TW201202367A - Solar cell and electroconductive paste used to form electrode thereof - Google Patents

Solar cell and electroconductive paste used to form electrode thereof Download PDF

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TW201202367A
TW201202367A TW100107251A TW100107251A TW201202367A TW 201202367 A TW201202367 A TW 201202367A TW 100107251 A TW100107251 A TW 100107251A TW 100107251 A TW100107251 A TW 100107251A TW 201202367 A TW201202367 A TW 201202367A
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particles
electrode
conductive paste
solar cell
weight
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TWI498398B (en
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Kazuo Muramatsu
Hideo Tanabe
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Namics Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/546—Polycrystalline silicon PV cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

Obtained by this invention is an electroconductive paste used to form electrode in a crystalline silicon solar cell, which can form a solar cell electrode having a lower contact resistance with a crystalline silicon substrate. The electroconductive paste of this invention is used to form the electrode of a crystalline silicon solar cell and comprises silver-containing electroconductive particles, glass frit, special addition particles, organic adhesive and solvent, whereinsaid special addition particles are one or more selected from aluminum silicate particles and silicic acid aluminum particles.

Description

201202367 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種太陽電池之電極形成用導電性糊漿， 尤其係關於將單結晶矽或多結晶矽等結晶系矽用作基板之 結晶系矽太陽電池之表面或背面電極形成用導電性糊漿， 使用該電極形成用導電性糊漿之太陽電池之製造方法及藉 由該製造方法而製造之太陽電池。 【先前技術】 近年來’將使單結晶矽或多結晶矽加工為平板狀之結晶 系石夕用作基板之結晶系矽太陽電池之生產量正大幅增加。 該等太陽電池具有用以將經發電之電力取出之電極。 作為一例，圖1表示結晶系矽太陽電池之剖面模式圖。 結晶系矽太陽電池中，一般而言，於卩型結晶系矽基板4之 光入射側即表面形成!!型擴散層（n型矽層）3。於n型擴散層3 之上形成抗反射膜2。進而，藉由網版印刷法等而使用導 電性糊漿於抗反射膜2上印刷光入射側電極丨（表面電極）之 圖案，並將導電性糊漿乾燥及燒成，藉此形成光入射側電 極1。於該燒成時，藉由將導電性糊漿燒成貫通抗反射膜 2，而光入射側電極丨可以接觸於n型擴散層3之方式而形 成。再者，所謂燒成貫通，係指由導電性糊漿中所包含之 玻璃料等而蝕刻絕緣膜即抗反射膜，使光入射側電極丨與η 型擴散層3導通。由於不使光自ρ型矽基板4之背面側入射 亦可，故而一般而言於大致整個表面形成背面電極5。於ρ 型矽基板4與η型擴散層3之界面形成有ρη接面。太陽光等 153910.doc 201202367 光透過抗反射膜2及η型擴散層3,入射至p型矽基板4，於 該過程中被吸收’產生電子電洞對。該等電子_電洞對藉 由Pn接面之電場而分離，電子向光入射側電極丨，電洞向 背面電極5。電子及電洞經由該等電極，而作為電流被取 出至外部。 先前之太陽電池、尤其結晶系矽太陽電池之電極形成， 使用包含導電性粒子、玻璃料、有機黏合劑、溶劑及其他 添加物之導電性糊漿。作為導電性粒子，主要使用銀粒 子。 作為用以形成太陽電池之電極之導電性組成物（導電性 糊漿）之例，引用文獻1中記載有如下導電性組成物：包括 含有銀粉末與PbO之玻璃粉末及包含有機物之媒劑，用以 形成與貫通氮化矽層而於上述氮化矽層之下形成型半 導體層導通之電極。進而，引用文獻丨中記載有該導電性 組成物之特徵在於：上述銀粉末於上述組成物中之比率為 70質量％以上95質量％以下，上述玻璃粉末相對於上述銀 粉末100質量份包含1質量份以上1〇質量份以下上述玻璃 粉末之驗度為0.6以上0.8以下且玻璃之轉移點為 300〇C 〜450〇C。 引用文獻2中記載有如下導電性組成物：包括銀粉末與 不含有PbO之玻璃粉末及包含有機物之媒劑，用以形成與 貫通氮化梦層於上述氮化矽層之下形成之η型半導體層導 通之電極。進而，引用文獻2中記載有該導電性組成物之 特徵在於：上述銀粉末於上述組成物中之比率為7〇質量％ 153910.doc 201202367 以上95質量。/。以下，上述玻璃粉末相對於上述銀粉末刚 質量份包含i質量份以上10質量份以下，上述玻璃粉末之 驗度為0_16以上0.44以下且玻璃之轉移點為扇c代 引用文獻3中記載有一種太陽電池元件之形成方法，於 呈-導電型之半導體基板之一主面側形成呈其他導電型之 區域，並且於該半導體基板之—主面側形成抗反射膜，於 該抗反射膜上與上述半導體基板之另_主面側㈣包含銀 粉末、有機媒劑、及玻璃料之電極材料。進而，引用文獻 3中記載有該太陽電池元件之形成方法之特徵在於：燒結 於上述抗反射膜上之電極材料含有Ti、Bi、c〇、Zn、^201202367 VI. Description of the Invention: [Technical Field] The present invention relates to a conductive paste for forming an electrode for a solar cell, and more particularly to a crystal system in which a crystalline ruthenium such as a single crystal ruthenium or a polycrystalline ruthenium is used as a substrate. A solar battery for forming a surface of a solar cell or a conductive paste for forming a back electrode, a solar cell using the electrode for forming a conductive paste, and a solar cell produced by the method. [Prior Art] In recent years, the production of solar cells, which is a crystal system in which a single crystal ruthenium or a polycrystalline ruthenium is processed into a flat crystal is used as a substrate, is increasing substantially. The solar cells have electrodes for taking out the generated electricity. As an example, Fig. 1 is a schematic cross-sectional view showing a crystal system solar cell. In the crystal system solar cell, generally, a diffusion layer (n-type germanium layer) 3 is formed on the surface on the light incident side of the germanium-type crystal system substrate 4. An anti-reflection film 2 is formed on the n-type diffusion layer 3. Further, a pattern of a light incident side electrode (surface electrode) is printed on the antireflection film 2 by a screen printing method or the like, and the conductive paste is dried and fired, thereby forming light incidence. Side electrode 1. At the time of the firing, the conductive paste is fired through the antireflection film 2, and the light incident side electrode 丨 can be formed in contact with the n-type diffusion layer 3. In addition, the term "fired through" means that the insulating film, that is, the antireflection film, is etched from the glass frit contained in the conductive paste, and the light incident side electrode 丨 and the n type diffusion layer 3 are electrically connected. Since the light is not incident on the back side of the p-type germanium substrate 4, the back surface electrode 5 is generally formed on substantially the entire surface. A pn junction is formed at the interface between the p-type germanium substrate 4 and the n-type diffusion layer 3. Sunlight, etc. 153910.doc 201202367 Light is transmitted through the anti-reflection film 2 and the n-type diffusion layer 3, and is incident on the p-type germanium substrate 4, and is absorbed in the process to generate an electron hole pair. The electron-holes are separated by the electric field of the Pn junction, and the electrons are incident on the light-emitting side electrode and the holes are directed to the back electrode 5. Electrons and holes are taken out as external currents through the electrodes. In the prior solar cells, particularly the electrodes of the crystalline solar cells, conductive pastes containing conductive particles, glass frits, organic binders, solvents and other additives were used. As the conductive particles, silver particles are mainly used. As an example of a conductive composition (conductive paste) for forming an electrode of a solar cell, the cited document 1 discloses a conductive composition including a glass powder containing silver powder and PbO and a medium containing an organic substance. An electrode for forming a semiconductor layer that is formed to penetrate the tantalum nitride layer and form a semiconductor layer under the tantalum nitride layer. Further, the conductive composition is characterized in that the ratio of the silver powder in the composition is 70% by mass or more and 95% by mass or less, and the glass powder contains 1 part by mass based on 100 parts by mass of the silver powder. The mass of the above-mentioned glass powder is not more than 0.6 parts by mass and not more than 0.6 parts by mass or less and the glass transition point is 300 〇C to 450 〇C. Citation 2 describes an electroconductive composition comprising a silver powder and a glass powder containing no PbO and a medium containing an organic substance for forming an n-type formed by penetrating the nitride layer under the tantalum nitride layer. An electrode in which the semiconductor layer is turned on. Further, the conductive composition is characterized in that the ratio of the silver powder in the above composition is 7 〇 mass% 153910.doc 201202367 or more and 95 mass. /. In the following, the glass powder is contained in an amount of from i part by mass to 10 parts by mass based on the mass of the silver powder, and the degree of verification of the glass powder is from 0 to 16 or more and 0.44 or less, and the transition point of the glass is a fan c. In the method of forming a solar cell element, a region of another conductivity type is formed on one main surface side of the semiconductor substrate of the conductivity type, and an antireflection film is formed on the main surface side of the semiconductor substrate, and the antireflection film is formed on the antireflection film. The other main surface side (four) of the semiconductor substrate contains an electrode material of silver powder, an organic medium, and a glass frit. Further, the method of forming the solar cell element described in the cited document 3 is characterized in that the electrode material sintered on the anti-reflection film contains Ti, Bi, c〇, Zn, ^

Fe、Cr成分中之任一種或複數種。 引用文獻4中記載有用以印刷於具有氮切膜之結晶系 石夕太陽電池之氮化石夕膜t夕·*哩φ、山‘ ^ /勝上之太％電池電極形成用導電性糊 聚。進而，引用文獻4中記載有，該導電性糊聚含有包含 銀之導電性粒子、_料、有機黏合織溶劑，玻璃料包 含氧化辞及氧化侧，氧化辞及氧化狀合計重量相對於玻 璃料全體之重量為9〇重量％以上，氧化辞之含有率相對於 氧化鋅及氧化硼之合計重量為5〇重量％〜8〇重量％。 引用文獻5中記載有如下導電性糊漿，其係含有包含銀 之導電性粒子、玻璃料' 有機黏合劑及溶劑且向結晶系石夕 太陽電池之㈣⑪層之電極形成料電性糊聚，破璃料及/ 或導電性糊漿中所包含之添加物含有自包含Mg、Ca、Sr 及Ba之群組中選擇之至少一個第2族系添加元素，導電性 糊漿中之pb含量為0.1重量％以下。 153910.doc 201202367 又，作為用以於陶竞基板上形成電極之導體糊漿，引用 文獻6中記載有一種導體糊聚，其係使包含銀與鈀之複合 粉末、玻璃粉末及氧化鉍粉末分散於媒劑中之導體糊漿， 且其特徵在於：糊漿固形物成分中含有2〜9重量％之玻璃 粉末，且每1〇〇重量份玻璃粉末中含有4~35重量份卜鋰霞 石（LuO.AhOWSiO2)粉末。又，引用文獻6中記載有卜鋰 霞石之熱膨脹係數較小。進而，引用文獻6中記載有，藉 由導體糊漿包含β-鋰霞石，而與玻璃混合熔融，藉此推測 為燒成後之無機結合劑層之熱應力被緩和，即便導體層之 體積膨脹亦難以被破壞者。亦即，引用文獻6中記載有， 推測對導體糊漿之β-鋰霞石之添加有利於緩和機械性的性 質即熱應力。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2009-23 1826號公報 [專利文獻2]曰本專利特表2009-23 1827號公報 [專利文獻3]日本專利特開2〇〇1_3134〇〇號公報 [專利文獻4]日本專利特開2〇〇9_194121號公報 [專利文獻5]曰本專利特開2009-194141號公報 [專利文獻6]日本專利特開平5_丨5丨8丨8號公報 【發明内容】 [發明所欲解決之問題] 於結晶系矽太陽電池中，對轉換效率等太陽電池特性所 帶來之電極之影響較大，尤其光入射側電極之影響非常 153910.doc 201202367 大。該光入射側電極與π型擴散層之接觸電阻十分低，必 須歐姆電性接觸。又，電極本身之電性電阻亦必須十分 低，因此，電極材料本身之電阻（導體電阻）較低之情況成 為重要。又，為了生產性之提高及長壽命化，而焊接於電 極之互連用之金屬帶之接著強度較高之情況進而重要。 因此，本發明之目的在於獲得於結晶系矽太陽電池中， 可形成與結晶系矽基板之接觸電阻較低之電極之太陽電池 電極形成用導電性糊漿。尤其，本發明之目的在於獲得可 形成與結晶系矽基板之η型擴散層之接觸電阻較低之電極 之太陽電池電極形成用導電性糊漿。又，本發明之目的在 於獲得具有高填充因數及高轉換效率之高性能之結晶系石夕 太陽電池及其製造方法。又，本發明之目的在於獲得焊接 於電極之互連用之金屬帶之接著強度較高的結晶系矽太陽 電池。 [解決問題之技術手段] 本發明之發明者們意外地發現，當於導電性糊漿中添加 β-鐘霞石粒子等之鋁矽酸鹽粒子之情形時，電性特性即結 晶系石夕基板與電極之間的接觸電阻變低。進而，本案發明 者們發現’當於結晶系矽太陽電池之電極形成用導電性糊 聚中添加β-鋰霞石粒子等之鋁矽酸鹽粒子之情形時，可择 得具有lij填充因數及高轉換硃率之高性能之結晶系石夕太陽 電池’從而完成了本案發明。 亦即，本發明係一種導電性糊漿，其係結晶系矽太陽電 池之電極形成用導電性糊漿，含有包含銀之導電性粒子、 153910.doc 201202367 玻璃料、特定之添加粒子、有機黏合劑及溶劑，且特定之 添加粒子係自鋁矽酸鹽粒子及矽酸鋁粒子中選擇之丨種以 上。藉由導電性糊漿包含上述材料，可形成與結晶系矽基 板之接觸電阻較低之電極。 以下表示本發明之導電性糊漿之較佳態樣。本發明中， 可將該等態樣適當組合。 (1) 鋁矽酸鹽粒子包含鋰。例如，如p鋰霞石粒子般，若使 用包含鋰之鋁矽酸鹽粒子，則可確實地形成與結晶系矽基 板之接觸電阻較低之電極。 (2) 紹石夕I鹽粒子為β_鐘霞石粒子。因此，可進而確實地形 成與結晶系矽基板之接觸電阻較低之電極。尤其，可形成 與結晶系矽基板之η型擴散層之接觸電阻較低之電極。因 此’可獲得高性能之結晶系矽太陽電池。 (3) 鋁矽酸鹽粒子之含量相對於導電性粒子1〇〇重量份為 0.1〜5重量份。鋁矽酸鹽粒子之含量相對於導電性粒子1〇〇 重量份為0.1重量份以上，藉此可確實地形成與結晶系石夕 基板之接觸電阻較低之電極。又，鋁矽酸鹽粒子之含量相 對於導電性粒子100重量份為5重量份，藉此可獲得焊接於 電極之互連用之金屬帶之接著強度較高的結晶系矽太陽電 池。 (4) 玻璃料包含PbO。於使用含有鋁矽酸鹽粒子等之特定之 添加粒子、與包含PbO之玻璃料的導電性糊漿之情形時， 可獲得太陽電池性能較高之太陽電池。 (5) PbO之含量相對於玻璃料1〇〇重量％為50〜90重量。於 153910.doc 201202367 使用含有鋁矽酸鹽粒子等之特定之添加粒子、與特定含量 之包含PbO之玻璃料的導電性糊漿之情形時，可獲得較高 之互連用之金屬帶之接著強度，並且可獲得太陽電池性能 較高之太陽電池。 又，本發明係一種太陽電池之製造方法，其包括如下步 驟：將上述導電性掬漿印刷於結晶系矽基板之nS矽層上 或η型石夕層上之抗反射膜上’並進行乾燥及燒成，藉此形 成電極。藉由使用本發明之導電性糊漿形成電極，可獲得 具有高填充因數及高轉換效率之高性能之結晶系矽太陽電 池。 又，本發明係藉由上述之本發明之製造方法而製造之太 陽電池。本發明之太陽電池係具有高填充因數及高轉換效 率之高性能之結晶系矽太陽電池。 [發明之效果] 根據本發明，可獲得於結晶系矽太陽電池中，可形成與 結晶系碎基板之接觸電阻較低之電極之太陽電池電極形成 用導電性《。尤其，根據本發明，可獲得可形成與結晶 系石夕基板之η型擴散層之接觸電阻較低之電極的太陽電池 電極形成用導電性糊m由使用本發明之太陽電池 電極形成用導電性糊㈣成電極，可獲得具有高填充因數 及高轉換效率之高性能之結晶系矽太陽電池…藉由使 用本發明之太陽電池電極形成用導電性糊漿形成電極，可 獲得焊接於f極之互❹之金屬帶之接著強度較高之結晶 系矽太陽電池。 153910.doc 201202367 【實施方式】 本說明書中，「結晶系石夕」包含單結晶及多結晶石夕。 又，名口日日系石夕基板」係、指為了電性元件或電子元件之形 成，而將結晶系矽成形為平板狀等適合於元件形成之形狀 之材料。結晶系石夕之製造方法可使用任一種方法。例如， 於單結晶石夕之情形時可使用直拉法，於多結晶石夕之情形時 可使用鑄造法。又，藉由其他製造方法例如帶提拉式長晶 法（ribbon pulHng)而製作之多結晶矽帶、玻璃等之異種基 板上所形成之多結晶石夕等亦可用作結晶系石夕基板。又，所 謂「結晶系石夕太陽電池」，係指使用結晶系碎基板而製作 出之太陽電池。又，作為表示太陽電池特性之指標，使用 根據光照射下之電流·電壓特性之敎而獲得之填充因數 ⑽factor’以下，亦稱為「FF」，將填充因數之值稱為 「FF值」）。 本發明之目的在於獲得用以製造電極與n型擴散層之接 觸電阻較低、具有高填充因數、高效率之結晶㈣太陽電 池的太陽電池電極形成用之導電性糊漿。本發明之發明者 們意外地發現，當於特定之導電性糊漿中添加Μ霞石粒 子等之鋁矽酸鹽粒子之情形時，電性特性即結晶系矽基板 與電極間之接觸電阻變低。X，發現於添加石夕酸紹而代替 鋁矽酸鹽粒子之情形時亦可獲得優異之電性特性。進而， 本案發明者們發明’當於結晶系石夕太陽電池之電極形成用 導電㈣漿中添加β-ϋ霞石粒子等之紹石夕酸鹽粒子或石夕酸 銘之情形時’可獲得具有高填充因數及高轉換效率之高性 153910.doc •10· 201202367 能之結晶系石夕太陽電池，從而完成了本案發明。以下，就 本發明之電極形成用導電性㈣進行詳細說明。 本發明之電極形成用導電性糊㈣結晶㈣太陽電池之 電極形士用導電性糊聚’含有包含銀之導電性粒子、玻璃 ;特疋之添加粒子、有機黏合劑及溶劑。所謂特定之添 、·：子、係私自鋁矽酸鹽粒子及矽酸鋁粒子中選擇之丨種 、上尤其’本發明之電極形成帛導電性糊聚可較佳地使 =向層开>成電極之情形。本發明之電極形成用導 電性糊t之特徵在於包含|g㈣鹽粒子及/或石夕酸铭粒 子作為紹石夕酸鹽，為任一種物質均可使用，但是較佳為 使用匕a n之！g鹽粒子’例如ρ·經霞石粒子。本發明 之電極形成用導電性糊漿含有包含鋰之鋁矽酸鹽粒子，例 如β-鋰霞石粒子，藉此可確實地形成與結晶系矽基板之接 觸電阻較低之電極。本發明之電極形成用導電性糊漿包含 導電性粒子、玻璃料、特定之添力口粒子(鋁矽酸鹽粒子及/ 或夕I鋁粒子)、有機黏合劑及溶劑，可根據需要進而包 含其他添加劑及/或添加物。 本發明之電極形成用導電性糊漿中所包含之導電性粒子 之主要成分為銀。本發明之電極形成用導電性糊漿中於 不損及太陽電池電極之性能之範圍内，可包含銀以外之其 他金屬。然而，自獲得較低之電性電阻及高可靠性之觀點 考慮，較佳為導電性粒子包含銀。 導電性粒子之粒子形狀及粒子尺寸並無特別限定。作為 粒子形狀，例如，可使用球狀及鱗片狀等形狀。粒子尺寸 153910.doc 201202367 係指-個粒子之最長之長度部分之尺寸。自操作性之觀點 等考慮，導電性粒子之粒子尺寸較佳為0 05〜2〇 μιη，更佳 為 〇· 1 〜5 μπι 〇 一般而言，由於微小粒子之尺寸具有固定之分佈，故而 無需所有粒子均為上述之粒子尺寸，較佳為所有粒子之累 計值50%之粒子尺寸（D5〇)為上述之粒子尺寸之範圍。又， 粒子尺寸之平均值（平均粒子尺寸）亦可處於上述範圍。關 於本說明書中所記載之導電性粒子以外之粒子之尺寸亦相 同。 又’導電性粒子之大小可表示為bet值（BET比表面 積）。導電性粒子之BET值較佳為(M〜5 m2/g，更佳為〇2〜2 m2/g 〇 作為本發明之電極形成用導電性糊漿中所包含之鋁矽酸 鹽粒子，可使用例如鋰霞石（LiAlSi〇4)、鋰輝石 (Li20.Al203.4Si02)及堇青石（2Mg0.2Al2〇3.5Si02)等任一種 類者。為了使結晶系石夕基板與電極間之接觸電阻更低，較 佳為使用包含鋰之鋁矽酸鹽粒子。作為包含鋰之鋁矽酸鹽 粒子，較佳為使用鐘霞石粒子。所謂鐘霞石（理論化學組 成式：LiAlSi04)，係指以Li20、A1203及Si〇2為主成分之 化合物。作為本發明之電極形成用導電性糊漿中所包含之 鋰霞石粒子，具體而言，使用卜鋰霞石（Li2〇.Al2〇3.2Si〇2) 粒子’自可確實地使結晶系石夕基板與電極間之接觸電阻更 低之觀點考慮較佳。 作為本發明之電極形成用導電性糊漿中所包含之鋁矽酸 153910.doc -12- 201202367 鹽粒子’可使用化學，组成式·· LiA叫邮為㈠之範圍，y 為㈡之範圍)者。…可為整數，又可為小數。㈣酸踏 :子既可為結晶構造，亦可為非晶狀態之構造。一般： 言，於X及y為整數之情形時成為特定之結晶構造，於… 不為整數之情形時成為非晶狀態之構造。作為紹石夕酸鹽粒 子’可使用i種紹石夕酸鹽粒子。χ，作為链石夕酸鹽粒子， 可使用1種以上之不同種類之矽酸鋁粒子。 本發明之電極形成科電性糊聚中，可使时酸紹粒子 (Al2Si〇5)作為特定之添加粒子，而代替上述之_酸鹽粒 子。於添加有矽酸鋁粒子（AljiO5)之情形時，亦可提高所 獲得之電極之電性特性。然而，A了獲得更高電性特性， 而特定之添加粒子較佳為鋁矽酸鹽粒子，特定之添加粒子 更佳為β-鐘霞石。 若使用本發明之電極形成用導電性糊漿，則可確實地使 結晶系矽基板與電極間之接觸電阻更低，作為此機制，本 發明者們推測如下。亦即，藉由添加鋁矽酸鹽例如鋰霞 石粒子作為與玻璃料不同之粒子，而於用以形成電極之導 電性糊漿之燒成時，可控制熔融之玻璃料之流動狀態^因 此’由於可使導電性粒子與結晶系矽基板接觸之部分之面 積比較大’故而可使藉由導電性糊漿之燒成而形成之電極 與結晶系矽基板之間的接觸電阻變低。又，各種鋁矽酸鹽 粒子於燒成時具有相同之性質，故而不僅藉由β·链霞石粒 子之添加’而且藉由各種鋁矽酸鹽粒子對導電性糊漿之添 加’可形成較低之接觸電阻之電極。然而，本發明並不拘 153910.doc -13- 201202367 泥於該等推測。 於添加有矽酸鋁粒子（AhSiO5)之情形時，亦藉由與上v 之鋁矽酸鹽之情形相同之推測，可形成較低之接觸電阻= 電極。然而，本發明並不拘泥於該等推測。 於本發明之電極形成用導電性糊襞中特定之添加粒子 (紹石夕酸鹽粒子及/或料铭粒子）之添加量較佳為相對於導 電性粒子100重量份為O.U重量份，更佳為〇5〜2重量份， 進而佳為0·5.5重量份^於特定之添加粒子之添加量:對 ^導電性粒子⑽重量份小㈣.i重量份之情形時成為太 陽電池之特性尤其填充因數（FF)降低之傾向。又，於特定 之添加粒子之添加量相對於導電性粒子⑽重量份超過^ 量份之情形時，亦成為太陽電池之特性尤其填充因數㈣ 降低之傾向。再者’於特^之添加粒子之添加量（相對於 導電性粒子1〇0重量份之重量份）超過2重量份之導電性糊 漿之If形時’電極形成後之金屬帶之焊接稍微變難，於超 = 重量，之導電性糊漿之情形時，存在電極形成後之金 屬帶之焊接變得困難之情形。 為了使特定之添加粒子之添加之效果確實，而特定之添 步子之平均粒控為0 Ho叫’更佳為〇 5〜5叫。平均 粒經可藉由如下方式而求出，利用驗⑽咖法（雷射繞射 =法）進行粒度分佈測定，根據粒度分佈測定之結果而 獲得D50值。 作為本發明之電極形成用導電性糊漿中所包含之玻璃 〇使用包3 Pb之破璃料，又，亦可使用不包含之無 153910.doc 201202367Any one or a plurality of Fe and Cr components. Citation 4 discloses a conductive paste for forming a battery electrode for printing on a nitride-based solar cell having a nitrogen-cut film, a nitride film of a solar cell, a tantalum film, and a mountain. Further, in the cited document 4, the conductive paste contains conductive particles containing silver, a material, and an organic binder solvent, and the glass frit contains an oxidation term and an oxidation side, and the total weight of the oxidation and oxidation is relative to the glass frit. The total weight is 9% by weight or more, and the content of the oxidized word is 5 〇% by weight to 8% by weight based on the total weight of the zinc oxide and the boron oxide. Citation 5 discloses a conductive paste containing a conductive particle containing silver, a glass frit 'organic binder, and a solvent, and forming an electrical paste on the electrode of the eleventh layer of the (4) layer of the crystal system. The additive contained in the glass frit and/or the conductive paste contains at least one Group 2 added element selected from the group consisting of Mg, Ca, Sr and Ba, and the pb content in the conductive paste is 0.1. Below weight%. 153910.doc 201202367 Further, as a conductor paste for forming an electrode on a ceramic substrate, reference 6 discloses a conductor paste which is obtained by dispersing a composite powder containing silver and palladium, glass powder and cerium oxide powder. a conductor paste in a vehicle, characterized in that the solid content of the paste contains 2 to 9 wt% of glass powder, and 4 to 35 parts by weight of pericyrite per 1 part by weight of the glass powder. (LuO.AhOWSiO2) powder. Further, the cited document 6 discloses that the thermal expansion coefficient of the diabase is small. Further, in the cited document 6, it is described that the conductor paste contains β-eucryptite and is mixed with glass, and it is presumed that the thermal stress of the inorganic binder layer after firing is moderated even if the volume of the conductor layer is small. Expansion is also difficult to destroy. That is, the reference 6 discloses that it is presumed that the addition of β-eucryptite to the conductor paste is advantageous for alleviating mechanical properties, i.e., thermal stress. [Prior Art Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-23 1826 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-23 No. 1827 [Patent Document 3] Japanese Patent Laid-Open No. 2 Japanese Patent Laid-Open Publication No. 2009-194141 (Patent Document 5) Japanese Patent Laid-Open Publication No. Hei No. Hei.丨8丨8号 [Invention] [The problem to be solved by the invention] In the crystallization solar cell, the influence of the solar cell characteristics such as conversion efficiency is large, especially the influence of the light incident side electrode. Very 153910.doc 201202367 big. The contact resistance between the light incident side electrode and the π type diffusion layer is extremely low, and ohmic electrical contact is necessary. Moreover, the electrical resistance of the electrode itself must also be very low, so that the resistance of the electrode material itself (conductor resistance) is low. Further, in order to improve the productivity and to extend the life, it is important to have a high bonding strength of the metal strip for soldering to the electrodes. Therefore, an object of the present invention is to obtain a conductive paste for forming a solar cell electrode which can form an electrode having a low contact resistance with a crystalline ruthenium substrate in a crystallization solar cell. In particular, it is an object of the present invention to obtain a conductive paste for forming a solar cell electrode which can form an electrode having a low contact resistance with an n-type diffusion layer of a crystalline ruthenium substrate. Further, the object of the present invention is to obtain a high-performance crystal system solar cell having a high filling factor and high conversion efficiency and a method for producing the same. Further, it is an object of the present invention to obtain a crystal-based solar cell having a high bonding strength of a metal strip for soldering to an electrode. [Means for Solving the Problems] The inventors of the present invention have unexpectedly found that when aluminum aluminate particles such as β-cambodia particles are added to a conductive paste, electrical properties are crystal ray The contact resistance between the substrate and the electrode becomes low. Furthermore, the inventors of the present invention have found that when aluminosilicate particles such as β-eucryptite particles are added to the conductive paste for electrode formation of a crystalline solar cell, a lij fill factor can be selected and The high-performance crystal of the high-conversion Zhu rate is the Shi Xi solar cell, thus completing the invention. That is, the present invention is a conductive paste which is a conductive paste for forming an electrode of a crystal system solar cell, and contains conductive particles containing silver, 153910.doc 201202367 glass frit, specific additive particles, organic bonding The agent and the solvent are specifically selected from the group consisting of aluminosilicate particles and aluminum silicate particles. By including the above material in the conductive paste, an electrode having a low contact resistance with the crystal ruthenium substrate can be formed. Preferred aspects of the conductive paste of the present invention are shown below. In the present invention, the isomorphs can be appropriately combined. (1) Aluminosilicate particles contain lithium. For example, if aluminosilicate particles containing lithium are used as in the case of p-eucryptite particles, an electrode having a low contact resistance with a crystalline ruthenium substrate can be surely formed. (2) The Shaoshixi I salt particles are β_Civilite particles. Therefore, it is possible to surely form an electrode having a low contact resistance with the crystal substrate. In particular, an electrode having a low contact resistance with the n-type diffusion layer of the crystalline germanium substrate can be formed. Therefore, a high-performance crystal system solar cell can be obtained. (3) The content of the aluminosilicate particles is 0.1 to 5 parts by weight based on 1 part by weight of the conductive particles. The content of the aluminosilicate particles is 0.1 part by weight or more based on 1 part by weight of the conductive particles, whereby an electrode having a low contact resistance with the crystal system can be reliably formed. Further, the content of the aluminosilicate particles is 5 parts by weight based on 100 parts by weight of the conductive particles, whereby a crystal-based solar cell having a high bonding strength of the metal strip for interconnection of the electrodes welded to the electrodes can be obtained. (4) The glass frit contains PbO. When a specific additive particle containing an aluminosilicate particle or the like and a conductive paste containing a glass frit containing PbO are used, a solar cell having high solar cell performance can be obtained. (5) The content of PbO is 50 to 90% by weight based on 1% by weight of the glass frit. At 153910.doc 201202367, when a specific additive particle containing an aluminosilicate particle or the like and a conductive paste containing a specific amount of a glass frit containing PbO are used, a higher metal strip for interconnection can be obtained. Intensity, and solar cells with high solar cell performance are available. Moreover, the present invention is a method of manufacturing a solar cell comprising the steps of: printing the conductive paste on an nS layer of a crystalline germanium substrate or an antireflection film on an n-type layer and drying it. And firing, thereby forming an electrode. By forming the electrode using the conductive paste of the present invention, a high performance crystalline solar cell having a high filling factor and high conversion efficiency can be obtained. Further, the present invention is a solar cell manufactured by the above-described manufacturing method of the present invention. The solar cell of the present invention is a high performance crystalline solar cell having a high fill factor and high conversion efficiency. [Effects of the Invention] According to the present invention, it is possible to obtain a conductivity for forming a solar cell electrode of an electrode having a low contact resistance with a crystal-based fractured substrate in a crystalline cerium solar cell. In particular, according to the present invention, it is possible to obtain a conductive paste m for forming a solar cell electrode which can form an electrode having a low contact resistance with an n-type diffusion layer of a crystalline system substrate, and to form conductivity for a solar cell electrode using the present invention. The paste (4) is used as an electrode to obtain a high-performance crystal system solar cell having a high filling factor and high conversion efficiency. By using the conductive paste for forming a solar cell electrode of the present invention to form an electrode, welding can be performed at the f-pole. The crystallization of the metal ribbon of the mutual entanglement is higher than that of the solar cell. 153910.doc 201202367 [Embodiment] In the present specification, "crystalline zea" includes a single crystal and a polycrystalline stone. In addition, it is a material suitable for the formation of an element such as a flat plate or the like, which is formed into a flat plate shape for the formation of an electric element or an electronic element. Any method can be used for the method of producing the crystal system. For example, the Czochralski method can be used in the case of a single crystal stone, and the casting method can be used in the case of a polycrystalline stone. Further, a polycrystalline stone formed on a different type of substrate such as a polycrystalline enamel tape or a glass produced by a different manufacturing method such as a ribbon pulHng method can also be used as a crystal system. . Further, the term "crystalline ceremonial solar cell" refers to a solar cell produced by using a crystallization-based substrate. In addition, as an index indicating the characteristics of the solar cell, a fill factor (10) factor' obtained in accordance with the current/voltage characteristics under light irradiation is used, which is also referred to as "FF", and the value of the fill factor is referred to as "FF value". . SUMMARY OF THE INVENTION An object of the present invention is to obtain a conductive paste for forming a solar cell electrode for producing a crystalline (IV) solar cell having a low contact resistance of an electrode and an n-type diffusion layer and having a high filling factor and high efficiency. The inventors of the present invention have unexpectedly found that when aluminosilicate particles such as a nepheline particle are added to a specific conductive paste, electrical properties, that is, contact resistance between the substrate and the electrode of the crystalline system are changed. low. X, it was found that excellent electrical properties were obtained in the case of adding a sulphate acid instead of the aluminosilicate particles. Furthermore, the inventors of the present invention have invented that 'when a β-maleite particle or the like is added to the conductive (four) slurry for forming an electrode of a crystal system, the solar cell is obtained. High filling factor and high conversion efficiency 153910.doc •10· 201202367 The crystal of the energy is the Shi Xi solar cell, thus completing the invention. Hereinafter, the conductivity (4) for electrode formation of the present invention will be described in detail. Conductive paste for electrode formation according to the present invention (4) Crystal (4) Conductive paste of electrode shape for solar cell 'Conductive particles containing silver, glass; special additive particles, organic binder and solvent. The specific addition, ·::, the selected from the aluminosilicate particles and the aluminum silicate particles, especially the 'electrode forming electrode of the present invention, the conductive paste can be preferably made to the layer> ; the case of forming an electrode. The conductive paste t for forming an electrode of the present invention is characterized in that it contains |g(tetra) salt particles and/or aspartic acid particles as a sulphate, and can be used as any of them, but it is preferable to use 匕a n! g salt particles 'e.g. ρ·nephew particles. The conductive paste for electrode formation of the present invention contains aluminum aluminosilicate particles containing lithium, for example, ?-eucryptite particles, whereby an electrode having a low contact resistance with a crystalline ruthenium substrate can be surely formed. The conductive paste for electrode formation of the present invention contains conductive particles, a glass frit, specific additive particles (aluminum silicate particles and/or an aluminum I particles), an organic binder, and a solvent, and may be further contained as needed. Other additives and / or additives. The main component of the conductive particles contained in the conductive paste for electrode formation of the present invention is silver. The conductive paste for electrode formation of the present invention may contain other metals than silver insofar as it does not impair the performance of the solar cell electrode. However, from the viewpoint of obtaining lower electrical resistance and high reliability, it is preferred that the conductive particles contain silver. The particle shape and particle size of the conductive particles are not particularly limited. As the particle shape, for example, a shape such as a spherical shape or a scaly shape can be used. Particle size 153910.doc 201202367 refers to the size of the longest part of a particle. From the viewpoint of operability, etc., the particle size of the conductive particles is preferably 0 05 to 2 〇 μιη, more preferably 〇 1 to 5 μπι 〇 Generally, since the size of the fine particles has a fixed distribution, it is not necessary All of the particles are of the above-described particle size, and preferably the particle size (D5〇) of 50% of the cumulative value of all the particles is in the range of the above-mentioned particle size. Further, the average value (average particle size) of the particle sizes may be in the above range. The sizes of the particles other than the conductive particles described in the present specification are also the same. Further, the size of the conductive particles can be expressed as a bet value (BET specific surface area). The BET value of the conductive particles is preferably (M to 5 m 2 /g, more preferably 〇 2 to 2 m 2 /g 〇 as the aluminosilicate particles contained in the conductive paste for electrode formation of the present invention. For example, any type such as eucryptite (LiAlSi〇4), spodumene (Li20.Al203.4SiO2), and cordierite (2Mg0.2Al2〇3.5Si02) is used. In order to make the contact resistance between the crystal system and the electrode Lower, it is preferred to use lithium aluminate particles containing lithium. As the aluminosilicate particles containing lithium, it is preferred to use the cryptite particles. The so-called zhongxia stone (theoretical chemical composition formula: LiAlSi04) means A compound containing Li20, A1203, and Si〇2 as a main component. As the lithopite particles contained in the conductive paste for electrode formation of the present invention, specifically, a lithium nepheline (Li2〇.Al2〇3.2) is used. It is preferable that the particle ' ) ) ) ) ) 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 Doc -12- 201202367 Salt particles 'can use chemistry, composition formula · LiA called post as (1) , Y is in the range of (ii)) were. ... can be an integer or a decimal. (4) Acid tread: The substructure may be a crystal structure or a structure in an amorphous state. In general, when X and y are integers, it becomes a specific crystal structure, and when it is not an integer, it becomes a structure of an amorphous state. As the sulphate particles, i kinds of sulphate particles can be used. Further, as the stearate particles, one or more different types of aluminum silicate particles may be used. In the electrode forming electron-electric paste of the present invention, the acid-containing particles (Al2Si〇5) can be used as specific additive particles instead of the above-mentioned acid crystal particles. When the aluminum niobate particles (AljiO5) are added, the electrical characteristics of the obtained electrode can also be improved. However, A has a higher electrical property, and the specific added particles are preferably aluminosilicate particles, and the specific added particles are more preferably β-cristobalite. When the conductive paste for electrode formation of the present invention is used, the contact resistance between the crystal ruthenium substrate and the electrode can be reliably made lower. As a mechanism, the inventors presume as follows. That is, by adding an aluminosilicate such as a eucryptite particle as a particle different from the glass frit, when the conductive paste for forming an electrode is fired, the flow state of the molten glass frit can be controlled. 'Because the area of the portion where the conductive particles are in contact with the crystal ruthenium substrate is relatively large, the contact resistance between the electrode formed by firing of the conductive paste and the crystallization substrate can be lowered. Further, since the various aluminosilicate particles have the same properties at the time of firing, they can be formed not only by the addition of β-chain nepheline particles but also by the addition of various aluminosilicate particles to the conductive paste. Low contact resistance electrode. However, the present invention is not limited to 153910.doc -13- 201202367 mud. In the case where aluminum silicate particles (AhSiO5) are added, a lower contact resistance = electrode can be formed by the same assumption as in the case of the aluminosilicate of the above. However, the present invention is not limited to such speculations. The amount of the additive particles (the sulphate particles and/or the material particles) specified in the conductive paste for electrode formation of the present invention is preferably OU parts by weight based on 100 parts by weight of the conductive particles. Preferably, it is 5 to 2 parts by weight, and more preferably 0. 5.5 parts by weight. The amount of the added particles is specific: the amount of the conductive particles (10) is small (four). The part by weight of the i. The tendency of the fill factor (FF) to decrease. Further, when the amount of the specific added particles is more than the amount by weight of the conductive particles (10), the characteristics of the solar cell, in particular, the filling factor (4) tends to decrease. Further, when the amount of the added particles (the amount by weight of the conductive particles of 1 〇 0 parts by weight) exceeds 2 parts by weight of the If shape of the conductive paste, the welding of the metal strip after the electrode formation is slightly When it is difficult to change, in the case of the weight of the conductive paste, there is a case where the welding of the metal strip after the electrode formation becomes difficult. In order to make the effect of adding specific particles added, the average grain control of the specific step is 0 Ho's better than 5~5. The average grain size can be obtained by the following method, and the particle size distribution measurement is carried out by the test (10) coffee method (laser diffraction = method), and the D50 value is obtained based on the result of the particle size distribution measurement. As the glass crucible included in the conductive paste for electrode formation of the present invention, the glass frit of the package 3 Pb is used, and it is also possible to use the non-containing 153910.doc 201202367

Pb系玻璃料。本發明之電極形成用導電性糊漿中，與玻璃 料之種類無關，作為與玻璃料不同之粒子，添加特定之添 加粒子（鋁矽酸鹽粒子及/或矽酸鋁粒子），藉此可獲得高轉 換效率之結晶系矽太陽電池。 藉由使用本發明之導電性糊漿，為了獲得更高轉換效率 之結晶系矽太陽電池，較佳為使用包含pb〇之玻璃料。為 了確實地獲得更高轉換效率之結晶系矽太陽電池，pb〇之 含量較佳為相對於玻璃料1〇〇重量％為5〇〜9〇重量％，更加 為60〜85重量％。 包含可含於本發明之電極形成用導電性糊漿中之pb之玻 璃料，可例示PbO-SiOrBW3系及 Bi2〇3_Pb〇_Si〇2_B2〇3系 等’但是並不限定於該等。 又，作為本發明之電極形成用導電性糊聚中所含之玻璃 料，可使用無Pb系玻璃料（例如Bi2〇3_B2〇3_si〇2系及si〇2_ b2〇3-r2〇系等’其令R表示鐘(u)、納(Na)、鉀㈨、铷 ㈣及铯(CS)等驗金屬），但是並不限定於該等。 玻璃料之粒子之形狀並未特別限定，可使用例如球狀、 不定形等形狀。又，粒子尺+介* &amp; 千尺寸亦並無特別限定，但是自操 作性之觀點等考慮，較 〇 , ln # 則圭為粒子尺寸之平均值_為 叫之已圍，更佳為〇·5〜5 _之範圍。向本發明之 電極形成用導電性糊漿中添加 雷 &lt; 坡璃枓之添加量相對於導 2粒子⑽重量份通常為W重量份，較佳為2〜8重量 為了使對本發明之電極形成用導電性糊裝添加特定之添 】539 丨 〇,d〇c -15· 201202367 加粒子（鋁石夕酸鹽粒子及/或矽酸鋁粒子）之效果更確實，玻 璃料之軟化點較佳為300〜70(TC，更佳為400〜600。(：。 本發明之電極形成用導電性糊漿可包含有機黏合劑及溶 劑。有機黏合劑及溶劑係擔負導電性糊漿之黏度調整等之 作用者，均無特別限定。亦可使有機黏合劑溶解於溶劑中 而使用。 作為有機黏合劑，可自纖維素系樹脂（例如乙基纖維 素硝基纖維素荨）、（甲基）丙烯系樹脂（例如聚丙稀酸甲 酯、聚甲基丙烯酸甲酯等）中選擇而使用。有機黏合劑之 添加量相對於導電性粒子100重量份通常為〇 2〜3〇重量 份’較佳為0.4〜5重量份。 作為溶劑，可自醇類（例如松油醇、α_松油醇、卜松油醇 等）、酯類（例如含羥基酯類、2,2,4·三曱基_Μ_戊二醇單異 丁酸酯、丁基卡必醇醋酸酯等）中選擇〗種或2種以上而使 用。溶劑之添加量相對於導電性粒子1〇〇重量份通常為 0.5〜30重量份，較佳為5〜25重量份。 進而，本發明之電極形成用導電性糊漿中，可根據需要 添加自可塑劑、消泡劑、分散劑、均化劑、穩定劑及密著 促進劑等中選擇者，作為添加劑。該等中，作為可塑劑， 可使用自鄰苯二甲酸酯類、乙醇酸酯類、磷酸酯類、癸二 酸酯類、己二酸酯類及檸檬酸酯類等中選擇者。 進而’本發明之電極形成用導電性糊漿中，作為添加 物，可於不損及所獲得之太陽電池電極之性能之範圍内包 含金屬氧化物粒子，例如，自氧化釩、氧化錳粒子及/或 153910.doc 201202367 氧化鋅等中選擇之金屬氧化物粒子。 就本發月之電極形成用導電性糊漿之製造方法進 亍說月a月之電極形成用導電性糊聚可藉由對有機黏 合劑及溶劑添加導電性粒子、特^之添加粒子（时酸鹽 粒子及/或石夕酸紹粒子）及玻璃料，並加以混合分散而製 造。 混合可利用例如行星式混合機而進行。又，分散可藉由 三輥研磨機而進行。混合及分散並不限定於該等方法，可 使用公知之各種方法。 ^其次，就使用有本發明之電極形成用導電性糊漿之結晶 系碎太陽電池m法進行說明。本發明之製造方法包 括如下步驟’ gp ’將上述之本發明之電極形成用導電性糊 襞印刷於結晶系石夕基板之η型石夕層上或n型⑪層上之抗反射 膜上，並進行乾燥及燒成，藉此形成電極。以下，參照圖 1就本發明之製造方法進行更詳細說明。 圖1表示表面電極丨附近之結晶系矽太陽電池之剖面模式 圖。圖1所不之結晶系矽太陽電池具有形成於光入射側之 表面電極1、抗反射膜2、n型擴散層（n型矽層）3、p型矽基 板4及背面電極5。 本發明之太陽電池之製造方法中，可將上述之本發明之 電極形成用導電性糊漿用於形成太陽電池用基板之表面電 極及/或背面電極。具體而言，本發明之太陽電池之製造 方法包括將上述之本發明之電極形成用導電性糊漿印刷於 結晶系矽基板（例如，P型矽基板4)之11型矽層3上或η型矽層 153910.doc 17 201202367 3上之抗反射膜2上的步驟。 本發明之電極形成用導電性糊漿亦可使用於在p型矽層 之表面形成電極之情形。藉由獲得基板與電極之間之更低 之接觸電阻，為了獲得更高性能之結晶系矽太陽電池，而 本發明之電極形成用導電性糊漿較佳為使用於形成η型矽 層3之表面之電極之情形。 圖1中表示了將本發明之電極形成用導電性糊漿用於表 面電極1之形成之示例。然而，本發明之電極形成用導電 性糊漿亦可使用於形成表面電極i及背面電極5之任一者之 情形。亦即，本發明之電極形成用導電性糊漿可使用於使 用有η型矽基板之情形時之背面之11型矽表面之電極形成。 於將本發明之電極形成用導電性糊漿用於形成單結晶矽 或多結晶矽之太陽電池用基板之表面電極丨之情形時，既 可直接印刷於矽基板之n型矽層上，亦可印刷於η型擴散層 (η型矽層）3上之抗反射膜2上。於將本發明之電極形成用導 電性糊漿印刷於抗反射膜2上之情形時，於以後之燒成時 導電性糊漿燒成貫通抗反射膜2，型擴散層3上形成表 面電極1。 再者，自獲得高轉換效率之觀點考慮，較佳為於結晶系 矽基板之光入射侧之表面具有棱錐狀之紋理構造。 於製造圖1所示之構造之太陽電池之情形時，可使用網 版印刷法等之方法，將本發明之電極形成用導電性糊裝於 表面具有η型擴散層3之結晶系矽基板上 '或η型擴散層3上 所形成之抗反射膜2上印刷電極圖案。 153910.doc • 18 - 201202367 本發明之太陽電池之製造方法中’包括將以上述方式而 印刷之電極形成用導電性糊毁乾燥並燒成之步驟。亦即， 首先，將經印刷之電極圖案以100〜15〇t左右之溫度乾燥 幾分鐘（例如0.5〜5分鐘）。同樣地，肖背面而言亦將本發明 之電極形成用導電性糊漿或其他導電性糊漿(例如，以鋁 為主成分之導電性糊漿）印刷於大致整個表面，並進行乾 燥。 其後，使用管狀爐等燒成爐使將導電性糊漿乾燥而成者 於大氣中，以500〜850。(：左右之溫度燒成〇 4〜3分鐘，形成 光入射側之表面電極1及背面電極5。具體而言，使燒成爐 之内-外之燒成時間為0.5分鐘。當於抗反射膜2上印刷本發 明之電極形成用導電性糊漿之情形時，為了於燒成過程中 高溫之糊漿材料燒成貫通抗反射膜2，可將表面電極丨與矽 基板上之η型擴散層3電性連接。其結果為，可獲得如圖i 所示之構造之太陽電池。再者，燒成條件並不限定於上 述，可適當選擇。 全煮面電極型（所謂背面接觸構造）或使光入射側電極通 過3又置於基板之貫通孔而與背面導通之構造之太陽電池 中’作為向η型矽層形成電極用，可使用本發明之電極形 成用導電性糊漿。 以上’就使用有ρ型矽基板之太陽電池之例進行了說 明’但是即便於使用有η型矽基板之結晶系矽太陽電池之 情形時，亦使形成擴散層之雜質自磷等η型雜質向硼等ρ型 雜質變更’形成ρ型擴散層來代替η型擴散層，僅藉由以上 153910.doc •19· 201202367 方面不同而可利用相同製程製造使用有本發明之電極形成 用導電性糊漿之太陽電池。 [實施例] 以下，根據實施例，對本發明進行具體說明，但是本發 明並不限定於該等實施例。 &lt;導電性糊漿之材料及調製比例&gt; 實施例及比較例之太陽電池製造所使用之導電性糊毁之 組成如下所述。 .導電性粒子：Ag(100重量份）^使用球狀、bET值為〇 6 m2/g、平均粒徑D50為1.4 μηι者。 .有機黏合劑：乙基纖維素（1重量份）。使用乙氧基含量 為48〜49.5重量°/。者。 .溶劑：丁基卡必醇醋酸酯（11重量份）。 .玻璃料：Pb系玻璃料（Pb0-B203-Si02)(5重量份），（平均 粒徑D50為2 μιη)，軟化點為480°C。 .實施例1〜4之鋁矽酸鹽粒子：實施例1〜4中，作為特定 之添加粒子添加β-鋰霞石粒子（LiAlSi04，平均粒徑D50為1 μιη)。實施例1〜4之β-鋰霞石粒子向導電性糊漿添加之添加 量如下所述根據實驗條件而變化地添加。 .實施例5及6之鋁矽酸鹽粒子：實施例5及6中，作為特 定之添加粒子即鋁矽酸鹽粒子，分別添加LiAlSi206粒子及 LiAlSi308粒子（平均粒徑D50為1 μιη)。鋁矽酸鹽粒子向導 電性糊漿添加之添加量相對於導電性粒子100重量份為1重 量份。 153910.doc •20· 201202367 貫施例7之矽酸鋁粒子：實施例7中，代替鋁矽酸鹽粒 子，而添加矽酸鋁粒子（ALSiO5)(平均粒徑D5〇為i μηι)。 矽酸鋁粒子向導電性糊漿添加之添加量相對於導電性粒子 100重量份為1重量份。 關於矽酸鋁粒子（Al2Si〇5)，購入試藥。 實施例1〜6中所使用之鋁矽酸鹽粒子（LiA丨si〇4粒子、 LiAlShO6粒子及LiAlSiaO8粒子）係以如下方式而合成。亦 即’作為出發原料使用UAO3(拿卡萊公司製造）、Pb glass frit. In the conductive paste for electrode formation of the present invention, depending on the type of the glass frit, specific particles (aluminum silicate particles and/or aluminum silicate particles) may be added as particles different from the glass frit. A crystal system solar cell with high conversion efficiency is obtained. By using the conductive paste of the present invention, in order to obtain a crystal-based solar cell having higher conversion efficiency, it is preferred to use a glass frit containing pb. In order to obtain a crystal system solar cell having a higher conversion efficiency, the content of pb is preferably from 5 Å to 9 Å by weight, more preferably from 60 to 85% by weight, based on 1% by weight of the glass frit. The glass material of pb which can be contained in the conductive paste for electrode formation of the present invention is exemplified by PbO-SiOrBW3 system and Bi2〇3_Pb〇_Si〇2_B2〇3 system, etc., but is not limited thereto. In addition, as the glass frit contained in the conductive paste for electrode formation of the present invention, a Pb-free glass frit (for example, Bi2〇3_B2〇3_si〇2 system and si〇2_b2〇3-r2〇 system, etc.) can be used. Let R denote a clock (u), a nano (Na), a potassium (nine), a ruthenium (four), and a ruthenium (CS) metal, but it is not limited thereto. The shape of the particles of the glass frit is not particularly limited, and a shape such as a spherical shape or an indeterminate shape can be used. Further, the particle size + mediation * &amp; thousand size is not particularly limited, but from the viewpoint of operability, etc., ln # is the average value of the particle size _ is called the surrounding, more preferably 〇 · 5~5 _ range. To the conductive paste for electrode formation of the present invention, the addition amount of the swill is usually W parts by weight, preferably 2 to 8 parts by weight, based on the weight of the conductive particles (10), in order to form the electrode of the present invention. Adding a specific additive to the conductive paste] 539 丨〇, d〇c -15· 201202367 Adding particles (aluminum silicate particles and/or aluminum silicate particles) is more effective, and the softening point of the glass frit is better. It is 300 to 70 (TC, more preferably 400 to 600. (: The conductive paste for electrode formation of the present invention may contain an organic binder and a solvent. The organic binder and the solvent are responsible for adjusting the viscosity of the conductive paste, etc.) The role of the organic binder is not particularly limited. It can also be used by dissolving an organic binder in a solvent. As an organic binder, it can be derived from a cellulose resin (for example, ethyl cellulose nitrocellulose oxime) or (methyl). The propylene resin (for example, polymethyl acrylate, polymethyl methacrylate, etc.) is selected and used. The amount of the organic binder added is usually 〇 2 to 3 〇 by weight with respect to 100 parts by weight of the conductive particles. It is 0.4 to 5 parts by weight. Solvent, which may be derived from alcohols (such as terpineol, α-terpineol, bussonol, etc.), esters (for example, hydroxyl-containing esters, 2,2,4·tridecyl-indole-pentanediol) The amount of the solvent to be added is preferably from 0.5 to 30 parts by weight, preferably from 0.5 to 30 parts by weight, based on 1 part by weight of the conductive particles, of isobutyrate or butyl carbitol acetate. Further, in the conductive paste for electrode formation of the present invention, a plasticizer, an antifoaming agent, a dispersing agent, a leveling agent, a stabilizer, and a adhesion promoter may be added as needed. As an additive, as a plasticizer, it can be selected from the group consisting of phthalic acid esters, glycolic acid esters, phosphate esters, sebacic acid esters, adipates, and citric acid esters. Further, in the conductive paste for electrode formation of the present invention, as an additive, metal oxide particles, for example, vanadium oxide or manganese oxide, may be contained within a range that does not impair the performance of the obtained solar cell electrode. Particles and/or 153910.doc 201202367 Metal oxide particles selected from zinc oxide, etc. In the method of producing a conductive paste for electrode formation in the present month, it is possible to add conductive particles to the organic binder and the solvent by adding conductive particles to the organic binder and the solvent. The acid salt particles and/or the alumite particles and the glass frit are produced by mixing and dispersing. The mixing can be carried out, for example, by a planetary mixer. Further, the dispersion can be carried out by a three-roll mill. The method is not limited to these methods, and various known methods can be used. Next, the method of using the crystal-based broken solar cell m having the conductive paste for electrode formation of the present invention will be described. The manufacturing method of the present invention includes the following steps. 'gp' The conductive paste for electrode formation of the present invention described above is printed on the n-type layer of the crystal system, or the anti-reflection film on the n-type 11 layer, and dried and fired. This forms an electrode. Hereinafter, the manufacturing method of the present invention will be described in more detail with reference to Fig. 1 . Fig. 1 is a schematic cross-sectional view showing a crystal system solar cell in the vicinity of a surface electrode 丨. The crystal solar cell of Fig. 1 has a surface electrode 1, an antireflection film 2, an n-type diffusion layer (n-type germanium layer) 3, a p-type germanium substrate 4, and a back electrode 5 which are formed on the light incident side. In the method for producing a solar cell of the present invention, the above-described conductive paste for electrode formation of the present invention can be used for forming a surface electrode and/or a back electrode of a substrate for a solar cell. Specifically, the method for producing a solar cell according to the present invention includes printing the above-described conductive paste for electrode formation of the present invention on a type 11 layer 3 of a crystal-based germanium substrate (for example, a P-type germanium substrate 4) or η. The step on the anti-reflection film 2 on the type 矽 layer 153910.doc 17 201202367 3 . The conductive paste for electrode formation of the present invention can also be used in the case where an electrode is formed on the surface of a p-type tantalum layer. The conductive paste for electrode formation of the present invention is preferably used to form the n-type germanium layer 3 by obtaining a lower contact resistance between the substrate and the electrode in order to obtain a higher performance crystalline solar cell. The case of the electrode on the surface. Fig. 1 shows an example in which the conductive paste for electrode formation of the present invention is used for the formation of the surface electrode 1. However, the conductive paste for electrode formation of the present invention can also be used for forming either of the surface electrode i and the back electrode 5. In other words, the conductive paste for electrode formation of the present invention can be formed by using an electrode of the surface of the 11-type crucible on the back side in the case of using an n-type germanium substrate. When the conductive paste for electrode formation of the present invention is used for forming a surface electrode of a substrate for a solar cell of a single crystal germanium or a polycrystalline germanium, it can be directly printed on the n-type germanium layer of the germanium substrate, It can be printed on the anti-reflection film 2 on the n-type diffusion layer (n-type germanium layer) 3. When the conductive paste for electrode formation of the present invention is printed on the antireflection film 2, the conductive paste is fired through the antireflection film 2 at the subsequent firing, and the surface electrode 1 is formed on the diffusion layer 3. . Further, from the viewpoint of obtaining high conversion efficiency, it is preferable that the surface on the light incident side of the crystalline ruthenium substrate has a pyramid-like texture structure. In the case of manufacturing a solar cell having the structure shown in FIG. 1, the electrode for forming an electrode of the present invention can be mounted on a crystal ruthenium substrate having an n-type diffusion layer 3 on its surface by a method such as a screen printing method. The electrode pattern is printed on the anti-reflection film 2 formed on the n-type diffusion layer 3. 153910.doc • 18 - 201202367 The method for producing a solar cell of the present invention includes the step of destroying and baking the conductive paste for electrode formation printed in the above manner. That is, first, the printed electrode pattern is dried at a temperature of about 100 to 15 Torr for a few minutes (e.g., 0.5 to 5 minutes). In the same manner, the conductive paste for electrode formation of the present invention or another conductive paste (for example, a conductive paste containing aluminum as a main component) is printed on substantially the entire surface and dried. Thereafter, the conductive paste is dried in a baking furnace such as a tubular furnace to obtain an atmosphere of 500 to 850. (: The left and right temperatures are baked for 4 to 3 minutes to form the surface electrode 1 and the back surface electrode 5 on the light incident side. Specifically, the firing time inside the firing furnace is 0.5 minutes. When the conductive paste for electrode formation of the present invention is printed on the film 2, the n-type diffusion on the surface electrode 丨 and the ruthenium substrate can be performed in order to burn the paste material having a high temperature during the firing process through the anti-reflection film 2. The layer 3 is electrically connected. As a result, a solar cell having the structure shown in Fig. i can be obtained. Further, the firing conditions are not limited to the above, and can be appropriately selected. Fully cooked surface electrode type (so-called back contact structure) In the solar cell of the structure in which the light-incident side electrode is placed in the through-hole of the substrate and is electrically connected to the back surface, the electrode for forming an electrode of the present invention can be used. 'An example of using a solar cell having a p-type germanium substrate has been described'. However, even when a crystal system having an n-type germanium substrate is used, the impurity forming the diffusion layer is made to be n-type impurity such as phosphorus. Boron and other p-type impurities In the case where the p-type diffusion layer is formed instead of the n-type diffusion layer, the solar cell using the conductive paste for electrode formation of the present invention can be manufactured by the same process only by the above-mentioned 153,910.doc •19·201202367. EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the examples. <Material and Modulation Ratio of Conductive Paste> Solar Cell Manufacturing Institute of Examples and Comparative Examples The composition of the electrically conductive paste used is as follows: Conductive particles: Ag (100 parts by weight) ^ using a spherical shape, a bET value of 〇6 m2/g, and an average particle diameter D50 of 1.4 μηι. Ethylcellulose (1 part by weight), using an ethoxy group content of 48 to 49.5 wt%. Solvent: butyl carbitol acetate (11 parts by weight). Glass frit: Pb frit (Pb0-B203-SiO2) (5 parts by weight), (average particle diameter D50 is 2 μηη), and the softening point is 480 ° C. The aluminosilicate particles of Examples 1 to 4: Examples 1 to 4, Adding β-eucryptite particles as a specific additive particle (LiAlSi04, average The diameter D50 is 1 μm). The addition amount of the β-eucryptite particles of Examples 1 to 4 to the conductive paste is changed as follows according to the experimental conditions. The aluminum citrates of Examples 5 and 6. Particles: In Examples 5 and 6, LiAlSi206 particles and LiAlSi308 particles (having an average particle diameter D50 of 1 μm) were added as a specific aluminosilicate particles, and aluminum alumite particles were added to the conductive paste. The amount of addition is 1 part by weight based on 100 parts by weight of the conductive particles. 153910.doc • 20· 201202367 The aluminum silicate particles of Example 7: In Example 7, aluminum silicate particles were added instead of the aluminum silicate particles. (ALSiO5) (average particle diameter D5〇 is i μηι). The amount of the aluminum silicate particles added to the conductive paste is 1 part by weight based on 100 parts by weight of the conductive particles. For the aluminum silicate particles (Al2Si〇5), a reagent was purchased. The aluminosilicate particles (LiA丨si〇4 particles, LiAlShO6 particles, and LiAlSiaO8 particles) used in Examples 1 to 6 were synthesized as follows. That is, using UAO3 (made by Naikalai) as a starting material,

Al2〇3(昭和電工製造 A-50-K)及 Si〇2(Admatechs 製造 SO_ E2)。將該等出發原料以成為目標之莫耳比之方式而秤量 為如下所述之莫耳比，並藉由球磨機使用離子交換水濕式 混合16小時。 作為 LiAlSi04 之原料，使用 Li2C03:Al2〇3:Si〇2=l:l:2(莫 耳比）。 作為 LiAlSi206 之原料，使用 Li2C03:Al2〇3:Si〇2=l:l:4(莫 耳比）。 作為 LiAlSi3〇8 之原料’使用 Li2C03:Al203:Si02=l:l:6(莫 耳比）。 將該等出發原料一面攪拌一面加熱，將漿料濃縮之後， 於15 0 C之乾燥爐内靜置12小時，並使之乾燥β利用乳砵 將乾燥粉末粉碎，形成混合粉末。 其次’將該混合粉末填充於模具中，藉由單軸加壓而製 作成型體’並將其以400 Κ/時間之升溫速度加熱至丨丨〇〇°c 為止並保持4小時之後’於爐内使之自然冷卻，從而獲得 153910.doc 201202367 目標物質。 以上述方式而獲得之目標物質之合成之可否係藉由X射 線繞射法（XRD(X-ray Diffraction)法）而判定。xrd法測定 使用Rigaku股份有限公司製造之Ultima IV，合成物質之相 之同定使用Rigaku股份有限公司製造之pDXL。經合成之 物質藉由乳缽而充分粉碎，製作出XRD法測定用粉末。藉 由XRD法，而確認實施例中所使用之目標物質具有特定之 結晶構造。 經合成之鋁矽酸鹽藉由乳缽粗粉碎之後藉由使用離子交 換水之濕式球磨機而粉碎，並微粉化。 其次’利用仃星式混合機將上述之特定之調製比例之材 料混合，進而利用三親研磨機進行分散，並糊漿化，藉此 調製出導電性糊漿。 &lt;太陽電池基板之試作&gt; 本發明之電極形成用導電性糊I之評估藉由使用經調製 之導電性糊漿試作太陽電池，並;収其特性而進行。太陽 電池之試作方法如下。 基板使用摻雜B⑷之”Si多結晶基板（基板厚度為· μιη)。 首先’於上述基板上藉由较, 精由乾式氧化而形成約20 μιη之 化矽層之後，利用混合有氟化翁 〜 另齓化虱、純水及氟化銨之溶液 行蝕刻，除去基板表面之損傷。 #進而’利用包含鹽酸與 氧化氫之水溶液進行重金屬清洗。 其次’藉由濕式蝕刻而於該甚 么成暴板表面形成紋理（凹凸 1539l0.doc -22- 201202367 狀）。具體而言，藉由濕式蝕刻法（氫氧化鈉水溶液）而於單 面（光入射側之表面）形成棱錐狀之紋理構造。其後，利用 包含鹽酸及過氧化氫之水溶液進行清洗。 繼而，於上述基板之具有紋理構造之表面，使用氧氣化 磷（poch)，藉由擴散法，而使磷以溫度95〇它擴散3〇分 鐘，使η型擴散層於約0.5 μΓη之深度形成n型擴散層。n型 擴散層之薄片電阻為50 Ω/口。 其次，於形成有η型擴散層之基板之表面，藉由電漿 CVD(Chemical Vapor Deposition，化學氣相沈積）法而使用 矽烷氣體及氨氣體將氮化矽薄膜形成為約6〇 nm之厚度。 具體而言，藉由將NH3/SiH4=0_5之混合氣體i T〇rr(133 pa) 輝光放電分解，而利用電漿CVD法形成膜厚約6〇 nm之氮 化矽薄膜（抗反射膜）。 將如此而獲得之太陽電池基板切斷為15 mmxl5 mm之正 方形而加以使用。 光入射側（表面）電極用之導電性糊漿之印刷藉由網版印 刷法而進行。於上述之基板之抗反射膜上，以使膜厚成為 約20 μηι而以包含2 mm見方之總電極部與1〇〇 ^爪寬之指形 電極部之圖案進行印刷’其後，以15 (TC乾燥約1分鐘。 其次，藉由網版印刷法而進行背面電極用之導電性糊漿 之印刷。於上述之基板之背面’印刷12 mm見方之以|呂粒 子、玻璃料、乙基纖維素及溶劑為主成分之導電性糊聚， 並以150。(：乾燥1分鐘。乾燥後之背面電極用之導電性糊漿 之膜厚約20 μπι。 1539l0.doc -23- 201202367 使用以鹵素燈為加熱源之近紅外燒成爐（日本GAISI公司 製作之太陽電池用高速燒成試驗爐），將如上述般於表面 及背面印刷有導電性糊漿之基板於大氣中利用特定之條件 而燒成。燒成條件係設為750°C或775。(：之峰值溫度，大氣 中’燒成爐之内-外以30秒同時燒成兩面。如以上般，試 作出太陽電池。 &lt;太陽電池特性之測定&gt; 太陽電池單元之電性特性之測定係如以下般進行。亦 即’於太陽模擬器光（AM1.5，能量密度1〇〇 mW/cm2)之照 射下測定經試作之太陽電池之電流-電壓特性，根據測定 結果算出填充因數（FF)、轉換效率（〇/〇)及串聯電阻Rs(Q)。 再者，試料係製作2個相同條件者，測定值係求出2個之平 均值。 &lt;接著強度之測定&gt; 經焊接之金屬帶之接著強度測定用之試料係如以下般製 作並測疋。首先，作為基板，與太陽電池特性測定用相 同，使用帶抗反射膜之15 _見方之太陽電池基板。於該 基板表面之大致中央，使用特定之導電性糊漿印刷寬度3 匪、長度12 _之焊接墊，並進行乾燥及燒成而形成。其 次，將互連用之金屬帶即銅帶（寬度15 mmx全厚度〇16 mm，以約40 μηι之膜厚包覆共晶焊錫[錫：鉛=64: %之重 使用助焊劑於焊接墊上以250°C之溫度焊接3秒 量比])， 鐘。其後’將帶之—端所設置之環狀部藉由數位拉伸計 (A&amp;T么司製造’數顯測力計ad·4%25叫而相對於基板 153910.doc • 24 - 201202367 表面向90度方向拉伸，測定接著之破壞強度’藉此進行接 著強度之測定。再者，試料係製作1〇個，測定值係求= 個之平均值。 〈實施例1〜4及比較例1及2&gt; 如表1所示，實施例i〜4中，將使向導電性糊漿之卜鋰霞 石粒子之添加量相對於導電性粒子丨〇 〇重量份而變化至 〇.〇〜1_〇重量份為止之導電性糊漿用於太陽電池之表面電極 形成用而試作出太陽電池。再者，太陽電池製作時之燒成 之峰值溫度係於比較例1、實施例丨及2之情形時為75〇它， 於比較例2、實施例3及4之情形時為775它。表】表示所獲 得之太陽電池之太陽電池特性之測定結果。再者，基板與 電極之間之接觸電阻對串聯電阻所帶來之影響較大。因 此，可謂之φ聯電阻之值為表示接觸電阻之大小的指標。 於串聯電阻之值較低之情形時，可謂之獲得高性能之I陽 電池。 &lt;實施例5〜7&gt; 如表1所示，實施例5〜7中，將使向導電性糊漿之特定之 添加粒子（LiAlShO6粒子' LiAlSisOs粒子或矽酸鋁粒子 (AhSi〇5))之添加量相對於導電性粒子1〇〇重量份為丄〇重量 伤的導電性糊漿用於太陽電池之表面電極形成用而試作出 太陽電池。再者，太陽電池製作時之燒成之峰值溫度係於 實施例5〜7之情形時為775t。表1表示所獲得之太陽電池 之太陽電池特性之測定結果。 153910.doc •25· 201202367 [表i] 燒成 峰值溫度 特定之 添加粒子 添加量 (相對於導 電性粒子100 重量份之 重量份） 填充因數 (FF) 轉換效率 串聯電阻 Rs(Q) 金屬帶之 接著強度 (N) 比較例1 750〇C - 0.0 0.748 16.32% 0.840 4.5 實施例1 750〇C β-鋰霞石 (LiAlSi04) 0.5 0.779 16.81% 0.610 4.3 實施例2 750〇C β-鋰霞石 (LiAlSi04) 1.0 0.783 16.84% 0.580 3.8 比較例2 775〇C _ 0.0 0.757 17.09% 0.680 4.8 實施例3 775〇C β-鋰霞石 (LiAlSi04) 0.5 0.774 17.34% 0.600 4.7 實施例4 775 °C β-鋰霞石 (LiAlSi04) 1.0 0.779 17.26% 0.555 4.5 實施例5 775〇C LiAlSi2〇6 1.0 0.777 17.25% 0.562 - 實施例6 775。。 LiAlSi3〇8 1.0 0.779 17.23% 0.581 - 實施例7 775 °C Al2Si05 1.0 0.776 17.20% 0.581 - 根據表1所示之測定結果明瞭，於燒成峰值溫度為750°c 之情形時，與比較例1相比較，實施例1及2之填充因數 (FF)及轉換效率較高，串聯電阻之值較低。同樣地，明瞭 於燒成峰值溫度為775°C之情形時，於實施例3及4之情形 時，可獲得與比較例2相比更優異之性能之太陽電池。根 據以上情況明瞭，於使用含有β-鋰霞石粒子之導電性糊漿 之情形時，可獲得更優異之性能之太陽電池。 根據表1所示之測定結果明瞭，與比較例1及2相比較， 實施例5及6之填充因數（FF)及轉換效率較高，串聯電阻之 值較低。因此，作為特定之添加粒子，於使用β -鐘霞石粒 子以外之鋰霞石粒子（LiAlSi206粒子或LiAlSi308粒子）之情 形時，可獲得與比較例1及2相比較更優異之性能之太陽電 池。然而，使用β-鋰霞石粒子之實施例3及4之太陽電池之 153910.doc -26- 201202367 性能，較使用β-鋰霞石粒子以外之鋰霞石粒子（LiAlsi2〇6 粒子或LiAlShO8粒子）之實施例5及6之情形高。 根據表1所示之測定結果明瞭，與比較例丨及2相比較， 實施例7之填充因數（FF)及轉換效率較高，串聯電阻之值 較低。因此，於作為特定之添加粒子，使用矽酸鋁粒子 (AhSiOd之情形時，可獲得與比較例丨及2相比較更優異之 性能之太陽電池。然而，使用鋰霞石粒子之實施例3〜6之 太陽電池之性能較使用實施例7之矽酸鋁粒子（AUiOs)之 情形高^ 再者，確認到於β-鋰霞石粒子添加量（相對於導電性粒 子1〇〇重量份之重量份）超過2重量份之導電性糊漿之情形 時，電極形成後之金屬帶之焊接變得稍微困難，於使用超 過5重量份之導電性糊漿之情形時，電極形成後之金屬帶 之焊接變得困難。 【圖式簡單說明】 圖1係結晶系矽太陽電池之表面電極附近之剖面模式 圖。 【主要元件符號說明】 1 光入射側電極（表面電極） 2 抗反射膜 3 η型擴散層（η型石夕層） 4 Ρ型矽基板 5 背面電極 153910.doc -27-Al2〇3 (A-50-K manufactured by Showa Denko) and Si〇2 (SO_E2 manufactured by Admatechs). These starting materials were weighed to the Mohr ratio as described below, and wet-mixed by ion milling using a ball mill for 16 hours. As a raw material of LiAlSi04, Li2C03:Al2〇3:Si〇2=l:l:2 (mole ratio) was used. As a raw material of LiAlSi206, Li2C03:Al2〇3:Si〇2=l:l:4 (mole ratio) was used. As a raw material of LiAlSi3〇8, Li2C03: Al203:SiO2 = 1: 1: 6 (Mo ratio) was used. These starting materials were heated while stirring, and the slurry was concentrated, and then allowed to stand in a drying oven at 150 ° C for 12 hours, and allowed to dry. The dried powder was pulverized by a mortar to form a mixed powder. Next, 'the mixed powder was filled in a mold, and the molded body was produced by uniaxial pressing, and it was heated to 丨丨〇〇°c at a heating rate of 400 Κ/time and held for 4 hours. The inside is naturally cooled to obtain the target substance of 153910.doc 201202367. The synthesis of the target substance obtained in the above manner can be determined by the X-ray diffraction method (XRD). The xrd method was measured using Ultima IV manufactured by Rigaku Co., Ltd., and the phase of the synthetic substance was pDXL manufactured by Rigaku Co., Ltd. The synthesized material was sufficiently pulverized by a mortar to prepare a powder for XRD measurement. It was confirmed by the XRD method that the target substance used in the examples had a specific crystal structure. The synthesized aluminosilicate is pulverized by a mash, and then pulverized by a wet ball mill using ion exchange water, and micronized. Next, the materials of the specific modulation ratio described above were mixed by a comet type mixer, and further dispersed and pulverized by a trimer mill to prepare a conductive paste. &lt;Testing of Solar Cell Substrate&gt; The evaluation of the electrode-forming conductive paste I of the present invention was carried out by using a prepared conductive paste as a solar cell and collecting the characteristics. The test method for the solar cell is as follows. The substrate is doped with a B-type (Si) polycrystalline substrate (the thickness of the substrate is μ μη). First, a layer of about 20 μm is formed by dry oxidation on the substrate, and then a mixed fluorinated layer is used. ~ Another solution of bismuth telluride, pure water and ammonium fluoride is etched to remove the damage on the surface of the substrate. # Further'A heavy metal cleaning is carried out using an aqueous solution containing hydrochloric acid and hydrogen peroxide. Next, what is done by wet etching? The surface of the slab is textured (concave and convex 1539l0.doc -22-201202367). Specifically, a pyramidal texture is formed on one side (the surface on the light incident side) by a wet etching method (aqueous sodium hydroxide solution). Thereafter, the cleaning is performed using an aqueous solution containing hydrochloric acid and hydrogen peroxide. Then, on the textured surface of the substrate, phosphorus is used, and phosphorus is diffused at a temperature of 95 Å by diffusion method. 3 minutes, the n-type diffusion layer is formed into an n-type diffusion layer at a depth of about 0.5 μΓη. The sheet resistance of the n-type diffusion layer is 50 Ω/□. Next, on the substrate on which the n-type diffusion layer is formed The tantalum nitride film is formed into a thickness of about 6 nm by using a CVD gas and an ammonia gas by a plasma CVD (Chemical Vapor Deposition) method. Specifically, by NH3/SiH4= The mixed gas i T〇rr (133 pa) of 0_5 is decomposed by glow discharge, and a tantalum nitride film (antireflection film) having a film thickness of about 6 Å is formed by a plasma CVD method. The solar cell substrate thus obtained is cut. It is used for a square of 15 mm x 15 mm. Printing of the conductive paste for the light incident side (surface) electrode is carried out by screen printing. On the antireflection film of the above substrate, the film thickness is made about 20 μηι is printed with a pattern of a total electrode portion of 2 mm square and a finger electrode portion of a width of 1 〇〇^, and then dried at 15 (TC for about 1 minute. Second, by screen printing) Printing of the conductive paste for the back electrode is performed. On the back surface of the above substrate, a conductive paste of 12 mm square, which is mainly composed of Lu particles, glass frit, ethyl cellulose and solvent, is printed, and is 150. (: Dry for 1 minute. Backside after drying The film thickness of the conductive paste is about 20 μm. 1539l0.doc -23- 201202367 A near-infrared firing furnace using a halogen lamp as a heating source (a high-speed firing test furnace for solar cells manufactured by GAISI, Japan) The substrate on which the conductive paste is printed on the front and back surfaces is fired in the air under specific conditions. The firing conditions are 750 ° C or 775. (: peak temperature, atmospheric "fired furnace" In the inside and outside, the two sides were simultaneously fired in 30 seconds. As described above, the solar cell was tried. &lt;Measurement of solar cell characteristics&gt; The measurement of the electrical characteristics of the solar cell was carried out as follows. That is, the current-voltage characteristics of the tested solar cell were measured under the illumination of the solar simulator light (AM 1.5, energy density 1 〇〇 mW/cm 2 ), and the filling factor (FF) and conversion efficiency were calculated based on the measurement results ( 〇/〇) and series resistance Rs(Q). Further, in the case of the sample, two identical conditions were produced, and the measured values were obtained as two average values. &lt;Measurement of Subsequent Strength&gt; The sample for measurement of the strength of the metal strip to be welded was prepared and tested as follows. First, as the substrate, a solar cell substrate having an anti-reflection film of 15 Å square is used in the same manner as for measuring solar cell characteristics. A solder pad having a width of 3 Å and a length of 12 Å is printed on the center of the substrate by using a specific conductive paste, and dried and fired. Secondly, the metal strip for interconnection is a copper strip (width 15 mmx full thickness 〇16 mm, coated with eutectic solder with a film thickness of about 40 μηι [tin: lead = 64: % weight using flux on the solder pad) Solder at a temperature of 250 ° C for 3 seconds ratio]), clock. Thereafter, the ring portion provided at the end of the belt is made by a digital tensile tester (A&amp;T made by the digital dynamometer dyad 4%25 and relative to the substrate 153910.doc • 24 - 201202367 The surface was stretched in the direction of 90 degrees, and the subsequent breaking strength was measured to measure the adhesive strength. Further, one sample was prepared, and the measured values were obtained as the average value of the samples. <Examples 1 to 4 and comparison Examples 1 and 2&gt; As shown in Table 1, in Examples i to 4, the amount of the lithium nepheline particles added to the conductive paste was changed to 丨〇〇.〇 with respect to the conductive particles. The conductive paste of ~1_〇 parts by weight is used for the formation of the surface electrode of the solar cell, and the solar cell is tried. Further, the peak temperature of the firing at the time of production of the solar cell is in Comparative Example 1 and Example 丨 and In the case of 2, it is 75 〇, and in the case of Comparative Example 2, Examples 3 and 4, it is 775. Table] shows the measurement result of the solar cell characteristics of the obtained solar cell. Further, between the substrate and the electrode The contact resistance has a great influence on the series resistance. Therefore, it can be said that φ is connected. The resistance value is an index indicating the magnitude of the contact resistance. When the value of the series resistance is low, it can be said that a high-performance I-yang battery is obtained. <Examples 5 to 7> As shown in Table 1, Example 5 In the case of ～7, the amount of the specific particles (LiAlShO6 particles 'LiAlSisOs particles or aluminum silicate particles (AhSi〇5)) added to the conductive paste is 丄〇 by weight relative to 1 part by weight of the conductive particles. The damaged conductive paste was used for the formation of the surface electrode of the solar cell, and the solar cell was tried. Further, the peak temperature of the firing at the time of production of the solar cell was 775 t in the case of Examples 5 to 7. Table 1 shows The measurement result of the solar cell characteristics of the obtained solar cell. 153910.doc •25· 201202367 [Table i] The amount of added particles specific to the peak temperature of firing (parts by weight relative to 100 parts by weight of the conductive particles) Filling factor ( FF) Conversion efficiency series resistance Rs(Q) Metal strip strength (N) Comparative Example 1 750〇C - 0.0 0.748 16.32% 0.840 4.5 Example 1 750〇C β-eucryptite (LiAlSi04) 0.5 0.779 16.81% 0.610 4.3 Example 2 750 C β-eucryptite (LiAlSi04) 1.0 0.783 16.84% 0.580 3.8 Comparative Example 2 775〇C _ 0.0 0.757 17.09% 0.680 4.8 Example 3 775〇C β-eucryptite (LiAlSi04) 0.5 0.774 17.34% 0.600 4.7 Example 4 775 °C β-eucryptite (LiAlSi04) 1.0 0.779 17.26% 0.555 4.5 Example 5 775〇C LiAlSi2〇6 1.0 0.777 17.25% 0.562 - Example 6 775. . LiAlSi3〇8 1.0 0.779 17.23% 0.581 - Example 7 775 °C Al2Si05 1.0 0.776 17.20% 0.581 - According to the measurement results shown in Table 1, when the peak temperature of firing was 750 ° C, it was compared with Comparative Example 1. In comparison, the fill factor (FF) and conversion efficiency of Examples 1 and 2 are high, and the value of series resistance is low. Similarly, in the case where the firing peak temperature was 775 ° C, in the case of Examples 3 and 4, a solar cell having superior performance as Comparative Example 2 was obtained. From the above, it is apparent that when a conductive paste containing ?-eucryptite particles is used, a solar cell having more excellent performance can be obtained. According to the measurement results shown in Table 1, the filling factor (FF) and the conversion efficiency of Examples 5 and 6 were higher than those of Comparative Examples 1 and 2, and the value of the series resistance was low. Therefore, as a specific additive particle, in the case of using a nepheticite particle (LiAlSi206 particle or LiAlSi308 particle) other than the β-homocite particle, a solar cell having superior performance as compared with Comparative Examples 1 and 2 can be obtained. . However, the performance of 153910.doc -26-201202367 of the solar cells of Examples 3 and 4 using β-eucryptite particles is higher than the use of the lithium nepheline particles (LiAlsi2〇6 particles or LiAlShO8 particles) other than the β-eucryptite particles. The cases of Examples 5 and 6 are high. According to the measurement results shown in Table 1, the filling factor (FF) and the conversion efficiency of Example 7 were higher than those of Comparative Examples and 2, and the value of the series resistance was low. Therefore, when aluminum silicate particles are used as the specific additive particles (in the case of AhSiOd, solar cells having superior performance as compared with Comparative Examples and 2 can be obtained. However, Example 3 using the nepheline particles is used. The performance of the solar cell of 6 is higher than that of the case of the aluminum silicate particle (AUiOs) of Example 7. Furthermore, the addition amount of the β-eucryptite particle (the weight of 1 part by weight relative to the conductive particle) was confirmed. In the case of more than 2 parts by weight of the conductive paste, the welding of the metal strip after the electrode formation becomes somewhat difficult, and when more than 5 parts by weight of the conductive paste is used, the metal strip after the electrode is formed Fig. 1 is a schematic cross-sectional view of the vicinity of the surface electrode of a crystalline solar cell. [Explanation of main component symbols] 1 Light incident side electrode (surface electrode) 2 Antireflection film 3 η type Diffusion layer (n-type sap layer) 4 Ρ-type 矽 substrate 5 back electrode 153910.doc -27-

Claims (1)

201202367 七、申請專利範圍： 1. 一種導電性糊漿，其係結晶系矽太陽電池之電極形成用 導電性糊漿，含有包含銀之導電性粒子、玻璃料、特定 之添加粒子、有機黏合劑及溶劑，且特定之添加粒子係 自鋁矽酸鹽粒子及矽酸鋁粒子_選擇之1種以上。 2.如請求項1之導電性糊漿，其中鋁矽酸鹽粒子包含鋰。 3 ·如請求項1之導電性糊漿，其中鋁矽酸鹽粒子為p_鋰霞石 粒子。 4. 如請求項1至3中任一項之導電性糊漿，其十鋁矽酸鹽粒 子之含量相對於導電性粒子100重量份為〇重量份。 5. 如請求項1至3中任一項之導電性糊漿，其中玻璃料包含 PbO。 中PbO之含量相對於玻璃料 6·如請求項5之導電性糊漿，各 100重量％為5 0〜90重量％。 7. 一種太陽電池之製造方法，其包括如下步驟：將如請求 項1至6中任一項之導電性糊漿印刷於結晶系石夕基板之η 型石夕層上或η型石夕層上 釺 、 /層上之抗反射膜上，並進行乾燥及燒 成，藉此形成電極。 8. 一種太陽電池，其藉由如請灰 月求項7之製造方法而製造。 153910.doc201202367 VII. Patent application scope: 1. A conductive paste, which is a conductive paste for forming an electrode of a crystal system solar cell, containing conductive particles containing silver, glass frit, specific additive particles, and organic binder. Further, the solvent is added, and the specific added particles are one or more selected from the group consisting of aluminosilicate particles and aluminum silicate particles. 2. The conductive paste of claim 1, wherein the aluminosilicate particles comprise lithium. 3. The conductive paste of claim 1, wherein the aluminosilicate particles are p-eucryptite particles. 4. The conductive paste according to any one of claims 1 to 3, wherein the content of the decanoic acid particles is 〇 by weight based on 100 parts by weight of the conductive particles. 5. The conductive paste of any one of claims 1 to 3, wherein the glass frit comprises PbO. The content of PbO in the middle is relative to the glass frit. 6. The conductive paste of claim 5 is 100% by weight to 50% by weight to 90% by weight. A method of manufacturing a solar cell, comprising the steps of: printing a conductive paste according to any one of claims 1 to 6 on a η-type sap layer of a crystalline system substrate or a η-type sap The anti-reflection film on the upper layer/on layer is dried and fired to form an electrode. A solar cell manufactured by the manufacturing method of the item 7 of the present invention. 153910.doc
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