by mass, and the total content of the solvent and the resin is 5 f#%~ Further, it is more preferable that the content of the above-mentioned _ particles and the silver particles is from 0 to 280% by mass, and the content of the glass particles is ι by mass. The total content of the granules and the above resins is more preferably 7% by mass to 2% by mass. (Flux) The paste composition for an electrode may further contain at least one flux. By including j agent, the oxidation resistance is further improved, and the formed electrode resistivity = one step down. It is also possible to obtain the effect of the adhesion of the electrode (4) to the substrate. The flux in the present invention is not particularly limited as long as it is a flux capable of removing an oxide film formed on the surface of a copper-containing sub-particle. Specifically, for example, a fatty acid, a boric acid compound, a fluoride, and a saponin can be cited as preferred fluxes. More specifically, it can be enumerated: dodecanoic acid, tetradecanoic acid, palmitic acid, stearic acid, sorbic acid, hard acetylene acid, boron oxide, potassium borate, sodium borate, boric acid 28 201135754 :: gas it ^ 匕Sodium, fluorinated clock, acidic potassium fluoride, acidic fluorination: difluorination clock, potassium fluoride, sodium fluoride, fluorinated clock, etc. The heat resistance during the sintering of the electrode material (the fluxing property of the flux in the sputum: the characteristics of the volatilization) and the supplementation of the copper-containing: the dichroic acid gasification unloading as a particularly good paste combination =:, _ separately used - The viewpoint of the 'refining agent' in the content of the flux and the reduction of the thunder; the viewpoint of the oxidation resistance of H-copper particles, R&A:. The void of the portion where the flux is removed at the end of the sintering of the bucket is (U mass. /. 5 to the total mass of the compound, preferably and more preferably 0.5 mass I to 3 °; = ° '3 mass% to 4 The mass % 'into θ 〇 / , 1 3.5 mass 篁 / 〇, particularly preferably 〇 7 mass % ~ 罝%, excellently 1% by mass to 2.5% by mass. (Other components) External preparations can be cited: plasticizer, Dispersing agents, surfactants: , , , metal oxides, pottery, organometallic compounds, etc. χ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 In other words, glass particles ^ ==·mixing method, the above-mentioned copper-containing particles and the like are dispersed, and the silver particles are optionally mixed and used; the electrode composition for electrode of the present invention is produced by using (4). Method for producing electrode of poor composition&gt; 29 201135754 As a paste combination for using the electrode of the present invention: after: two: pole: a paste composition is imparted to form electricity == post-slot finishing sintering, thereby being The desired region n, the above-mentioned electro-engraved f-form, even if it is purely ordered, 2 2 虱 1Μ into the sintering process 'can also form electricity The electrode with a low rate. The volt-like method is applied to the Shixi substrate, and after drying, it is added into the ^=2, and the paste composition is used, even in the presence of oxygen (for example, the sintering treatment can form a low resistivity). (2) An example of a method of applying a paste composition for an electrode to a Shih-ray substrate. =p brush, inkjet method, and distribution method, etc., from the viewpoint of productivity, the vehicle is coated by screen printing. When the paste composition for an electrode of the present invention is applied by screen printing, it preferably has a van_viscosity of 8 G Pa.s Mooo Pa.s. Further, the viscosity of the compound is the utilization price under the pit (8). The amount of the paste composition for the iC electrode on the viscosity of the coffee and the coffee may be appropriately selected in accordance with the small amount. For example, the electrode may be paste-likely combined with 里5 and 疋2 g/m2 to 1〇g/m2. It is preferably 4 g/m2 to 8 g/m2. Further, as heat treatment conditions (sintering conditions) when the electrode is formed using the paste composition for an electrode of the present invention, heat treatment conditions generally used in the technical field can be applied. /HVZpif 敖 and 5, heat treatment temperature (sintering temperature) is 8 〇〇 it ~ 9 〇〇. 〇, ΐ当用发发(四) In the case of the electrode (four) composition, a lower temperature and lower heat treatment condition can be applied, for example, an electrode having good characteristics at a heat treatment temperature of 〜8 。. Further, the heat treatment time can be appropriately adapted to the heat treatment temperature and the like. The selection may be, for example, i seconds to 20 seconds. &lt;Photovoltaic cell&gt; The photovoltaic cell of the present invention has an electrode formed by sintering the g-shaped composition applied to the electrode on the substrate. It is possible to obtain a good hybrid battery and to have excellent productivity. Hereinafter, a specific example of the photovoltaic cell of the present invention will be described with reference to the drawings, but the present invention is not limited thereto. ~ A schematic diagram showing the cross-sectional view of the instrument, the light-receiving surface and the back surface of the photovoltaic cell element having the dynasty is shown in Fig. 2, Fig. 2 and Fig. 3. Usually, single crystal or eve aa Si or the like is used in the semiconductor substrate 13 of the photovoltaic cell element. The semiconductor substrate 13 〇 contains boron or the like to constitute a p-type semiconductor. In order to suppress the reflection of sunlight, the light-receiving side is shaped by a secret, and has irregularities (texture, not shown). Phosphorus or the like is doped on the light-receiving surface side, and a diffusion layer (3) of an n-type semiconductor is provided in a thickness of a submicron order, and a pn junction portion is formed at a boundary with the P-type bulk portion. Further, on the light-receiving side, an anti-reflection layer 132 such as tantalum nitride having a thickness of 1 〇〇 nm & right is provided on the diffusion layer 131 by a vapor deposition method or the like. Next, the light-receiving surface electrode 133 provided on the light-receiving surface side and the collector electrode 134 and the power extraction electrode 135 formed on the back surface will be described. 31 201135754 The under-surface electrode 133 and the power take-out electrode 135 are formed of the above-mentioned electrode paste composition. Further, the collector electrode m is formed of a fine paste composition containing a lang powder. These electrodes are formed by applying the above-mentioned paste composition to a desired pattern by screen printing (4), and then sintering it in an atmosphere of about 6 G () ° C to 85 ° ° C. In the present invention, by using the above-mentioned paste composition for an electrode, an electrode excellent in the rate of the low-grade Tit is obtained. At this time, the receiving electrode is formed on the light-receiving surface side, and the electrode is subjected to a reaction (or a splicing-through) of the glass-contacted Wei-reflecting layer (3) included in the "shaped composition towel", and the light-receiving surface electrode 133 and the diffusion layer 131 are formed. Electrical connection (ohmic contact). ^ is a light-receiving surface electrode which is formed by using the above-mentioned paste composition for an electrode to form a further surface electrode 133, and the surface contains copper as a conductive metal while suppressing = oxidation to form a low resistivity with good productivity. 133 〇 In addition, on the back side, when the sintering is performed, the squeaky body composition in the paste composition is =; and the electric charge is 2 into the scatter layer 136'# which can be between the semiconductor substrate 135 Obtain an ohmic contact. In addition, as a light-receiving surface and an AA cross-sectional structure of another example of the photovoltaic cell element of the present invention, a plan view of the pole structure (8) = V: _ (a), and a back side of the electric circuit as shown in Fig. 4 (a) As shown in the perspective view, on the unit wafer 1 of the Shihki 32 201135754 J /'tuz.pif board including the P-type semiconductor, a through hole j = side and a back surface are formed by laser drilling or surface etching. Through hole of the surface. Further, a texture (not shown) having a radiation efficiency is formed on the light-receiving surface side. Further, an n-type semiconductor layer 3 formed by an n-type diffusion treatment is formed on the light-receiving surface side, and an anti-reverse (four) is formed on the n-type J conductor layer 3 (the core is not shown by the previous crystalline Si) The photovoltaic cell is fabricated in the same step. The paste composition of the electrode of the present invention is filled into the through hole of the previously formed through hole by a printing method or an inkjet method, and further, the light receiving surface side is similarly The paste composition for an electrode of the present invention is printed in a grid shape to form a composition layer of the composition layer forming the via electrode 4 and the collector gate electrode 2. Here, for filling and printing It is preferable that the paste is a paste which is most suitable for the composition of each process, and the paste of the same composition can be filled and printed at one time. On the other hand, on the opposite side (back side) of the light receiving surface A high-concentration doping layer 5 for preventing the recombination of the plant is formed. Here, boron or aluminum (A1) is used as an impurity element forming the high-concentration doping layer 5 to form a p+ layer. For example, it can be obtained by the single film before the formation of the anti-reflection film In the meta-manufacturing step, a thermal diffusion treatment using B as a diffusion source is carried out, or when A1 is used, 'can be formed by printing the A1 paste on the opposite side in the above printing step. Then, 'at 650 ° C to Sintering at 850 ° C, filling and printing on the anti-reflection film formed on the inside of the through-hole and the anti-reflection film on the side of the light-receiving surface, the paste-like and ruthenium-containing compound are sintered and penetrated, and the lower n-type is achieved. 33 201135754 In addition, on the opposite side, as shown in FIG. 4 (the paste composition for electrodes of the present invention is formed in the η side y' plane, respectively, and is sintered, thereby forming the back electrode 6, 7P. In the present invention, the paste electrode 4 for the electrode, the gate electrode 2 for the current collector 2, the back electrode 6 and the back surface electrode are formed to contain copper as a conductive metal. This is the production of the low-power (four) through-hole, and the excellent surface electrode 6 and the back electrode 7. The collector gate electrode 2, the back of the electrode of the present invention is a combination of the photovoltaic cell electrode Use, for example, can also be compared to: detector circuit, semi-guided Zhao The second component; the use of: line circuit, various sensations [example] π fixed 2 J The present invention will be more specifically described by way of example, but the present invention is not in the _ example. Moreover, as long as nothing is specified and %" Quality basis. &lt;Example 1&gt; (a) Preparation and preparation of a paste-like composition for an electrode comprising vanadium oxide (V2〇5) 1 part of a 'phosphorus oxide (p2〇5) 29 6 Injisted barium oxide (BaO) 10.4 parts, molybdenum oxide (M〇〇3) 1 part, oxidized crane (W〇3) 30 wounds, potassium oxide (κ2〇) parts of glass (hereinafter, abbreviated as "Κ41"). The softening point of the glass K41 was 554. 〇, the crystallization temperature exceeded 600. 2011 34 201135754 Using the obtained glass K41, glass particles having a particle diameter (D5〇%) of 1.7 μm were obtained. Copper particles (manufactured by Mitsui Mining & Mining Co., Ltd., purity 99.9%, particle size (D50%) 丨5 μπ〇39 2 parts, silver particles (particle diameter (D50%) 3 μιη 'High by Aldrich) 45 parts of purity chemicals, 1.7 parts of glass particles (K41), and 132 parts of butyl carbitol acetate (BCA) solution containing 4% ethyl cellulose (EC), and then mixed with Ma Yao In the milking spider, the paste composition 1 for electrodes was prepared in 2 minutes. (b) Preparation of photovoltaic cell unit A film in which an n-type semiconductor layer, a texture, and an anti-reflection film (tantalum nitride film) were formed on the light-receiving surface was prepared. A p-type semiconductor substrate having a thickness of 19 μm was cut into a size of 125 mm &gt;&lt; 125 mm. The paste composition for electrodes obtained above was twisted by a screen printing method as shown in Fig. 2 The pattern of the electrode pattern is printed on the light receiving surface. The pattern of the electrode is composed of a finger line (Finger Une) of 15 〇 (four) width and a bus bar (Busbar) of u mm width, so that the film thickness after sintering reaches 2 〇 μιη. The way is suitable to adjust the printing conditions (screening hole, printing speed, printing? Force). Heat the obtained one to 15 (TC for 15 minutes in the box, and remove the solvent by evapotranspiration.), and Lu also prints the electrode paste on the entire back surface by screen printing. After the film thickness reaches 40, the printing conditions are appropriately adjusted from the melon. The obtained one is placed in an oven heated to 15 (rc for 15 minutes, and evaporated to remove the solvent. Then in the infrared rapid heating furnace, in the atmosphere) The solar cell 1 having a desired electrode was formed by heat treatment (sintering) of 85 35 35 201135754 J / wzpif for 2 seconds. <Example 2 to Example In Example 1, copper particles were used. Particle size (D50%) and content, silver=subparticles only (D5〇%) and content, type and content of glass particles, butyl carbitol B containing 4〇/❶ of ethyl cellulose (EC) The electrode composition 2 to the electric fine composition 8 was prepared in the same manner as in Example i except that the content of the acid ester (bca) solution was changed as shown in Table i. _ =, glass particles ( AY1) contains vanadium oxide (v2〇5) 45 parts, (/205) 24 2 parts, oxidized lock (Ba〇) 2〇.8 Oxidation recorded 2 3 5 injury, oxidized crane (w〇3) 5 parts, and the grain (D5〇%) is 1 典 7 qing. In addition, the softening point of the glass is 492 〇c, the crystallization temperature is super-customer The paste composition for electrode 2 to the paste composition 8 for electrodes were used, respectively, and the temperature and the treatment time of the heat treatment were as shown in Table, and the same manner as in Example 1 was carried out. The wire material 2 to light (Comparative Example 1) of the financial (four) pole is used as a silver paste for commercial photovoltaic cells (PV 159 manufactured by DuPont Co., Ltd.) containing silver particles and glass particles. In the same manner as in Example 制成, a photovoltaic cell C was prepared in the same manner as in Example & <Comparative Example 2> In the preparation of the electrode-time composition of the Example 1 towel, the use of 36 201135754 was not used. The electrode paste composition C2 was prepared in the same manner as in Example 1 except that the particles of the copper were changed so as to have the composition shown in Table 1. Photovoltaic cell C2 was fabricated in the same manner as in Example 1 except that paste composition C2 for electrodes containing no particles containing copper was used. 37 201135754 J-aCNOKe

【II 處理溫度/ 處理時間 850°C/2 秒 850〇C/2 秒 850°C/2 秒 850°C/2 秒 85(TC/2 秒 850°C/2 秒 850。(3/2 秒 850°C/2 秒 850°C/2 秒 U赵 茭钕A ^ ^ 4«? ® ^ 13.2 13.2 13.2 i 13.2 13.2 10.1 13.2 13.2 13.2 屮 種類 K41 1—— — K41 I AY1 L K41 I K41 K41 1 AY1 1 K41 K41 含量 (份） 卜 T—Η 卜 卜 1-Η r—&lt; 寸 cn oo r*H r-H 銀粒子 粒徑（D50%) (μπι) m m c〇 cn cn 含量 (份） 145,9_I 145,9_I I_45,9_I 1_45^__I | 45.0 | |_47.5 I 50.2 | 28.9 | 85.1 含有銅的粒子 粒徑（D50%) (μιη) 1-Η τ—Η 1-H in 1—H in to ψ H 1 含量 (份） | 39.2 1 1 39.2 1 39.2 | | 39.2 | | 38.4 | | 40.6 | 1 34.9 1 56.2 | 〇 ci 實例 實例1 實例2 1實例3 1 實例4 | 實例5 實例6 實例7 實例8 比較例2 20113575么 &lt;評價&gt; 所製作的光伏電池單元的評價是將作為模擬太陽光的 Wacom Electric (股份）製造的 wxs_155S_1〇、作為電流_ 電壓（I-V)評價測定器的 ϊ_ν CURVE TRACER Mp_16〇 (EKO INSTRUMENT公司製造）的測定裝置加以組合來 進行。表示作為光伏電池的發電性能的Eff (轉換效率）、 FF (fillfactor,填充因數）、Voc (開路電壓）及jsc (短路 電流）分別為藉由依據 JIS-C-8912、JIS-C-8913、JIS-C-8914 進行測定而獲得的測定值。將所獲得的各測定值換算成將 比較例1的測定值設定為1⑻·〇的相對值並示於表2。 39 201135754 J-as寸卜£ 【&lt;Nd 作為光伏電池的發電性能 Jsc (相對值）短路電流 103.1 107.4 106.6 112.6 105.3 99.8 100.4 99.5 100.0 103.1 Voc (相對值）開路電壓 96.9 98.2 97.9 97.2 97.2 100.9 103.0 100.6 100.0 98.9 FF (相對值） 填充因數 95.7 103.4 102.9 108.4 101.4 102.7 98.7 103.4 100.0 99.5 Eff (相對值） 轉換效率 99.1 103.9 102.9 104.9 101.9 99.6 100.1 101.1 100.0 100.9 處理溫度/ 處理時間 850°C/2 秒 850。(：/2 秒 850°C/2 秒 850〇C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850〇C/2 秒 850°C/2 秒 1-H 實例2 實例3 實例4 實例5 實例6 實例7 實例8 比較例1 比較例2 201135754 根據以上可知’藉由使用本發明的電 物，即便使用以銅為主成分的金屬粒子作為電極^電ς 金屈’亦可形成電阻率低的電極，並可構 特性的紐電池。 顿如幻憂異的 將曰本申請案2〇10-013514號、曰本 2010-222202號所揭示的所有内容引用於本說明蚩二&gt;、 本說明書巾所記载的全部文獻、日本專ζ 及技術規格是以與具舰且烟地記載財照的^式 各個文獻、日本補巾請案、以及技術規 作為參照而被引驗本朗㈣。 則的％度， 雖然本發明已以較佳實施例揭露如上，然 限定本發明，任何熟習此技藝者，在不脫‘發明$二 ::範圍内’當可作些許之更動與潤飾，因此本二= 範圍當視伽之巾請專·_界定者轉。 保濩 【圖式簡單說明】 圖1是本發明的光伏電池的剖面圖。 ==示本發明的光伏電池的受光面侧的平面圖。 圖3疋表示本發明的光伏電池的背面側的平面圖。 圖4 (a)是表示本發明的單元背接觸型光伏 1剖面構成的立體圖。（b)是表示本發明的單元背接觸 聖光伏電池的背面側電極構造的平面圖。 【主要元件符號說明】 1 :包含P型矽基板的單元晶圓 2:集電用栅電極 201135754 3 : n型半導體層 4:通孔電極 5:高濃度摻雜層 6:背面電極 7 :背面電極 130 :半導體基板 131 :擴散層 132 :抗反射層 133 :受光面電極 134 :集電電極 135 :功率取出電極 136 :電極成分擴散層 42[II Processing temperature / processing time 850 ° C / 2 sec 850 〇 C / 2 850 ° C / 2 850 ° C / 2 sec 85 (TC / 2 850 ° C / 2 850 850. (3 / 2 seconds 850°C/2 850°C/2 sec U Zhao茭钕A ^ ^ 4«? ® ^ 13.2 13.2 13.2 i 13.2 13.2 10.1 13.2 13.2 13.2 屮Type K41 1———— K41 I AY1 L K41 I K41 K41 1 AY1 1 K41 K41 Content (parts) Bu T-Η Bu Bu 1-Η r-&lt; Inch cn oo r*H rH Silver particle size (D50%) (μπι) mmc〇cn cn Content (parts) 145,9_I 145,9_I I_45,9_I 1_45^__I | 45.0 | |_47.5 I 50.2 | 28.9 | 85.1 Particle size of copper-containing particles (D50%) (μιη) 1-Η τ—Η 1-H in 1—H in to ψ H 1 content (parts) | 39.2 1 1 39.2 1 39.2 | | 39.2 | | 38.4 | | 40.6 | 1 34.9 1 56.2 | 〇ci Instance 1 Instance 2 1 Instance 3 1 Instance 4 | Instance 5 Instance 6 Instance 7 Instance 8 Comparative Example 2 20113575 &lt;Evaluation&gt; The photovoltaic cell produced was evaluated as wxs_155S_1〇 manufactured by Wacom Electric (share) which simulates sunlight, and ϊ_ν CURVE TRACER as a current_voltage (IV) evaluation tester Mp_16〇 (EKO INS The measuring devices manufactured by TRUMENT Co., Ltd. are combined and shown. Eff (conversion efficiency), FF (fill factor), Voc (open circuit voltage), and jsc (short circuit current), which are photovoltaic power generation performances, are respectively based on Measurement values obtained by measurement in JIS-C-8912, JIS-C-8913, and JIS-C-8914. Each measured value obtained was converted into a relative value obtained by setting the measured value of Comparative Example 1 to 1 (8)·〇. Shown in Table 2. 39 201135754 J-as inch £ [&lt;Nd as photovoltaic cell power generation performance Jsc (relative value) short circuit current 103.1 107.4 106.6 112.6 105.3 99.8 100.4 99.5 100.0 103.1 Voc (relative value) open circuit voltage 96.9 98.2 97.9 97.2 97.2 100.9 103.0 100.6 100.0 98.9 FF (relative value) Filling factor 95.7 103.4 102.9 108.4 101.4 102.7 98.7 103.4 100.0 99.5 Eff (relative value) Conversion efficiency 99.1 103.9 102.9 104.9 101.9 99.6 100.1 101.1 100.0 100.9 Processing temperature / processing time 850 ° C / 2 seconds 850. (:/2 seconds 850 °C/2 seconds 850〇C/2 seconds 850 °C/2 seconds 850 °C/2 seconds 850 °C/2 seconds 850 °C/2 seconds 850 〇C/2 seconds 850 °C /2 seconds 1-H Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 201135754 According to the above, 'by using the electrical substance of the present invention, even metal particles containing copper as a main component are used. As an electrode ^Electric ς ς 屈 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可 亦可All the contents of the disclosure are referred to in the second note of the present specification, and all the documents, Japanese specialties, and technical specifications described in the specification sheet are the documents of the Japanese version of the Japanese version of the document. The case and the technical specifications are referred to as a reference (4). The percentage of the present invention, although the invention has been disclosed in the preferred embodiments as above, and the invention is not limited to the invention of the invention. ::In the scope of 'When you can make some changes and retouching, so this two = the scope of the gaze to the towel, please _ define the person to turn. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a photovoltaic cell of the present invention. Fig. 3A is a plan view showing a light-receiving side of a photovoltaic cell of the present invention. Fig. 3A is a plan view showing the back side of the photovoltaic cell of the present invention. a) is a perspective view showing a cross-sectional structure of the unit back contact type photovoltaic 1 of the present invention. (b) is a plan view showing the structure of the back side electrode of the unit back contact solar photovoltaic cell of the present invention. [Explanation of main element symbols] 1: Containing P Unit wafer 2 of type germanium substrate: gate electrode for current collection 201135754 3 : n-type semiconductor layer 4: via electrode 5: high-concentration doping layer 6: back surface electrode 7: back surface electrode 130: semiconductor substrate 131: diffusion layer 132 : anti-reflection layer 133 : light-receiving surface electrode 134 : collector electrode 135 : power extraction electrode 136 : electrode component diffusion layer 42

Claims (1)

201135754 七、申請專利範圍： L —種電極用膏狀組合物，包含： 以鋼為主成分的金屬粒子； 3有五氧化二磷及五氧化二釩且上述五氧化二釩的含 有率為1質量％以上的玻璃粒子； 溶劑；以及 樹脂。 2.如申請專利範圍第1項所述之電刻膏狀組合物， 八中上述玻璃粒子的玻璃軟化點為60〇。〇以下，結晶化起 始溫度超過6〇〇。〇。 嘗狀組合物 3.如申請專利範圍第1項所述之電極用 更包含銀粒子。 《-種光伏電池，其具有频料至錄板上的 :專利範圍第i項至第3項中任—項所述之電極用膏狀组 合物進行燒結所形成的電極。 43201135754 VII. Patent application scope: L—A paste composition for electrodes, comprising: metal particles mainly composed of steel; 3 having phosphorus pentoxide and vanadium pentoxide and the content of vanadium pentoxide is 1 Glass particles of mass % or more; solvent; and resin. 2. The electrostable paste composition according to claim 1, wherein the glass particles of the above-mentioned glass particles have a softening point of 60 Å. In the following, the crystallization starting temperature exceeds 6 〇〇. Hey. Taste composition 3. The electrode as described in claim 1 further contains silver particles. A photovoltaic cell having an electrode formed by sintering a paste composition of an electrode according to any one of the items (i) to (3) of the patent. 43
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TWI508311B (en) * 2013-04-23 2015-11-11 Motech Ind Inc Solar cell and manufacturing method thereof
CN105122379A (en) * 2012-12-28 2015-12-02 赫劳斯德国有限两和公司 An electro-conductive paste comprising coarse inorganic oxide particles in the preparation of electrodes in mwt solar cells
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