TW201249771A - Electronic component, aluminum electrode conductive paste for application in same, and aluminum electrode glass composition - Google Patents

Electronic component, aluminum electrode conductive paste for application in same, and aluminum electrode glass composition Download PDF

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TW201249771A
TW201249771A TW101112860A TW101112860A TW201249771A TW 201249771 A TW201249771 A TW 201249771A TW 101112860 A TW101112860 A TW 101112860A TW 101112860 A TW101112860 A TW 101112860A TW 201249771 A TW201249771 A TW 201249771A
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glass
electrode
aluminum
conductive paste
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TW101112860A
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TWI478890B (en
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Takashi Naito
Takuya Aoyagi
Shinichi Tachizono
Kei Yoshimura
Yuji Hashiba
Yuichi Sawai
Naoya KOMATSU
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Hitachi Chemical Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • 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
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/10—AC-PDPs with at least one main electrode being out of contact with the plasma
    • H01J2211/12—AC-PDPs with at least one main electrode being out of contact with the plasma with main electrodes provided on both sides of the discharge space
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/22—Electrodes
    • H01J2211/225—Material of electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Sustainable Development (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Sustainable Energy (AREA)
  • Power Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Glass Compositions (AREA)
  • Photovoltaic Devices (AREA)
  • Conductive Materials (AREA)
  • Gas-Filled Discharge Tubes (AREA)

Abstract

The present invention provides an aluminum electrode conductive paste whereby high performance and high reliability can be achieved in a solar cell or other electronic component employing a silicon substrate; a glass composition contained therein; and an electronic component in which performance and reliability are improved thereby. This aluminum electrode conductive paste contains an aluminum electrode plus a V-P-B-O based, low-melting point glass, whereby the amount of aluminum diffusion into the silicon substrate can be increased, while the amount of oxygen diffusion can be reduced, and therefore the electronic component can be made highly reliable. Moreover, because the glass and aluminum have good wettability and reactivity, electrode reliability can be improved.

Description

201249771 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種形成於矽基板上之鋁電極用導電性 糊、其中所含有之鋁電極用玻璃組合物、及使用該鋁電極 用導電性糊而製造之電子零件。 【先前技術】 使用具有pn接面之矽基板之太陽電池單元等電子零件上 形成有銀電極或鋁電極。該等電極係藉由塗佈含有大量銀 或鋁之金屬粒子之導電性糊並進行乾燥、煅燒而形成於矽 基板等上。通常，該導電性糊以該金屬粒子為主，包含玻 璃粒子 '黏合劑樹脂及溶劑等。藉由於電極煅燒時加熱至 導電性糊中之玻璃粒子之軟化點以上，使該玻璃粒子軟化 流動而形成緻密之電極，並且牢固地密接於基板等上。 該玻璃粒子先前一直使用於低溫下軟化流動之以氧化鉛 作為主成分之低熔點玻璃。但是，該玻璃所含之鉛係[Technical Field] The present invention relates to a conductive paste for an aluminum electrode formed on a ruthenium substrate, a glass composition for an aluminum electrode contained therein, and conductivity for using the aluminum electrode Electronic parts made by paste. [Prior Art] A silver electrode or an aluminum electrode is formed on an electronic component such as a solar cell using a tantalum substrate having a pn junction. These electrodes are formed on a ruthenium substrate or the like by applying a conductive paste containing a large amount of metal particles of silver or aluminum, drying and calcining. Usually, the conductive paste is mainly composed of the metal particles, and includes glass particles 'adhesive resin, solvent, and the like. When the electrode is heated to a temperature higher than the softening point of the glass particles in the conductive paste during firing, the glass particles are softened and flowed to form a dense electrode, and are firmly adhered to the substrate or the like. This glass particle has been used for a low-melting glass which has a lead oxide as a main component which softens and flows at a low temperature. However, the lead contained in the glass

RoHS指令等中所規制之有害物f，$ 了降低對環境負荷 之影響，即為了謀求生態系統之保護，於太陽電池單元或 電漿顯示面板等電子零件中，已將無錯之低炼點玻璃應用 於電極形成。例如，專利文獻i中揭示有於太陽電池單元 上所形成之銀電極或電極巾使用含有氧化_氧化砂之 無錯低熔點玻璃。X，專利文獻2中提出有含有氧化叙與 氧化硼之低熔點玻璃。 尤其是以鋁粒子或鋁合金粒子等金屬粒子作為主體之導 電性糊’因其金屬粒子表面之氧化古膜而你4 孔化反膜而無法緻密地煅 163196.doc 201249771 燒，於低電阻化方面存在問題。就此方面而言，提出有藉 由於導電性糊中添加釩或氧化釩之粒子，m改善金屬粒子 之燒結性，使其低電阻化之手法（專利文獻3)。又，亦揭示 有藉由添加碳、鍺、錫、氫化金屬化合物及磷化金屬化合 物等而提高耐氧化性，使其低電阻化之手法等（專利文獻 4) 〇 另一方面，於如太陽電池單元等所代表之強烈要求提高 發電效率及壽命之電子零件中，上述專利文獻丨〜4之電極 就提高電子零件之性能與可靠性兩方面而言絕非經充分考 慮者。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2008-543080號公報 [專利文獻2]曰本專利特開2〇〇6-332〇32號公報 [專利文獻3]曰本專利特開平7-7373 1號公報 [專利文獻4]曰本專利特開平5-298917號公報 【發明内容】 [發明所欲解決之問題] 關於使用具有pn接面之矽基板之太陽電池單元等電子零 件，於η型半導體側多使用銀電極，於p型半導體側多使用 鋁電極。若於該等之電極中使用先前之以氧化鉛作為主成 分之低熔點玻璃’則太陽電池單元之發電效率即轉換效率 較高，但若使用專利文獻1或2中所揭示之無鉛低熔點玻 璃’則存在其轉換效率下降之問題。認為其原因在於受到 I63196.doc 201249771 電極之燒結狀態及與石夕基柄 界面狀態所影響。又，關於 哥命4可靠性，對於先前之以 .^ ^ ^ 乳化釓作為主成分之低熔點 玻璃或專利文獻Η所揭示之材料或方法難以進行改良。 尤其於鋁電極中，會因水合 而緩慢地腐蝕，生成氫氧化 鋁，而導致電極性能劣化。 因此，本發明之目的在於， 、鑒於上述問題，同時實現使 用具有ρη接面之石夕基板之太陽電池單元等電子零件之高性 此化與高可靠化兩方面。又，提供可同時實現該等之 極用導電性糊及適用於其之紹電極用玻璃組合物。 [解決問題之技術手段] 解決本發明之問題之手段如下。 其係於矽基板上形成 並且該玻璃相為含有 (1) 一種電子零件，其特徵在於 有具有金屬粒子與玻璃相之電極者 飢、磷及硼之氧化物玻璃。 ⑺如上述⑴之電子零件，其中上述玻璃相以如 化物換算含有V2〇5 60〜80重量。/。、Ρ2〇5 10〜25重量％、Β 〇 5〜15重量％，並且ρ2〇5量高於Β2〇3量。 ^如上述⑴或⑺之電子零件，其中上述破蹲相以如 化物換算，V2〇5為70〜8〇重量％、Ρ2〇5為10〜20重晉 %'Β203為5〜10重量％，並且⑽、Β2〇3之合計量為 相之20〜40重量％。 為破璃 ⑷如上述⑴之電子零件，其中上述玻璃相進而含 碑、銻、鉍及鋅令之1種以上。 爷 (5)如上述（4)之電子零件，其中上述玻璃相以如下之氧 J63196.doc 201249771 化物換算，V2〇5為40〜80重量。/。、⑽為心^重量％、 B2〇3為5〜15重量％，為〇〜25重量％、％〇3為〇〜2〇重量 % ' Bi2〇3為0〜20重量％、及Zn〇為〇〜2〇重量％，並且p2〇5 量南於B2〇3量’且P2〇5、B2〇3及Te〇2之合計量為玻璃相之 20〜50重量％。 W如上述（4)或（5)之電子零件，其中上述玻璃相以如 下之氧化物換算’ v2〇5為60〜80重量％、p2〇5為1〇〜2〇重量 〇/。、B2〇3為5〜10重量％、吨為〇〜15重量％、％〇3為〇〜1〇 重量％、Bi2〇3為0〜10重量％、及Zn〇為〇〜ι〇重量％，並且 P2〇5、B2〇3及Te〇2之合計量為玻璃相之2〇〜4〇重量％。 ⑺如上述⑴至（6)中任-項之電子零件，其中相對於 上述金屬粒子100重量份，上述玻璃相之含有比例為^ 重量份。 (8) 如上述（1)至⑺中任一項之電子零件，其中上述金 屬粒子為鋁或鋁合金，且上述矽基板具有？型半導體，該p 型半導體上形成有上述電極。 (9) 如上述（1)至（8)中任一項之電子零件，其係上述矽 基板具有pn接面之太陽電池單元。 (1〇)如上述（1)至（9)中任一項之電子零件，其中上述鋁 電極用玻璃組合物之鉛之含量為1〇〇〇 ppm以下。 (Π) —種鋁電極用導電性糊，其特徵在於：其係將包 含鋁或鋁合金之金屬粒子與玻璃粒子分散於溶解有黏合劑 樹脂之溶劑中而成者，並且該玻璃粒子為含有釩、磷及硼 之氧化物玻璃。 163196.doc 201249771 (12) 如上述（11)之鋁電極用導 电Γ生糊’其中上述玻璃粒 子以如下之氧化物換算，合古ν η 3 有 ν205 60〜80 重量 0/〇、ρ2〇5 10〜25重量％、Β2〇3 5〜15重詈〇/ ^ 重。’並且Ρ2〇5量高於β2〇3 量。 (13) 如上述（11)之鋁電極用導 .,u + ^ + 电f生糊’其中上述玻璃粒 子以如下之次氧化物換算，合古ν μ ， 3 有 V2〇5 70〜80 重量 ％、ρ2〇5 10〜20重量％、Β2〇3 5〜1〇重蚤。/ „ υ垔量/〇，並且Ρ2〇5量高於Β2〇3 量0 (14) 如上述⑽或（13)之紐電極用導電性糊，其中上述 玻璃粒子進而含有碲、銻、鉍及鋅中之丨種以上。 (15) 如上述（14)之電極用導電性糊，其中上述玻璃粒 子以如下之氧化物換算，％〇5為4〇〜8〇重量％、匕…為 10〜25重量％、B2〇3為5〜15重量％、Te〇2為〇〜25重量％、 Sb203為0〜20重量。/。、Bi2〇3為〇〜2〇重量％、及Zn〇為〇〜⑽重 量％，並且p2o5量高於b2〇3量，且P2〇5、b2〇3及Te〇2之合 計量為玻璃相之20〜50重量％。 (16) 如上述（14)之鋁電極用導電性糊，其中上述玻璃粒 子以如下之氧化物換算，％〇5為6〇〜8〇重量％、p2〇5為 10~20重量。/。、b2〇3為5〜1〇重量。/。、Te〇2為重量％、 sb2o^〇〜1〇4t%、Bi2〇3為〇〜1〇重量％、及Zn〇為〇〜⑺重 量/〇 ’並且p2〇5、B2〇3及Te〇2之合計量為20〜40重量％。 (17) 如上述（11)至（15)中任一項之鋁電極用導電性糊， 其中相對於上述金屬粒子100重量份，上述玻璃粒子之含 有比例為0.2〜15重量份。 163196.doc 201249771 (18) 如上述（π)至（15)中任一項之鋁電極用導電性糊， 其中相對於上述金屬粒子100重量份，上述玻璃粒子之含 有比例為0.2〜2重量份。 (19) 如上述（11)至（18)中任一項之鋁電極用導電性糊， 其中上述鋁電極用玻璃組合物之鉛之含量為1〇〇〇 ppm& 下。 (20) —種鋁電極用玻璃組合物，其特徵在於：其係含 有銘或紹合金粉末之鋁電極所含有者，並且該玻璃組合物 係含有飢、填及硼，進而含有碲、銻、鉍及鋅中之丨種以 上之氧化物玻璃，軟化點為420。(：以下，於500°C下流動。 (21) 如上述（20)之紹電極用玻璃組合物，其以如下之氧 化物換算’ V205為40〜80重量。/〇、p2〇5為1〇〜25重量％、 B203為5〜15重量％、Te02為〇〜25重量。/。、Sb203為〇〜2〇重量 %、Bi203為〇〜20重量％、及ZnO為〇〜20重量％，並且p2〇5 量高於b2o3量，且p2〇5、b2〇3及Te〇2之合計量為2〇〜5〇重 量％ » (22) 如上述（20)之鋁電極用玻璃組合物，其以如下之氧 化物換算，V205為60〜80重量％、p2〇5為丨〇〜2〇重量0/〇、 B2〇3為5〜1〇重量％、1^〇2為0〜15重量％、％2〇3為〇〜1〇重量 %、Bi2〇3為〇〜1〇重量％、及Zn〇為〇〜1〇重量％，並且 P2O5、B2O3及Te02之合計量為20〜40重量％。 (23) 如上述（20)至（22)中任一項之鋁電極用玻璃組合 物，其中上述鋁電極用玻璃組合物之鉛之含量為1〇〇〇 ppm 以下。 163196.doc 201249771 作為上述金屬粒子，除了鋁、銀、鋼及各自之合金以 外’亦可使用以、犯、！>卜如，較佳為紐、銅及銀。 本發明係關於一種於矽基板上形成有具有上述金屬粒子 與玻璃相之電極的電子零件，並且此玻璃相為含有飢、填 及硼之氧化物玻璃，進而此玻璃相可含有碲、銻、鉍及鋅 中之1種以上。又，進而亦可含有811、M〇、Nb。於用作太 陽電池等之碎基板之電極時，由於Ba、Cr、Fe、c。、Ni、 w對石夕有損害性’故而較佳為不含有。 又，上述玻璃相之組成範圍較佳為以如下之氧化物換 算，ν2〇5為40〜80重量％、p2〇5為1〇〜25重量％h…為 5〜15重量％、Te〇24〇〜25重量％、Sb2〇3為〇〜2〇重量％、 則2〇3為0〜20重量％、及Zn〇為〇〜2〇重量％，並且p2〇5量高 於β2〇3里，且p2〇5、Β2〇3及Te〇2之合計量為20〜50重量 %。尤其有效之組成範圍為¥2〇5為60〜80重量％、匕…為 10〜20重量％、B2〇3為5〜1〇重量％、Te〇2為〇〜15重量％、 Sb203為〇〜10重量％、出2〇3為〇〜1〇重量％、及Zn〇為〇〜重 量〆〇，並且P2〇5、B2〇3及Te02之合計量為20〜40重量〇/0。 再者，於不將Te、Sb、Bi及Zn加入計算時，％〇5為 60 80重量y。' p2〇5為1〇〜25重量。/。、B2〇3為5〜15重量％， 使f205量高於32〇3量。 進而’上述玻璃相之比例相對於電極所含之金屬粒子 1〇〇重量份，較佳為〇 2〜2重量份。又，作為金屬粒子，尤 其是對鋁或鋁合金可獲得較大之效果，該電極形成於矽基 板之P型半導體側較為有效^作為形成此種電極之電子零 163196.doc 201249771 件’可舉出使用具有pn接面之矽基板之太陽電池單元作為 代表例。 又，本發明之特徵在於關於一種將包含鋁或鋁合金之複 數個金屬粒子與複數個玻璃粒子分散於溶解有黏合劑樹脂 之溶劑令而成之鋁電極用導電性糊，並且該玻璃粒子係含 有釩、磷及硼之氧化物玻璃。進而，該玻璃粒子較理想為 含有碲、銻 '鉍及鋅中之1種以上。玻璃粒子之較佳組成 範圍以如下之氧化物換算，WO5為4〇〜8〇重量％、ho,為 10 25重量/〇、B2〇3為5〜1 5重量。/〇、Te〇2為〇〜25重量y。、 Sb203為〇〜20重量。/0、Bi2〇3為〇〜2〇重量％ '及Zn〇為〇〜2〇重 量％，並且P2〇5量高於B2〇3量，並且p2〇5、82〇3及。〇2之 合計量為20〜50重量％。尤其有效之組成範圍為：V2〇5為 60〜80重量。/。'卩2〇5為1〇〜2〇重量％、ίο]為5〜1〇重量〇/〇、 〇2為0 1 5重量/〇、sb203為0〜1 〇重量％、Bi2〇3為〇〜1 〇重 量0/〇、及ZnO為〇〜1〇重量％，並且p2〇5、匕…及心仏之合 計量為20〜40重量〇/〇。 再者，上述情形於不將Te、Sb、Bi及Zn加入計算時， V205為60〜80重量％、？2〇5為1〇〜25重量％、b2〇3為5〜15重 量％ ’使P2O5量高於B2〇3量。 又，上述鋁電極用導電性糊所含之玻璃粒子之含量，相 對於金屬粒子100重量份為0.2〜15重量份。於矽基板上形 成電極之情形時’即獲得與#基板之導通之情形時，以相 對於金屬粒子丨00重量份’坡璃粒子之含有比例較佳為 0.2〜2重量份。 163t96.doc 201249771 進而，對於上述鋁電極中所含有之玻璃粒子而言，有效 的是軟化點為420°C以下，並且於500°c下顯示出良好之流 動性的玻璃組合物。並且，該玻璃組合物實質上不含有 釔，若將其鉛之含量設為1 〇〇〇 ppm以下，則可減少對環境 負荷之影響。 於導電性糊之情形時，較佳為包含金屬粒子及玻璃粒子 之固形物成分為70〜75重量％、黏合劑成分（樹脂及溶劑）為 30〜25重量％，該黏合劑成分較佳為樹脂為2〜5重量％、溶 劑為98〜95重量。/〇。 [發明之效果] 根據本發明，藉由將含有釩、磷及硼之氧化物玻璃應用 於電極，可同時實現電子零件之高性能化與高可靠化。例 如具體而§，於使用具有pn接面之矽基板之太陽電池單元 中，藉由於p型半導體侧形成含有上述氧化物玻璃之鋁電 極，可同時提高單元轉換效率與壽命。 【實施方式】 本發明者發現：若將含有包含釩、磷及硼之氧化物玻璃 之電極般燒、形成於石夕基板上，則使用該石夕基板之電子零 件之性能與可靠性同時提高。明確了例如於使用具有pn接 面之石夕基板之太陽電池單元中，若使形成於作為p型半導 體側之單元背面之鋁電極中含有上述氧化物玻璃，並進行 煅燒，則即使該玻璃中不含有鉛’亦可將單元轉換效率提 而至與先前之氧化錯系玻璃相同水平。查明其原因，結果 得知含有包含叙、麟及爛之氧化物玻璃之鋁電極可促進链 163196.doc 201249771 於矽基板上之擴散，另一方面可抑制氧之擴散。認為由於 在Ρ型半導體面上形成良好之ρ+層（Back Surface Field : BSF層，背面電場層），故而單元轉換效率提高。 又’亦明確得知可同時提高氧化鉛系玻璃未實現之鋁電 極之耐濕性及耐水性等可靠性，亦可對長壽命化做出貢 獻查明其原因，結果得知含有釩、磷及硼之氧化物玻璃 與鋁粒子顯示出良好之濕潤性與反應性’可抑制鋁電極被 水腐蝕而生成氫氧化鋁之情況。進而得知，若將該玻璃應 用於鋁電極，則可減少自鋁電極產生異物及由凹凸引起之 不良，亦可對提高太陽電池單元等電子零件之生產性做出 貝獻。又’該鋁電極對矽基板等之密接性亦良好。 本發明之上述氧化物玻璃進而藉由含有碲、銻、鉍及辞 中之1種以上，可提高耐候性，有利於將所製造之玻璃粉 碎，或保管經粉碎之玻璃粒子。即，可提高玻璃粒子之操 作性。上述氧化物玻璃之較佳組成範圍以如下之氧化物換 算，v205為40〜80重量。/。、p2〇5為10〜25重量％、β2〇3為 5〜15重量％、！^〇2為〇〜25重量％、Sb2〇3為〇〜2〇重量％、 BhCh為〇〜20重量。/。、及Zn〇為〇〜2〇重量。/。，並且Ρζ〇5量高於 B203f，且p2〇5、B2〇3&Te〇2之合計量為2〇〜5〇重量％。 若V2〇5未達40重量。/。’則鋁電極之煅燒溫度變高，紐電 極之密接性及耐水性下降。太陽電池單元之轉換效率下 降。另一方面’若νζ〇5超過80重量％，則易結晶化，無法 以低溫獲得良好之軟化流動性。又，玻璃自身之耐候性明 顯劣化’於粉碎玻璃，或對經粉碎之玻璃粒子實施操作 I63196.doc -12- 201249771 時，其加工性降低。認為若p205未達10重量％，則易結晶 化’無法獲得良好之軟化流動性，另一方面若超過25重量 %，則有太陽電池單元之轉換效率降低之傾向。 若B2〇3未達5重量％，則無法提高太陽電池單元之轉換 效率，另一方面若超過15重量。/〇，則反而會降低太陽電池 單元之轉換效率。又，即使Te〇2超過25重量％，太陽電池 單元之轉換效率亦降低。若Sb2〇3、Βίζ〇3及ZnO各自超過 20重量％，則發生玻璃之軟化點高溫化或結晶化等情況， 難以以低溫獲得良好之軟化流動性。進而，若量高於 量，則結晶化傾向增大，導致太陽電池單元之轉換效 率反而降低。 又’若P2〇5、B2〇3及Te〇2之合計量未達2〇重量〇/0，則易 結晶化，無法以低溫獲得良好之軟化流動性，另一方面若 超過50重量％ ,則無法期待太陽電池單元之轉換效率之提 尚0 考慮到提兩太陽電池單元之轉換效率與可靠性兩方面， 及玻璃粒子之操作性，最有效之玻璃組成範圍以如下氧化 物換算，V205為60〜80重量％、！>2〇5為10〜2〇重量％、匕〇3 為5〜10重量。/D、1>〇2為0〜15重量％、％2〇3為〇〜1〇重量％、 81203為〇〜1〇重量％、及211〇為〇〜1〇重量％，並且匕〇5、 B2〇3及Te02之合計量為20〜40重量％。 進而，形成於太陽電池單元上之鋁電極中之玻璃含量相 對於鋁粒子100重量份，較佳為〇·2〜2重量份，若未達〇 2重 量份或超過2重量份，則單元轉換效率降低。然而，擴展 I63196.doc -13- 201249771 至太陽電池單元 玻璃達15重量份 大。 以外之電子零件之電極之情形時，可含有 。若超過15重#份，則紹電極之電阻增 進而，玻璃顯示出軟化點為42()UT，於5QQt下軟化 流動性越良好，銘電極對基板之密接性及耐濕性等可靠性 越兩’並且應用於太陽電池單元時轉換效率越高之傾向。 以下，具體說明本實施形態 所列舉之實施例。 [實施例1] 。但本發明並不限定於此處 將本實施例中研究之玻璃系，其主成分氧化物及其特性 示於表1。表1中，G-01為實施例之玻璃，g 〇2〜i〇為比較 例之玻璃。表1中之r有無有害規制物質」係判斷是否含 有R〇HS指令及聯合產業指南（J〇int Industry 中 所規制之有害物質。「軟化點」係使用各自之玻璃粉末並 藉由差熱分析（DTA)而測定。DTA之分析升溫條件設為大 氣中5°C/分。 圖1中揭示代表性之玻璃之DTA曲線之一例。第一吸熱 波峰之開始溫度為轉移點Tg、其波峰溫度為變形點， 第二吸熱波峰溫度為軟化點Ts，各自之特性點係由黏度所 定義。此黏度相當於Tg為1013.3泊、Mg為1011泊、丁3為 1 07.65 泊。 「軟化流動性」係藉由使用各自之玻璃粉末製作直徑1〇 mm、 厚度5 mm之壓粉成形體，並於氧化鋁基板上加熱而評價。 加熱條件係將置於氧化鋁基板上之壓粉成形體分別放入在 163196.doc -14- 201249771 大氣中分別保持於 40(TC、500〇c、6〇(TC、700〇c、8〇(Γ(： 之電爐中1分鐘後取出。目測觀察下獲得良好之流動性之 It形δ平價為「〇」’雖未獲得良好之流動性但已軟化之情 形評價為「△」，仍為壓粉成形體亦未軟化之情形評價為 「X」。 於表1所示之玻璃中，含有害規制物質之玻璃僅為 09。 該Pb-B_Si-〇系之玻璃至今廣泛應用於太陽電池單元 及電漿顯示面板等電子零件之各種電極。軟化點亦為相對 較低之390 C，500〜800°C下之流動性良好。作為該系之玻 璃之代替品，被廣泛研究並開始實用化之無鉛玻璃為G_ 10。 該Bi-B-Si-Ο系之玻璃雖然不含有害規制物質，但與 G-09相比’軟化點及軟化流動性高溫化。 軟化點咼於G-10之玻璃為Zn-B-V-O系之G-06與P-Zn-K_ 0系之G-08，軟化流動性亦高溫化。軟化點位於G 〇9與& 1 0之間之玻璃為V-P-Ba-Ο系之G-02、V-P-Fe-Ο系之G-03及 Sn-P-Zn-Ο系之G-07，但軟化流動性與G_1〇大致相同。軟 化點低於G-09之玻璃為v_P_B_〇系之G_01、v_P_Te_〇系之 G-04及V-Te-Ζη-Ο系之G_05，軟化流動性亦低溫化。5〇〇r 下顯示出良好流動性之玻璃為不含有害規制物質之G· 01、-04及-05，及含有害之鉛之G_〇9i4種。 藉由分別使用表1所示之各種玻璃製作銘電極用導電性 糊，將其搭載於太陽電池單元上，並評價轉換效率及環境 保護。又，亦評價各自形成之鋁電極之外觀、密接性及耐 水性。 163196.doc -15· 201249771 對表1之G-01~l0之每一種玻璃分別製作鋁電極用導電性 糊。首先，利用捣碎機與喷射磨機將玻璃粉碎為3 μηι以下 之粒子。銘粒子係使用藉由霧化法所製作之平均粒徑為3 μπι者，相對於鋁粒子100重量份，於G-01〜08之玻璃粒子 中混合0.4重量份，於G-09與-10之玻璃粒子申混合〇.7重量 份0 表1 玻璃No. 玻璃.系 玻璃主 成分氧 化物 有無有 害規制 物質 軟化點 CC) 軟化流動性 (驟熱、保接蚌間1分艟、 400。。 500°C 600°C 700°C 800°C 實施例 G-01 V-P-B-0 V2〇5 無 355 Λ ο Ο Ο 〇 G-02 V-P-Ba-O V2〇5 無 443 X Δ Ο Ο 〇 G-03 V-P-Fe-O V2〇5 無 435 X Λ 〇 ο Ο G-04 V-P-Te-0 V2〇5 無 336 △ 〇 Ο ο G-05 V-Te-Zn-O V2〇5 「無 332 Δ Ο ο ο 〇 比較例 G-06 Zn-B-V-0 ZnO 無 546 X X Λ ο 〇 G-07 Sn-P-Zn-0 SnO 無 428 X Δ Ο ο 〇 G-08 P-Zn-K-0 PA 無 564 X X Λ ο 〇 G-09 Pb-B-Si-0 PbO 有(Pb) 390 X 〇 Ο ο 〇 G-10 Bi-B-Si-0 Bi203 無 458 X Λ 〇 〇 〇 改變玻璃粒子之混合量的原因在於：G 〇9與·1〇之玻璃 之比重為G-01〜8之玻璃之約2倍大，欲於同體積比下使玻 璃含氧量大致相同。相對於該等之混合物1〇〇重量份，添 加預先溶解有黏合劑樹脂2重量％之溶劑4〇重量份，藉由 混練而製作⑪電極科電㈣。此處，黏合騎脂係使用 乙基纖維素，溶劑係使用α_松脂醇。 使用所製作之㈣極用導電糊，對適用於作為本發明之 電子零件的太陽電池單元之例進行說明係表示代表 性太陽電池單元之光接收面之一例之平面示意圖。又，圖 3係表示其背面之一例之平面示意圖，圖4α係圖2中之A], 163196.doc 201249771 線之剖面示意圖，及圖4B係背面附近之放大剖面示意圖 (圖4八之〇所示部分）。 太陽電池單元10之半導體基板丨通常使用單晶矽基板或 多晶矽基板’並含有硼等而成為p型半導體。光接收面側 為了抑制太陽光之反射而藉由化學蝕刻等形成有凹凸。 又，光接收面摻雜有磷等，形成有厚度約為丨μιη左右之n 型半導體層2»並且，於與ρ型主體部分之邊界形成有胙接 面部。進而，光接收面上藉由蒸鍍法形成有厚度為1〇〇 nm 左右之氮化矽等之抗反射層3。 其次，對光接收面上所形成之光接收面電極4、背面上 所形成之背面電極5及輸出電極6之形成進行說明。 通常，光接收面電極4及輸出電極6之形成係使用含有銀 粒子與玻璃粒子之銀電極用導電性糊，背面電極5之形成 係使用含有鋁粒子與玻璃粒子之鋁電極用導電性糊。各導 電性糊係藉由絲網印刷法等塗佈於半導體基板1之光接收 面上所形成之抗反射層3及半導體基板丨之背面之表面上。 使導電性糊乾燥後，於大氣中' 8〇〇t左右下煅燒，形 成各電極。此時，於光接收面，光接收面電極4所含之玻 璃組合物與抗反射層3發生反應，而使光接收面電極4與11 型半導體層2電性連接又，於背面，背面電極5中之銘成 分與半導體基板丨發生反應，生成鋁與矽之合金層8,進而 形成鋁擴散至半導體基板1之鋁擴散層（Back Surface Field · BSF層，背面電場層）7。藉由形成該BSI^ 7，可防 止產生於太陽電池單元内部之載子於背面再結合，而提高 163I96.doc 17 201249771 =電池單元之性能…合金層8亦具有將入射至太陽 電池单㈣之光於背面反射，而㈣光封閉於半導體基板 1中之效果’從而對提高太陽電池單元之性能發揮作用。 再者，於太陽電池單元中，背面電極用料前使用含有 铭粒子與作為㈣點玻璃的有害之pbBsi〇系及不含有 害之船之Bi.B-Si-O系之玻璃組合物的導電性糊，但無論何 種玻璃均存在無法提高㈣電㈣㈣極之耐濕性及耐水 性等可靠性之問題。進而，兩種玻璃均存在於紹電極上產 生異物及凹凸之問題。因此，業界需要一種可使太陽電池 單兀之性能、安全性（無鉛）、可靠性及生產性均提高即 可改善上述問題之鋁電極用玻璃組合物。 製作本發明之電子零件之太陽電池單元。半導體基板1係 也用P型單晶矽基板。該矽基板之尺寸設為125 mm見方、 厚度為2 0 0 μπι。其次，為了提高光入射效率，使用包含 苛性鈉（氩氧化鈉：NaOH)與10%異丙醇（CH3CH(〇H)CH3)之 強驗性水溶液，蝕刻半導體基板1之光接收面而形成凹 凸。藉由於該光接收面上塗佈含有五氧化二磷（p2〇5)之液 體’於900°C下熱處理30分鐘，使磷（P)擴散至半導體基板 1上，而於光接收面上形成厚度為1 μπι左右之η型半導體層 2。去除五氧化二磷後，於η型半導體層2上同樣地形成厚 度約為100 nm之氮化石夕膜作為抗反射層3。該氮化石夕膜係 以矽烷（SiH4)與氨氣（NH3)之混合氣體作為原料，藉由電漿 CVD(Chemical Vapor Deposition，化學氣相沈積）法等而形 成0 163196.doc • 18 - 201249771 其次，為了形成光接收面電極4,藉由絲網印刷法將含 有銀粒子與玻璃粒子之銀電極用導電性糊以栅格狀塗佈於 抗反射層3上，並於15(rc下乾燥1〇分鐘。銀粒子係使用平 均粒徑約為2㈣者…玻璃粒子係使用平均粒徑約為2 μ^η且不含有害之錯之V_Ag_P_Te，低熔點玻璃。對於形 成於半導體基板1之背面之輸出電極6，亦使用與上述相同 之銀電極用導電性糊，相同地藉由絲網印刷法塗佈並乾 繼而，作為背面電極5用，亦同樣地塗佈、乾燥含有鋁 粒子與玻璃粒子之㈣極用導電性糊。_電㈣導_ 糊係採用分別使用上文所說明之實施例玻璃"哨比較例 玻璃G-02〜10而製作之鋁電極用導電性糊。又，為作比 較，亦使用不含有玻璃粒子之銘電極用導電性糊。其後， 藉由使用穿隧爐於大氣中迅速加熱至8_並保持3〇秒 鐘’同時锻燒、形成光接收面電極4、f面電極5及輸出電 極6，而製作太陽電池單元10。光接收面電極4與輸出電極 6於炮燒後之膜厚約為20㈣，背面電極之膜厚約為4〇 μιη ° 如上所述，針對作為背面電極5用，改變銘電極用導電 性糊而製作之太陽電池單元1〇，冑用態樣模擬器測定單元 轉換效率。又’亦自環境保護之觀點(有無有害規制物 對所製作之太陽電池單元1G進行評價。進而，亦對作為背 面電極5用而形成之紹電極之外觀、密接性及耐水性進扞 評價。 163196.doc 19 201249771 將所製作之太陽電池單元之評價結果示於表2。表2中之 「轉換效率」欄所記載之「◎」設為單元轉換效率為Μ% 以上，「〇」設為17.5〜18.0%，「△」設為17 〇〜17 5%， 「X」設為未達17%。 關於「環境保護」，係判斷所製作之太陽電池單元〖〇中 是否含有有害規制物質，不含有害規制物質之情形設為 「〇」’含有之情形設為「X」。鋁電極之外觀藉由目測觀 察而未見表面異物或較大凹凸之情形係評價為「〇」，可 見若干之情形評價為「△」，明顯可見之情形評價為 又，紹電極之「密接性」係藉由剝離試驗而評價。該^ 離試驗係將市售之透明膠帶貼附於铭電極上，剝離時鋁$ 極未剝離之情形係、設為「〇」，僅—部分剝離之情形設』 「△」’剝離較多之情形設為「χ」β「耐水性」係將所製子 之太陽電池單元於夕，田rk分 平騎5GC之恤水中浸潰8小時，銘電極於夕 :上基本未變色之情形係評價為「〇」，僅部分黑色化$ 價為「△」，-個面黑色化之情形評價為「X」。 二各評價結果進行綜合地研究及判斷，實用上自 好之^電池單元係評價為「〇」，不充分之太陽電池岸 兀為△」，存在問題之太陽電池單元評價為「X」。 [表2] 163196.doc •20- 201249771 表2The harmful substances f, which are regulated in the RoHS Directive, etc., reduce the impact on the environmental load, that is, in order to protect the ecosystem, in the electronic components such as solar cells or plasma display panels, there is no error. Glass is applied to electrode formation. For example, Patent Document i discloses that a silver electrode or an electrode towel formed on a solar cell unit uses an error-free low-melting glass containing oxidized oxidized sand. X, Patent Document 2 proposes a low melting point glass containing oxidized sulphur and boron oxide. In particular, the conductive paste which is mainly composed of metal particles such as aluminum particles or aluminum alloy particles is not densely oxidized due to the oxidized ancient film on the surface of the metal particles, and is hardly 163196.doc 201249771. There are problems in the aspect. In this respect, a method of improving the sinterability of the metal particles and reducing the resistance of the metal particles by adding vanadium or vanadium oxide particles to the conductive paste has been proposed (Patent Document 3). In addition, it is also known that a method of improving oxidation resistance and reducing resistance by adding carbon, antimony, tin, a hydrogenated metal compound, a phosphating metal compound, or the like (Patent Document 4) Among the electronic components represented by the battery unit and the like which are required to have high power generation efficiency and longevity, the electrodes of the above-mentioned Patent Documents 丨4 have not been sufficiently considered to improve the performance and reliability of electronic components. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-543080 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 2-6-332 No. 32 [Patent Document 3] [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei No. Hei No. 5-298917. For the electronic component, a silver electrode is often used on the n-type semiconductor side, and an aluminum electrode is often used on the p-type semiconductor side. If the low-melting glass using lead oxide as a main component is used in the electrodes, the power generation efficiency of the solar cell unit is high, but the lead-free low-melting glass disclosed in Patent Document 1 or 2 is used. 'There is a problem of reduced conversion efficiency. The reason is believed to be due to the sintering state of the electrode of I63196.doc 201249771 and the state of the interface with the Shixi base handle. Further, regarding the reliability of the scorpion 4, it is difficult to improve the material or method disclosed in the low-melting glass or the patent document which has previously used emulsified oxime as a main component. Especially in the aluminum electrode, it is slowly corroded by hydration to form aluminum hydroxide, which deteriorates the performance of the electrode. Accordingly, an object of the present invention is to achieve both high performance and high reliability of electronic components such as solar cells using a ray substrate having a ρη junction in view of the above problems. Further, it is possible to provide such a highly conductive paste which can be used at the same time and a glass composition for the electrode which is suitable for the same. [Technical means for solving the problem] The means for solving the problem of the present invention are as follows. It is formed on a ruthenium substrate and the glass phase contains (1) an electronic component characterized by an oxide glass of hunger, phosphorus and boron having electrodes of metal particles and a glass phase. (7) The electronic component according to (1) above, wherein the glass phase contains V2〇5 60 to 80 by weight in terms of a compound. /. Ρ2〇5 10~25% by weight, Β 〇 5~15% by weight, and the amount of ρ2〇5 is higher than Β2〇3. The electronic component according to the above (1) or (7), wherein the above-mentioned ruthenium phase is converted to a weight ratio of 70 to 8 〇% by weight, 〇2〇5 is 10 to 20% by weight, and Β203 is 5 to 10% by weight. Further, the total of (10) and Β2〇3 is 20 to 40% by weight of the phase. (4) The electronic component according to (1) above, wherein the glass phase further comprises one or more of a monument, a bismuth, a bismuth and a zinc. (5) The electronic component according to the above (4), wherein the glass phase is converted to a weight of 40 to 80 by V2〇5 in terms of oxygen as follows: J63196.doc 201249771. /. (10) is a heart weight %, B2〇3 is 5 to 15% by weight, 〇 25% by weight, % 〇 3 is 〇 〇 2 〇 重量 % ' Bi 2 〇 3 is 0 〜 20% by weight, and Zn 〇 is 〇~2〇% by weight, and p2〇5 is south in the amount of B2〇3 and the total amount of P2〇5, B2〇3 and Te〇2 is 20 to 50% by weight of the glass phase. The electronic component according to the above (4) or (5), wherein the glass phase is 60 to 80% by weight in terms of an oxide of 'v2〇5', and p2〇5 is 1〇2 to 2% by weight 〇/. , B2〇3 is 5 to 10% by weight, ton is 〇15% by weight, %〇3 is 〇~1〇% by weight, Bi2〇3 is 0~10% by weight, and Zn〇 is 〇~ι〇% by weight. And the total amount of P2〇5, B2〇3, and Te〇2 is 2〇~4〇% by weight of the glass phase. (7) The electronic component according to any one of the above (1) to (6), wherein the glass phase is contained in a ratio of parts by weight based on 100 parts by weight of the metal particles. (8) The electronic component according to any one of (1) to (7) wherein the metal particles are aluminum or an aluminum alloy, and the germanium substrate has ? A type semiconductor having the above electrode formed on the p-type semiconductor. (9) The electronic component according to any one of (1) to (8) above wherein the 矽 substrate has a pn junction solar cell. The electronic component according to any one of the above (1) to (9) wherein the glass composition for the aluminum electrode has a lead content of 1 〇〇〇 ppm or less. (Π) A conductive paste for an aluminum electrode, characterized in that a metal particle containing aluminum or an aluminum alloy and glass particles are dispersed in a solvent in which a binder resin is dissolved, and the glass particles are contained. Oxide glass of vanadium, phosphorus and boron. 163196.doc 201249771 (12) The conductive paste for aluminum electrodes according to the above (11) wherein the glass particles are converted to the following oxides, and the total amount of ν η 3 has ν 205 60 to 80 weights 0 / 〇, ρ 2 〇 5 10~25wt%, Β2〇3 5~15重詈〇/^重. And the amount of Ρ2〇5 is higher than the amount of β2〇3. (13) For the aluminum electrode of the above (11), u + ^ + electric f paste, wherein the glass particles are converted to the following sub-oxides, and the total amount of V 2 〇 5 70 to 80 %, ρ2〇5 10~20% by weight, Β2〇3 5~1〇. / „ υ垔 quantity/〇, and Ρ2〇5 quantity is higher than Β2〇3 quantity 0 (14) The conductive paste for the electrode of the above (10) or (13), wherein the glass particles further contain yttrium, lanthanum, ytterbium and (15) The conductive paste for electrodes according to the above (14), wherein the glass particles are converted to the following oxides, % 〇 5 is 4 〇 to 8 〇 by weight, 匕 ... is 10 〜 25 wt%, B2〇3 is 5 to 15 wt%, Te〇2 is 〇25 wt%, Sb203 is 0-20 wt%, Bi2〇3 is 〇~2〇% by weight, and Zn〇 is 〇 ~ (10)% by weight, and the amount of p2o5 is higher than the amount of b2〇3, and the total amount of P2〇5, b2〇3 and Te〇2 is 20 to 50% by weight of the glass phase. (16) Aluminum as described in (14) above The conductive paste for an electrode, wherein the glass particles are converted to an oxide of the following, % 〇 5 is 6 〇 to 8 〇 by weight, and p 2 〇 5 is 10 to 20% by weight. /, b2 〇 3 is 5 to 1 〇 by weight. .., Te〇2 is % by weight, sb2o^〇~1〇4t%, Bi2〇3 is 〇~1〇% by weight, and Zn〇 is 〇~(7)weight/〇' and p2〇5, B2〇3 And the total amount of Te〇2 is 20 to 40% by weight. (17) The conductive paste for aluminum electrodes according to any one of (11) to (15), wherein the glass particles are contained in an amount of 0.2 to 15 parts by weight based on 100 parts by weight of the metal particles. 163196.doc 201249771 (18) The conductive paste for aluminum electrodes according to any one of the above-mentioned (1) to (15), wherein the content of the glass particles is 0.2 to 2 parts by weight based on 100 parts by weight of the metal particles. The conductive paste for an aluminum electrode according to any one of the above aspects, wherein the glass composition for the aluminum electrode has a lead content of 1 〇〇〇 ppm & (20) a glass composition for an aluminum electrode It is characterized in that it is contained in an aluminum electrode containing a powder of Ming or Shao alloy, and the glass composition contains hunger, fill and boron, and further contains an oxide of more than one of lanthanum, cerium, lanthanum and zinc. The glass has a softening point of 420. (: The following is a flow rate at 500 ° C. (21) The glass composition for an electrode according to the above (20) is 40 to 80 by weight in the following oxides. 〇, p2〇5 is 1〇~25% by weight, B203 is 5~15% by weight, Te02 〇~25 weight%, Sb203 is 〇~2〇% by weight, Bi203 is 〇~20% by weight, and ZnO is 〇~20% by weight, and p2〇5 is higher than b2o3, and p2〇5, b2 (20) The glass composition for aluminum electrodes according to the above (20), which has a V205 of 60 to 80% by weight, in terms of the following oxides, P2〇5 is 丨〇~2〇weight 0/〇, B2〇3 is 5~1〇% by weight, 1^〇2 is 0~15% by weight, %2〇3 is 〇~1〇% by weight, Bi2〇 3 is 〇~1〇% by weight, and Zn〇 is 〇~1〇% by weight, and the total amount of P2O5, B2O3 and Te02 is 20 to 40% by weight. (23) The glass composition for an aluminum electrode according to any one of the above (20), wherein the glass composition for the aluminum electrode has a lead content of 1 〇〇〇 ppm or less. 163196.doc 201249771 As the above-mentioned metal particles, in addition to aluminum, silver, steel and their respective alloys, it is also possible to use, commit, and! > Bu Ru, preferably New Zealand, copper and silver. The present invention relates to an electronic component in which an electrode having the above metal particles and a glass phase is formed on a substrate, and the glass phase is an oxide glass containing hunger, boron and boron, and the glass phase may contain bismuth, antimony, One or more of bismuth and zinc. Further, it may further contain 811, M〇, and Nb. When used as an electrode of a broken substrate such as a solar battery, it is due to Ba, Cr, Fe, and c. Ni and w are detrimental to Shi Xi. Therefore, it is preferably not contained. Further, the composition range of the glass phase is preferably 40 to 80% by weight in terms of the following oxide, and p2〇5 is 1 to 25% by weight of h... 5 to 15% by weight, Te〇24 〇~25% by weight, Sb2〇3 is 〇~2〇% by weight, then 2〇3 is 0~20% by weight, and Zn〇 is 〇~2〇% by weight, and p2〇5 is higher than β2〇3 And the total amount of p2〇5, Β2〇3, and Te〇2 is 20 to 50% by weight. Particularly effective composition range is ¥2〇5 is 60~80% by weight, 匕... is 10~20% by weight, B2〇3 is 5~1〇% by weight, Te〇2 is 〇~15% by weight, and Sb203 is 〇 〜10% by weight, 2〇3 is 〇~1〇% by weight, and Zn〇 is 〇~weight〆〇, and the total amount of P2〇5, B2〇3 and Te02 is 20~40 weight 〇/0. Further, when Te, Sb, Bi, and Zn were not added to the calculation, % 〇 5 was 60 80 y. 'p2〇5 is 1〇~25 weight. /. B2〇3 is 5 to 15% by weight, and the amount of f205 is higher than 32〇3. Further, the ratio of the glass phase is preferably 〇 2 to 2 parts by weight based on 1 part by weight of the metal particles contained in the electrode. Further, as a metal particle, particularly for aluminum or an aluminum alloy, a large effect can be obtained, and the electrode is formed on the P-type semiconductor side of the ruthenium substrate, and is effective as an electron 193196.doc 201249771 which can form such an electrode. A solar battery cell using a ruthenium substrate having a pn junction is used as a representative example. Further, the present invention relates to a conductive paste for an aluminum electrode obtained by dispersing a plurality of metal particles containing aluminum or an aluminum alloy and a plurality of glass particles in a solvent in which a binder resin is dissolved, and the glass particle system is An oxide glass containing vanadium, phosphorus and boron. Further, the glass particles are preferably one or more selected from the group consisting of ruthenium, osmium and zinc. The preferred composition range of the glass particles is in the range of 4 〇 to 8 〇 wt%, ho, 10 25 wt/〇, and B2 〇 3 5 to 15 weight, in terms of oxides as follows. /〇, Te〇2 is 〇~25 weight y. , Sb203 is 〇 ~ 20 weight. /0, Bi2〇3 is 〇~2〇% by weight 'and Zn〇 is 〇~2〇% by weight, and P2〇5 is higher than B2〇3, and p2〇5, 82〇3 and. The total amount of 〇2 is 20 to 50% by weight. A particularly effective composition range is: V2 〇 5 is 60 to 80 weight. /. '卩2〇5 is 1〇~2〇% by weight, ίο】 is 5~1〇 weight〇/〇, 〇2 is 0 1 5 weight/〇, sb203 is 0~1 〇% by weight, Bi2〇3 is 〇 〜1 〇weight 0/〇, and ZnO is 〇~1〇% by weight, and the total amount of p2〇5, 匕... and palpitations is 20 to 40 weight 〇/〇. Furthermore, in the above case, when Te, Sb, Bi, and Zn are not added to the calculation, V205 is 60 to 80% by weight, ? 2〇5 is 1〇255% by weight, b2〇3 is 5~15% by weight ’, and the amount of P2O5 is higher than B2〇3. Further, the content of the glass particles contained in the conductive paste for aluminum electrodes is 0.2 to 15 parts by weight based on 100 parts by weight of the metal particles. In the case where an electrode is formed on the substrate, that is, when the conduction to the substrate is obtained, the content ratio of the granules is preferably 0.2 to 2 parts by weight based on 00 parts by weight of the metal particles. Further, the glass particles contained in the above aluminum electrode are effective as a glass composition having a softening point of 420 ° C or less and exhibiting good fluidity at 500 ° C. Further, the glass composition does not substantially contain antimony, and if the content of lead is 1 〇〇〇 ppm or less, the influence on the environmental load can be reduced. In the case of the conductive paste, it is preferable that the solid content of the metal particles and the glass particles is 70 to 75% by weight, and the binder component (resin and solvent) is 30 to 25% by weight, and the binder component is preferably The resin is 2 to 5% by weight and the solvent is 98 to 95 parts by weight. /〇. [Effects of the Invention] According to the present invention, by applying an oxide glass containing vanadium, phosphorus and boron to an electrode, it is possible to simultaneously achieve high performance and high reliability of electronic components. For example, in a solar cell using a germanium substrate having a pn junction, by forming an aluminum electrode containing the above oxide glass on the p-type semiconductor side, cell conversion efficiency and lifetime can be simultaneously improved. [Embodiment] The present inventors have found that when the electrode containing an oxide glass containing vanadium, phosphorus, and boron is fired and formed on a Shih-hs substrate, the performance and reliability of the electronic component using the Shishi substrate are simultaneously improved. . It is clarified that, for example, in a solar battery cell using a stellite substrate having a pn junction, if the oxide glass is contained in an aluminum electrode formed on the back surface of a cell as a p-type semiconductor side, and calcined, even in the glass Without lead 'can also increase the unit conversion efficiency to the same level as the previous oxidized staggered glass. The reason was ascertained, and it was found that an aluminum electrode containing an oxide glass containing ruthenium, ruthenium and ruthenium promoted the diffusion of the chain 163196.doc 201249771 on the ruthenium substrate, and on the other hand, inhibited the diffusion of oxygen. It is considered that a good ρ+ layer (Back Surface Field: BSF layer, back surface electric field layer) is formed on the Ρ-type semiconductor surface, so that the cell conversion efficiency is improved. In addition, it is also known that the reliability of the moisture resistance and water resistance of the aluminum electrode which is not realized by the lead oxide-based glass can be improved at the same time, and it is also possible to contribute to the longevity, and as a result, it is found that vanadium and phosphorus are contained. And the boron oxide glass and the aluminum particles exhibit good wettability and reactivity, which can inhibit the aluminum electrode from being corroded by water to form aluminum hydroxide. Further, when the glass is applied to an aluminum electrode, it is possible to reduce foreign matter generated from the aluminum electrode and defects caused by irregularities, and it is also possible to improve the productivity of electronic components such as solar cells. Further, the aluminum electrode is also excellent in adhesion to a substrate or the like. Further, the above-mentioned oxide glass of the present invention can improve weather resistance by containing one or more of ruthenium, osmium, iridium and rhodium, and it is advantageous to pulverize the produced glass or to store the pulverized glass particles. That is, the workability of the glass particles can be improved. The preferred composition range of the above oxide glass is calculated by the following oxides, and v205 is 40 to 80% by weight. /. , p2〇5 is 10 to 25% by weight, and β2〇3 is 5 to 15% by weight, ^〇2 is 〇~25% by weight, Sb2〇3 is 〇~2〇% by weight, and BhCh is 〇~20 by weight. /. And Zn〇 is 〇~2〇 weight. /. And the amount of Ρζ〇5 is higher than B203f, and the total amount of p2〇5, B2〇3&Te〇2 is 2〇~5〇% by weight. If V2〇5 does not reach 40 weight. /. The calcination temperature of the aluminum electrode becomes high, and the adhesion and water resistance of the neopolar electrode are lowered. The conversion efficiency of the solar cell unit is reduced. On the other hand, if ν ζ〇 5 exceeds 80% by weight, it is easily crystallized, and good softening fluidity cannot be obtained at a low temperature. Further, the weather resistance of the glass itself is significantly deteriorated. When the glass is pulverized or the pulverized glass particles are operated, I63196.doc -12-201249771, the workability is lowered. It is considered that if p205 is less than 10% by weight, it is easy to crystallize, and good softening fluidity cannot be obtained. On the other hand, if it exceeds 25% by weight, the conversion efficiency of the solar cell tends to decrease. If B2〇3 is less than 5% by weight, the conversion efficiency of the solar cell unit cannot be improved, and if it exceeds 15% by weight. /〇, it will reduce the conversion efficiency of the solar cell unit. Further, even if Te〇2 exceeds 25% by weight, the conversion efficiency of the solar cell unit is lowered. When Sb2〇3, Βίζ〇3, and ZnO each exceed 20% by weight, high temperature or crystallization of the softening point of the glass occurs, and it is difficult to obtain good softening fluidity at a low temperature. Further, if the amount is higher than the amount, the tendency of crystallization increases, and the conversion efficiency of the solar cell unit is rather lowered. Further, if the total amount of P2〇5, B2〇3, and Te〇2 is less than 2〇wt〇/0, it is easy to crystallize, and it is impossible to obtain good softening fluidity at a low temperature, and if it exceeds 50% by weight, It is impossible to expect the conversion efficiency of the solar cell unit to be zero. Considering the conversion efficiency and reliability of the two solar cell units and the operability of the glass particles, the most effective glass composition range is converted by the following oxides, V205 is 60~80% by weight,! > 2〇5 is 10 to 2% by weight, and 匕〇3 is 5 to 10% by weight. /D, 1> 〇2 is 0 to 15% by weight, %2〇3 is 〇~1〇% by weight, 81203 is 〇~1〇% by weight, and 211〇 is 〇~1〇% by weight, and 匕〇5 The total amount of B2〇3 and Te02 is 20 to 40% by weight. Further, the glass content in the aluminum electrode formed on the solar cell unit is preferably 2 to 2 parts by weight based on 100 parts by weight of the aluminum particles, and if not more than 2 parts by weight or more than 2 parts by weight, the unit is converted. Reduced efficiency. However, the expansion of I63196.doc -13- 201249771 to solar cell glass is up to 15 parts by weight. In the case of an electrode other than an electronic component, it may be included. If it exceeds 15 parts by weight, the electric resistance of the electrode is improved, and the glass shows a softening point of 42 () UT. The softer fluidity at 5QQt is better, and the reliability of the adhesion between the electrode and the substrate and the moisture resistance are higher. Two's tendency to be more efficient when applied to solar cells. Hereinafter, embodiments of the present embodiment will be specifically described. [Example 1]. However, the present invention is not limited to the glass system studied in the present example, and the main component oxide and its characteristics are shown in Table 1. In Table 1, G-01 is the glass of the example, and g 〇2~i〇 is the glass of the comparative example. The presence or absence of harmful substances in Table 1 is judged whether it contains the R〇HS Directive and the Joint Industry Guide (Hazardous Substances regulated in J〇int Industry. The “softening point” is the use of the respective glass powder and analyzed by differential thermal analysis. The measured temperature rise condition of DTA is set to 5 ° C / min in the atmosphere. An example of a representative glass DTA curve is shown in Fig. 1. The starting temperature of the first endothermic peak is the transfer point Tg, and its peak temperature For the deformation point, the second endothermic peak temperature is the softening point Ts, and the respective characteristic points are defined by the viscosity. The viscosity is equivalent to a Tg of 1013.3 poise, a Mg of 1011 poise, and a D3 of 10.07.25 poise. "Softening fluidity" A powder compact having a diameter of 1 mm and a thickness of 5 mm was produced by using each of the glass powders and evaluated by heating on an alumina substrate. The heating conditions were such that the powder compacts placed on the alumina substrate were placed separately. In the atmosphere of 163196.doc -14- 201249771, it was kept at 40 (TC, 500 〇 c, 6 〇 (TC, 700 〇 c, 8 〇 (Γ:: in the electric furnace, taken out after 1 minute. Obtained well under visual observation) The liquidity of the It-shaped δ parity is " 〇"', although it did not obtain good fluidity, it was evaluated as "△" in the case of softening, and it was evaluated as "X" in the case where the powder compact was not softened. The glass shown in Table 1 contained harmful regulations. The material glass is only 09. The Pb-B_Si-lanthanum glass has been widely used in various electrodes of electronic components such as solar cells and plasma display panels. The softening point is also relatively low 390 C, 500~800°. The fluidity under C is good. As a substitute for the glass of this system, the lead-free glass which has been extensively studied and put into practical use is G_10. The Bi-B-Si-lanthanum glass does not contain harmful substances, but G-09 is higher in temperature than softening point and softening fluidity. The softening point of G-10 glass is G-06 of Zn-BVO system and G-08 of P-Zn-K_ 0 system, softening fluidity The glass having a softening point between G 〇9 and & 10 is G-02 of VP-Ba-lanthanide, G-03 of VP-Fe-lanthanide and Sn-P-Zn-lanthanide of lanthanum G-07, but the softening fluidity is almost the same as G_1〇. The glass with softening point lower than G-09 is G_01 of v_P_B_〇, G-04 of v_P_Te_〇 and G_05 of V-Te-Ζη-Ο ,soften The fluidity is also low-temperature. The glass showing good fluidity at 5〇〇r is G· 01, -04 and -05, which contain no harmful substances, and G_〇9i, which contains harmful lead. The conductive paste for the electrode was prepared using various kinds of glass shown in Table 1, and mounted on a solar cell, and the conversion efficiency and environmental protection were evaluated. The appearance, adhesion, and water resistance of the aluminum electrodes formed were also evaluated. . 163196.doc -15· 201249771 A conductive paste for an aluminum electrode was prepared for each of G-01 to 10 in Table 1. First, the glass is pulverized into particles of 3 μη or less by a masher and a jet mill. Ming particles are made by using an atomization method with an average particle diameter of 3 μπι, and 0.4 parts by weight of G-01 to 08 glass particles are mixed with respect to 100 parts by weight of aluminum particles, and G-09 and -10 are mixed. Glass particles are mixed. 重量7 parts by weight. 0 Table 1 Glass No. Glass. Glass main component oxide with or without harmful substances Softening point CC) Softening fluidity (sudden heat, 1 minute 保, 400 。). 500°C 600°C 700°C 800°C Example G-01 VPB-0 V2〇5 No 355 Λ ο Ο Ο 〇G-02 VP-Ba-O V2〇5 No 443 X Δ Ο Ο 〇G- 03 VP-Fe-O V2〇5 No 435 X Λ 〇ο Ο G-04 VP-Te-0 V2〇5 No 336 △ 〇Ο ο G-05 V-Te-Zn-O V2〇5 “No 332 Δ ο ο ο 〇Comparative Example G-06 Zn-BV-0 ZnO No 546 XX Λ ο 〇G-07 Sn-P-Zn-0 SnO No 428 X Δ Ο ο 〇G-08 P-Zn-K-0 PA No 564 XX Λ ο 〇G-09 Pb-B-Si-0 PbO Yes (Pb) 390 X 〇Ο ο 〇G-10 Bi-B-Si-0 Bi203 No 458 X Λ 〇〇〇 Change the mix of glass particles The reason for the quantity is that the proportion of the glass of G 〇9 and ·1〇 is about twice as large as that of the glass of G-01~8. The oxygen content of the glass is substantially the same in the volume ratio. The amount of the solvent of 2% by weight of the binder resin dissolved in advance is added to 1 part by weight of the mixture, and the 11 electrode electric power is produced by kneading (4). Here, ethyl cellulose is used for the bonding and fat riding, and α-rosin alcohol is used as the solvent. The solar battery unit to be used as the electronic component of the present invention is described using the prepared (4) conductive paste for the pole. A schematic plan view showing an example of a light receiving surface of a representative solar cell unit. Further, Fig. 3 is a plan view showing an example of a back surface thereof, and Fig. 4 is a schematic cross-sectional view of the line A], 163196.doc 201249771 of Fig. 2, and Fig. 4B is an enlarged cross-sectional view of the vicinity of the back surface (portion shown in Fig. 4). The semiconductor substrate of the solar cell unit 10 is usually a single crystal germanium substrate or a polycrystalline germanium substrate, and contains boron or the like to form a p-type semiconductor. The surface side is formed with irregularities by chemical etching or the like in order to suppress reflection of sunlight. Further, the light-receiving surface is doped with phosphorus or the like, and an n-type having a thickness of about 丨μηη is formed. Conductor layer 2 »and, in the boundary portion of the ρ-body contact portion formed confer. Further, on the light receiving surface, an antireflection layer 3 such as tantalum nitride having a thickness of about 1 〇〇 nm is formed by a vapor deposition method. Next, the formation of the light-receiving surface electrode 4 formed on the light-receiving surface and the back surface electrode 5 and the output electrode 6 formed on the back surface will be described. In general, the light-receiving surface electrode 4 and the output electrode 6 are formed by using a conductive paste for silver electrodes containing silver particles and glass particles, and the back electrode 5 is formed by using a conductive paste for aluminum electrodes containing aluminum particles and glass particles. Each of the conductive pastes is applied onto the surface of the back surface of the antireflection layer 3 and the semiconductor substrate formed on the light receiving surface of the semiconductor substrate 1 by a screen printing method or the like. After the conductive paste was dried, it was calcined in the atmosphere at about 8 Torr to form electrodes. At this time, on the light receiving surface, the glass composition contained in the light receiving surface electrode 4 reacts with the antireflection layer 3, and the light receiving surface electrode 4 and the 11 type semiconductor layer 2 are electrically connected to each other, and the back surface and the back surface electrode are electrically connected. The component of the middle portion of the film 5 reacts with the semiconductor substrate , to form an alloy layer 8 of aluminum and tantalum, and further forms an aluminum diffusion layer (Back Surface Field, BSF layer, back surface field layer) 7 in which aluminum is diffused to the semiconductor substrate 1. By forming the BSI^7, it is possible to prevent the carrier generated inside the solar cell unit from recombining on the back side, and improve 163I96.doc 17 201249771 = performance of the battery unit... The alloy layer 8 also has a single (4) incident on the solar cell The effect of light reflection on the back surface and (4) light encapsulation in the semiconductor substrate 1 contributes to the improvement of the performance of the solar cell unit. Further, in the solar cell unit, the conductive material containing the inscription particles and the harmful pbBsi system as the (four) point glass and the Bi.B-Si-O system glass composition not containing the harmful ship are used in front of the back electrode material. Sex paste, but no matter what kind of glass, there is a problem that the reliability of (4) electricity (four) (four) extreme moisture resistance and water resistance cannot be improved. Furthermore, both types of glass are present on the electrodes to cause foreign matter and irregularities. Therefore, there is a need in the industry for a glass composition for an aluminum electrode which can improve the performance, safety (lead-free), reliability, and productivity of a solar cell unit, thereby improving the above problems. A solar cell unit for producing the electronic component of the present invention. The semiconductor substrate 1 is also a P-type single crystal germanium substrate. The size of the crucible substrate is set to 125 mm square and the thickness is 200 μm. Next, in order to increase the light incident efficiency, a photosensitive aqueous solution containing caustic soda (sodium argon oxide: NaOH) and 10% isopropyl alcohol (CH3CH (〇H) CH3) is used to etch the light-receiving surface of the semiconductor substrate 1 to form irregularities. . By applying a liquid containing phosphorus pentoxide (p2〇5) on the light receiving surface to heat treatment at 900 ° C for 30 minutes, phosphorus (P) is diffused onto the semiconductor substrate 1 to form on the light receiving surface. The n-type semiconductor layer 2 having a thickness of about 1 μm. After the removal of phosphorus pentoxide, a nitride film having a thickness of about 100 nm is similarly formed on the n-type semiconductor layer 2 as the antireflection layer 3. The nitriding film is formed by a mixed gas of decane (SiH4) and ammonia (NH3) as a raw material, and is formed by a plasma CVD (Chemical Vapor Deposition) method, etc. 0 163196.doc • 18 - 201249771 Next, in order to form the light-receiving surface electrode 4, a silver paste-containing conductive paste containing silver particles and glass particles is applied to the anti-reflection layer 3 in a grid shape by a screen printing method, and dried at 15 (rc). 1 minute. The silver particles are those having an average particle diameter of about 2 (four). The glass particles are V_Ag_P_Te having an average particle diameter of about 2 μm and containing no harmful errors, and a low-melting glass. For the back surface of the semiconductor substrate 1. The output electrode 6 is also coated with a conductive paste for a silver electrode similar to the above, and is applied by the screen printing method in the same manner as the back electrode 5, and similarly coated and dried with aluminum particles and glass. The (4) electrode of the particle is made of a conductive paste. _Electric (four) conduction _ paste is a conductive paste for an aluminum electrode produced by using the glass of the example " whistle comparative example glass G-02 to 10 described above. For comparison, also use without a conductive paste for the electrode of the glass particle. Thereafter, it is rapidly heated to 8 Å in the atmosphere by using a tunneling furnace and held for 3 sec seconds while calcining, forming the light-receiving surface electrode 4, the f-surface electrode 5, and The solar cell unit 10 is fabricated by outputting the electrode 6. The film thickness of the light-receiving surface electrode 4 and the output electrode 6 after firing is about 20 (four), and the film thickness of the back electrode is about 4 〇 μηη. 5, use the solar cell unit 1 manufactured by changing the conductive paste for the electrode, and measure the conversion efficiency of the unit by using the state simulator. Also, from the viewpoint of environmental protection (with or without harmful catalysts, the solar cell produced) The appearance, adhesion, and water resistance of the electrode formed as the back surface electrode 5 were also evaluated. 163196.doc 19 201249771 The evaluation results of the produced solar battery cells are shown in Table 2. In the "conversion efficiency" column in Table 2, "◎" indicates that the unit conversion efficiency is Μ% or more, "〇" is set to 17.5 to 18.0%, and "△" is set to 17 〇 to 17 5%, "X". Set to less than 17%. About "Environmental protection" is to determine whether the solar cell unit produced contains harmful harmful substances, and the case where no harmful substances are contained is set to "〇". The case of the inclusion is "X". The appearance of the aluminum electrode is visually observed. The case where the surface foreign matter or the large unevenness was observed was evaluated as "〇", and it was found that a certain number of cases were evaluated as "△", and the case where the visible state was evaluated was again, and the "adhesiveness" of the electrode was by the peeling test. In the evaluation test, a commercially available scotch tape was attached to the electrode, and when the aluminum was not peeled off during peeling, it was set to "〇", and only the part of the peeling was set to "△". In many cases, it is set to "χ" β "water resistance". The solar cell unit produced by the company is immersed in the water of the 5GC shirt for 8 hours, and the electrode is not discolored. The situation is evaluated as "〇", and only the partial blackening price is "△", and the case where the face is blackened is evaluated as "X". The results of the two evaluations were comprehensively studied and judged. The battery unit was evaluated as "〇" in practical terms, the solar cell bank was insufficient as △", and the solar cell in question was evaluated as "X". [Table 2] 163196.doc •20- 201249771 Table 2

表中搭載使用實施例V-P-B-O系玻璃G-〇 1與比較例 〜B-S卜◦系玻璃G_G9之㉝電極作為背面電極之太陽電池 單凡具有非常高之轉換效率。又，使用比較例Bi-B-Si-Ο系 玻璃G-1 〇之情形時亦顯示出較高之轉換效率。使用其以外 之玻璃之情形時轉換效率較低。又，不含有玻璃之情形 時，轉換效率低於使用任何玻璃之情形。關於環境保護， 由於G-09大量含有有害之鉛，故而用於太陽電池單元時在 環i兄方面存在問題，但使用其以外之玻璃之情形時無問 題。在考慮到環境之前提下，轉換效率最高之太陽電池單 凡、即性能最高之電子零件為將實施例G_01之ν_ρ_Β_〇系 玻璃應用於電極之情形。 又’如表2所示，形成於太陽電池單元上之鋁電極之外 觀於使用以V2〇5作為主成分之低熔點玻璃G-01〜05之情形 時均良好。確認使用其以外之玻璃之情形及不含有玻璃之 163196.doc 21 201249771 情形時，紹電極表面部可見大量之異物或凹凸。銘電極之 密接性於使用軟化點較低、5〇(rc下軟化流動之玻璃g_ 〇1〜05、-07、_〇9及-10之情形時良好。 另一方面，使用軟化點較高為5〇(rc以上之玻璃〇〇6與_ 之情形時，及不含有玻璃之情形時，密接性不充分。鋁 電極之耐水性與上文說明之外觀之結果相同，使用以％… 作為主成分之低溶點玻璃G-〇 1〜〇5之情形時均良好。 由以上得知，鋁電極之外觀、密接性、耐水性均為良好 之玻璃為G-01〜05，若為以％〇5作為主成分之低熔點玻 璃，則可改善或提高鋁電極之生產性及可靠性。認為其原 因在於：鋁粒子與以V2〇5作為主成分之低熔點玻璃粒子於 锻燒及形成電極時具有良好之濕潤性與反應性。但是，幾 乎所有以V2〇5作為主成分之低熔點玻璃均降低單元轉換效 率。唯一可將單元轉換效率提高至與Pb_B_Si_〇系玻璃G· 09相同程度之玻璃僅為實施例G_〇1之含有釩、碟及蝴之氧 化物玻璃。 又，該玻璃中實質上不含有鉛等有害規制物質，亦充分 考慮到環境’故而應用該玻璃之電極用導電性糊、及具有 由該導電性糊形成之電極之電子零件亦可減少對環境負荷 之影響。RoHS規制及聯合產業指南中規定電子零件之錯 含量為1000 ppm以下。 因此’構成電子零件之各材料中，不應主觀含有有宝之 鉛。但是，存在鉛作為雜質而混入之情況，於構成電子零 件之各材料中電子零件亦較佳為同樣地設為1000 ppmJ^ 163196.doc •22· 201249771 下。本發明之電極用ν_Ρ_Β·〇系玻壤係為了減少對環境負 荷之影響，而以此為前提進行開發，結果發現其與使用先 前之Pb_B-Si_0系玻璃或Bi各Si•◦系破璃之情形相比更加 提高電子零件之性能及可靠性。 [實施例2] 於實施例丨中，得知太陽電池單元之轉換效率根據銘電 極中含有之玻璃而有所不同。為了查明其原因，藉由 SEM-EDX(scanning electron microprobe and energy dispersive X-ray micr〇analysis，掃描式電子顯微鏡及能量 色散X射線分析）對據說影響單元轉換效率之BSF層7及合 金層8之狀態進行詳細地觀察及分析。圖5中揭示使用含有 表1及表2所示之V-P-B-0系玻璃G-01之鋁電極用導電性糊 所製作之太陽電池單元之背面附近之剖面SEM照片。由於 通常無法觀測BSF層7，故而藉由使用硝氟酸水溶液進行蝕 刻而觀察。 如實施例1所述，BSF層7係藉由背面電極5之鋁成分擴 散至包含石夕基板之半導體基板1上而形成。此時，藉由銘 與矽之反應於背面電極5與BSF層7之間亦生成合金層8。使 用G-01以外之玻璃G-02〜10之情形時亦與圖5相同地進行觀 察。 詳細地進行SEM觀察，結果對於BSF層7及合金層8之厚 度’未觀測到由鋁電極用玻璃引起之較大差異。即，未見 到太陽電池單元之轉換效率與BSF層7及合金層8之厚度有 明確之相關性。因此，藉由高感度之EDX對BSF層7及合金 163196.doc -23· 201249771 層8之組成進行分析。於合金層8中，無論使用何種玻璃， 均檢測出鋁與矽兩者。於此分析組成中，鋁非常多而為9〇 原子％以上，另一方面’矽較少而為1〇原子％以下。該組 成範圍内之偏差即使於同一太陽電池單元内亦較大未能 發現太陽電池單元之轉換效率與合金層8之組成之明確關 係。 其次，同樣地藉由高感度之丑1);?(對8817層7之組成進行分 析。可見到BSF層7之組成因玻璃所致之差異。圖6中揭示 BSF層7中之鋁（A1)濃度與鋁電極用玻璃組合物之軟化點之 間之關係得知玻璃之軟化點越低，BSF層7中之銘漢度越 高。但是，如表1與表2所示，並非玻璃之鋁濃度越高、即 軟化點越低，太陽電池單元之轉換效率越高。因此，亦對 BSF層7中之氧濃度進行調查。 圖7中揭示BSF層7中之氧（0)濃度與鋁電極用玻璃組合物 之軟化點之間之關係。與8卯層7中之鋁濃度同樣地，顯示 出玻璃之軟化點越低，BSF層7中之氧濃度越高之傾向，但 實施例2V_P-B-〇系玻璃g_〇i、比較例之pb_Bsi_〇系玻璃 G-09與Bi-B-Si-Ο系玻璃G_10並不符合該傾向，即使軟化 點降低BSF層7中之氧濃度亦較低。即，亦可說是該等玻璃 難以使矽基板氧化。 如表2所示，將g-οι、_〇9及- ίο之玻璃用於鋁電極之情 形時’太陽電池單元之轉換效率較高。 由以上内容得知可使BSF層7之鋁濃度較高且使氧濃度 較低之銘電極用玻璃組合物可提高太陽電池單元之轉換效 163196.doc -24- 201249771 率。可認為，為了增加自背面電極5至半導體基板1之鋁擴 散量’即增加自鋁電極至矽基板之鋁擴散量，只要降低電 極中含有之玻璃組合物之軟化點即可’另一方面，為了同 時減少氧擴散量’必須於軟化、流動之玻璃組合物接觸矽 基板時不自該玻璃組合物奪取氧至矽基板。 由於比較例之Pb-B-Si-Ο系玻璃G-09與Bi-B-Si-O系玻璃 G-10係極易還原之玻璃’故而認為於鋁電極中容易被還 原’導致氧被奪取，而未到達將矽基板氧化之程度。作為 其證據’若對分別含有G-09與-10之背面電極5進行X射線 繞射分析’則可見金屬鉛及金屬鉍之析出。其原因在於： G-09及-10之玻璃於鋁電極中被還原，而自該等玻璃中析 出。 由於以V2〇5作為主成分之低熔點玻璃G-02〜05與G-09及-10相比較難還原，無法獲得此種效果，故而認為矽基板易 氧化。但是’儘管實施例之V-P-B-0系玻璃G-01為與比較 例之G-02〜05同樣地以V205作為主成分之低熔點玻璃，但 卻特異性地抑制了矽基板之氧化。其原因在於G-01與G-02〜05之玻璃之構造不同。圖8中示意性地揭示玻璃構造中 之P205與B2〇3之狀態。 P2〇5於玻璃構造中如圖8(1)所示相對於一個磷（P)具有一 個雙鍵氧（0)，並藉由3個交聯氧（〇)而形成玻璃之網狀構 造。B2〇3於玻璃構造中如圖8(2)所示相對於一個硼（B)，藉 由3個交聯氧（0)而形成玻璃之網狀構造。 與該等相對’若含有P2〇5與B2o3兩者，則於玻璃構造中 163I96.doc •25· 201249771 如圖8(3)所示磷（p)與硼（b)可分別鍵結4個交聯氧（〇)，而 使玻璃之網狀構造緻密化。此時，磷（Ρ)帶正（+)電荷，删 (Β)帶負㈠電荷而相互電性中和。此情況係稱為删酸異常 現象的玻璃之特異現象，理論上為了使該現象最有效率地 表現，Ρζ〇5與Βζ〇3之含有比例以莫耳比計為1:1，以重量 比計為2:1。 實施例之V-P-B-O系低熔點玻璃G-01之玻璃構造採用該 現象。藉此，抑制氧衿矽基板上之擴散，即抑制矽基板之 氧化。該技術只要為形成於矽基板上之電極，則當然即使 為鋁電極以外亦可有效地運用。又，藉由以Ah作為主成 分可使軟化點低溫化，增加鋁於矽基板上之擴散量。如此 藉由減少氧於矽基板上之擴散量及增加鋁於矽基板上之擴 散量，而提尚太陽電池單元之轉換效率。以上，雖然以太 陽電池單元為例進行了說明，但該技術可運用於所有使用 矽基板之電子零件。 進而，由於為以V2〇5作為主成分之低熔點玻璃，故而可 減，紹電極之外觀等之不良率，並且可提高密接性及耐濕 性等可靠性。此係由與鋁之濕潤性及反應所引起，以鋁作 為主成刀之鋁合金中當然亦可獲得相同之效果。又以 上雖然以適用於太陽電池單元之背面電極為例進行了說 明’但當然亦可適用於其以外之電子零件之紹電極及紹合 金電極。 [實施例3] 於本實施例中’詳細地研究對使用⑪基板之電子零件及 I63196.doc -26 - 201249771 鋁電極有效之V-P-B-O系低熔點玻璃之組成。將所製作之 V-P-B-O系低熔點玻璃之調配組成與其特性示於表3。對表 3所示之GA-01〜30之玻璃製作方法進行說明。 [表3] 表3In the table, a solar cell using the 33 electrodes of the example V-P-B-O-based glass G-〇 1 and the comparative example-B-S bismuth glass G_G9 as the back electrode was provided with a very high conversion efficiency. Further, when the comparative example Bi-B-Si-lanthanum glass G-1 was used, the conversion efficiency was also exhibited. The conversion efficiency is low when using a glass other than the other. Also, in the case where glass is not contained, the conversion efficiency is lower than in the case of using any glass. Regarding environmental protection, since G-09 contains a large amount of harmful lead, there is a problem in the case of a solar cell unit, but there is no problem in the case of using a glass other than the glass. Before considering the environment, the solar cell with the highest conversion efficiency, that is, the highest performance electronic component, is the case where the ν_ρ_Β_〇 glass of the embodiment G_01 is applied to the electrode. Further, as shown in Table 2, the aluminum electrode formed on the solar cell unit was excellent in the case of using the low melting point glass G-01 to 05 having V2〇5 as a main component. When using a glass other than the glass and 163196.doc 21 201249771, a large amount of foreign matter or unevenness is visible on the surface of the electrode. The adhesion of the electrode is good when the softening point is low, 5 〇 (the glass of softening flow under rc, g_ 〇1~05, -07, _〇9 and -10) is good. On the other hand, the softening point is higher. When it is 5 Å (in the case of glass 〇〇6 and _ of rc or more, and when glass is not contained, the adhesion is insufficient. The water resistance of the aluminum electrode is the same as the result of the appearance described above, and is used as %... In the case of the low melting point glass G-〇1 to 〇5 of the main component, it is good. From the above, it is known that the appearance, adhesion, and water resistance of the aluminum electrode are both G-01 to 05, if The low-melting glass with %〇5 as the main component can improve or improve the productivity and reliability of the aluminum electrode. The reason is believed to be that the aluminum particles and the low-melting glass particles with V2〇5 as the main component are calcined and formed. The electrode has good wettability and reactivity. However, almost all low-melting glass with V2〇5 as the main component reduces the unit conversion efficiency. The only unit conversion efficiency can be improved to be the same as Pb_B_Si_〇 glass G·09. The degree of glass is only included in the example G_〇1 An oxide glass of a vanadium, a dish, or a butterfly. The glass does not substantially contain a harmful substance such as lead, and the conductive paste for the electrode of the glass is used in consideration of the environment, and the conductive paste is formed of the conductive paste. The electronic components of the electrodes can also reduce the impact on the environmental load. The RoHS regulations and the joint industry guidelines stipulate that the electronic components have a fault content of less than 1000 ppm. Therefore, the materials that constitute the electronic components should not be subjectively containing lead. However, in the case where lead is mixed as an impurity, the electronic component is preferably set to 1000 ppmJ 163196.doc •22·201249771 in the respective materials constituting the electronic component. The electrode of the present invention is ν_Ρ_Β·〇 In order to reduce the impact on the environmental load, the Bolivia system was developed on the premise of the environmental load, and it was found that it was more improved than the case of using the previous Pb_B-Si_0-based glass or Bi-Si-lanthanum-based glass. [Embodiment 2] In the examples, it was found that the conversion efficiency of the solar cell unit differs depending on the glass contained in the electrode. In order to ascertain the cause, the BSF layer 7 and the alloy layer 8 which are said to affect the unit conversion efficiency by SEM-EDX (scanning electron microprobe and energy dispersive X-ray micr〇analysis, scanning electron microscope and energy dispersive X-ray analysis) The state of the solar cell unit produced by using the conductive paste of the VPB-0-based glass G-01 shown in Table 1 and Table 2 is observed in detail. Photograph. Since the BSF layer 7 is usually not observed, it is observed by etching using a hydrofluoric acid aqueous solution. As described in the first embodiment, the BSF layer 7 is formed by diffusing the aluminum component of the back surface electrode 5 onto the semiconductor substrate 1 including the stone substrate. At this time, the alloy layer 8 is also formed between the back electrode 5 and the BSF layer 7 by the reaction of 铭 and 矽. When the glasses G-02 to 10 other than G-01 were used, they were observed in the same manner as in Fig. 5. When SEM observation was carried out in detail, as a result, the thickness of the BSF layer 7 and the alloy layer 8 was not observed to be largely different from that of the glass for aluminum electrodes. Namely, there is no clear correlation between the conversion efficiency of the solar cell unit and the thickness of the BSF layer 7 and the alloy layer 8. Therefore, the composition of the BSF layer 7 and the alloy 163196.doc -23· 201249771 layer 8 was analyzed by high-sensitivity EDX. In the alloy layer 8, both aluminum and tantalum were detected regardless of the type of glass used. In the analysis composition, aluminum is very large and is 9 原子 atom% or more, and on the other hand, 矽 is less than 1 〇 atom%. The variation in the range of the composition is large even in the same solar cell unit, and the clear relationship between the conversion efficiency of the solar cell unit and the composition of the alloy layer 8 cannot be found. Secondly, by the high sensitivity ugly 1);? (analysis of the composition of the 8817 layer 7 can be seen. The composition of the BSF layer 7 is due to the difference in glass. Figure 6 reveals the aluminum in the BSF layer 7 (A1 The relationship between the concentration and the softening point of the glass composition for an aluminum electrode is that the lower the softening point of the glass, the higher the brightness of the BSF layer 7. However, as shown in Tables 1 and 2, it is not glass. The higher the aluminum concentration, that is, the lower the softening point, the higher the conversion efficiency of the solar cell. Therefore, the oxygen concentration in the BSF layer 7 is also investigated. The oxygen (0) concentration in the BSF layer 7 is disclosed in FIG. The relationship between the softening points of the glass composition for electrodes. Similarly to the aluminum concentration in the 8 layer 7 , the lower the softening point of the glass, the higher the oxygen concentration in the BSF layer 7 tends to be higher, but the example 2V_P -B-lanthanum glass g_〇i, comparative example pb_Bsi_lanthanum glass G-09 and Bi-B-Si-lanthanum glass G_10 do not conform to this tendency, even if the softening point lowers the oxygen concentration in the BSF layer 7. It is also lower. That is to say, it is difficult for these glasses to oxidize the ruthenium substrate. As shown in Table 2, the glass of g-οι, _〇9 and - ίο is used for aluminum. In the extreme case, the conversion efficiency of the solar cell unit is high. It is known from the above that the glass composition of the electrode for the electrode having a higher aluminum concentration of the BSF layer 7 and a lower oxygen concentration can improve the conversion efficiency of the solar cell unit. 163196.doc -24- 201249771 rate. It is considered that in order to increase the amount of aluminum diffusion from the back electrode 5 to the semiconductor substrate 1, that is, to increase the amount of aluminum diffusion from the aluminum electrode to the ruthenium substrate, it is only necessary to reduce the glass composition contained in the electrode. The softening point can be 'on the other hand, in order to simultaneously reduce the amount of oxygen diffusion', it is necessary to not take oxygen from the glass composition to the ruthenium substrate when the softened, flowing glass composition contacts the ruthenium substrate. Pb-B-Si of the comparative example - The bismuth glass G-09 and the Bi-B-Si-O glass G-10 are extremely easy to reduce the glass 'so it is considered to be easily reduced in the aluminum electrode', causing the oxygen to be captured without reaching the oxidation of the ruthenium substrate. As a result of the evidence, if X-ray diffraction analysis is performed on the back electrode 5 containing G-09 and -10, the precipitation of metal lead and metal ruthenium can be seen. The reason is: G-09 and -10 glass are The aluminum electrode is reduced, and In the glass, the low-melting glass G-02~05 having V2〇5 as a main component is difficult to be reduced compared with G-09 and -10, and this effect cannot be obtained. Therefore, the ruthenium substrate is considered to be easily oxidized. Although the VPB-0-based glass G-01 of the example is a low-melting glass containing V205 as a main component similarly to G-02 to 05 of Comparative Example, the oxidation of the ruthenium substrate is specifically suppressed. -01 is different from the structure of the glass of G-02~05. The state of P205 and B2〇3 in the glass structure is schematically disclosed in Fig. 8. P2〇5 is in the glass structure as shown in Fig. 8(1) One phosphorus (P) has a double bond oxygen (0) and a network of glass is formed by three crosslinked oxygens (〇). B2〇3 forms a network structure of glass in the glass structure with respect to one boron (B) as shown in Fig. 8 (2) by three crosslinked oxygens (0). Relative to these, if both P2〇5 and B2o3 are contained, in the glass structure 163I96.doc •25· 201249771 As shown in Fig. 8(3), phosphorus (p) and boron (b) can be bonded to 4 respectively. The oxygen (〇) is crosslinked to densify the network structure of the glass. At this time, phosphorus (Ρ) carries a positive (+) charge, and (删) has a negative (a) charge and is electrically neutralized with each other. This condition is called the specific phenomenon of the glass-deletion anomaly. In theory, in order to make the phenomenon most efficient, the ratio of Ρζ〇5 to Βζ〇3 is 1:1 in molar ratio, in weight ratio. Counted as 2:1. The glass structure of the V-P-B-O-based low-melting glass G-01 of the examples employs this phenomenon. Thereby, the diffusion on the ruthenium substrate is suppressed, i.e., the oxidation of the ruthenium substrate is suppressed. As long as the technique is an electrode formed on a substrate, it can be effectively used even if it is an aluminum electrode. Further, by using Ah as a main component, the softening point can be lowered to increase the amount of diffusion of aluminum on the ruthenium substrate. Thus, the conversion efficiency of the solar cell unit is improved by reducing the amount of diffusion of oxygen on the germanium substrate and increasing the amount of diffusion of aluminum on the germanium substrate. Although the solar cell unit has been described as an example, the technique can be applied to all electronic components using a germanium substrate. Further, since it is a low-melting glass having V2〇5 as a main component, the defect rate such as the appearance of the electrode can be reduced, and reliability such as adhesion and moisture resistance can be improved. This is caused by the wettability and reaction with aluminum, and of course the same effect can be obtained in an aluminum alloy mainly composed of aluminum. Further, although the back electrode applied to the solar cell unit has been described as an example, it is of course applicable to the electrode of the electronic component other than the electrode and the gold electrode. [Embodiment 3] In the present embodiment, the composition of the V-P-B-O low-melting glass which is effective for an electronic component using 11 substrates and an aluminum electrode of I63196.doc -26 - 201249771 is studied in detail. The composition of the prepared V-P-B-O low-melting glass and its characteristics are shown in Table 3. The glass production method of GA-01 to 30 shown in Table 3 will be described. [Table 3] Table 3

將表3之調配組成中所示之氧化物作為玻璃原料，以各 比例为別調配、混合2〇〇 g。將其添加至銘掛渦中， ;電爐中以分之升溫速度加熱至900〜11〇〇。〇，一面 擾掉一 '面保持2小時後，使其流至不鏽鋼板上，分別製作 GA 〇1〜30之破璃。藉由捣碎機與喷射磨機將所製作之玻 163196.doc •27· 201249771 璃粉碎成平均粒徑為1〜2 μηι ’而獲得各玻璃粒子。 所製作之玻璃之密度係藉由阿基米德法而測定，軟化點 與軟化流動性係以與實施例1相同之方式評價。所製作之 V Ρ-Β-0系低溶點玻璃ga_〇i〜3〇之密度為2 6〇〜3 g/Cr^3 之範圍’與先前之Pb-B-Si-O系低炫點玻璃G-09及Bi-B-Si. 〇系低炫點玻璃G-10之密度相比約為一半。 密度尤其小之玻璃為GA-27〜30，P2〇5之含量為IQ3之同 等以下。其以外之玻璃係將P2〇5之含量增加至B2〇3之含量 之約2倍，積極地運用實施例2中所說明之硼酸異常現象。 另一方面’於上述密度範圍中，密度尤其大之玻璃為含有The oxides shown in the composition of Table 3 were used as glass raw materials, and 2 〇〇 g was prepared and mixed in each ratio. Add it to the hanging vortex, and heat it to 900~11〇〇 in the electric furnace at a heating rate. 〇, while disturbing one side for 2 hours, let it flow to the stainless steel plate to make the glass of GA 〇1~30. Each of the glass particles was obtained by pulverizing the produced glass 163196.doc •27·201249771 glass into an average particle diameter of 1 to 2 μηι ′ by a masher and a jet mill. The density of the produced glass was measured by the Archimedes method, and the softening point and the softening fluidity were evaluated in the same manner as in Example 1. The V Ρ-Β-0 series of low-melting point glass ga_〇i~3〇 has a density of 2 6〇~3 g/Cr^3 and is lower than the previous Pb-B-Si-O system. Point glass G-09 and Bi-B-Si. The density of the lanthanide low-focus glass G-10 is about half. The glass having a particularly small density is GA-27 to 30, and the content of P2〇5 is equal to or lower than IQ3. The glass other than this increased the content of P2〇5 to about twice the content of B2〇3, and actively used the boric acid abnormality described in Example 2. On the other hand, in the above density range, the glass having a particularly large density is contained.

Te02 30重量 ％以上之 GA-15、-22〜24及-26。 顯示出玻璃之V2〇5及Te〇2之含量越高，p2〇5越少則軟化 點越低之傾向。軟化流動性於600°C以上，無論何種玻璃 均具有良好之流動性。於500 °C下，除GA-27、-28及-3 0以 外均具有良好之流動性。又，於400°C下，GA-05〜07、-09、 -13 及-16 僅軟化’僅 GA-01 〜04、-14、-15、-22 及-23 顯示 出良好之流動性。與軟化點同樣地，顯示出玻璃之V205及 Te〇2之含量越高，p2〇5越少，則低溫下之軟化流動性越良 好之傾向。 使用GA-01~30之玻璃粒子，以與實施例1相同之方式製 作鋁電極用導電性糊。其中，黏合劑樹脂係使用硝化纖維 素，溶劑係使用丁基卡必醇乙酸酯。又，為了進行比較， 以與實施例1相同之方式製作分別含有Pb-B-Si-Ο系低熔點 玻璃G-09與Bi-B-Si-O系低熔點玻璃G-10之鋁電極用導電 I63196.doc • 28 · 201249771 性糊、及無玻璃之鋁電極用導電性糊。 使用所製作之鋁電極用導電性糊，以與實施例1相同之 方式製作圖2〜4所示之太陽電池單元，並進行評價。其 中，半導體基板1係使用150 mm見方、厚度200 μιη之p型多 晶石夕基板。所製作之太陽電池單元之評價結果示於表4。 [表4] 表4Te02 30% by weight or more of GA-15, -22~24 and -26. It is shown that the higher the content of V2〇5 and Te〇2 of the glass, the lower the softening point tends to be the smaller the p2〇5. The softening fluidity is above 600 °C, and it has good fluidity regardless of the glass. At 500 °C, it has good fluidity except GA-27, -28 and -3 0. Further, at 400 ° C, GA-05 〜 07, -09, -13 and -16 were only softened. Only GA-01 ～04, -14, -15, -22 and -23 showed good fluidity. Similarly to the softening point, the higher the content of V205 and Te〇2 in the glass, the less the p2〇5, the better the softening fluidity at low temperatures tends to be. A conductive paste for an aluminum electrode was produced in the same manner as in Example 1 using glass particles of GA-01 to 30. Among them, nitrocellulose was used as the binder resin, and butyl carbitol acetate was used as the solvent. Further, for comparison, in the same manner as in Example 1, aluminum electrodes each containing Pb-B-Si-antimony low melting glass G-09 and Bi-B-Si-O low melting glass G-10 were produced. Conductive I63196.doc • 28 · 201249771 Conductive paste for paste and glass-free aluminum electrodes. The solar battery cells shown in Figs. 2 to 4 were produced and evaluated in the same manner as in Example 1 using the produced conductive paste for aluminum electrodes. Among them, the semiconductor substrate 1 is a p-type polycrystalline substrate of 150 mm square and 200 μm thick. The evaluation results of the produced solar battery cells are shown in Table 4. [Table 4] Table 4

玻璃編號 玻璃含量 (重量份） 轉換效率 (%) 環境保護 鋁電極(背面電極） 综合 評價 外觀 密接性 耐水性 實施例 GA-01 0.4 17.2(@) 〇 〇 〇 〇 ◎ GA-02 0.4 17.3(©) 〇 〇 〇 〇 ◎ GA-03 0.4 17.4(©) 〇 〇 〇 〇 ◎ GA-04 0.4 17.0(®) 〇 〇 〇 〇 ◎ GA-05 0.4 17.2(©) 〇 〇 〇 〇 ◎ GA-06 0.4 17.0(®) 〇 〇 〇 〇 ◎ GA-07 0.4 17.1(@) 〇 〇 〇 〇 ◎ GA-08 0,4 16.8(〇) 〇 〇 〇 〇 〇 GA-09 0.4 17.0(©) 〇 〇 〇 〇 ◎ GA-10 0.4 17.2(@) 〇 〇 〇 〇 ◎ GA-11 0.4 17._ 〇 〇 〇 〇 ◎ GA-12 0.4 17.3(®) 〇 〇 〇 〇 ◎ GA-13 0.4 17.1(®) 〇 〇 〇 〇 ◎ GA-14 0.4 16.6(0) 〇 〇 〇 〇 〇 GA-15 0.4 16.4(Δ) 〇 〇 〇 〇 Δ GA-16 0.4 16.7(0) 〇 〇 〇 〇 〇 GA-17 0.4 16.9(0) 〇 〇 〇 〇 〇 GA-18 0.4 16.7(0) 〇 〇 〇 〇 〇 GA-19 0.4 16.9(0) 〇 〇 〇 〇 〇 GA-20 0.4 16.7(0) 〇 〇 〇 〇 〇 GA-21 0.4 16.9(0) 〇 〇 〇 〇 〇 GA-22 0.4 16.3(Δ) 〇 〇 〇 〇 Δ GA-23 0.4 16.0(Δ) 〇 〇 〇 〇 Δ GA-24 0.4 16.1 (Δ) 〇 〇 〇 〇 Δ GA-25 0.4 16.5(〇) 〇 〇 〇 〇 〇 GA-26 0.4 16.2(Δ) 〇 〇 〇 〇 Δ GA-27 0.4 16.1(Δ) 〇 〇 Δ 〇 Δ GA-28 0.4 16.0(Δ) 〇 〇 Δ 〇 Δ GA-29 0.4 16.2(Δ) 〇 Δ 〇 Δ Δ GA-30 0,4 16.0(Δ) 〇 Δ Δ Δ Δ 比較例 G-09 0.7 16.9(〇) χ(含有Pb) X 〇 X X G-10 0.7 16.4(A) 〇 X 〇 X X 無玻璃 0 14.3(Χ) 〇 X X X X -29- 163196.doc 201249771 ® »平價表4中之「轉換效率」_，由於本實施例令半導 體基板1係使用單元轉換效率低於單晶石夕基板的多晶石夕基 板’故而作為多晶矽基板’將非常高之轉換效率之”篇 以上設為「◎」，16·5〜17.G%設為「〇」，i6〇〜i65%設為 「△」’未達16.0%設為「χ」β其以外之評價以與實施例^ 相同之方式進行。其中，「综合評價」中，「〇」評價之中 轉換效率尤其優異之太陽電池單元評價為「@」。 根據表4之太陽電池單元之評價結果得知，作為铭電極 用玻璃組合物，以ν·Ρ-Β_〇系為基礎亦可含有L、沘、Glass No. Glass Content (parts by weight) Conversion Efficiency (%) Environmental Protection Aluminum Electrode (Back Electrode) Comprehensive Evaluation of Appearance Adhesion Water Resistance Example GA-01 0.4 17.2(@) 〇〇〇〇◎ GA-02 0.4 17.3 (© 〇〇〇〇◎ GA-03 0.4 17.4(©) 〇〇〇〇◎ GA-04 0.4 17.0(®) 〇〇〇〇◎ GA-05 0.4 17.2(©) 〇〇〇〇◎ GA-06 0.4 17.0 (®) 〇〇〇〇◎ GA-07 0.4 17.1(@) 〇〇〇〇◎ GA-08 0,4 16.8(〇) 〇〇〇〇〇GA-09 0.4 17.0(©) 〇〇〇〇◎ GA -10 0.4 17.2(@) 〇〇〇〇◎ GA-11 0.4 17._ 〇〇〇〇◎ GA-12 0.4 17.3(®) 〇〇〇〇◎ GA-13 0.4 17.1(®) 〇〇〇〇◎ GA-14 0.4 16.6(0) 〇〇〇〇〇GA-15 0.4 16.4(Δ) 〇〇〇〇Δ GA-16 0.4 16.7(0) 〇〇〇〇〇GA-17 0.4 16.9(0) 〇〇〇 〇〇GA-18 0.4 16.7(0) 〇〇〇〇〇GA-19 0.4 16.9(0) 〇〇〇〇〇GA-20 0.4 16.7(0) 〇〇〇〇〇GA-21 0.4 16.9(0) 〇 〇〇〇〇GA-22 0.4 16.3(Δ) 〇 〇〇Δ GA-23 0.4 16.0(Δ) 〇〇〇〇Δ GA-24 0.4 16.1 (Δ) 〇〇〇〇Δ GA-25 0.4 16.5(〇) 〇〇〇〇〇GA-26 0.4 16.2(Δ) 〇〇〇〇Δ GA-27 0.4 16.1(Δ) 〇〇Δ 〇Δ GA-28 0.4 16.0(Δ) 〇〇Δ 〇Δ GA-29 0.4 16.2(Δ) 〇Δ 〇Δ Δ GA-30 0,4 16.0(Δ) 〇Δ Δ Δ Δ Comparative Example G-09 0.7 16.9(〇) χ(containing Pb) X 〇XX G-10 0.7 16.4(A) 〇X 〇XX No glass 0 14.3(Χ) 〇XXXX -29 - 163196.doc 201249771 ® » "Conversion efficiency" in the parity table 4, since the semiconductor substrate 1 uses a cell conversion efficiency lower than that of a single crystal substrate, so as a polycrystalline germanium substrate. "Higher conversion efficiency" is set to "◎", 16·5 to 17.G% is set to "〇", i6〇~i65% is set to "△", and less than 16.0% is set to "χ" The evaluation other than β was carried out in the same manner as in Example 2. Among them, in the "comprehensive evaluation", the solar cell evaluation with particularly excellent conversion efficiency among the "〇" evaluations was "@". According to the evaluation result of the solar cell of Table 4, it is known that the glass composition for the electrode can contain L, 沘, and ν based on the ν·Ρ-Β_〇 system.

Bi、Zn中之1種以上。藉由含有該等Te、訃 ' 出、a中之1 種以上’可提高玻璃之耐候性，提高至製作铭電極用導電 性糊為止之玻璃粒子之操作性。 太陽電池單元之综合評價為「〇」以上之玻璃組成範圍 以如下之氧化物換算，AOs為4〇〜8〇重量％、？2〇5為1〇〜25 重量％、B2〇3為5〜15重量。/。、Te〇2為0〜25重量％、Sb2〇3為 〇〜20重量。/〇、Bi203為〇〜2〇重量％、及Zn〇為〇〜2〇重量〇/〇， 並且P2〇5量高於B2〇3量，且Pah、82〇3及1>〇2之合計量為 20〜50重量％。若自玻璃之特性進行考察，則可舉出密度 為2.81〜3.25§/〇1113、軟化點為42〇。〇以下、及5〇〇<»(：下之流 動性為良好之V-P-B-0系低熔點玻璃較為有效。尤其良好 之「◎」之綜合評價之玻璃組成範圍以如下之氧化物換 算，V2〇5為60〜80重量％、p2〇5為1〇〜20重量。/。' b2〇3為 5〜10重量％、Te02為〇〜15重量％、Sb203為〇〜1〇重量。/〇、 Bi2〇3為0~10重量％ '及ZnO為0〜10重量。/〇，並且p2〇5、 163196.doc •30· 201249771 B2〇3及Te02之合計量為20〜40重量％。 上述組成範圍之銘電極用玻璃組合物可促進至石夕基板之 鋁成分之擴散，另一方面，可抑制氧之擴散，此並不限於 太陽電池單元，當然亦可有效地適用於所有使用矽基板之 電子零件。又，對鋁電極尤其有效，但亦可運用於鋁電極 以外者。 [實施例4] 於本實施例中，詳細地研究鋁電極中之ν·ρ·Β_〇系低熔 點玻璃之含量對太陽電池單元之轉換效率產生之影響。_該 玻璃係使用表3與表4所示之實施例3中之GA_〇5。〇八_〇5之 於0〜5重量份之範圍内 1.5 、 2,0 、 2.5 、 3.0 、 玻璃含量相對於鋁粒子1 〇〇重量份 進行研究（0、0.2、0.4、〇>7、1>() 3.5、4.0及5.0重量份）。 與實施例3相同地改變玻璃含量而製作12種鋁電極用導 電性糊。將所製作之銘電極用導電性糊用於背面電極，以 與實施例3相同之方式製作圖2、圖3、圖4八、圖4B所示之 太陽電池單元，並測定嚴开錢搞从右 池單元之轉換效率與::=二。圖9中揭示太陽電 之…間之關係Γ:二，玻璃組合物 右作為者面電極之鋁電極不 璃，則太、陽電池單元之轉換效率明顯降低，但若僅含有 0.2重量份之GA-05破璃，則轉換效率瞬間提高。 GA-05玻璃以〇 2〜〇 7番县々、★林m 高之轉換效率…上 極少之轉換效率—上之良好之㈣效率= 163196.doc 201249771 超過2重量份’則轉換效率明顯下降，2.5重量份以上時低 於1 6.0¼。作為如此轉換效率隨著鋁電極中之玻璃含量下 降之原因，認為係由於氧於矽基板上之擴散量增加，即進 行矽基板之氧化。 根據以上情況’作為太陽電池單元之背面電極而應用之 銘電極中之V-P-B-0系低熔點玻璃之含量較佳為〇 2〜2重量 伤之範圍。尤其有效為〇2〜〇_7重量份之範圍。此並不限於 太陽電池單元，當然亦可有效地適用於所有矽基板之電子 零件。又’雖然對鋁電極尤其有效，但當然亦可運用於鋁 電極以外。 [實施例5] 於本實施例中’研究鋁合金電極中之v_p_B_〇系低熔點 玻璃之含量對該電極之比電阻產生之影響。作為鋁合金， 使用Al-1 〇重量。/〇銀之粒子。藉由利用霧化法進行製作，並 進打分級，而製成3 μηι以下之鋁合金粒子。該玻璃係使用 表3與表4所示之實施例3中之ga 〇9。 GA-09之玻璃含量相對於鋁合金粒子1〇〇重量份，於 0〜25重量份之範圍内進行研究（〇、〇 2、2 〇、5 〇、〇、 15.0、20.0、及 25.0 重量份）。 以與實施例3相同之方式改變玻璃含量而製作8種鋁合金 電極用導電性糊°其中’黏合劑樹脂係使用乙基纖維素代 替硝化纖維素。溶劑為丁基卡必醇乙酸酯。將所製作之鋁 合金電極用導電性糊藉由絲網印刷法塗佈於單晶矽基板 上於15〇C下乾燥10分鐘。其後，放入電爐中，於大氣 I63196.doc •32- 201249771 中以urc/分之升溫速度加熱至50(rc，保持ι〇分鐘後爐内 冷卻。銘合金電極之膜厚約為2G μιηβ藉由四探針法測定 石夕基板上形成之銘合金電極之比電阻。 圖10中揭示鋁合金電極之比電阻與該電極所含之玻璃組 纟物之含量之間之關係。如圖1G所示，若lg合金電極中不 • 含玻璃，則其比電阻顯著提高，但若僅含有0.2重量份之 GA-09玻璃，則比電阻瞬間下降。以GA_G5_為〇2〜15 重量份之範圍’實現了10-5 Qcm級之比電阻。含量為2〇重 量份以上時，鋁合金電極之比電阻再次變大。 由此得知，鋁合金電極僅用作配線之情形及應用於不使 用矽基板之電子零件之情形時，電極中之系低熔 點玻璃之含量較佳為0.2〜15重量份之範圍。於本實施例 中，雖然研究了銘合金電極中之ν·ρ_Β_〇系低熔點玻璃， 但當然亦可運用於鋁電極及其以外之電極。 [實施例6] 於本實施例中，對應用於電漿顯示面板（PDp)之電極之 例進行說明。圖11係表示電漿顯示面板之一例之剖面示意 圖。以下’參照圖11進行說明。 首先，對一般之電漿顯示面板進行說明。於電漿顯示面 板11中，前面板12與背面板13以100〜150 μηι之間隙對向配 置，各基板（前面板12與背面板π)之間隙係利用隔壁14進 行維持。以密封材料15氣密地密封前面板12與背面板13之 周緣部，並於面板内部填充稀有氣體。 於前面板12上形成顯示電極2〇，於顯示電極2〇上形成介 163196.doc -33- 201249771 電質層23，於介電質層23上形成用於保護顯示電極20等使 之不受放電影響的保護層25(例如MgO之蒸鍍膜）^又，於 背面板13上形成定址電極21，於定址電極21上形成介電質 層24 ’於介電質層24上設有用以構成單元16之隔壁14。該 隔壁14係將至少含有玻璃組合物與填料之材料於 500〜600°C下燒結而成之構造體，通常為條狀或盒狀之構 造體。又，以與前面板12之顯示電極20正交之方式形成有 背面板13之定址電極21。 利用隔壁14分隔之微小空間（單元16)中填充有螢光體。 單元16中之螢光體係藉由將螢光體用之糊填充於單元“並 於450〜500 C下煅燒而形成。由紅色螢光體17所填充之單 元、綠色螢光體18所填充之單元及藍色勞光體19所填充之 單元之3色之單元構成！個像素。各像素根據顯示電極2〇與 定址電極21所發出之信號而發出各種顏色之光。 密封材料15藉由分注器法或印刷法等預先塗佈於前面板 或背面板13之任意-個周緣部上。所塗佈之密封材料Η 亦有與螢光體17〜19之炮燒同時進行預㈣n其原 因在於藉由預般燒塗佈之密封材料，可顯著減少玻璃密封 部之氣泡，獲得可靠性較高（即氣密性較高）之玻璃密封 部。 前面板12與背面板13之穷44及必、 在封係將分別製作之前面板12與 背面板13準確地定位並對向 、 J门配置，加熱至420〜500。(：。此 時，一面加熱一面排出單亓彳 内。P之氣體並填充稀有氣體 代替，而完成作為電子零件之 1干之電漿顯示面板。再者，密封 163196.doc -34· 201249771 材料之預煅燒時及玻璃密封時，密封材料15雖然有時與顯 示電極20或定址電極21直接接觸，但重要的是以電極配線 材料與密封材料不發生化學反應之方式構成。 將電漿顯示面板之單元16點亮（發光），於欲點亮之單元 ' 16之顯示電極20與定址電極21之間施加電壓而於單元16内 • 進行定址放電，將稀有氣體激發為電漿狀態而使單元内聚 集壁電荷。其次，藉由對顯示電極對施加一定電壓，僅使 聚集有壁電荷之單元中引起顯示放電而產生紫外線22。接 著，利用該紫外線22使螢光體17〜19發光，而顯示圖像資 訊。 此處’作為顯示電極20及定址電極21，考慮到良好之電 性與製造中之耐氧化性，先前—直使用銀厚膜之電極配 線。顯示電極20及定址電極21之形成雖然可藉由濺鍍法進 行，但為了降低製造成本，印刷法較為有利。再者，介電 質層23、24通常藉由印刷法形成。又，藉由印刷法而形成 之顯示電極20、定址電極21、介電質層23、24, 一般於氧 化環境中、550〜620°C之溫度範圍下煅燒。 如上所述，銀厚膜之電極配線存在銀容易引起電子遷移 • 現象之問題，同時亦存在材料成本較高之問題。為了解決 、 該等問題，較佳為自銀厚膜之電極配線變更為鋁厚膜或鋁 合金厚膜之電極配線。然而，為了變更為鋁厚膜或鋁合金 厚膜之電極配線’需要滿足電極配線之比電阻較低、電極 配線與介電質層不發生化學反應、進而所形成之電極配線 之附近不會產生空隙（氣泡等）而使耐電壓性下降等條件。 163196.doc 35- 201249771 作為紹電極用導電性糊所含有之金屬粒子，準備實施例 5中使用之紹合金粒子（Α1·1〇重量0/〇Ag)e又，實施例5中使 用之V-P-B-0系低熔點玻璃ga_〇9之玻璃粒子於將上述鋁 合金粒子設為1〇〇重量份之情形時為1〇重量份於以此方 式混合之粉末中進而添加、混練黏合劑樹脂與溶劑而製作 在呂電極用導電性糊。此時，黏合劑樹脂係使用乙基纖維 素’溶劑係使用（X-松脂醇。 製作本發明之電毁顯示面板。首先，使用上述紹電極用 導電吐糊，藉由絲網印刷法塗佈於前面板12與背面板13之 整個面上，於大氣中' 15〇艽下進行乾燥。藉由光微影法 去除塗佈膜之多餘部位而將電極配線圖案化，其後於大氣 中以580°C煅燒1〇分鐘而形成顯示電極2〇與定址電極21。 其次，分別塗佈介電質層23、24，並於大氣中、56〇<t 下煅燒30分鐘。將以如此方式製作之前面板以與背面板" 對象配置，iU字外緣部玻璃冑封而製作具有所示之 構造之電襞顯示面板。 對於使用本發明之18電極用導電性糊所形成之電極配線 (顯示電極20與定址電極21)，於顯示電極2〇與介電質層23 之界面部 '定址電極21與介電質層24之界面部亦未見產生 空隙’可以外觀上良好之狀態製作電梁顯示面板。 繼而，進行製作之電漿顯示面板之點亮實驗。顯示電極 20及定址電極21之比電阻未增加。又，無需降低对電愿性 即可點亮面板。進而’亦未產生如銀厚膜之電極配線之電 子遷移現象，.此外亦未見特別產生障礙之方面。由以上情 163196.doc -36 - 201249771 況確認’本發明之鋁電極用導電性糊可用作電漿顯示面板 之電極配線。又，由於可代替高價之銀厚膜之電極配線， 故而亦可對降低成本做出較大貢獻。 [實施例7] 於本實施例中’對作為本發明之電子零件而應用於多層 配線基板之電極之例進行說明。圖丨2係表示ltcc(l〇w Temperature Co-fired Ceramics’低溫共燒陶究）之多層配 線基板（5層）於煅燒前之構造例之剖面示意圖。如圖丨之所 示’多層配線基板3 0係立體地形成配線（配線用導電性糊 3 1)之配線基板。以下’參照圖丨2進行說明。 多層配線基板之製造通常以如下順序進行。首先，準備 含有玻璃粉末、陶瓷粉末及黏合劑之生胚片材32，於所需 位置上開貫通孔33。對開有貫通孔33之生胚片材32，將配 線用導電性糊31以印刷法塗佈於所需之配線圖案上，同時 亦填充貫通孔33。視需要亦可將配線用導電性糊3丨藉由印 刷法塗佈於生胚片材32之背面。塗佈於生胚片材32之背面 之情形時，係將塗佈於表面之配線用導電性糊3丨乾燥後再 塗佈背面。 藉由使形成有特定之配線圖案之複數個生胚片材32積 層，並一體地煅燒而製造LTCC之多層配線基板。再者’ 作為煅燒條件，一般為大氣中、9〇〇t左右之溫度◊又， 作為配線用導電性糊，考慮到良好之電性與製造中之耐氧 化性’通常使用銀之導電性糊。 亦進行有對電子遷移現象之對策有利並且使用低價之鋼 163196.doc -37- 201249771 之導電性糊之研究。然而，由於目的在於防止銅粒子氧化 而於氮氣環境中烺燒’故而無法順利地將導電性糊3 i及生 胚片材32中之黏合劑鍛燒去除（脫黏合劑），難以獲得緻密 之多層配線基板。 又，使用銅之先前之導電性糊存在如下問題：於煅燒_ 生胚片材32與導電性糊31接觸之部分，玻璃相易軟化、流 動而使銅粒子氧化，導致電極配線之比電阻增大。進而， 存在與玻璃相之化學反應而導致該界面部產生空隙之情 況。 製作本發明之多層配線基板。作為配線用導電性糊3丄， 使用實施例6中研究之鋁電極用導電性糊，以與上述相同 之順序形成如圖12所示之多層配線之積層體，並於大氣 中、900°C下煅燒30分鐘。 測定所製作之多層配線基板中之電極配線之比電阻，結 果獲得正如設計之值。其次，對所製作之多層配線基板進 行剖面觀察。其結果為，所製作之多層配線基板獲得充分 緻密地煅燒。因此，可認為比電阻亦為良好之正如設計之 值。認為其廣、因在於：於彳降過財大致完全地完成脫黏 合劑。又，確認並未產生由玻璃相與電極配線之化學反應 引起之界面附近之空隙。由以上情況確認，本發明之鋁電 極用導電性糊可用作多層配線基板之電極配線。又，由於 可代替尚價之銀厚膜之電極配線，故而亦可對降低成本做 出較大貢獻。 【圖式簡單說明】 163196.doc •38· 201249771 圖1係玻璃組合物之藉由差熱分析（DTA)所獲得之代表性 DTA曲線。 圖2係表示代表性太陽電池單元之光接枚面之一例的平 面示意圖。 圖3係表示代表性太陽電池單元之背面之一例的平面示 意圖。 圖4A係圖2中之A-A'線之剖面示意圖。 圖4B係圖2中之A-A’線之背面附近之放大剖面示意圖。 圖5係代表性太陽電池單元之背面附近之剖面SEM觀察 照片。 圖6係表示玻璃組合物之軟化點與矽基板中之鋁濃度之 關係的圖表。 圖7係表示玻璃組合物之軟化點與矽基板中之氧濃度之 關係的圖表。 圖8係表示玻璃構造中之ΙΑ與ΙΑ之狀態的示意圖。 圖9係表示太陽電池單元之轉換效率與背面鋁電極所含 有之玻璃組合物之含量之間之關係的圖表。 圖10係表示鋁合金電極之比電阻與該電極所含有之玻璃 組合物之含量之間之關係的圖表。 圖11係表示代表性電漿顯示面板之一例的剖面示意圖。 圖 12係表示 LTCC(Low Temperature c0-fired Ceramics， 低溫共燒陶兗）之多層配線基板（5層）之構造例的剖面示意 圖。 、 【主要元件符號說明】 163196.doc -39- P型半導體基板 η型半導體層 抗反射層 光接收面電極 背面電極 輸出電極 BSF層 合金層 太陽電池單元 電漿顯示面板 前面板 背面板 隔壁 密封材料 單元 紅色螢光體 綠色螢光體 藍色螢光體 顯示電極 定址電極 紫外線 介電質層 介電質層 保護層 -40· 201249771 30 多層配線基板 3 1 配線用導電性糊 32 生胚片材 33 貫通孔 163196.docOne or more of Bi and Zn. By including the above-mentioned ones of Te, 讣', and a', the weatherability of the glass can be improved, and the operability of the glass particles until the conductive paste for the electrode is produced can be improved. The solar cell unit has a comprehensive evaluation of the glass composition range of "〇" or higher. In terms of oxides, the AOs is 4〇~8〇% by weight. 2〇5 is 1〇~25% by weight, and B2〇3 is 5~15 weight. /. Te〇2 is 0 to 25% by weight, and Sb2〇3 is 〇~20 by weight. /〇, Bi203 is 〇~2〇% by weight, and Zn〇 is 〇~2〇weight〇/〇, and the amount of P2〇5 is higher than B2〇3, and the total of Pah, 82〇3 and 1>〇2 The amount is 20 to 50% by weight. When the characteristics of the glass are examined, the density is 2.81 to 3.25 §/〇1113, and the softening point is 42 Å. 〇The following, and 5〇〇<»(:The VPB-0-based low-melting glass with good fluidity is effective. Especially the glass composition range of the comprehensive evaluation of "◎" is converted into the following oxides, V2 〇5 is 60 to 80% by weight, and p2〇5 is 1 〇 to 20% by weight. /. 'b2〇3 is 5 to 10% by weight, Te02 is 〇~15% by weight, and Sb203 is 〇~1〇 by weight. , Bi2〇3 is 0~10% by weight 'and ZnO is 0~10 weight. /〇, and p2〇5, 163196.doc •30· 201249771 B2〇3 and Te02 are 20~40% by weight. The glass composition for the electrode of the composition range can promote the diffusion of the aluminum component to the Si Xi substrate, and on the other hand, can suppress the diffusion of oxygen. This is not limited to the solar cell unit, and can be effectively applied to all the substrates used. The electronic component is also particularly effective for the aluminum electrode, but can be applied to other than the aluminum electrode. [Example 4] In the present embodiment, the ν·ρ·Β_〇 low melting point in the aluminum electrode was studied in detail. The effect of the glass content on the conversion efficiency of the solar cell unit. _ The glass system uses Tables 3 and 4 GA_〇5 in Example 3 is shown. 〇8_〇5 is in the range of 0 to 5 parts by weight, 1.5, 2, 0, 2.5, 3.0, and the glass content is relative to 1 part by weight of the aluminum particles. (0, 0.2, 0.4, 〇 > 7, 1 > () 3.5, 4.0, and 5.0 parts by weight) The glass content was changed in the same manner as in Example 3 to prepare 12 kinds of conductive pastes for aluminum electrodes. The conductive paste was used for the back electrode, and the solar cell unit shown in Fig. 2, Fig. 3, Fig. 4, and Fig. 4B was produced in the same manner as in the third embodiment, and the right cell was measured. The conversion efficiency is::=2. The relationship between solar energy is revealed in Fig. 9: Second, the aluminum electrode of the right side of the glass composition is not glass, and the conversion efficiency of the solar cell is significantly reduced, but If only 0.2 parts by weight of GA-05 glass is contained, the conversion efficiency will increase instantaneously. GA-05 glass has a conversion efficiency of 〇2~〇7番县々, ★林米高...very little conversion efficiency-good (4) Efficiency = 163196.doc 201249771 More than 2 parts by weight 'the conversion efficiency is significantly reduced, and 2.5 parts by weight or less is low. In the case of such a conversion efficiency, as the glass content in the aluminum electrode is lowered, it is considered that the amount of diffusion of oxygen on the ruthenium substrate is increased, that is, oxidation of the ruthenium substrate is performed. The content of the VPB-0-based low-melting glass in the electrode used for the back electrode is preferably in the range of 〇2 to 2 weight damage, and particularly effective in the range of 〇2 to 〇7 parts by weight. This is not limited to the solar cell. The unit, of course, can also be effectively applied to all electronic components of the substrate. Further, although it is particularly effective for an aluminum electrode, it can of course be applied to an aluminum electrode. [Example 5] In the present example, the effect of the content of the v_p_B_〇-based low-melting glass in the aluminum alloy electrode on the specific resistance of the electrode was investigated. As the aluminum alloy, an Al-1 〇 weight is used. / 〇 Silver particles. The aluminum alloy particles of 3 μη or less are produced by being produced by an atomization method and classified. This glass was used as ga 〇9 in Example 3 shown in Tables 3 and 4. The glass content of GA-09 was studied in the range of 0 to 25 parts by weight based on 1 part by weight of the aluminum alloy particles (〇, 〇2, 2 〇, 5 〇, 〇, 15.0, 20.0, and 25.0 parts by weight). ). Eight kinds of aluminum alloy electrode conductive pastes were produced by changing the glass content in the same manner as in Example 3, wherein the 'adhesive resin was ethyl cellulose instead of nitrocellulose. The solvent is butyl carbitol acetate. The produced aluminum alloy electrode conductive paste was applied onto a single crystal germanium substrate by a screen printing method and dried at 15 ° C for 10 minutes. Thereafter, it is placed in an electric furnace and heated to 50 (rc) at a temperature increase rate of urc/min in atmosphere I63196.doc •32-201249771. After ι〇min, the furnace is cooled. The film thickness of the alloy electrode is about 2G μιηβ. The specific resistance of the alloy electrode formed on the Shixi substrate was determined by the four-probe method. The relationship between the specific resistance of the aluminum alloy electrode and the content of the glass group contained in the electrode is shown in Fig. 10. As shown in the figure, if the glass is not included in the lg alloy electrode, the specific resistance is remarkably improved. However, if only 0.2 part by weight of the GA-09 glass is contained, the specific resistance is instantaneously decreased. The GA_G5_ is 〇2 to 15 parts by weight. The range 'achieves the specific resistance of 10-5 Qcm. When the content is 2 〇 or more, the specific resistance of the aluminum alloy electrode becomes larger again. It is known that the aluminum alloy electrode is used only for wiring and is applied to In the case of using an electronic component of the substrate, the content of the low-melting glass in the electrode is preferably in the range of 0.2 to 15 parts by weight. In the present embodiment, although the ν·ρ_Β_〇 in the alloy electrode is studied Low melting glass, but of course it can also be used in aluminum Electrode and other electrodes. [Embodiment 6] In the present embodiment, an example of an electrode for a plasma display panel (PDp) will be described. Fig. 11 is a schematic cross-sectional view showing an example of a plasma display panel. The description will be made with reference to Fig. 11. First, a general plasma display panel will be described. In the plasma display panel 11, the front panel 12 and the back panel 13 are arranged to face each other with a gap of 100 to 150 μm, and each substrate (front panel) The gap between the 12 and the back panel π) is maintained by the partition wall 14. The peripheral portion of the front panel 12 and the back panel 13 is hermetically sealed by the sealing material 15, and a rare gas is filled inside the panel. Display electrodes are formed on the front panel 12. 2〇, a dielectric layer 23 is formed on the display electrode 2〇, and a protective layer 25 for protecting the display electrode 20 and the like from being affected by the discharge is formed on the dielectric layer 23 (for example, The vapor deposited film of MgO is further formed with an address electrode 21 formed on the back surface plate 13, and a dielectric layer 24' is formed on the address electrode 21, and a partition wall 14 for constituting the unit 16 is provided on the dielectric layer 24. The partition wall 14 The system will contain at least glass The structure in which the material of the composition and the filler is sintered at 500 to 600 ° C is usually a strip-shaped or box-shaped structure. Further, a back plate is formed in a manner orthogonal to the display electrode 20 of the front panel 12 . The address electrode 21 of 13. The small space (unit 16) separated by the partition wall 14 is filled with a phosphor. The fluorescent system in the unit 16 is filled in the unit by using a paste for the phosphor "at 450 to 500 C It is formed by calcination, and is composed of a unit filled with the red phosphor 17, a unit filled with the green phosphor 18, and a unit of three colors filled by the unit of the blue mortar 19! Pixels. Each pixel emits light of various colors in accordance with a signal from the display electrode 2A and the address electrode 21. The sealing material 15 is applied to any of the peripheral portions of the front panel or the back panel 13 in advance by a dispenser method or a printing method. The applied sealing material Η is also pre-prepared with the firing of the phosphors 17 to 19 because the sealing material is pre-fired to significantly reduce the bubbles in the glass sealing portion, thereby obtaining reliability. High (ie, high air tightness) glass seal. The front panel 12 and the back panel 13 are inevitably 44, and the panel 12 and the back panel 13 are accurately positioned and aligned with the front panel, and heated to 420 to 500. (: At this time, one side of the heating is discharged into the unit. The gas of P is filled with a rare gas instead, and the dry plasma display panel as an electronic part is completed. Further, the seal 163196.doc -34· 201249771 In the case of pre-baking and glass sealing, the sealing material 15 may be in direct contact with the display electrode 20 or the address electrode 21, but it is important that the electrode wiring material and the sealing material do not chemically react. The unit 16 is lit (illuminated), and a voltage is applied between the display electrode 20 and the address electrode 21 of the unit to be lit, and is placed in the unit 16 to perform an address discharge, and the rare gas is excited into a plasma state to make the unit. The wall charges are accumulated in the inner wall. Secondly, by applying a constant voltage to the pair of display electrodes, only the display discharge is caused in the cells in which the wall charges are accumulated to generate the ultraviolet rays 22. Then, the ultraviolet rays 22 are used to cause the phosphors 17 to 19 to emit light. Display image information. Here, as the display electrode 20 and the address electrode 21, in consideration of good electrical properties and oxidation resistance during manufacturing, the former - straight silver thickness is used. Although the formation of the display electrode 20 and the address electrode 21 can be performed by a sputtering method, the printing method is advantageous in order to reduce the manufacturing cost. Further, the dielectric layers 23 and 24 are usually formed by a printing method. Further, the display electrode 20, the address electrode 21, and the dielectric layers 23 and 24 formed by the printing method are generally fired in an oxidizing atmosphere at a temperature ranging from 550 to 620 ° C. As described above, the silver thick film is There is a problem that silver is liable to cause electron migration and phenomenon in the electrode wiring, and there is also a problem of high material cost. In order to solve such problems, it is preferable to change the electrode wiring from the silver thick film to an aluminum thick film or an aluminum alloy thick film. Electrode wiring. However, in order to change the electrode wiring of the aluminum thick film or the aluminum alloy thick film, it is necessary to satisfy the lower specific resistance of the electrode wiring, the chemical reaction between the electrode wiring and the dielectric layer, and the electrode wiring formed. Conditions such as voids (air bubbles, etc.) are generated in the vicinity, and the withstand voltage is lowered. 163196.doc 35-201249771 As a metal particle contained in the conductive paste for the electrode, it is prepared to be implemented. The alloy particles used in 5 (Α1·1〇 weight 0/〇Ag) e, the VPB-0-based low-melting glass ga_〇9 glass particles used in Example 5, the above aluminum alloy particles were set to 1 In the case of 〇〇 by weight, the conductive paste is prepared by adding and kneading the binder resin and the solvent to the powder mixed in this manner. In this case, the binder resin is ethylcellulose. The solvent is used (X-rosinol). The electro-destructive display panel of the present invention is produced. First, the conductive paste is applied to the entire surface of the front panel 12 and the back panel 13 by screen printing. The film was dried in the atmosphere at 15 Torr. The electrode wiring was patterned by removing the excess portion of the coating film by photolithography, and then calcined at 580 ° C for 1 minute in the atmosphere to form a display electrode. 2〇 and address electrode 21. Next, the dielectric layers 23 and 24 were applied separately, and calcined in the atmosphere at 56 Torr < t for 30 minutes. The front panel will be fabricated in such a manner as to be fabricated with the back panel" object configuration, iU-shaped outer edge glass, to produce an electro-optical display panel having the configuration shown. The electrode wiring (display electrode 20 and address electrode 21) formed using the conductive paste for 18 electrodes of the present invention addresses the electrode 21 and the dielectric layer 24 at the interface portion between the display electrode 2A and the dielectric layer 23. In the interface portion, no gap is formed, and the electric beam display panel can be produced in a state of good appearance. Then, a lighting experiment of the plasma display panel produced was carried out. The specific resistance of the display electrode 20 and the address electrode 21 is not increased. Moreover, the panel can be illuminated without reducing the desire for electricity. Further, the electron migration phenomenon of the electrode wiring such as the silver thick film was not produced, and no particular obstacle was observed. From the above, it is confirmed that the conductive paste for an aluminum electrode of the present invention can be used as an electrode wiring of a plasma display panel. Moreover, since the electrode wiring of the expensive silver thick film can be replaced, it is possible to make a large contribution to cost reduction. [Embodiment 7] In the present embodiment, an example of an electrode applied to a multilayer wiring board as an electronic component of the present invention will be described. Fig. 2 is a schematic cross-sectional view showing a structural example of a multilayer wiring substrate (5 layers) of ltcc (l〇w Temperature Co-fired Ceramics') before calcination. As shown in the figure, the multilayer wiring board 30 is a wiring board in which wiring (conductive paste 3 1 for wiring) is three-dimensionally formed. The following description will be made with reference to Fig. 2 . The manufacture of the multilayer wiring board is usually performed in the following order. First, a green sheet 32 containing a glass powder, a ceramic powder, and a binder is prepared, and a through hole 33 is opened at a desired position. The green sheet 32 having the through holes 33 is opened, and the wiring paste 31 for the wiring is applied to the desired wiring pattern by a printing method, and the through holes 33 are also filled. The conductive paste 3 for wiring may be applied to the back surface of the green sheet 32 by a printing method as needed. When it is applied to the back surface of the green sheet 32, the wiring applied to the surface is dried with a conductive paste 3, and then the back surface is applied. A multilayer wiring board of LTCC is produced by laminating a plurality of green sheets 32 on which a specific wiring pattern is formed and integrally calcining. In addition, as a calcination condition, it is generally a temperature of about 9 〇〇t in the atmosphere, and as a conductive paste for wiring, in consideration of good electrical properties and oxidation resistance during production, a conductive paste of silver is usually used. . Research on conductive pastes that are beneficial to the phenomenon of electron transfer and use low-cost steel 163196.doc -37- 201249771. However, since the purpose is to prevent the copper particles from being oxidized and to be calcined in a nitrogen atmosphere, it is difficult to obtain a dense one by forcibly removing the binder in the conductive paste 3 i and the green sheet 32 (debonding agent). Multilayer wiring substrate. Further, the prior conductive paste using copper has a problem that the glass phase is easily softened and flows to partially oxidize the copper particles in the portion where the calcined raw green sheet 32 is in contact with the conductive paste 31, resulting in an increase in the specific resistance of the electrode wiring. Big. Further, there is a chemical reaction with the glass phase to cause voids in the interface portion. The multilayer wiring board of the present invention is produced. As a conductive paste for wiring, the laminate of the multilayer wiring shown in FIG. 12 was formed in the same manner as described above using the conductive paste for aluminum electrodes studied in Example 6, and was exposed to the atmosphere at 900 ° C. Calcined for 30 minutes. The specific resistance of the electrode wiring in the produced multilayer wiring substrate was measured, and the result was obtained as designed. Next, the multilayer wiring board produced was subjected to cross-sectional observation. As a result, the multilayer wiring board produced was sufficiently densely fired. Therefore, the specific resistance can be considered to be good as the design value. It is considered to be because of the fact that the debonding agent is almost completely completed after the annihilation. Further, it was confirmed that voids in the vicinity of the interface caused by the chemical reaction between the glass phase and the electrode wiring did not occur. From the above, it was confirmed that the conductive paste for aluminum electrodes of the present invention can be used as the electrode wiring of the multilayer wiring board. Moreover, since it can replace the electrode wiring of the expensive silver thick film, it can also contribute greatly to cost reduction. BRIEF DESCRIPTION OF THE DRAWINGS 163196.doc •38· 201249771 Figure 1 is a representative DTA curve obtained by differential thermal analysis (DTA) of a glass composition. Fig. 2 is a plan view showing an example of a light-joining surface of a representative solar battery unit. Fig. 3 is a plan view showing an example of the back surface of a representative solar battery unit. 4A is a schematic cross-sectional view taken along line AA' of FIG. 2. Fig. 4B is an enlarged schematic cross-sectional view showing the vicinity of the back side of the line A-A' in Fig. 2. Fig. 5 is a cross-sectional SEM observation photograph of the vicinity of the back surface of a representative solar cell unit. Fig. 6 is a graph showing the relationship between the softening point of the glass composition and the aluminum concentration in the ruthenium substrate. Fig. 7 is a graph showing the relationship between the softening point of the glass composition and the oxygen concentration in the ruthenium substrate. Fig. 8 is a schematic view showing the state of ruthenium and iridium in a glass structure. Fig. 9 is a graph showing the relationship between the conversion efficiency of the solar cell unit and the content of the glass composition contained in the back surface aluminum electrode. Fig. 10 is a graph showing the relationship between the specific resistance of the aluminum alloy electrode and the content of the glass composition contained in the electrode. Fig. 11 is a schematic cross-sectional view showing an example of a representative plasma display panel. Fig. 12 is a schematic cross-sectional view showing a structural example of a multilayer wiring board (5 layers) of LTCC (Low Temperature C0-fired Ceramics). [Major component symbol description] 163196.doc -39- P-type semiconductor substrate n-type semiconductor layer anti-reflection layer light-receiving surface electrode back electrode output electrode BSF layer alloy layer solar cell unit plasma display panel front panel back panel partition sealing material Unit red phosphor green phosphor blue phosphor display electrode address electrode UV dielectric layer dielectric layer protective layer -40·201249771 30 Multilayer wiring board 3 1 Conductive paste for wiring 32 Raw sheet 33 Through hole 163196.doc

Claims (1)

201249771 七、申請專利範圍·· 二=件，其特徵在於：其係於妙基板上形成具有 t子與破璃相之電極者，並且該破璃相為含有釩、 磷及硼之氧化物玻璃。 2. 如凊求項1之雷+愛彼 物換算“中上述玻璃相以如下之氧化 物換算’含有v2〇5 60〜80重量％、P2〇5 1〇〜25重量％、 B2〇35 15重量％，並且P2〇5量高於b2〇3量。 3. 如凊求項1之雷+愛彼 零件，其中上述玻璃相以如下之氧化 、，V2〇5為70〜8〇重量❶/。、P2〇5為10〜2〇重量0/〇、 B2O3為5〜1〇重量％。 I Hi項2之電子零件，其中上述玻璃相以如下之氧化 、V2〇5為70〜80重量。/。、P2〇5為10〜2〇重量％、 B2O3為5〜1〇重量％。 5.如凊求項1之電子愛此 電子零件，其中上述玻璃相進而含有碲、 録、叙及鋅中之1種以上。 6·如請求項5之電子 物換篡，v 中上述玻璃相以如下之氧化 、 2〇5為40〜80重量％、P2〇5為10〜25重量％、 =為5〜！ 5重量％、⑽為Q〜25重量％、％处為㈣重 二2〇3為〇〜2〇重量％、及Zn〇為〇〜2〇重”。，並且 P2〇5里鬲於B2〇量，B p 〇 璃相之2〇〜50%β 5办及⑽之合計量為玻 π求項5之電子零件，其中上述玻璃相以 物拖笪，λ/ ^ <乳化 、 2 5為60〜80重量％、P2〇5為10〜20重量％、 B2〇3為5〜1〇重量％、τ n炎 重量/〇、 Te〇2為0〜15重量％、Sb2〇3為〇〜10重 163196.doc 201249771 8. Γ:: Γ〇3為0〜10重量％ '及Zn〇為0〜10重量％，並且 2 5 2〇3及Te〇2之合計量為玻璃相之20〜40重量0/〇。 如請求項6之電子零件，其中上述玻璃相以如下之°氧化 物換算，V2〇5為60〜80重量％、Ρ2〇5為10〜20重量％、 為5〜10重量。心⑽為㈡5重量％、％〇淋1:重 量％、出2〇3為〇〜10重量％、及Zn〇為〇〜1〇重量％，並且 9. P2〇5 B2〇3及Te〇2之合計量為玻璃相之2〇〜的重量％。 如請求項1至8中任一項之電子零件，其中相對於上述金 屬粒子100重量份’上述玻璃相之含有比例為0.2〜2重量 份。 置 W如請求項⑴中任一項之電子零件，其中上述金屬粒子 為紹或銘合金，且上述石夕基板具有p型半導體，該P型半 導體上形成有上述電極。 11.如請求項1至8中任一項之電子零件，其係上述石夕基板具 有pn接面之太陽電池單元。 A如請求項⑴令任一項之電子零件，其中上述紹電極用 玻璃組合物之鉛之含量為1000 ppm以下。 η•-種㈣極用導電性糊’其特徵在於：其係將包含紹或 紹合金之金屬粒子與玻璃粒子分散於溶解有黏合劑樹脂 之溶劑中而成者，並且該玻璃粒子為含有訊、鱗及棚之 氧化物玻璃。 14.如請求項13之㈣㈣導電性糊，其中上述玻璃粒子以 如下之氧化物換算，含有V2〇5 6〇〜8〇重量。/。、Ρ2〇5 1〇〜25 重量％、8203 5〜15重量％，並且1>2〇5量高於1〇3量。 163196.doc -2- 201249771 15.如請求項13之銘電極用導電性糊，其中上述玻璃粒子以 如下之氧化物換算，含有AO5 7〇〜8〇重量％、ρ2〇5 ι〇〜2〇 重量/〇 B2〇3 5〜1〇重量％，並且p2〇5量高於量。 f长項13之銘電極用導電性糊，其中上述玻璃粒子進 而含有碲、銻、鉍及鋅令之丨種以上。 17.如睛求項16之鋁電極用導電性糊，其中上述玻璃粒子以 如下之氧化物換算，V2〇5為4〇〜80重量％、1>2〇5為1〇~25 重量％、β2〇3為5〜15重量％、Te〇2為〇〜25重量％、Sb2〇3 為0 20重量％、Bi2〇3為〇〜2〇重量％、及Zn〇為〇〜2〇重量 〆〇，並且P2〇5量高於B2〇3量，並且ρ2〇5、ΙΑ及之 合計量為玻璃相之20〜50重量〇/0。 18·如請求項16之鋁電極用導電性糊，其中上述玻璃粒子以 如下之氧化物換算，％〇5為6〇〜8〇重量％、匕…為⑺〜⑼ 重里％、B2〇3為5〜10重量％、丁6〇2為〇〜15重量％、 為〇〜10重量％、Bi203為〇〜1〇重量％、及Zn〇為〇〜1〇重量 /〇，並且P2〇5、B2〇3及Te〇2之合計量為20〜40重量％。 19. 如請求項13至18中任一項之鋁電極用導電性糊，其中相 對於上述金屬粒子1〇〇重量份，上述玻璃粒子之含有比 例為0.2〜15重量份。 20. 如請求項13至18中任一項之鋁電極用導電性糊，其中相 對於上述金屬粒子1〇〇重量份，上述玻璃粒子之含有比 例為0.2〜2重量份。 21.如請求項13至18中任一項之鋁電極用導電性糊，其中上 述紹電極用玻璃組合物之鉛之含量為1〇〇〇 ppm“下。 163196.doc 201249771 22. —種鋁電極用玻璃组合物，其特徵在於：其係含有鋁或 紹合金粉末之鋁電極所含有之玻璃組合物，並且該玻璃 組合物為含有釩、磷及硼，進而含有碲、銻、鉍及鋅中 之1種以上之氧化物玻璃，軟化點為420°C以下，於 5〇〇°C下流動。 23. 如請求項22之鋁電極用玻璃組合物，其以氧化物換算， V205為40〜80重量％、P2〇5為1〇〜25重量。/0、b2〇3為5〜15 重量％、Te02為0〜25重量％、Sb203為0〜20重量％、：Bi2〇3 為0〜20重量％、及ZnO為〇〜20重量。/。，並且p2〇5量高於 B2〇3量’且P2〇5、B2〇3及Te02之合計量為20〜50重量％。 24·如請求項22之銘電極用玻璃組合物，其以如下之氧化物 換算’ V205為60〜80重量％、p2〇5為1〇〜2〇重量％、b2〇3 為5〜10重量％、Te02為〇〜15重量。/。、81?2〇3為〇〜1〇重量 %、Bi203為0〜10重量％、及ZnO為〇〜1〇重量％，並且 P2O5、B2〇3及Te02之合計量為20〜40重量0/〇。 25.如請求項22至24中任一項之鋁電極用玻璃組合物，其中 上述銘電極用玻璃組合物之鉛之含量為1〇〇〇 ppm以下。 163196.doc201249771 VII. Patent application scope · · Two parts, which are characterized in that they are formed on the substrate with the electrode of t and glass, and the glass phase is an oxide glass containing vanadium, phosphorus and boron. . 2. For the thunder of the item 1 + the conversion of the object of love, "the above glass phase is converted to the following oxides" containing v2〇5 60~80% by weight, P2〇5 1〇~25% by weight, B2〇35 15 % by weight, and the amount of P2〇5 is higher than the amount of b2〇3. 3. For the item 1 of the mine + Audemars Piguet part, wherein the above glass phase is oxidized as follows, and V2〇5 is 70~8〇 weight❶/ P2〇5 is 10~2〇weight 0/〇, B2O3 is 5~1〇% by weight. The electronic component of I Hi 2, wherein the glass phase is oxidized as follows, and V2〇5 is 70-80 weight. /, P2〇5 is 10~2〇% by weight, and B2O3 is 5~1〇% by weight. 5. If the electronic item of the item 1 is loved, the above-mentioned glass phase further contains yttrium, yttrium, yttrium and zinc. In the case of the electronic material of claim 5, the glass phase in v is oxidized as follows, 2〇5 is 40 to 80% by weight, and P2〇5 is 10 to 25% by weight, = 5 to! 5 wt%, (10) is Q 25 wt%, % is (4) wt 2 2 〇 3 is 〇 〇 2 〇 wt%, and Zn 〇 is 〇 2 〇 ”. And P2〇5 is in the B2 quantity, Bp glass phase 2〇~50%β 5 and (10) is the electronic part of the glass π item 5, wherein the glass phase is dragged by the object, λ / ^ < emulsification, 25 is 60 to 80% by weight, P2 〇 5 is 10 to 20% by weight, B2 〇 3 is 5 to 1% by weight, τ n inflammatory weight / 〇, Te 〇 2 is 0 〜 15% by weight, Sb2〇3 is 〇~10 weight 163196.doc 201249771 8. Γ:: Γ〇3 is 0~10% by weight 'and Zn〇 is 0~10% by weight, and 2 5 2〇3 and Te〇 The total amount of 2 is 20~40 weight 0/〇 of the glass phase. The electronic component according to claim 6, wherein the glass phase is 60 to 80% by weight, V2〇5 is 60 to 80% by weight, and Ρ2〇5 is 10 to 20% by weight, and is 5 to 10% by weight. The heart (10) is (2) 5% by weight, % 〇 1 1: wt%, 2 〇 3 is 〇 10 10% by weight, and Zn 〇 is 〇 〜 1 〇 重量 %, and 9. P2 〇 5 B2 〇 3 and Te 〇 2 The total amount is 2% by weight of the glass phase. The electronic component according to any one of claims 1 to 8, wherein the content of the glass phase is from 0.2 to 2 parts by weight based on 100 parts by weight of the metal particles. The electronic component according to any one of the preceding claims, wherein the metal particle is a Schneider alloy, and the austenitic substrate has a p-type semiconductor, and the electrode is formed on the P-type semiconductor. 11. The electronic component of any one of claims 1 to 8, which is a solar cell unit having a pn junction. The electronic component according to any one of the preceding claims, wherein the glass composition of the above-mentioned electrode has a lead content of 1000 ppm or less. η•- (4) Electroconductive paste for extreme use is characterized in that it is obtained by dispersing metal particles and glass particles of Shao or Shao alloy in a solvent in which a binder resin is dissolved, and the glass particles are contained , scales and shed oxide glass. 14. The conductive paste according to (4) (IV) of claim 13, wherein the glass particles have a weight of V2 〇 5 6 〇 8 〇 in terms of an oxide as follows. /. Ρ2〇5 1〇~25 wt%, 8203 5~15 wt%, and 1 > 2〇5 amount is higher than 1〇3. 163196.doc -2- 201249771 15. The conductive paste for the electrode of claim 13, wherein the glass particles contain AO5 7 〇 8 8% by weight, ρ 2 〇 5 ι 〇 〇 2 换算 in terms of the following oxides. Weight / 〇 B2 〇 3 5 〜 1 〇 wt%, and p2 〇 5 amount is higher than the amount. f. The conductive paste for the electrode of the long term 13 wherein the glass particles further contain lanthanum, cerium, lanthanum and zinc. 17. The conductive paste for an aluminum electrode according to Item 16, wherein the glass particles are in an amount of from 4 to 80% by weight, and from 1 to 25% by weight, in an amount of from 4 to 80% by weight, in the range of from 4 to 20% by weight. Β2〇3 is 5 to 15% by weight, Te〇2 is 〇~25% by weight, Sb2〇3 is 0% by weight, Bi2〇3 is 〇~2〇% by weight, and Zn〇 is 〇~2〇 weight 〆 〇, and the amount of P2〇5 is higher than the amount of B2〇3, and the total amount of ρ2〇5, ΙΑ and is 20~50 weight 〇/0 of the glass phase. 18. The conductive paste for aluminum electrodes according to claim 16, wherein the glass particles are converted to an oxide of the following, % 〇 5 is 6 〇 to 8 〇 wt%, 匕 ... is (7) 〜 (9) 重量 %, B2 〇 3 is 5 to 10% by weight, butyl 6〇2 is 〇~15% by weight, 〇~10% by weight, Bi203 is 〇~1〇% by weight, and Zn〇 is 〇~1〇weight/〇, and P2〇5, The total amount of B2〇3 and Te〇2 is 20 to 40% by weight. The conductive paste for aluminum electrodes according to any one of claims 13 to 18, wherein the glass particles are contained in an amount of 0.2 to 15 parts by weight based on 1 part by weight of the metal particles. The conductive paste for aluminum electrodes according to any one of claims 13 to 18, wherein the glass particles are contained in an amount of 0.2 to 2 parts by weight based on 1 part by weight of the metal particles. The conductive paste for aluminum electrodes according to any one of claims 13 to 18, wherein the glass composition of the above-mentioned glass electrode has a lead content of 1 〇〇〇 ppm "下下. 163196.doc 201249771 22. A glass composition for an electrode, characterized in that it is a glass composition contained in an aluminum electrode containing aluminum or a sinter alloy powder, and the glass composition contains vanadium, phosphorus and boron, and further contains lanthanum, cerium, lanthanum and zinc. One or more of the oxide glasses have a softening point of 420 ° C or lower and flow at 5 ° C. 23. The glass composition for aluminum electrodes of claim 22, in terms of oxide, V205 is 40 ～80% by weight, P2〇5 is 1〇~25 weight. /0, b2〇3 is 5~15% by weight, Te02 is 0~25% by weight, Sb203 is 0~20% by weight, and Bi2〇3 is 0. 〜20% by weight, and ZnO is 〇20-20%, and the amount of p2〇5 is higher than the amount of B2〇3' and the total amount of P2〇5, B2〇3, and Te02 is 20 to 50% by weight. The glass composition for the electrode of claim 22, which is converted into an oxide of 60 to 80% by weight and p2〇5 is 1 to 2% by weight. B2〇3 is 5 to 10% by weight, Te02 is 〇~15 weight, /, 81?2〇3 is 〇~1〇% by weight, Bi203 is 0~10% by weight, and ZnO is 〇~1〇% by weight. And the total amount of P2O5, B2〇3, and Te02 is 20 to 40% by weight. The glass composition for aluminum electrodes according to any one of claims 22 to 24, wherein the glass composition for the above-mentioned electrode is The lead content is below 1 〇〇〇 ppm. 163196.doc
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