TW201133512A - Paste composition for electrode and photovoltaic cell - Google Patents
Paste composition for electrode and photovoltaic cell Download PDFInfo
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- TW201133512A TW201133512A TW100102726A TW100102726A TW201133512A TW 201133512 A TW201133512 A TW 201133512A TW 100102726 A TW100102726 A TW 100102726A TW 100102726 A TW100102726 A TW 100102726A TW 201133512 A TW201133512 A TW 201133512A
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- electrode
- particles
- mass
- copper
- silver
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- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 239000002245 particle Substances 0.000 claims abstract description 228
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- 239000010949 copper Substances 0.000 claims abstract description 122
- 229910052802 copper Inorganic materials 0.000 claims abstract description 122
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- 239000004332 silver Substances 0.000 claims description 81
- -1 metal compound salts Chemical class 0.000 claims description 37
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- 238000004381 surface treatment Methods 0.000 claims description 23
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- 235000003441 saturated fatty acids Nutrition 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
- H01L31/02245—Electrode arrangements specially adapted for back-contact solar cells for metallisation wrap-through [MWT] type solar cells
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Conductive Materials (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
201133512 六、發明說明: 【發明所屬之技術領域】 本發明是有關於一種電極用膏狀組合物及光伏電池。 【先前技術】 一般於光伏電池中設置有表面電極,該表面電極的配 線電阻或接觸電阻與同轉換效率相關的電壓損失有關聯, 另外’配線寬度或形狀會對太陽光的入射量產生影響(例 如’參照濱川圭弘著’「太陽光發電最新的技術與系統」, CMC 出版社 ’ 2001 年,p26-p27)。 光伏電池的表面電極通常是以如下方式形成。即,於 藉由使磷等在高溫下熱擴散於p型矽基板的受光面側而形 成的η型半導體層上,利用網版印刷等塗佈導電性組合 物’然後於麵。C〜900。(:下對其進行煅燒,藉此形成表面 電極。形成該表面電極的導電性組合物中包含導電性金屬 粉末、玻璃粒子、以及各種添加劑等。 作為上述導電性金屬粉末,一般使用銀粉末,但因各 種理由,業界j£研究使祕粉末以外的金屬粉末。例如, 揭示有可形成包含銀與_光伏電池用電極的導電性组人 物(例如’參照日本專利特開2〇〇6_313744號公趣另:,201133512 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a paste composition for an electrode and a photovoltaic cell. [Prior Art] A surface electrode is generally provided in a photovoltaic cell, and the wiring resistance or contact resistance of the surface electrode is related to a voltage loss associated with conversion efficiency, and 'the width or shape of the wiring affects the incident amount of sunlight ( For example, 'Recognition of Hiroshi Kawakawa's "The Latest Technology and System for Solar Power Generation," CMC Press, 2001, p26-p27). The surface electrodes of photovoltaic cells are typically formed in the following manner. In other words, the conductive composition is applied to the n-type semiconductor layer formed by thermally diffusing phosphorus or the like on the light-receiving surface side of the p-type germanium substrate at a high temperature, and then applied to the surface by screen printing or the like. C~900. (The surface electrode is formed by calcination, and the conductive composition forming the surface electrode contains conductive metal powder, glass particles, various additives, etc. As the conductive metal powder, silver powder is generally used. However, for various reasons, the industry has studied the use of metal powders other than powders. For example, it has revealed that there are conductive groups that can form electrodes for silver and photovoltaic cells (for example, see Japanese Patent Laid-Open No. 2-6-313744). Interesting another:,
现公報 J 〇 由於資源的問題、 是出一種替代含有銀 -般用於電極形成的銀是貴金屬,由於 以及原料金屬本身價格高,因此期望提出二 3 201133512 性組合物(含有銀的膏)的膏狀材料。作為有希望 ,可列舉應用於半導體配線材料中的鋼。銅 不僅資源豐富1且原料金屬成本亦為銀_百分之 廉價。但是,銅是於以上的高溫下容易氧化的材料, 例如’為料敎獻2中所記載的電極形成用組合物 成電極,需要於氮氣等的環境下進行煅燒這-特 【發明内容】 本發明的課題在於提供一種抑制炮燒時的銅的氧化膜 的形成’可形成電阻率低的電極的電極用膏狀組合物,以 及具有使⑽電極料狀組合物所形成的t極的光伏電 池。 入本發明的第-型態是—種電極用膏狀組合物,其包 3以銅為主成分的金屬粒子、助熔劑、玻璃粒子、溶劑、 以及樹脂。電極用膏狀組合物較佳為更包含銀粒子。上述 以銅為主成分的金屬粒子較佳為選自含磷的銅合金粒子, 被銀包覆_粒子,以及_選自由三魏合物、飽和脂 肪酸、不飽和脂肪酸、無機金屬化合物鹽、有機金屬化= 物鹽、聚笨胺系樹脂、及金屬烷氧化物所組成的組群中的 至種進行表面處理而成的銅粒子的至少一種。上述助 熔劑較佳為選自脂肪酸、硼酸化合物、氟化物、以及硼氟 化物的至少一種。上述玻璃粒子較佳為含有包含磷的氧化 物。 本發明的第2型態是一種光伏電池,其具有對被賦予 4 201133512 —.•泰· 膏狀組合物進行魏卿成的電 至梦基板上的上述電極用 極0 [發明的效果] 所形 為^發明之上述和其他目的、特徵和伽能更明顯 文特舉難實_,並配合所關式,作詳細說 時亦抑制鋼化::::種藉由助熔劑的添加而於煅燒 =£?===:電 明如下 【實施方式】 以下 對本發明的實施形態進行詳細說明。再者, 最T 2: i「〜」表示分別包含其前後所記載的數值作為 最小值及敢大值的範圍。 <電極用膏狀組合物> 本發明的電極用膏狀組合物包含:至少一種以鋼為主 成分的金屬粒子、至少—種祕劑、至少—種玻璃粒子、 至少一種溶劑、以及至少一種樹脂。 藉由為上述構成,於煅燒時亦抑制銅的氧化膜的生 成,可形成電阻率低的電極。 (以銅為主成分的金屬粒子) 本發明中的以銅為主成分的金屬粒子(以下,有時稱 為「含有銅的粒子」)表示1個金屬粒子中的銅成分的含量 為50質量%以上的金屬粒子。 201133512 構成上述銅粒子的銅可為除純銅以外,亦可於盔 =效==有實質上由鋼構成的金屬粒^的其 村為包含銅及對銅賦㈣氧化㈣成分的金屬 作為上述實質上由銅構成的金屬The current publication J 〇 is a precious metal due to the resource problem, and silver which is used for electrode formation instead of silver. Since the raw material metal itself is expensive, it is desirable to propose a 2 3 201133512 composition (silver containing paste). Paste material. As a promising, steel used in a semiconductor wiring material can be cited. Copper is not only rich in resources, but also the cost of raw metal is also silver. However, copper is a material which is easily oxidized at the above-mentioned high temperature. For example, the composition for forming an electrode described in the above-mentioned item 2 is an electrode, and it is necessary to be calcined in an atmosphere such as nitrogen gas. An object of the invention is to provide a paste composition for an electrode which suppresses formation of an oxide film of copper during firing, and which can form an electrode having a low specific resistance, and a photovoltaic cell having a t-pole formed by (10) an electrode material composition. . The first embodiment of the present invention is a paste composition for an electrode, which comprises metal particles containing copper as a main component, a flux, glass particles, a solvent, and a resin. The paste composition for an electrode preferably further contains silver particles. The metal particles mainly composed of copper are preferably selected from the group consisting of phosphorus-containing copper alloy particles, coated with silver particles, and _ selected from the group consisting of triweis, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, and organic Metallization = at least one of copper particles obtained by surface treatment of a group consisting of a salt of a salt, a polyaniline resin, and a metal alkoxide. The flux is preferably at least one selected from the group consisting of a fatty acid, a boric acid compound, a fluoride, and a borofluoride. The above glass particles preferably contain an oxide containing phosphorus. A second aspect of the present invention is a photovoltaic cell having the above-mentioned electrode for the electrode on the Dream substrate which is imparted with the composition of the 4 201133512-.•Tai paste composition. The above and other purposes, features and gamma of the invention are more obvious and difficult to _, and in conjunction with the closed type, the tempering is also inhibited in detail:::: by the addition of flux Calcination = £? ===: The following is a description of the embodiments of the present invention. Further, the most T 2: i "~" indicates a range including the numerical values described before and after the minimum value and the dare value. <Paste composition for electrode> The paste composition for an electrode of the present invention comprises: at least one metal particle containing steel as a main component, at least a seed agent, at least one type of glass particle, at least one solvent, and at least A resin. According to the above configuration, the formation of an oxide film of copper is suppressed during firing, and an electrode having a low specific resistance can be formed. (Metal particles containing copper as a main component) The metal particles containing copper as a main component in the present invention (hereinafter sometimes referred to as "particles containing copper") mean that the content of the copper component in one metal particle is 50 mass. More than % of metal particles. 201133512 The copper constituting the copper particles may be a metal other than pure copper, or may be a metal particle composed substantially of steel, and a metal containing copper and a component of oxidizing (4) to copper may be used as the above substance. Metal made of copper
Au 等 S、T卜 V、%、八卜心、W、M〇、Ti、Co、Ni、 ^圭為Ϊ;Α1賴細氧雜、溶‘料雜喊點而言, 率例=上= :中所包含的其他原子的含有 ^ 中,可設^為3質量%以下, ml低電阻率的觀點而言,較㈣1質量%以下。 佳為與對鋼賦予耐氧化性的成分的金屬粒子較Au, etc. S, T Bu V, %, Ba Bu Xin, W, M〇, Ti, Co, Ni, ^ Gui is Ϊ; Α 1 细 氧 氧 、, dissolved 'material 喊 shouting point, rate example = up = The content of the other atoms contained in the middle may be 3% by mass or less, and from the viewpoint of the low resistivity of the liquid, it is (4) or less by mass%. It is better to use metal particles with a component that imparts oxidation resistance to steel.
Themd A 1 .同時測定(丁^咖抑—卿服⑽如1 ^ennd Analysis ’ TG_DTA)中表示最大 燒時氧化性的含有_子’圾 以M抑制’可形成低電阻率的電極。 定#署:敎;' 二時剩定是於通常的大氣中,使用作為測 =裝置的熱D㈣置(SII Nan 造,TG/DTA-6200型)來進行。 gy A J製 作為上賴f-衫叫;収(TGDTA)巾表示 面積的發熱波峰的波峰溫度為·。c以上的含有銅的粒 6 201133512 子,具體而言,例如可列舉:含磷的銅合金粒子、被銀包 覆的銅粒子、以及經表面處理的銅粒子。 上述含有鋼的粒子可單獨使用一種,亦可組合使用 種以上。 上述含有鋼的粒子的粒徑並無特別限制,作為累計的 =為50%時的粒徑(以下,有時略記為「〇5〇%士較 為〇.4卿〜10卿’更佳為1哗〜7师。藉由設定為〇 4 μηι以上’耐氧化性更有效地提昇。另外,藉】 2 ’電極t的含有銅的粒子彼此的接觸面積變大,電阻Themd A 1 . Simultaneously measuring (in the case of 1 ^ennd Analysis 'TG_DTA), the electrode containing the maximum oxidization at the time of oxidization of M can suppress the formation of a low resistivity electrode.设定#署:敎;' The second time is left in the normal atmosphere, using the heat D (four) set as the test = device (SII Nan, TG / DTA-6200 type). The gy A J system is called the upper-f-shirt; the TGDTA towel indicates the peak temperature of the heat peak of the area. Specific examples of the above-mentioned copper-containing particles 6 201133512 include phosphorus-containing copper alloy particles, silver-coated copper particles, and surface-treated copper particles. The steel-containing particles may be used singly or in combination of two or more. The particle diameter of the steel-containing particles is not particularly limited, and the particle diameter when the cumulative value is 50% (hereinafter, it may be abbreviated as "〇5〇% 〇.4 qing~10 qing" is preferably 1哗~7 division. By setting it to 〇4 μηι or more, the oxidation resistance is more effectively improved. In addition, the contact area of the copper-containing particles of the 2' electrode t becomes larger, and the resistance is increased.
St::再者,含有銅的粒子的粒徑是藉由粒度 〇叫(曰機裝公司製造,㈣_型) ㈣另f ’上述含有朗粒子的形狀並鱗·制,可為 ^狀、扁平狀、塊狀、板狀、及鱗片狀等中的任 肤,、 生與低電阻率的觀點而言,較佳為球狀、扁ί狀: 銅的;膏所包含的上述含* 有銅的粒子與銀粒子的總含有率^1^!^立7子2的含 72 f *〇/o^9〇 t4〇/o , ?4 -含麟的銅合金粒子- 質里/〇。 2為含磷的銅合金,已知有被稱為 質遣右)的釺焊材料。•釺料亦可用作鋼:度的 201133512 =。齊]#由使用含磷的銅合金粒 :狀=中所包含的含有銅的粒子,可形成耐氧= 心 Γ&的電極。進而’可獲得電極的低溫锻燒成為 可月b,可削減製程成本的效果。 作為本發明中的含磷的銅合金中所包含的填含有率, 熱差同時測^中表示最大面積的發熱波峰 歎以上的含有率。具體而言,作為含 =銅合金中所包含_含有率,於㈣的銅合金的總質 士 佳為設定成°·。1質量%〜8質量%,更佳為設定 .量/〇〜7·8質量%,進而更佳為設定成1質量。/。〜 7.5質量%。 藉由含碟的銅合金中所包含的鱗含有率為8質量%以 下’可達成更低的電阻率’且含翻銅合金的生產性優異。 另外藉由W含有率為〇 〇1質量%以上可達成更優異的 耐酸性。 上述含碌的銅合金粒子是包含銅與翻合金,但亦可 更Ο 3其他原子。作為其他原子,例如可列舉:%、si、 K Na、Li、Ba、Sr、Ca、Mg、Be、Zn、Pb、Cd、Ή、V、 =、A卜 Zr、W、Mo、Ti、Co、Ni、Au 等。其中,就調 整耐氧化性、熔點等特性的觀點而言,較佳為包含. 另外’上述含鱗的銅合金粒子中所包含的其他原子的 S有率例如於上述含磷_合金粒子巾,可設定為3質量 %以下,就耐氧化性與低電阻率的觀點而言,較佳 量%以下。 8 201133512 上述含_銅合金粒子的粒徑並無特別限制 計的質量為50%時的粒徑(以下’有時略記為「⑽/、’、 較佳為0.4 μιη〜10卿’更佳為! _〜5㈣。藉由_ 0.4㈣以上’耐氧化性更有效地提昇。另外,藉由為^^ 以下’電極中的含_銅合金粒子彼此的接觸 , 電阻率更有效地下降。 八 另外’上述含磷_合錄子的额並無特別限制, 可為球狀、扁平狀、塊狀、板狀、及鱗片狀等中的任 =’就耐氧化性與低電阻率的觀點而言,較佳為球狀種 局平狀、或板狀。 含填的銅合金可藉由通常所使用的方法來製造 =含填的銅合金粒子可使用以達到所期望的碟含有率的 =製備的含磷的銅合金,製備金屬粉末的通常的方 =製備,例如’可水霧化法肋钱 法於金屬便覽(丸善(股份)出版事業部有 具體而言’例如使含磷的銅合金溶解,藉由喷嘴喷霧 2粉末化後’對所獲得的粉末進行乾燥、分級 級條件’可製造具有所期望的粒徑的含二 =為本發_電極用纽組合物巾所包含的上述含碟 的i:金粒子的含有率,另外,作為包含後述的銀粒子時 =的銅合金粒子與銀粒子的總含有率,例如可設定為 量%〜94質量%’就耐氧化性與低電阻率的觀點而 9 201133512 言,較佳為72質量%〜90質量%,更佳為74質量。/ 8 質量%。 ° 8 另外’於本發明中,上述含磷的銅合金粒子可單獨使 用一種,亦可組合使用兩種以上。另外,亦可與含磷的鋼 合金粒子以外的含有銅的粒子組合使用。 進而,於本發明中,就耐氧化性與電極的低電阻率的 觀點而言,較佳為於電極用膏狀組合物中包含磷含有率為 0.01質量%〜8質量%的含磷的銅合金粒子7〇質量%二pi 質量%,更佳為於電極用膏狀組合物中包含磷含有率為^ 質量%〜7·5質量%的含磷的銅合金粒子74質量 量%。 貞 -被銀包覆的銅粒子_ 作為本發明中的被銀包覆的銅粒子,只要是銅粒子的 少一部分被銀包覆的銅粒子即可。藉由使用被銀 銅粒子作為本發_電極用膏狀組合物巾所包含的 2 =子’可形成耐氧化性優異、電阻率低的電極。 粒:’銅粒子與銀粒子的界面電阻 卜啤4成電阻率進-步下降的 合物中時,藉由使用被銀包= L用:效果_·可抑制室溫下的銅的氧化,並可提 率),作 包覆的銅粒子中的_包覆量(銀含有 率)較佳為如熱重-熱差同時測 波峰的波料度翻娜⑶切包覆 201133512St:: In addition, the particle size of the particles containing copper is squeaked by particle size (manufactured by 曰 Machine Co., Ltd., (4) _ type) (4) The other shape of the above-mentioned granules is scaly, and can be Any of the flat, block, plate, and scaly shapes, in terms of raw and low resistivity, is preferably spherical or flat: copper; the above-mentioned inclusions included in the paste have The total content of copper particles and silver particles is ^1^!^ 7 7 2 contains 72 f *〇/o^9〇t4〇/o, ?4 - copper alloy particles containing lining - quality / 〇. 2 is a phosphorus-containing copper alloy, and a soldering material called a right-handed right is known. • Dip can also be used as steel: degree 201133512 =. Qi] # By using phosphorus-containing copper alloy particles: the shape of the copper-containing particles contained in the shape can form an electrode with oxygen resistance = Γ & Further, the low-temperature calcination of the electrode can be obtained as the monthly b, and the effect of the process cost can be reduced. The content ratio of the filling ratio included in the phosphorus-containing copper alloy in the present invention is the ratio of the heat loss to the peak area of the maximum area. Specifically, the total mass of the copper alloy in (4) is preferably set to °· as the _ content ratio contained in the copper alloy. 1% by mass to 8 mass%, more preferably set. The amount / 〇 ~ 7.8 mass%, and more preferably set to 1 mass. /. ~ 7.5 mass%. The content of the scale contained in the copper alloy containing the dish is 8 mass% or less, and the lower resistivity can be achieved, and the productivity of the copper-containing alloy is excellent. Further, by having a W content of 〇 〇 1% by mass or more, more excellent acid resistance can be achieved. The above-mentioned copper alloy particles contain copper and alloy, but may also be more than 3 other atoms. Examples of the other atom include, for example, %, Si, K Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Ή, V, =, A, Zr, W, Mo, Ti, Co. , Ni, Au, etc. In addition, from the viewpoint of adjusting characteristics such as oxidation resistance and melting point, it is preferable to include. Further, the S ratio of other atoms contained in the scale-containing copper alloy particles is, for example, the phosphorus-containing alloy particle towel. The amount can be set to 3% by mass or less, and from the viewpoint of oxidation resistance and low electrical resistivity, the amount is preferably 5% or less. 8 201133512 The particle size of the above-mentioned copper-containing alloy particles is not particularly limited, and the particle diameter is 50% (hereinafter, it is abbreviated as "(10)/, ', preferably 0.4 μιη to 10 qing". _~5(4). The oxidation resistance is more effectively improved by _0.4 (four) or more. In addition, the resistivity is more effectively lowered by the contact of the copper-containing alloy particles in the 'electrode below'. The amount of the phosphorus-containing conjugate is not particularly limited, and may be any of spherical, flat, massive, plate-like, and scaly, etc., from the viewpoint of oxidation resistance and low electrical resistivity. Preferably, the spherical seed is flat or plate-shaped. The filled copper alloy can be produced by a commonly used method = the filled copper alloy particles can be used to achieve the desired dish content = preparation Phosphorus-containing copper alloy, the usual method for preparing metal powder = preparation, for example, 'water atomization method rib money method in metal handbook (Maruzen (stock) publishing division has specific 'for example, phosphorus-containing copper alloy Dissolved, dried by nozzle spray 2, 'drying the obtained powder The classification condition can produce a content ratio of the above-mentioned dish-containing i: gold particles contained in the composition containing the desired particle diameter, and the inclusion of the silver particles included in the present invention. The total content of the copper alloy particles and the silver particles may be, for example, from 0.01% to 94% by mass, from the viewpoint of oxidation resistance and low electrical resistivity. 9 201133512, preferably 72% by mass to 90% by mass, More preferably, it is 74 mass% / 8 mass%. ° 8 In the present invention, the phosphorus-containing copper alloy particles may be used singly or in combination of two or more. In addition, it may be combined with a phosphorus-containing steel alloy. Further, in the present invention, in the present invention, it is preferable that the phosphorus content of the paste composition for an electrode is 0.01 mass in terms of oxidation resistance and low resistivity of the electrode. % to 8 mass% of the phosphorus-containing copper alloy particles, 7 〇 mass%, two pi mass%, more preferably the phosphorus content in the paste composition for an electrode, containing phosphorus, and having a phosphorus content of 5% by mass to 7.5 mass% Copper alloy particles 74% by mass. The coated copper particles _ as the silver-coated copper particles in the present invention may be copper particles coated with a small amount of copper particles, and silver silver particles are used as the present invention. The 2 = sub- included in the compositional towel can form an electrode having excellent oxidation resistance and low electrical resistivity. Particles: 'The interface resistance between the copper particles and the silver particles is 4% in the resistivity of the composition. By using the silver package = L: effect _· can suppress the oxidation of copper at room temperature, and the extraction rate), the _ coating amount (silver content) in the coated copper particles is preferably For example, the thermogravimetry-heat difference is simultaneously measured by the peak of the wave crest (3) cut and covered 201133512
L 體而言,於被銀包覆的銅粒子的總 上,但就耐氧化性與電_低電阻質量如 =為3質量%〜80質量%,進而更佳為$質量二❶質 L被銀包覆的銅粒子的粒徑並無特別限制,作為 Ϊ:為【4 ;Γ的粒徑(以下,有時略記為「D5〇%」) ,佳為〇.4μιη〜10μιη,更佳為—〜— 0.4 μ^η以上,耐氧化性更有效地提昇。另外,藉^疋為 2率==包覆的銅粒子彼此的接觸面積變大阳 形狀’就耐氧化性與低電阻率的翻 種 扁平狀、或板狀。相觀點較佳為球狀、 =上賴銀包覆的銅粒子_亦可於無損本發 =範圍内包含其他原子嘈為其他原子,例如财The L body is on the total of the copper particles coated with silver, but the oxidation resistance and the electric_low resistance mass are, for example, 3% by mass to 80% by mass, and more preferably, the mass of the bismuth L is The particle size of the silver-coated copper particles is not particularly limited, and is Ϊ: [4; Γ particle size (hereinafter sometimes abbreviated as "D5 〇 %"), preferably 〇. 4 μιη to 10 μιη, more preferably —~— Above 0.4 μ^η, the oxidation resistance is improved more effectively. Further, the contact area between the copper particles coated with the second rate == becomes a large shape, and the oxidation resistance and the low resistivity are flattened in a flat shape or a plate shape. The phase is preferably spherical, and the copper particles coated with silver can also contain other atoms in the range of the loss = the range of other atoms, such as wealth.
Cd τ; λ Ll、如、Sr、Ca、岣、Be、Zn、Pb、 = Tl、V、Sn、A1、Zr、w、M〇、Ti、c〇、NiA4。 =αΓ調整耐氧化性、溶點等特性的觀點而言,較佳為 含所包含的其他原子的 0/,、,二 这被銀包覆的銅粒子中,可設定為3質量 /〇以下,就耐氧化性與低電阻率的觀點而言,較佳為ι質 201133512 量%以下。 另外,上述被銀包覆的銅粒子為藉由銀包覆已 磷的銅合金而成者亦較佳。藉此,耐氧化性進一步提= 所形成的電極的電阻率進一步下降。 ’ 關於被銀包覆的銅粒子中的含嶙的銅合金的詳 =其含義與已述的含鱗的銅合金相同,較佳的型態亦^ 作為上述被銀包覆的銅粒子的製備方法, 由銀包覆銅粒子(較佳為含磷的鋼合 :二: =分的製備方法,則並無特別限制 (或者含翻銅合金粉)分散於硫:: 二中’然後向該銅粉分散液中添加“ ===代::獲得的銅粉漿料中添加銀離子溶 ? 於銅粉表面上形成銀層。 酸鹽三乙二劑並=制’例如可使用:乙二胺四乙 作為銀離子溶液,五乙酸、亞胺二乙酸等。另外, 液例如可使用硝酸銀溶液等。 包覆==;;用另膏:組, :被銀包覆的鋼粒子與銀粒子的總含3後=粒子時 質量°/°,就耐氧化性與低電阻率的 2質量一量%,更佳 ;本發明中,上述被銀包覆的銅粒子可單獨使 12 2011335Π 用-種’亦可粗合使用兩種以上。 的銅粒子以外的含有銅的粒子組合使用。亦可,、被銀包覆 言,較ΐ:::二 低電阻率的觀點而 的總質量中的銀含有Ϊ。中包含被銀包覆的銅粒子 狀 覆的銅粒子74質量%〜88 #量 °、匕 被銀包覆_粒子與銀粒子的總==:4的銀粒子時的 曰進而’較佳為於電極用膏狀組合物中包含銀含有率為 1質$%〜88質量%、磷含有率為〇〇1質量%〜8質量〇/。的 被銀包覆的含伽銅合金粒子7G f量%〜94質量%(包含 後述的絲子_魏包覆的含磷_合錄子與銀粒子 的總含有率)’更佳為於電極用膏狀組合物中包含銀含有率 為5質量。/〇〜75質量%、磷含有率為i質量%〜7 5質量% 的被銀包覆的含磷的銅合金粒子74質量%〜88質量。/。(包 含後述的銀粒子時的被銀包覆的含碟的銅合金粒子與銀粒 子的總含有率)。 •經表面處理的銅粒子_ 本發明中的含有銅的粒子為利用選自由三唑化合物、 飽和脂肪酸、不飽和脂肪酸、無機金屬化合物鹽、有機金 屬化合物鹽、聚笨胺系樹脂、以及金屬烷氧化物所組成的 組群(以下,有時稱為「表面處理劑」)中的至少一種進行 13 201133512 表面處理而成的鋼粒子雜佳,更佳為利用選自由三嗤化 合物、飽和麟酸、不飽和麟酸、以及無機金屬化合物 鹽所組成的組群中的至少—誠行表面處理而成的銅粒 藉由使用以表面處理劑的至少―種進行表面處理而成 的銅粒子作為本發_電细纽組合物巾所包含的含有 銅的粒子’可形成耐氧化性優異、電阻率低的電極。進而, 當水分混人至電極用膏狀組合物巾時,藉由使用經表面處 理的銅粒子,可獲得如下效果:可抑制室溫下的銅的氧化, 並可提昇使用期限。 種 另外’於本發明中,上述表面處理劑可單獨使用 亦可組合使用兩種以上。 於本發明令,經表面處理的鋼粒子是利用選自由三唑 化合物、飽和脂肪酸、不飽和脂肪酸、無機金屬化合物鹽、 有,金屬化&物鹽、聚苯胺系樹脂、以及金屬烧氧化物所 組、的組群中的至少一種進行了表面處理, 併用其他表面處理劑。 “要方了 —,為上述表面處理劑中的三唑化合物,例如可列舉: 苯并一坐二唑等。另外,作為上述表面處理劑中的飽和 脂肪酸,例如可列身.在祕立鉍工缺外也和 _ j幻舉.庚酸、辛酸、壬酸、癸酸、十一酸、 酸、t三酸、十四酸、十五酸、硬脂酸、十九酸、花 酸等。另外,作為上述表面處理射的不餘 #月曰肪I ’例如可列舉:丙烯酸、甲基丙烯酸、丁烯酸、 異丁烯酸、十、油酸、反油酸、鯨油酸、蕓苔酸、 201133512 芥子酸、山梨酸、亞麻油酸、次亞麻油酸、花生油酸等。 另外’作為上述表面處理劑中的無機金屬化合物鹽, 例如可列舉:矽酸鈉、錫酸鈉、硫酸錫、硫酸鋅、鋅酸鈉、 硝酸鍅、锆酸鈉、氧氣化锆、硫酸鈦、氯化鈦、草酸鈦酸 鉀等。另外,作為上述表面處理劑中的有機金屬化合物鹽, 例如可列舉:硬脂酸鉛、乙酸鉛、四烷氧基锆的對異丙笨 基苯基衍生物、四烷氧基鈦的對異丙苯基苯基衍生物等。 另外,作為上述表面處理劑中的金屬烷氧化物,例如可列 舉:鈦烷氧化物、锆烷氧化物、鉛烷氧化物、矽烷氧化物、 錫烷氧化物、銦烷氧化物等。 々作為其他表面處理劑,例如可列舉十二烷基苯磺酸 等。另外,當使用硬脂酸或硬脂酸鉛作為表面處理劑時, 藉由併用硬脂酸及硬脂酸㈣至少—種與乙酸㈣為表面 處理劑,可形成耐氧化性進一步提昇、電阻率更低的電極。 本發明中的經表面處理的銅粒子只要銅粒子的表面的 至J 一部分被上述表面處理劑的至少一種包覆即可。作為 經表面處理的練子中所包含的表面處理_含量,較佳 2熱質·熱差同相定中表示最大面積的發熱波峰的波 ,度達到28CTC以上的含量。具體而言,較佳為於經表 ^處理的銅粒子的質量為請質量%以上,就魏化性與 率的觀點而言’較佳為於經表面處理的銅粒 中為0,01質量%〜1〇質量%,更佳為於經表面處 理的銅粒子的質量中為0.05質量%〜8質量%。 構成上述經表面處理的銅粒子的銅亦可於無損本發明 15Cd τ; λ Ll, such as, Sr, Ca, 岣, Be, Zn, Pb, = Tl, V, Sn, A1, Zr, w, M〇, Ti, c〇, NiA4. From the viewpoint of adjusting characteristics such as oxidation resistance and melting point, it is preferable that the copper particles coated with silver, which are 0/, and two other atoms contained, can be set to 3 mass/〇 or less. From the viewpoint of oxidation resistance and low electrical resistivity, it is preferably mascara 201133512 or less. Further, it is also preferable that the copper particles coated with silver are a copper alloy coated with phosphorus by silver. Thereby, the oxidation resistance is further improved = the resistivity of the formed electrode is further lowered. The details of the copper alloy containing bismuth in the copper particles coated with silver are the same as those of the scaly copper alloy described above, and the preferred form is also used as the preparation of the silver-coated copper particles. Method, the method for preparing copper-coated copper particles (preferably phosphorus-containing steel: two: = points, there is no particular limitation (or containing copper alloy powder) dispersed in sulfur:: two in the 'then Adding "=== generation:: added copper powder slurry to the copper powder dispersion to form a silver layer on the surface of the copper powder. The acid salt triethyl sulphate and the system can be used as follows: The amine tetraethyl is used as a silver ion solution, pentaacetic acid, imine diacetic acid, etc. Further, for example, a silver nitrate solution or the like can be used for the liquid. Coating ==;; Another paste: Group: Silver coated steel particles and silver particles The total content of 3 after = particle mass ° / °, in terms of oxidation resistance and low resistivity of 2 mass%, more preferably; in the present invention, the above-mentioned silver coated copper particles can be used alone 12 2011335 - The species may be used in combination of two or more kinds of copper particles, and copper-containing particles other than copper particles may be used in combination. ΐ::: The silver in the total mass from the viewpoint of the two low resistivity contains yttrium. The copper particles coated with silver-coated copper particles are 74% by mass to 88%, and the yttrium is coated with silver. In the case of the silver particles of the total ==:4 of the silver particles, it is preferable that the content of the silver contained in the paste composition for the electrode is 1% by mass to 88% by mass, and the phosphorus content is 〇〇1 by mass. The amount of 7g f of the gamma-containing alloy particles coated with silver of % to 8% by mass is ~% by mass to 94% by mass (including the total content of the phosphorus-containing synthons and silver particles of the filaments described below) It is more preferable that the paste composition for an electrode contains silver-containing phosphorus-containing copper having a silver content of 5 mass%, 〇 to 75 mass%, and a phosphorus content of i mass% to 7.5 mass%. The alloy particles are 74% by mass to 88% by mass (the total content of the silver-coated disk-containing copper alloy particles and silver particles when silver particles are described later). • Surface-treated copper particles _ In the present invention The copper-containing particles are selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, and organic metals. At least one of a group consisting of a salt composed of a salt of a salt, a polystyrene-based resin, and a metal alkoxide (hereinafter sometimes referred to as a "surface treatment agent") is subjected to a surface treatment of 13 201133512, and the steel particles are excellent. More preferably, copper particles obtained by at least one surface treatment selected from the group consisting of triterpenoids, saturated linoleic acid, unsaturated linonic acid, and inorganic metal compound salts are used by using a surface treating agent. At least the copper particles which have been subjected to the surface treatment can form an electrode having excellent oxidation resistance and low electrical resistivity as the copper-containing particles contained in the hair stylus composition towel. Further, when the moisture is mixed to the electrode When a paste composition towel is used, by using the surface-treated copper particles, the following effects can be obtained: oxidation of copper at room temperature can be suppressed, and the lifespan can be improved. In the present invention, the above surface treatment agents may be used singly or in combination of two or more. In the present invention, the surface-treated steel particles are selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, metallization & salts, polyaniline resins, and metal oxide oxides. At least one of the groups of the groups is subjected to surface treatment and other surface treatment agents are used. In the above-mentioned surface treatment agent, for example, benzo-soxadiazole, etc., and as a saturated fatty acid in the above surface treatment agent, for example, can be listed. Work is also lacking and _ j magical. Heptanoic acid, octanoic acid, citric acid, citric acid, undecanoic acid, acid, t triacid, tetradecanoic acid, pentadecanoic acid, stearic acid, nineteen acid, floral acid, etc. Further, as the above-mentioned surface treatment shot, there may be mentioned, for example, acrylic acid, methacrylic acid, crotonic acid, methacrylic acid, oleic acid, oleic acid, whale oleic acid, oleic acid, 201133512 sinapic acid, sorbic acid, linoleic acid, linoleic acid, peanut oleic acid, etc. Further, as the inorganic metal compound salt in the above surface treatment agent, for example, sodium citrate, sodium stannate, tin sulfate, sulfuric acid may be mentioned. Zinc, sodium zincate, cerium nitrate, sodium zirconate, zirconium oxychloride, titanium sulphate, titanium chloride, potassium oxalate, etc. Further, examples of the organometallic compound salt in the surface treatment agent include hard fat. The difference between lead acid, lead acetate and tetraalkoxy zirconium Further, as the metal alkoxide in the surface treatment agent, for example, titanium alkoxide and zirconium alkoxide are exemplified. Examples, lead alkoxides, decane oxides, stannous oxides, indium alkoxides, etc. 々 As other surface treatment agents, for example, dodecylbenzenesulfonic acid, etc., when stearic acid or hard is used, When lead oleate is used as a surface treatment agent, at least a combination of stearic acid and stearic acid (4) and acetic acid (4) as a surface treatment agent can form an electrode having further improved oxidation resistance and lower resistivity. The surface-treated copper particles may be coated with at least one of the surface treatment agents of at least one of the surface of the copper particles. The surface treatment content contained in the surface-treated trainer is preferably 2 thermal masses. In the thermal phase difference, the wave of the heat generation peak having the largest area is at a level of 28 CTC or more. Specifically, it is preferable that the mass of the copper particles treated by the surface is more than or equal to the mass%, and the degree of the chemical property is high. View In particular, it is preferably from 0. 01% by mass to 1% by mass in the surface-treated copper particles, more preferably from 0.05% by mass to 8% by mass based on the mass of the surface-treated copper particles. Copper of surface treated copper particles can also be used without destructive invention 15
201133512 L $效果的範_包含其他原^作為其他原子 ,:sb、Si、K、Na、Li、Ba、Sr、Ca、Mg、BeZnpb:201133512 L $effect model _ contains other primitives as other atoms, :sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, BeZnpb:
OiH、Sn、Ab Zr、w、M〇、Ti、c〇、见、以及OiH, Sn, Ab Zr, w, M〇, Ti, c〇, see, and
Au等。其中,就調整耐氧化性,點特 較佳為包含A卜 J職而5 另外,上述經表面處理的銅粒子中所包含的其 的含有率例如於上述經表面處理的銅粒子巾—或 質量〇/〇以下,就耐氧化性與低電阻率的觀3^ 3 1質量%以下。 1 又佳為 -金表面處理的銅粒子為對已述的含磷的銅 ^進仃表面處理而成者亦較佳。藉此,耐氧化性進 棱昇,所形成的電極的電阻率進一步下降。 面處理的銅粒子中的含有磷的合金的詳細情 ^ U與已述的含有翻合金相同,較佳的型態亦相 制卜累面處理的銅粒子的粒徑並無特別限 「D50%」),較佳為〇.4叫〜 下=4 以上’耐氧化性更有效地提昇。另外, 2^ 下’電㈣的上述經表面處理的銅粒子彼 此的接觸面積變大,電阻率更有效地下降。 制,2 ’上述經表面處理的銅粒子的形狀並無特別限 心二A致球狀、扁平狀、塊狀、板狀、及鱗片狀等中 ’壬一種形狀,就耐氧化性與低電阻率的觀點而言,較佳 201133512 為大致球狀、扁平狀、或板狀。 應於所面^理劑的銅粒子的表面處理方法’可對 i理劑溶解於可===適宜選擇。例如’製備使表面 此可利用該表面處進行乾燥,藉 上述可溶解矣而♦覆的表面的至少一部分。 適宜選擇。例如可對應&表面處_而 溶劑、乙-辟”甲每、乙醇、異丙醇等醇系 必醇系溶ίτ:广等二醇系溶劑、二乙二醇單丁醚等卡 劑等。 —醇單乙_乙酸酯等卡必醇乙酸酯系溶 具體而言’例如#使用笨并三唾、三唾 姚作為表面處理_,可使_系溶& 洛液,然後對銅粒子進行表面處理。製備表面處理 的表=====二農度可對應於所使用 例如,可設定為i曾10/ 0的表面處理量而適宜選擇。 85質量^ 頁%〜% f量%,較佳為2質量。/。〜 面處====合:::包含的上述經表 時的經表面處理的銅粒子與銀粒子的乍述^粒子 定為7。質―量%,就耐氧:二革= 17 20113351} 而言,較佳為72質量。/。〜90質量%,更佳為74質量%〜 88質量%。 ° 另外,於本發明中,上述經表面處理的鋼粒子可單獨 使用一種,亦可組合使用兩種以上。另外,亦可與經表面 處理的銅粒子以外的含有銅的粒子組合使用。 於本發明中,就耐氧化性與電極的低電阻率的觀點而 5,較佳為於電極用膏狀組合物中包含以含有選自由三0坐 化合物、飽和脂肪酸、不飽和脂肪酸、無機金屬化合物鹽、 有機金屬化合物鹽、聚苯胺系樹脂、以及金屬烷氧化物所 組成的組群中的至少一種〇 〇1質量%〜1〇質量%的方式進 行了表面處理的銅粒子7〇質量%〜94質量%(當包含後述 的銀粒子時為經表面處理的銅粒子與銀粒子的總含有 率)’更佳為於電極用膏狀組合物中包含以含有選自由三咬 化合物、飽和脂肪酸、不飽和脂肪酸以及無機金屬化合物 鹽所組成的組群中的至少一種〇〇5質量%〜8質量%的方 式進行了表面處理的銅粒子74質量%〜88質量%(包含後 述的銀粒子時的經表面處理的銅粒子與銀粒子的總含有 率)。 進而,較佳為於電極用膏狀組合物中包含以含有選自 由二唑化合物、飽和脂肪酸、不飽和脂肪酸、無機金屬化 合物鹽、有機金屬化合物鹽、聚苯胺系樹脂、以及金屬烷 氧化物所組成的組群中的至少一種〇 〇1質量%〜1〇質量0/〇 的方式進行了表面處理,且磷含有率為8質量%以下的經 表面處理的含磷的銅合金粒子7〇質量%〜94質量%(當包 201133512 含後述的銀粒子時為經表面處理的含磷的銅合金粒子與銀 粒子的總含有率)’更佳為於電極用膏狀組合物中包含以含 有選自由三嗤化合物、飽和脂肪酸、不飽和脂肪酸以及無 機金屬化合物鹽所組成的組群中的至少一種0 05質量%〜 8質量%的方式進行了表面處理,且磷含有率為1質量%〜 7.5質量%以下的經表面處理的含填的銅合金粒子%質量 %〜88質量% (包含後述的銀粒子時的經表面處理的含磷 的銅合金粒子與銀粒子的總含有率)。 (玻璃粒子) 本發明的電極用膏狀組合物包含至少一種玻璃粒子。 藉由電極用膏狀組合物包含玻璃粒子,於電極形成溫度 下,利用所s胃的般燒貫穿(fire thr0Ugh)來去除作為抗反 射膜的氮化矽膜,並形成電極與矽基板的歐姆接觸。 上述玻璃粒子若為於電極形成溫度下軟化及熔融,使 所接觸的氮化矽膜氧化,並插入經氧化的二氧化矽,藉此 可去除抗反射膜的玻璃粒子,則可無特別限制地使用該技 術領域中通常所使用的玻璃粒子。 於本發明中’就耐氧化性與電極的低電阻率的觀點而 言,較佳為包含玻璃軟化點為600〇c以下,結晶化起始溫 度超過600 C的玻璃的玻璃粒子。再者,上述玻璃軟化點 疋利用熱機械为析裝置(Thermo Mechanical Analyzer, TMA)以通常的方法來測定,另外,上述結晶化起始溫度 是利用熱重-熱差分析裝置(ThermalAu et al. In addition, it is preferable to adjust the oxidation resistance, and it is preferable to include A A and J. In addition, the content of the surface-treated copper particles contained therein is, for example, the surface-treated copper particle towel or mass. In the case of 〇/〇, the oxidation resistance and the low resistivity are 3 to 31% by mass or less. 1 It is also preferred that the gold surface-treated copper particles are also preferably surface treated with the phosphorus-containing copper. Thereby, the oxidation resistance is increased, and the resistivity of the formed electrode is further lowered. The details of the phosphorus-containing alloy in the surface-treated copper particles are the same as those described above, and the preferred type of copper particles are not particularly limited to "D50%". "), preferably 〇.4 叫~下=4 or more 'oxidation resistance is more effectively improved. Further, the contact area of the surface-treated copper particles of the above-mentioned electric (four) is increased, and the specific resistance is more effectively lowered. 2', the shape of the above-mentioned surface-treated copper particles is not particularly limited to a spherical shape, a flat shape, a block shape, a plate shape, and a scale shape, etc., and is resistant to oxidation and low resistance. From the viewpoint of the rate, it is preferable that 201133512 is substantially spherical, flat, or plate-shaped. The surface treatment method of the copper particles to be applied to the agent can be suitably selected by dissolving the agent. For example, the preparation is such that at least a portion of the surface that can be dried by the surface can be dried by the surface. Suitable choice. For example, it is possible to correspond to the surface of the & solvate, the solvent, the acetaminophen, the alcohol, the isopropyl alcohol, and the like, and the like, such as a wide diol solvent or a card reagent such as diethylene glycol monobutyl ether. - Alcohol monoethyl acetate, such as carbitol acetate, specifically, 'for example, #using stupid and saliva, Sansao Yao as a surface treatment _, can make _ system dissolve & Lok, then Surface treatment of copper particles. Table of preparation of surface treatment ===== The second degree of agriculture can be appropriately selected according to the surface treatment amount which can be set to, for example, i has 10/0. 85 mass ^ page %~% f The amount %, preferably 2 mass. /. ~ Surface ==== Combined::: The above-mentioned surface-treated copper particles and silver particles are included in the above-mentioned surface. %, in terms of oxygen resistance: 2 leather = 17 20113351}, it is preferably 72 mass% to 90% by mass, more preferably 74% by mass to 88% by mass. Further, in the present invention, the above surface is The steel particles to be treated may be used singly or in combination of two or more. In addition, they may be used in combination with copper-containing particles other than the surface-treated copper particles. In the present invention, from the viewpoint of oxidation resistance and low electrical resistivity of the electrode, it is preferable that the paste composition for an electrode contains a compound selected from the group consisting of a quinone compound, a saturated fatty acid, an unsaturated fatty acid, and an inorganic metal. Surface-treated copper particles 7 〇 mass%, at least one of 组1% by mass to 1% by mass of the compound salt, the organometallic compound salt, the polyaniline resin, and the metal alkoxide ~94% by mass (when the silver particles described later are contained, the total content of the surface-treated copper particles and the silver particles) is more preferably contained in the paste composition for an electrode to contain a compound selected from the group consisting of three bite compounds and saturated fatty acids. When at least one of the group consisting of the unsaturated fatty acid and the inorganic metal compound salt is 5% by mass to 8% by mass, the surface-treated copper particles are 74% by mass to 88% by mass (including silver particles to be described later) The total content of the surface-treated copper particles and the silver particles). Further, it is preferably contained in the paste composition for an electrode to contain a compound selected from the group consisting of diazoles. At least one of a group consisting of a saturated fatty acid, an unsaturated fatty acid, an inorganic metal compound salt, an organometallic compound salt, a polyaniline resin, and a metal alkoxide is 1% by mass to 1% by mass 0/〇 The surface-treated phosphorus-containing copper alloy particles having a phosphorus content of 8 mass% or less are 7% by mass to 94% by mass (when the package 201133512 contains silver particles described later, the surface-treated phosphorus is contained. The total content of the copper alloy particles and the silver particles is more preferably included in the electrode paste composition to contain a group selected from the group consisting of triterpenoids, saturated fatty acids, unsaturated fatty acids, and inorganic metal compound salts. The surface-treated copper alloy particles having a phosphorus content of at least one of 0. 05% by mass to 8% by mass and having a phosphorus content of 1% by mass to 7.5% by mass or less are % by mass to 88% by mass ( The total content of the surface-treated phosphorus-containing copper alloy particles and silver particles in the case of containing silver particles described later). (Glass Particles) The paste composition for an electrode of the present invention contains at least one kind of glass particles. The paste composition for an electrode contains glass particles, and at a temperature at which the electrode is formed, a tantalum nitride film as an anti-reflection film is removed by a fire-through of the stomach, and an ohmic electrode is formed on the electrode and the substrate. contact. The glass particles are softened and melted at the electrode formation temperature, and the contacted tantalum nitride film is oxidized, and the oxidized cerium oxide is inserted, whereby the glass particles of the antireflection film can be removed, and the glass particles can be removed without particular limitation. Glass particles commonly used in the art are used. In the present invention, from the viewpoint of oxidation resistance and low resistivity of the electrode, glass particles containing glass having a glass softening point of 600 〇 c or less and a crystallization initiation temperature exceeding 600 C are preferable. Further, the glass softening point is measured by a usual method using a thermomechanical analyzer (TMA), and the crystallization starting temperature is a thermogravimetric-thermal difference analyzing device (Thermal)
Gravimetry-Differential Thermal Analyzer,TG-DTA )以通 201133512 常的方法來測定。 就可面效地取入二氧化石夕而言,一般包含於電極 狀組合物中的玻璃粒子亦可由包含錯的玻璃構成。作為此 種包含錯的玻璃,例如可列舉日本專利第_5_4號 等中所記載的玻璃,於本發明巾亦可較佳地使用該些破瑪。 另外,於本發明中,若考慮對於環境的影響則較佳 為使用實質上不切的無財璃。作為無财璃,例如可 列舉i日本專利特開2006-313744號公報的段落編號〇〇24 〜段洛編號0025中所記載的無錯玻璃、或者日本專利特 2009-188281號公報等中所記載的無錯玻璃,自該些# 玻璃中適宜選擇後應用於本發明中亦較佳。 μ ° 另外,為高效地插入二氧化石夕,上述玻璃粒子較佳為 包含含有含_氧化物的玻璃,更佳為包含含有五氧化二 填的玻璃⑽酸玻璃’ ρ2〇5系玻璃)。進而更佳為包含除 五氧化二填以外更含有五氧化二飢的玻璃(Ρ2〇5_ν办系 玻璃)。藉由更含有五氧化二鈒,财氧化性進一步提昇,電 極的電阻率進-步下降。可認為其是由例如以下原因所造 成的.藉由更含有五氧化二釩,玻璃的軟化點下降。 當上述玻璃粒子包含五氧化二磷·五氧化二叙系玻璃 (P2〇5-V205系玻璃)時’作為五氧化二鈒的含有率,於 玻璃的總質量中,較佳為1質量%以上,更佳為i質量% 〜70質量%。 另外’上述五氧化二填_五氧化二飢系玻璃視需要可更 包含其他成分。作為其他成分’可列舉:氧化鋇(Ba〇)、 201133512 =氧化猛(Mn〇2)、氧化钥(Mg〇3)、氧 氧化納(Na2〇)、氧化_ (K2〇)、二氧化 2、3 化鶴(W〇3)、氧化碲⑽)等。藉由更。包含^成丨 ^溫度進—步下降。進而,可抑制與含有銅的粒見 鸪要而包含的銀粒子的反應。 二 織曾=上f玻璃粒子的含有率,於電極用膏狀組合物的 ,質0,較佳為〇」質量%〜1〇質量%,更佳為〇 ϋΐίτ進而更佳為1質量%〜7質量%。藉由以上 包含玻璃粒子’更有效地達成耐氧化性、 電極的低電阻率及低接觸電阻。 於本發明中,較佳為含有作為玻_+@ 1·ν2〇5系玻璃的玻璃粒子(U質量%〜1〇質量%,更佳 有作為玻璃粒子的包含从5的含量為01質量%以上 的p2〇5_v2o5系玻璃的玻璃粒子〇J質量%〜 (溶劑及樹脂) 一本發明的電極用膏狀組合物包含至少一種溶劑虚 藉此,可對應於賦予轉基㈣⑽予ϊ法將 月的電極用膏狀組合物的液體物性(例如,黏度 面張力等)調整為所需的液體物性。The Gravimetry-Differential Thermal Analyzer (TG-DTA) was measured by the usual method of 201133512. The glass particles generally contained in the electrode composition may also be composed of glass containing the wrong glass. As such a glass containing the error, for example, the glass described in Japanese Patent Laid-Open No. Hei-5-4, and the like can be preferably used. Further, in the present invention, it is preferable to use a substantially uncut glass without considering the influence on the environment. For example, the error-free glass described in paragraph number 〇〇24 to Duanluo number 0025 of Japanese Patent Laid-Open Publication No. 2006-313744, or the Japanese Patent Publication No. 2009-188281, and the like. The error-free glass is also preferably used in the present invention since it is suitably selected from the glass. Further, in order to insert the silica dioxide efficiently, the glass particles preferably contain a glass containing an _oxide, and more preferably a glass (10) acid glass ρ2〇5-based glass containing a pentoxide. Further, it is more preferable to include a glass containing bismuth pentoxide in addition to the pentoxide oxide (Ρ2〇5_ν system glass). By further containing antimony pentoxide, the oxidizing property is further improved, and the resistivity of the electrode is further lowered. It is considered to be caused, for example, by the fact that by further containing vanadium pentoxide, the softening point of the glass is lowered. When the glass particles include phosphorus pentoxide and pentoxide oxide glass (P2〇5-V205 glass), the content of the bismuth pentoxide is preferably 1% by mass or more based on the total mass of the glass. More preferably, i mass% ~ 70 mass%. Further, the above-mentioned five-oxide five-filled pentoxide-based glass may further contain other components as needed. As other components, 'barium oxide (Ba〇), 201133512 = oxidized (Mn 〇 2), oxidized key (Mg 〇 3), oxynitride (Na 2 〇), oxidized _ (K 2 〇), dioxide 2 3, crane (W〇3), yttrium oxide (10)). By more. Contains ^ into 丨 ^ temperature into - step down. Further, it is possible to suppress the reaction with the silver particles contained in the copper-containing particles. The content of the glass particles of the second weave = upper f glass, the mass of the paste composition for the electrode, preferably 0% by mass to 1% by mass, more preferably 〇ϋΐίτ and even more preferably 1% by mass. 7% by mass. The oxidation resistance, the low resistivity of the electrode, and the low contact resistance are more effectively achieved by including the glass particles described above. In the present invention, it is preferable to contain glass particles (U mass% to 1% by mass) of glass as _+@1·ν2〇5-based glass, and it is more preferable that the content of the glass particles is from 01 to 01% by mass. The glass particles of the above p2〇5_v2o5-based glass 〇J% by mass (solvent and resin). The paste composition for an electrode of the present invention contains at least one solvent, thereby being compatible with the transfer of the base (4) (10). The liquid physical properties (for example, viscosity surface tension, etc.) of the electrode paste composition are adjusted to the desired liquid physical properties.
甲笑if ΐ劑並無特別限制。例如可列舉:己烧、環己燒、 系j系溶劑;二氣乙稀、二氣乙院、二氣苯等氣化烴 ,二劏:四虱吱喃、七南、四氫σ比喃"比喃、二喔烧、H 戊環、二噁烷等環狀醚系溶劑;Ν,Ν-二曱基甲醯胺、 21 201133512 N,N-二曱基乙醯胺等酿胺系溶劑; 二 砜等亞砜系溶劑;丙酮、曱 土 等酮系溶劑;乙醇、2 ^乙基_、二乙基酮、環己酮 合物;2 2^- ^ ^醇、二丙_等醇系化 戊二醇單丙r2m ^單乙_、2,2,4_三甲基W- =甲其η丄 ,2,4_二甲基戊二醇單丁酸酯、2,2,4-一 Τ基-1,3-戊二醇單g 丁舱 乙酸龍、乙酸§日、2,2,4·三乙基-1,3·戊二醇單 多元醇的二々早丁醚乙酸酯、二乙二醇單丁醚乙酸酯等 夕兀醇的酉曰糸溶劑;丁基溶 醇的醚系溶劑;01紅。说齊J 一乙一醇一乙醚4多凡 稀、檸_、私Π//品醇、月桂油烯、別羅勒 雙戍烯α_凌烯、P-蒎烯、松脂醇、香旱芹 竹炎、水芽婦等的莊埽系溶劑’以及該些的混合物。 薈心I本發明中的上述溶劑,就神基板上形成電極用 夕元i5,夺的塗佈性、印刷性的觀點而言,較佳為選自 至少二的s曰系溶劑、萜烯系溶劑、多元醇的醚系溶劑中的 種’更佳為選自多元醇的酯系溶劑及萜烯系溶劑中 的至少一種。 於本發明中,上述溶劑可單獨使用一種,亦可組合使 用兩種以上。 樹月 >=:另外,作為上述樹脂,只要是可藉由煅燒而熱分解的 •曰則可無特別限制地使用該技術領域中通常所使用的 扣f月旨0且鹏—. /、耀而& ’例如可列舉:曱基纖維素、乙基纖維素、 緩基甲基纖維素、硝化纖維素等纖維素系樹脂;聚乙烯醇 t、’聚乙烯吡咯啶酮類;丙烯酸樹脂;乙酸乙烯酯-丙烯酸 酉曰共聚物;聚乙烯丁醛等的丁醛樹脂;酚改性醇酸樹脂、 22 201133512 脂f酸改性醇酸樹脂之類的醇酸樹脂;環氧樹脂; 紛樹爿a ;松香酯樹脂等。 作^本發明巾的上職脂,就锻燒時的消失性的觀點 吕’較佳為選自纖維素系樹脂、以及丙_樹脂中的至 卜種’更佳為選自纖維素系樹脂中的至少-種。 於本發明中,上述樹脂可單獨使用一種,亦可組合使 用兩種以上。 於本發明的電極用膏狀組合物中,上述溶劑盘上述樹 脂的含量可對應於所期望的液難性與所使㈣溶劑及樹 脂的種類而適宜選擇。 例如,樹脂的含有率於電極用膏狀組合物的總質量 中,較佳為0.01質量%〜5質量%,更佳為〇 〇5質量%〜4 質量%’進而更佳為(U f量%〜3質量%,進而更佳為〇15 質量%〜2.5質量%。 日另外,溶劑與樹脂的總含量於電極用膏狀組合物的總 質I中,較佳為3質量〇/〇〜29.8質量0/〇,更佳為5質量〇/0 〜25質量。/。,進而更佳為7質量%〜2〇質量%。 藉由溶劑與樹脂的含量為上述範圍内,將電極用膏狀 組合物賦予至矽基板時的賦予適應性變得良好,可更容易 地形成具有所期望的寬度及高度的電極。 (助溶劑) 電極用貧狀組合物包含至少一種助熔劑。藉由包含助 熔劑,耐氧化性進一步提昇,所形成的電極的電阻率進_ 步下降。進而,亦可獲得電極材料與矽基板的密接性提彝 23 201133512 的效果^ 作為本發明中的助熔劑,只要是可抑制於含有銅的粒 f的表面形成氧化膜的助熔劑,則並無特別限制。具體而 °例如"T列舉脂肪酸、硼酸化合物、氟化物、以及硼氟 化物荨作為較佳的助溶劑。 更具體而言,可列舉:十二酸、十四酸、八小$千y 酸、硬脂酸、山梨酸、只以口 —小酸、氧化硼、硼酸鉀、 硼酉久納爛酸鐘、硼氟化卸、硼氟化鈉、删氟化鐘、酸性 氣化卸'酸性氟化納、酸性氟化鐘、氟化卸、氟化鈉、氟 化裡等。 田其中’就電極材料煅燒時的耐熱性(助熔劑於煅燒的 低溫時不揮發的特性)及補充含有銅的粒子的耐氧化ς的 觀點而言’可列舉職躲魏化_為特佳的助_。 於本發明中,該些助熔劑可分別單獨使用一種, 組合使用兩種以上。 另外’作為本發明的電刻錄組合物巾_溶劑的 s量’就有效地表現出含有銅的粒子的耐氧化性的觀點、 以及降低電極材料的職結束時魏繼去除的部分的办 隙率的觀點而言,於電極用f狀組合物的總f量中,較ς 為o.i質量%〜5質量%,更佳為μ f量%〜4質量% 2佳為G.5質量%〜3.5質量%,特佳為Q 7質量質 (銀粒子) 本發明的電極用膏狀組合物較麵更包含至少一種銀 24 201133512 粒子。藉由包含銀粒子,耐氧化性進一步提昇,電極的電 ,率進一步下降。進而,亦可獲得製成光伏電池模組時的 焊接性提昇的效果。此種情況例如可如下般考慮。 般於作為電極形成溫度區域的6〇〇。〇至9〇〇它的溫 =域中,產生銀於銅中的少量的固溶、以及銅於銀中的 少量的固溶’而在銅與銀的界面形 溶_>可糾纽含有_粒子與絲子的 至同溫後’緩慢地冷卻至室溫時,不產生隨區域,但因 形成電極時崎秒自高溫域冷卻至常溫,故可認為高溫下 體的層作為非平衡的固溶體相或銅與銀的共晶組織 粒子及含有銅的粒子的表面。可認為此種銅-銀固 =體層有助於電極形成溫度下的含有銅的粒子的耐氧化 銀固溶體層於300〇c至·。c以上的溫度下開始形 2='為藉由將熱質·熱差同時測定中表示最大面 ,的=波峰的波峰溫度為看α上的含有銅的粒子* 併用,可更有效地提昇含有銅晚子的耐氧化性, 所形成的電極的電阻率進一步下降。 構=親粒子祕料μ何避統混人的其他 二作)不可避免地混入的其他原子,例如可列舉务 :、m、Ba、sr、ca、Mg、Be、znpbcd、 Ή、V、Sn、八卜 Zr、w、M〇、Ti、c〇、祕、Au 等。 本發明中的銀粒子的粒徑並無特別限制, 為50〇/〇時的粒徑(D50%)較佳為〇 '、貪里 μΓη〜1〇μιη,更佳為 25 201133512 1 μπι〜7 μιη。藉由設定為0.4帅以上,耐氧化性更有效地 提昇。料’藉由為10 μιη以下,電極中的銀粒子及 銅的粒子等金屬粒子彼此的接觸面積變大,電阻率更有效 地下降。 於本發明的電極用膏狀組合物中,上述含有銅的粒子 與上述銀粒子的粒徑(⑽%)的關係並 無特別限制,較佳躲-方的粒徑(D5G%)小於另 ^徑㈤G%),更佳為任-方的粒徑與另—方的粒徑的 比為1〜10。藉此,電極的電畔更有效地下降。可 下原因所造成的:電極内的含有銅的“及 銀粒子荨金屬粒子彼此的接觸面積變大。 ,外’作為本發明㈣细錄組合物巾的銀粒子的 ,就耐氧化性與電極的低電阻率的觀點而言, f用膏狀組合物中,較佳為8.4 f量%〜85 5 f量%,更佳 為8.9質量❶/。〜80.1質量〇/〇。 進:’於本發明中,就耐氧化性與電極的低電阻率的 為1^1 ’將上述含有朗粒子與上述銀粒子的總量設定 的含有銅的粒子的含有率較佳為9質量% 銅的粒^相°對質量%〜77質量%。藉由上述含有 如當上述玻璃粒子==為,%以上’例 光伏電:=! 進一步下降。另外,於以提昇製成 氟酸水溶液處=轉t效率為目的之電極形成石夕基板的氫 電極材料的对氫氟酸水溶液性(電極 26 201133512 氟酸水溶液而自絲板剝離的性質)得到提 下 由上述含有銅的粒子的含有率為88質量。/〇以 觸,卩制含有銅陳子巾所包含的銅與縣板接 觸電極的接觸電阻進一步下降。 雷搞於本發明的電極时狀組合物巾,就耐氧化性、 人右相阻率、對於石夕基板的塗佈性的觀點而言 ,上述 二暂二沒子及上述銀粒子的總含量較佳為7Q質量%〜 質4里,;8 f圭為72質量%〜92質量%,進而更佳為74 買里A〜88質量%。 藉=述含有_粒子及上述練子的總含量為% 的黏^ ^賦予電極用^組合物時可容易地達成較佳 含量;二1藉由上述含有鋼的粒子及上述銀粒子的總 合可更有舰抑制料電则膏狀組 盘電SI::本?明的電極用膏狀組合物中,就耐氧化性 電阻率的觀點而言,較佳為上述含有銅的粒子 ==總含有率為7〇質量%,質量%,上述玻 =子的含有率為(Π f量%〜⑴f量%,上述溶劑及上 述祕脂的總含有率為3質量%〜29 的含有率為〇 烏里/〇’上速助溶劑 為(U質量/。〜5質量%,更佳為上述含有銅的粒 ^及上述銀粒子的總含有率為74 f量%〜88 f量%,上述 率為1 f 4%〜7 f量%,上述溶劑及上述 Γ车 =二質量%〜20質量%,上述助熔劑的含 有率為0.7質篁%〜3質量%。 27 201133512 (含有填的化合物) 上述電極用膏狀組合物較佳為更包含至少一種含有碟 的化合物。藉此,耐氧化性更有效地提昇,電極的電阻率 進一步下降。進而,亦可獲得如下效果:含有碳的化合物 中的元素作為η型摻雜劑於矽基板中擴散,當製成光伏電 池時發電效率提昇。 作為上述含有磷的化合物,就耐氧化性與電極的低電 阻率的觀點而言,較佳為分子内的磷原子的含有率大且 於200°C左右的溫度條件下不產生蒸發或分解的化合物。 ▲作為上述含有磷的化合物,具體而言,可列舉:磷酸 等^系無機酸、磷酸銨等磷酸鹽、磷酸烷基酯及磷酸芳基There is no special restriction on a smile. For example, it may be exemplified by calcined, cyclohexane, and j-based solvents; gasified hydrocarbons such as diethylene glycol, Erqiyiyuan, and digasbenzene, and diterpene: tetraterpene, henan, tetrahydropyridinium "cyclic ether solvent such as butyl, diterpene, H-pentane, dioxane; hydrazine, hydrazine-dimercaptocarbamide, 21 201133512 N,N-dimercaptoacetamide Solvent; sulfoxide solvent such as disulfone; ketone solvent such as acetone or alumina; ethanol, 2^ethyl_, diethyl ketone, cyclohexanone; 2 2^- ^ ^ alcohol, dipropyl _, etc. Alcoholized pentanediol monopropane r2m ^ monoethyl _, 2, 2, 4 - trimethyl W- = methyl η 丄, 2, 4 dimethyl diol diol monobutyrate, 2, 2, 4-anthracenyl-1,3-pentanediol monoglycidylacetate, acetic acid §, 2,2,4·triethyl-1,3·pentanediol monool An oxime solvent such as acetate, diethylene glycol monobutyl ether acetate or the like; an ether solvent of butyl alcohol; 01 red. Said Qi J-Ethyl Alcohol-Ethyl ether 4 more rarity, lemon _, private Π / / alcohol, laurel olefin, belles diterpene α_ lingene, P-pinene, rosin, fragrant celery , Zhuangzi solvent of water buds, etc. 'and mixtures of these. The above-mentioned solvent in the present invention is preferably a s-based solvent or a terpene system selected from at least two, from the viewpoint of coating properties and printability of the electrode for forming an electrode on the substrate. The seed in the ether solvent of the solvent or the polyol is more preferably at least one selected from the group consisting of an ester solvent of a polyhydric alcohol and a terpene solvent. In the present invention, the above solvents may be used singly or in combination of two or more. In addition, as the above-mentioned resin, any one which can be thermally decomposed by calcination can be used without any particular limitation, and the commonly used ones in the technical field are used. "Yaohe & 'For example, cellulose-based resins such as mercapto cellulose, ethyl cellulose, slow-acting methyl cellulose, and nitrocellulose; polyvinyl alcohol t, 'polyvinyl pyrrolidone; acrylic resin Vinyl acetate-acrylic acid ruthenium copolymer; butyral resin such as polyvinyl butyral; phenol-modified alkyd resin; alkyd resin such as 2011 f 13 13 13 13 13 13 13 13 13 13 13 13 Tree 爿 a; rosin ester resin, etc. The viewpoint of the disappearance of the upper body fat of the invention towel in the case of calcination is preferably selected from the group consisting of cellulose resin and propylene resin, and is preferably selected from cellulose resin. At least one of them. In the present invention, the above resins may be used alone or in combination of two or more. In the paste composition for an electrode of the present invention, the content of the resin in the solvent disk may be appropriately selected in accordance with the desired liquid difficulty and the type of the solvent and resin to be used. For example, the content of the resin is preferably 0.01% by mass to 5% by mass based on the total mass of the paste composition for an electrode, more preferably 5% by mass to 4% by mass, and even more preferably (Uf amount) %〜3质量%, and more preferably 〇15% by mass to 2.5% by mass. Further, the total content of the solvent and the resin is preferably 3 mass 〇/〇 in the total mass I of the paste composition for an electrode. 29.8 mass 0 / 〇, more preferably 5 mass 〇 / 0 〜 25 mass / /, and more preferably 7 mass % ~ 2 〇 mass %. By using the solvent and resin content within the above range, the electrode paste The composition of the composition is excellent in imparting flexibility to the substrate, and an electrode having a desired width and height can be formed more easily. (Cosolvent) The electrode-depleted composition contains at least one flux. The flux, the oxidation resistance is further improved, and the resistivity of the formed electrode is further decreased. Further, the adhesion between the electrode material and the tantalum substrate can be obtained. 23 201133512 Effect ^ As the flux in the present invention, as long as Is a surface that can be suppressed to the copper-containing particles f The flux for forming the oxide film is not particularly limited. Specifically, for example, a fatty acid, a boric acid compound, a fluoride, and a borofluoride oxime are preferred cosolvents. More specifically, ten Diacid, tetradecanoic acid, eight small $ thousand y acid, stearic acid, sorbic acid, only mouth-small acid, boron oxide, potassium borate, borax long-lasting acid clock, boron fluorination, sodium borofluoride , fluorination clock, acid gasification unloading 'acidic sodium fluoride, acid fluorination clock, fluorination unloading, sodium fluoride, fluorination, etc.. Among them, the heat resistance of the electrode material during calcination (the flux is calcined) The non-volatile property at low temperature) and the anti-oxidation enthalpy of the copper-containing particles can be listed as "excellent aids". In the present invention, the fluxes can be used separately. One type is used in combination of two or more. In addition, 'the amount of s of the solvent of the electric recording composition of the present invention' effectively exhibits the oxidation resistance of the particles containing copper, and the viewpoint of lowering the end of the electrode material. Depending on the aspect of the removed portion In the total amount of f of the electrode composition for the electrode, it is oi mass% to 5% by mass, more preferably μf amount% to 4 mass%, preferably G.5 mass% to 3.5 mass%, especially Preferably, the Q 7 mass (silver particles) of the electrode composition of the present invention further comprises at least one silver 24 201133512 particle. By containing silver particles, the oxidation resistance is further improved, and the electric conductivity of the electrode is further lowered. Further, the effect of improving the weldability in the production of the photovoltaic cell module can be obtained. For example, it can be considered as follows. Generally, it is 6 〇〇 as the electrode forming temperature region. 〇 to 9 〇〇 its temperature = domain In the middle, a small amount of solid solution of silver in copper and a small amount of solid solution of copper in silver are formed, and the interface between copper and silver is dissolved. _> The correction can contain _ particles and filaments to the same temperature. 'When slowly cooling to room temperature, no area is generated, but since the formation of the electrode is cooled from the high temperature range to normal temperature, it can be considered that the layer of the high temperature lower body acts as a non-equilibrium solid solution phase or a eutectic of copper and silver. The surface of the tissue particles and the particles containing copper. It is considered that such a copper-silver solid layer contributes to the oxidation resistant silver solid solution layer of the copper-containing particles at the electrode formation temperature at 300 〇c to . When the temperature is higher than c, the shape 2 = ' is the peak of the peak indicated by the simultaneous measurement of the thermal mass and the thermal difference, and the peak temperature of the peak is the copper-containing particle* on the α, and the content can be more effectively enhanced. The oxidation resistance of the copper eclipse further decreases the resistivity of the formed electrode. Other atoms that are inevitably mixed in, such as m, Ba, sr, ca, Mg, Be, znpbcd, Ή, V, Sn , Ba Bu Zr, w, M〇, Ti, c〇, secret, Au, etc. The particle diameter of the silver particles in the present invention is not particularly limited, and the particle diameter (D50%) at 50 Å/〇 is preferably 〇', greedy μΓη~1〇μηη, more preferably 25 201133512 1 μπι~7 Ιιη. By setting it to 0.4 or more, oxidation resistance is more effectively improved. When the material is 10 μm or less, the contact area between the metal particles such as silver particles and copper particles in the electrode is increased, and the specific resistance is more effectively lowered. In the paste composition for an electrode of the present invention, the relationship between the particles containing copper and the particle diameter ((10%%) of the silver particles is not particularly limited, and it is preferable that the particle diameter (D5G%) of the chi-square is smaller than that of the other. The diameter (five) G%), more preferably the ratio of the particle diameter to the particle diameter of the other side is 1 to 10. Thereby, the electric side of the electrode is more effectively lowered. The reason for the following is that the contact area between the copper-containing "metal particles in the electrode and the silver particles and the metal particles becomes larger. The outer portion of the silver particles of the composition of the present invention (4) is oxidized and resistant to the electrode. From the viewpoint of low resistivity, it is preferably 8.4 f % % to 85 5 f % by weight, more preferably 8.9 mass ❶ /. ~ 80.1 mass 〇 / 〇 in the paste composition. In the present invention, the content of the copper-containing particles in which the total amount of the silver particles and the silver particles are set is preferably 9% by mass in terms of the oxidation resistance and the low resistivity of the electrode. ^ phase ° to mass% ~ 77% by mass. By the above, if the above glass particles == is, more than % of the example photovoltaic power: =! further decline. In addition, in the lift to make a hydrofluoric acid aqueous solution = turn t The electrode for efficiency is formed into a hydrofluoric acid aqueous solution of the hydrogen electrode material of the Shih-hss substrate (the property of the electrode 26 201133512 aqueous solution of hydrofluoric acid and peeled off from the silk plate) is obtained. The content of the copper-containing particles is 88%. 〇 〇 〇 卩 卩 卩 含有 含有 含有 含有 含有 含有 含有 含有The contact resistance between the copper and the plate contact electrode is further lowered. In view of the oxidation resistance, the right phase resistivity, and the coating property of the stone substrate, the above-mentioned electrode composition of the present invention is the above. The total content of the second silver particles and the above silver particles is preferably 7Q% by mass to 4% by mass; 8 f is 72% by mass to 92% by mass, and more preferably 74% by weight of A to 88% by mass. The content of the composition containing the _ particles and the above-mentioned trainer is %, and the content of the composition for the electrode can be easily achieved. The ratio of the particles containing the steel and the silver particles can be easily achieved. Further, it is preferable that the above-mentioned copper-containing particles ==total content, from the viewpoint of oxidation resistance resistivity in the paste composition for an electrode of the present invention. The content rate is 7〇 mass%, mass%, and the content ratio of the above glassy substance is Πf amount%~(1)f%%, and the total content of the solvent and the above-mentioned secret fat is 3% by mass to 29%.里 / 〇 'Upper speed cosolvent is (U mass / ~ ~ 5 mass%, more preferably the above copper containing particles ^ and the above silver particles The total content is 74 f % % to 88 f % %, the above ratio is 1 f 4% to 7 f % by weight, the solvent and the above-mentioned brake = 2% by mass to 20% by mass, and the content of the above flux is 0.7 篁% to 3% by mass. 27 201133512 (compound-containing compound) The paste composition for an electrode preferably further contains at least one compound containing a dish. Thereby, oxidation resistance is more effectively improved, and resistance of the electrode Further, the effect is further obtained: an element in the compound containing carbon is diffused as an n-type dopant in the ruthenium substrate, and the power generation efficiency is improved when the photovoltaic cell is fabricated. From the viewpoint of oxidizability and low resistivity of the electrode, a compound having a large content of phosphorus atoms in the molecule and not evaporating or decomposing at a temperature of about 200 ° C is preferable. ▲ Specific examples of the phosphorus-containing compound include a phosphate such as phosphoric acid, a phosphate such as ammonium phosphate, an alkyl phosphate, and an aryl phosphate.
Sa等鱗酸自旨、六笨氧基罐腈等環狀麟腈、以及該些的衍生 物。 一 本發明中的含有磷的化合物就耐氧化性與電極的低售 P率^觀點而δ ’較佳為選自由填酸、填酸錄、碌酸醋、 =環狀磷腈所組成的組群中的至少—種,更佳為選自由 、以及環狀碟腈所組成的組群中的至少一種。 為本發月甲的上述含有碌的化合物的含量,就耐氧 的低電阻率的觀點而言,於電極用膏狀組合物 ^二’較佳為a5fi%〜1G質量%,更佳為1質 ® /。〜7質量%。 哲吾於本發财’較佳為於f狀組合物的總 德13作為含有磷的化合物的選自由磷酸、磷酸銨、 磷1-曰、Μ及環狀磷腈所組成的組群中的至少一種〇5質 28 201133512 :^二更佳為於電極用膏狀組合物的總質量中 腈所組成的組群中的至少一種 ,而’當本發0_電極时狀組合物包含含有麟的化 =丄,化性與電極的低電阻率的觀點而言,較佳 。為上述^,粒子及上述絲子的總含有率為%質量 4里/〇,上述玻璃粒子的含有率為0·1質量%〜10 =/°炎上述*劑、上述樹脂及上述含树的化合物的總 :有率為5Θ質量%〜20質量%,助溶劑的含有率為(U質 里/〇 5質量/。。更佳為上述含有銅的粒子及上述銀粒子的 總含有率為74質量%〜88 f量%,上述玻璃粒子的含有率 為1質量%〜7質量%,上述溶劑、上述樹脂及上述含有填 J化合物的,含有率為i f量%〜7 f量%,助熔劑的含有 率為0.7質量%〜3質量%。 (其他成分) 、心進而,本發明的電極用膏狀組合物除上述成分以外, 視病要可更包含該技術領域巾通常所使用的其他成分。作 為其他成分,例如可列舉:塑化劑、分散劑、界面活性劑、 無機結合劑、金屬氧化物、陶瓷、有機金屬化合物等。 本發明的電極用膏狀組合物的製造方法並無特別限 制。可利用it常所使用的分散及混合方法對上述含有銅的 粒,、、玻璃粒子、溶劑、樹脂、以及視需要而包含的銀粒 子等進行分散及混合,藉此製造本發明的電極用膏狀組合 物0 、〇 29 201133512 (使用電極用膏狀組合物的電極的製造方法) =為㈣本發明的電细f狀組合物來製造電極 燁後進ΐίϊ極財狀組合物解轉成雜的區域,乾 =述電極用膏狀組合物,即使於氧的存在下(例如,ί ' 進行煅燒處理,亦可形成電阻率低的電極。 伏電例如#使用上述電極用膏狀組合物形成光 狀電極用纽組合物以成為所期望的形 =2夕基板上’乾燥後進行烺燒,藉此可將電 電池電極形成為所期望的形狀。另外,藉由 亡,電極用膏狀組合物,即使於氧的存在下(例:, 大乳中)進行般燒處理,亦可形成電阻率低的電極。 如將電極用膏狀組合物賦予至石夕基板上的方法’例 點^ 網版印刷、喷墨法、分配法等,就生產性的觀 ”占而5,較佳為利用網版印刷的塗佈。 利用網版印職佈本發_電制膏狀組合物時, 1 ΐί ii80Pa.s〜10oopa.s的範圍的黏度。再者,電極 騰)來:;物的黏度是於25t下利用黏度雜。。咖 魅ΐ述電極用膏狀組合物的賦予量可對應於要形成的電 晋而適^選擇。例如’可將電極用膏狀組合物賦予 。又疋為2 g/m〜1〇 g/m2,較佳為4咖2〜8咖2。 a#沾ίί,作為使用本發明的電極用膏狀組合物形成電極 、’、’、雜件(城條件)’可應用該技術領域中通常所 201133512 使用的熱處理條件。 一般而言’熱處理溫度(烺燒溫度)為_。〇〜9〇(rc, ί當使用本發明的電極时狀組合物時,可應用更低的溫 又下的熱處理條件,例如,可職於_。〇〜8耽的熱處 理溫度下具有良好的特性的電極。 另外’熱處理時間可對應於熱處理溫度等而適宜選 擇,例如可設定為1秒〜20秒。 <光伏電池> 本毛明的光伏電池具有於氧的存在下對被賦予至石夕基 板上的上,電極用膏狀、组合物進行锻燒而形成的電極。藉 此,可獲仵具有I好的特性的光伏電池,且該光伏 生產性優異。 '下 面參照圖式一面說明本發明的光伏電池的具 體例,但本發明並不限定於此。 將具有代表性的光伏電池元件的一例的剖面圖、受光 面及背面的概要示於圖1、圖2及圖3。 、户,常1於光伏電池元件的半導體基板130中使用單晶 或^曰曰Sl等。該半導體基板130中含有硼等,而構成ρ型 半導體。受光面側為了抑制太陽光的反射,藉由钱刻而形 凹凸(紋理,未圖示)。於該受光面側摻雜磷等,並以 次微米級的厚歧置有n型半導體的擴散層ΐ3ι,並且在 與P ^塊狀部分的邊界形成有pn接合部。進而於受光面 側,藉由蒸鍍法等在擴散層131上設置膜厚為10〇 nm& 右的氮化矽等的抗反射層 31 132。 201133512 其次’對設置於受光面侧的受光面電極133、以及形 成於背面的集電電極134及功率取出電極135進行說明。 受光面電極133與功率取出電極135是由上述電極用膏狀 組合物形成。另外,集電電極134是由包含玻璃粉末的紹 電極膏餘合_成。該些電較_職印解將上述 ,狀組合物塗佈成所期望的圖案後,進行乾燥,紐於大 氣中以_°C〜8耽左右進行锻燒而形成。 此時’於受光面側,形成受光面電極133的上述電極 用膏狀組合物中所包含的玻璃粒子與抗反射層m進行反 應(煅燒貫穿)’而使受光面電極133與擴散層131電性連 接(歐姆接觸)。 < ,於本II由使用上述電極用膏狀組合物來形成 受光面電S 133,-面含有銅作為導電性金屬,一面抑制 銅的氧化’而以優制生紐形成低電阻率的受光極 133。 另外’於背面側’當進行锻燒時,形成集電電極134 _電極纽組合物巾的_散至半導體基板 130的背 面’而形成電極成分擴散層136,藉此可在半導體基板別 與集電電極134、功率取出電極135之間獲得歐姆接觸。 另夕,,將作為本發明的其他型態的光伏電池元件的一 例的又光面及AA剖面構造的立體圖(a)、以及背面侧電 極構造的平面圖(b)示於圖4。 如=4所不’於包含p型半導體的石夕基板的單元晶圓 上’日由雷射鑽錢糊等而形成有貫穿受光面側及背 32 201133512 l ^則兩面的通孔。另外,於受絲_成有提 進而,於受光面側形成有利用n型化 ,,形成的η型半導體層3,且於η型半導體層3 上形成有抗反射膜(未圖示)。該此是 si型光伏電池單元相同的步驟來製與先刖的結晶 繼而,藉由印刷法或喷墨法將本發明的電極 至先前所形成的通孔内部,進而,於受光面側同 樣也將本發_電極用f狀組合物印刷成栅狀,而形成如 ^的組合物層’該組合物層形成通孔電極4及集電用拇 極2。 % 此處,用於填充用與印刷用的膏較理想的是使用以黏 度為首的特性最適合於各個製程的組成的膏亦可使用相 同組成的膏一次性地進行填充、印刷。 另一方面,於受光面的相反側(背面側)形成用於防 止載子再結合的高濃度摻雜層5。此處,使用硼(B)或鋁 =(亡 1匕作為形成高濃度摻雜層5的雜質元素來形成p+層。 該尚,度摻雜層5例如可藉由於上述抗反射膜形成前的單 二製^步驟t實施將B作為擴鱗雜擴散處理來形成, 或者當使用A1時’可藉由於上述印刷步驟中將A1膏印刷 在相反面側來形成。 其後,於050Ό至850¾下進行煅燒,被填充、印刷於 上述通孔内部與受光面側所形成的抗反射膜上的上述電極 用膏狀組合物藉由煅燒貫穿效果,而達成與下部η型層的 歐姆接觸。 33 201133512 另外,於相反面侧,如由圖4 (b)的平面圖 本發明的電極时狀組合物分麟n侧、請均印 狀,並進行般燒,藉此形成背面電極6、7。 ’、 於本發明中,使用上述電極用膏狀組合物 極4、集電用柵電極2、背面電極6及背面電極 = 有銅作為導電性金屬,㈣抑_的氧化,而以優: 產性形成低電阻率的通孔電極4、集電用柵電極2、北 極6及背面電極7。 月電 再者,本發明的光伏電池用電極膏狀組合物並不吧 於如上所述的光伏電池電極的贱,例如,村較佳地用 於電漿顯示器的電極線及屏蔽線、陶瓷電容器、天線電路、 各種感測器電路、半導體元件的散熱材料等用途: 再者,日本申請案2010-013516及日本申於幸 2〇10-2222〇5所揭示的所有内容是作為參料被引用= 說明書中。 ' 本說明書中所記載的全部文獻、日本專利申請案、以 及技術規格是以與具體地且個別地記載以參照的形式引用 各個文獻、日本專利申請案、以及技術規格時相同的程度, 作為參照而被引用於本說明書中。 [實例] 以下,藉由實例更具體地說明本發明,但本發明並不 限定於該些實例。再者,只要事先無特別說明,則「份」 及「%」為質1基準。 <實例1A> 34 201133512. (a) 電極用膏狀組合物的製備 製備包含1質量%的填的含磷的鋼合金,使其溶解後 藉由水霧化法將其粉末化’然後進行乾燥、分級了混合經 分級的粉末,並進行脫氧及脫水分處理,製成包含1質旦 °/〇的磷的含填的銅合金粒子。再者,含碟的鋼上二粒子^ 粒徑(D50%)為 1.5 μιη。 製備包含氧化飢(V205) 32份、氧化磷(ρ2〇5) % 伤、氧化鋇(BaO) 10份、氧化嫣(w〇3) 1〇份、氧化納 (Na20) 1份、氧化奸(K20) 3份、氧化辞(Zn〇) 1〇 份、氧化錳(ZnO)8份的玻璃(以下,有時略記為「G19 )。 所獲得的玻璃G19的軟化點為447。。,結晶化溫度為6〇」叱 以上。 使用所獲得的玻璃G19 ’獲得粒徑(d5〇q/。)為1 7 的玻璃粒子。 將上述所獲得的含磷的銅合金粒子39 2份、銀粒子 (粒徑(D50%)為3 μιη,Aldrich公司製造的高純度化學 品)45.9份、玻璃粒子l7份、作為助熔劑的硼氟化鉀t ^、以及含有4。/〇的乙基纖維素(EC)的丁基卡必醇乙酸 酉曰(BCA)溶液13.2份加以混合,然後於瑪瑙製乳缽中攪 拌20分鐘,製成電極用膏狀組合物ία。 (b) 光伏電池單元的製作 準備於党光面形成有η型半導體層、紋理及抗反射膜 (氮化矽膜)的膜厚為190 μιη的ρ型半導體基板,並切 成125 mmxl25 mm的大小。利用網版印刷法,將上述所 35 201133512 獲得的電極用膏狀組合物1以成為如圖2所示的電極圖案 的方式印刷於其受光面。電極的圖案是由15〇 μηι寬度的 手指線(Finger line)與U mm寬度的匯流條(Busbar) 構成,且以使煅燒後的膜厚達到2〇 的方式適宜調整印 刷條件(篩板的篩孔、印刷速度、印刷壓力 > 將所獲得者 放入加熱至150。〇的烘箱中15分鐘,藉由蒸散來去除溶劑。 繼而,同樣利用網版印刷將鋁電極膏印刷於整個背 面。以使緞燒後的獏厚達到40 μιη的方式適宜調整印刷條Sa is an acid such as a cyanoic acid, a cyclic cyanohydrin such as a hexaoxy oxonitrile, and derivatives thereof. The phosphorus-containing compound in the present invention has a oxidation resistance and a low P yield of the electrode, and δ' is preferably selected from the group consisting of acid filling, acid filling, acid vinegar, and cyclic phosphazene. At least one of the group, more preferably at least one selected from the group consisting of and a ring-shaped nitrile. The content of the above-mentioned compound containing a compound of the present invention is preferably a5fi% to 1G% by mass, more preferably 1%, from the viewpoint of the low resistivity of the oxygen resistance in the paste composition for the electrode. Quality® /. ~ 7 mass%. Zhewu is in the fortune of the present invention. Preferably, the total de 13 of the f-shaped composition is selected from the group consisting of phosphoric acid, ammonium phosphate, phosphorus 1-germanium, anthracene and cyclic phosphazene as a phosphorus-containing compound. At least one of the 〇5 质 28 201133512 : ^ 2 is preferably at least one of the group consisting of nitriles in the total mass of the paste composition for the electrode, and 'when the present invention has a composition containing 0 It is preferable from the viewpoint of the chemical resistance and the low resistivity of the electrode. In the above, the total content of the particles and the above-mentioned filaments is % mass 4 liters/〇, and the content of the glass particles is 0.1% by mass to 10 = /°. The above-mentioned agent, the above resin, and the above-mentioned tree-containing The total content of the compound is from 5% by mass to 20% by mass, and the content of the co-solvent is (U mass / 〇 5 mass /.) More preferably, the total content of the copper-containing particles and the silver particles is 74. The mass % to 88 f is %, the content of the glass particles is 1% by mass to 7% by mass, and the solvent, the resin, and the above-mentioned J-containing compound are contained in an amount of % by amount to 7 f %, and a flux The content of the composition is from 0.7% by mass to 3% by mass. (Other components), and further, in addition to the above components, the paste composition for an electrode of the present invention may further include other components generally used in the technical field of the technical field. Examples of the other component include a plasticizer, a dispersant, a surfactant, an inorganic binder, a metal oxide, a ceramic, an organometallic compound, etc. The method for producing the paste composition for an electrode of the present invention is not particularly limited. Restriction. Available it often The above-mentioned copper-containing particles, glass particles, a solvent, a resin, and optionally silver particles are dispersed and mixed to produce the paste composition for an electrode of the present invention, 〇29 201133512 (Manufacturing method of electrode using paste composition for electrode) = (IV) The electric fine f-shaped composition of the present invention is used to produce an electrode 烨 烨 ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ 解 解 解 解 解 解 , , , The paste composition for an electrode can form an electrode having a low specific resistance even in the presence of oxygen (for example, cal' calcination treatment). For example, using the above-mentioned electrode paste composition to form a photoelectrode combination The material is formed into a desired shape, and then dried, and then calcined, whereby the electrode of the electric battery can be formed into a desired shape. Further, by using the paste composition for the electrode, even in the case of oxygen In the presence of (for example, large milk), it is also possible to form an electrode with a low electrical resistivity. For example, a method of applying a paste composition for an electrode to a stone substrate is described. law , the distribution method, etc., in terms of the production of the concept of 5, preferably by screen printing. Using the screen printing cloth to send the hair _ electric paste composition, 1 ΐί ii80Pa.s~10oopa The viscosity of the range of .s. In addition, the electrode is tempered); the viscosity of the material is the viscosity at 25t. The amount of the paste composition for the electrode can correspond to the electricity to be formed. For example, 'the electrode can be given a paste composition. Further, it is 2 g/m~1〇g/m2, preferably 4 coffee 2 to 8 coffee 2. a# ίίί, as the use of the present invention The paste composition for an electrode is used to form an electrode, ', ', and a miscellaneous member (City condition). The heat treatment conditions generally used in the technical field of 201133512 can be applied. Generally, the heat treatment temperature (heating temperature) is _. 〇~9〇(rc, ί When the electrode composition of the present invention is used, lower temperature and lower heat treatment conditions can be applied, for example, it can be used at a heat treatment temperature of _. 8 耽 8 具有Further, the 'heat treatment time can be appropriately selected in accordance with the heat treatment temperature and the like, and can be set, for example, to 1 second to 20 seconds. <Photovoltaic cell> The photocell of the present invention is given to the presence of oxygen in the presence of oxygen. An electrode formed by calcining a paste or a composition on a stone substrate, whereby a photovoltaic cell having excellent characteristics can be obtained, and the photovoltaic productivity is excellent. A specific example of the photovoltaic cell of the present invention will be described, but the present invention is not limited thereto. A cross-sectional view, an example of a light-receiving surface and a back surface of an exemplary photovoltaic cell element are shown in Figs. 1, 2, and 3. In the semiconductor substrate 130 of the photovoltaic cell element, a single crystal or a S1 or the like is used. The semiconductor substrate 130 contains boron or the like to form a p-type semiconductor. The light-receiving surface side suppresses the reflection of sunlight. by a concave-convex shape (texture, not shown) is doped with phosphorus or the like on the light-receiving surface side, and a diffusion layer n3ι of an n-type semiconductor is disposed with a thickness of a submicron order, and at a boundary with the P ^ block portion Further, a pn junction portion is formed. Further, on the light-receiving surface side, an anti-reflection layer 31 132 having a thickness of 10 Å nm & right ytterbium nitride is provided on the diffusion layer 131 by a vapor deposition method or the like. The light-receiving surface electrode 133 on the light-receiving surface side and the current-collecting electrode 134 and the power-extracting electrode 135 formed on the back surface will be described. The light-receiving surface electrode 133 and the power extraction electrode 135 are formed of the paste composition for the electrode. The electrode 134 is made of a glass paste containing a glass powder, and the above-mentioned composition is applied to a desired pattern, and then dried, and the atmosphere is _°C~ In this case, the glass particles contained in the electrode paste composition for forming the light-receiving surface electrode 133 are reacted (calcined through) with the anti-reflection layer m on the light-receiving surface side. Light-receiving electrode 133 and expansion The layer 131 is electrically connected (ohmic contact). In the present invention, the light-receiving surface electric S 133 is formed by using the paste composition for an electrode, and the copper is used as a conductive metal on the surface to suppress oxidation of copper. The yoke is formed into a low-resistivity light-receiving electrode 133. In addition, when the sinter is performed on the back side, the collector electrode 134_electrode composition sheet _ is dispersed to the back surface of the semiconductor substrate 130 to form an electrode component. The diffusion layer 136 can thereby obtain an ohmic contact between the semiconductor substrate and the collector electrode 134 and the power extraction electrode 135. Further, as an example of another type of photovoltaic cell element of the present invention, A perspective view (a) of the AA cross-sectional structure and a plan view (b) of the back side electrode structure are shown in FIG. If the number is not 4, the through-holes are formed on the unit wafer of the Shishi substrate including the p-type semiconductor by the laser drill paste or the like, and the both sides of the light-receiving surface side and the back surface 32 201133512 l ^ are formed. Further, in addition to the wire receiving, an n-type semiconductor layer 3 formed by n-type formation is formed on the light-receiving surface side, and an anti-reflection film (not shown) is formed on the n-type semiconductor layer 3. This is the same step as the si-type photovoltaic cell unit to form the crystallization of the precursor, and then the electrode of the present invention is transferred to the inside of the through hole formed by the printing method or the ink jet method, and further, on the side of the light receiving surface. The f-shaped composition for the hair-electrode was printed in a grid shape to form a composition layer of 'the composition layer' to form the via electrode 4 and the collector thumb 2 for current collection. % Here, it is preferable that the paste for filling and printing is a paste which is characterized by a viscosity-based property which is most suitable for each process, and can be filled and printed at one time using a paste of the same composition. On the other hand, a high-concentration doping layer 5 for preventing recombination of carriers is formed on the opposite side (back side) of the light receiving surface. Here, boron (B) or aluminum = (1) is used as an impurity element forming the high concentration doping layer 5 to form a p+ layer. The still doped layer 5 can be, for example, due to the formation of the antireflection film described above. The single-step process t is performed by using B as a diffusion diffusion treatment, or when A1 is used, which can be formed by printing the A1 paste on the opposite side in the above printing step. Thereafter, at 050 Ό to 8503⁄4 Calcination is carried out, and the paste composition for the electrode which is filled and printed on the antireflection film formed on the inside of the through hole and the light receiving surface side is ohmically contacted with the lower n-type layer by the effect of firing through. 33 201133512 Further, on the opposite side, as shown in the plan view of Fig. 4 (b), the electrode-like composition of the present invention is printed on the n-side, and is uniformly printed, whereby the back electrodes 6 and 7 are formed. In the present invention, the paste composition electrode 4 for the electrode, the gate electrode 2 for current collection 2, the back electrode 6 and the back electrode = copper is used as the conductive metal, and (4) oxidation is suppressed, and the yield is excellent. Low-resistivity via electrode 4, collector gate electrode 2 Arctic 6 and back electrode 7. In addition, the electrode paste composition for photovoltaic cells of the present invention does not correspond to the electrode of the photovoltaic cell as described above, for example, the electrode of the village is preferably used for a plasma display. Wires and shielded wires, ceramic capacitors, antenna circuits, various sensor circuits, heat-dissipating materials for semiconductor components, etc.: In addition, all the Japanese disclosures of 2010-013516 and Japan, Yusuke 2〇10-2222〇5 The content is quoted as a reference = in the specification. 'All documents, Japanese patent application, and technical specifications described in the specification are cited in the form of a reference to the specific and individual reference, the Japanese patent application. The same extent as in the technical specifications is referred to in the present specification as a reference. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. Unless otherwise stated, "parts" and "%" are the mass 1 basis. <Example 1A> 34 201133512. (a) Preparation of paste composition for electrode contains 1% by mass Filling the phosphorus-containing steel alloy, dissolving it and then pulverizing it by water atomization method, then drying, classifying and mixing the classified powder, and performing deoxidation and dehydration treatment to obtain a mass of 1 / 〇 Phosphorus containing copper alloy particles. Furthermore, the particle size (D50%) of the steel containing the dish is 1.5 μιη. Preparation contains 32 parts of oxidative hunger (V205), phosphorus oxide (ρ2〇5) % injury, barium oxide (BaO) 10 parts, strontium oxide (w〇3) 1 part, sodium oxide (Na20) 1 part, oxidized (K20) 3 parts, oxidized (Zn〇) 1 part, manganese oxide (ZnO) 8 parts of glass (hereinafter, abbreviated as "G19"). The obtained glass G19 had a softening point of 447. . The crystallization temperature is 6 〇" 叱 or more. Glass particles having a particle diameter (d5〇q/.) of 17 were obtained using the obtained glass G19'. 39 parts of the phosphorus-containing copper alloy particles obtained above, 45.9 parts of silver particles (particle diameter (D50%) of 3 μm, high purity chemicals manufactured by Aldrich Co., Ltd.), 17 parts of glass particles, and boron as a flux Potassium fluoride t ^, and contains 4. A mixture of 13.2 parts of butyl carbitol (BCA) solution of ethylcellulose (EC) was mixed, and then stirred in an agate mortar for 20 minutes to prepare a paste composition for electrodes ία. (b) Photovoltaic cell fabrication The p-type semiconductor substrate with a thickness of 190 μm formed of an n-type semiconductor layer, a texture and an anti-reflection film (tantalum nitride film) was formed on the party's surface and cut into 125 mm×l25 mm. size. The paste composition 1 for an electrode obtained in the above-mentioned 35 201133512 was printed on the light-receiving surface so as to have an electrode pattern as shown in Fig. 2 by a screen printing method. The pattern of the electrode is composed of a finger line of 15 〇 μηι width and a bus bar of U mm width, and the printing condition is appropriately adjusted so that the film thickness after calcination reaches 2 ( (screen sieve sieve) Hole, Printing Speed, Printing Pressure> The obtained person was placed in an oven heated to 150 Torr for 15 minutes, and the solvent was removed by evapotranspiration. Then, the aluminum electrode paste was printed on the entire back surface by screen printing. It is suitable to adjust the printing strip in such a way that the thickness of the satin is 40 μm
件。將所獲得者放入加熱至15〇。(:的烘箱中15分鐘藉由 蒸散來去除溶劑。 S 繼而’於紅外線急速加熱爐内,在大氣環境下以850。〇 進行2秒的加熱處理(職),製成形成有所期 光伏電池單元1A。 <實例2A> 於貫例1A巾,將電極形成時的力口熱處理 溫度變更為75〇t來代替,卄,隹—的 代替85〇C並進订10秒的加熱處理 D ’除此W卜’以與實例1A相同 所期望的電_光伏電池單元2A。 械有 <實例3A> 於實例1A中’進而添加磷酸 徑(D50%)變更AΛ 儿肘龈粒子的粒 的方刊㈣Λ 陣’除此以外,以與實例1Α相同 i實例4A>物望㈣簡光伏電池單元3A。 於實例1A中,將作為今y ”的删氣化軒的添加量自 36 201133512 A l 為2份’並將含有4%的乙基纖維素(EC)的 醇乙㈣(BCA)溶液的添加量 二的 此以外,以避每 q 伤,除 極的光,也式製成形成有所期望的電 〈只例5A、實例7A、實例8A> 於實例1A中,將助熔劑替換成表1 除此以外,賴㈣丨1Δ 4 所,助炼劑,Pieces. The winner was placed in a heat of 15 〇. (In the oven: remove the solvent by evapotranspiration for 15 minutes. S Then, in the infrared rapid heating furnace, heat treatment at 850 ° C for 2 seconds in the atmosphere, to form a photovoltaic cell Unit 1A. <Example 2A> In the case of Example 1A, the heat treatment temperature at the time of electrode formation was changed to 75 〇t instead of 〇, 隹- instead of 85 〇C and the heat treatment for 10 seconds was repeated. This is the same as that of the example 1A. The electro-photovoltaic cell unit 2A is the same as that of the example 1A. [Example 3A> In the example 1A, the addition of the phosphoric acid diameter (D50%) to the grain of the AΛ elbow particle is changed. (4) Array 'In addition to this, the same example 4A> is the same as the example 1A> (4) simple photovoltaic cell unit 3A. In the example 1A, the amount of the depleted gasification as the current y" is from 36 201133512 A l is 2 In addition to the addition amount of the alcohol B (tetra) (B) solution containing 4% of ethyl cellulose (EC), in order to avoid every bit of damage, the light of the pole is also formed to form a desired Electricity (Example 5A, Example 7A, Example 8A) In Example 1A, the flux was replaced with Table 1. In addition, Lai (4) 丨 1Δ 4, a refining agent,
電極的光式製細彡財所期望的 =先伙電池單元5Α、光伏電池單元7八、光伏電J <實例6Α> ㈣tr,MA中’使用下述所製備的玻璃粒子(ΑΥ1) SSI4: (G19),除此以外’以與實例5Α相同的方 式衣成形成有所期望的電極的光伏電池單元6α ^ ,璃粒子(ΑΥ1)包含氧她(V2〇5) 45份、氧化碟 (、2〇5 ) 24.2 份、氧化鋇(Ba〇) 2() 8 份、氧化録(sb2〇3) 伤、氧化鶴(W03) 5份,且粒徑(D5〇%)為i 7㈣。 另外’該玻璃的軟化點為492t,結晶化溫度為6〇〇。〇以上。 <比較例1A> 除於製備實例1A中的電極用膏狀組合物時不添加助 熔劑以外,以與實例1A相_方式料形成有所期望的 電極的用於比較的光伏電池單元1A。 37 201133512 J-aSI 寸卜 ε 【1<】The light-made fine electrode of the electrode is expected to be the first battery unit 5Α, the photovoltaic battery unit 7-8, the photovoltaic power J < example 6Α> (4) tr, MA 'using the following prepared glass particles (ΑΥ1) SSI4: (G19), other than that, in the same manner as in Example 5, a photovoltaic cell 6α^ was formed to form a desired electrode, and the glass particles (ΑΥ1) contained oxygen (V2〇5) 45 parts, and an oxidation disk (, 2〇5) 24.2 parts, bismuth oxide (Ba〇) 2 () 8 parts, oxidation record (sb2〇3) injury, oxidized crane (W03) 5 parts, and particle size (D5〇%) is i 7 (four). Further, the glass had a softening point of 492 t and a crystallization temperature of 6 Å. 〇 Above. <Comparative Example 1A> A photovoltaic cell 1A for comparison with a sample having a desired electrode was formed in the same manner as in Example 1A except that the flux composition for the electrode was prepared without adding a flux. 37 201133512 J-aSI inch ε [1<]
處理溫度/ 處理時間 850°C/2 秒 750°C/l〇 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 <0 ¥蓉 含量 (份) 〇 Ο o o o o o o 助溶劑 種類 硼氟化鉀 硼氟化鉀 硼氟化鉀 硼氟化鉀 十二酸 十二酸 硼氟化鈉 硼酸鉀 1 含量 (份) (N o 含有4% EC 的BCA溶 液 (份) CN rn CN rn CN <N 〇 (S CO (N rn cs rn <N ΓΟ <s rn 玻璃粒子 種類 〇\ Ο 〇\ O On 5 On 3 〇\ o ON 〇 〇\ 〇 Os o 含量 (份) r-; r-; 卜 卜 銀粒子 粒徑(D50%) (μπι) m m m CO cn m 含量 (份) 〇\ 〇\ jri Os On JO 〇\ jo Os Os On »〇 00 含有銅的粒子 粒徑 (D50%) (μπι) in l〇 含量 (份) <Ν σ; CO cs cK fS O'; m (N 〇; m CN CO σί cn <N Os m <N 〇\ m cs 〇\ m 種類 含有ρ I 含有p I 含有P I 含有P I 含有p I |含有p I |含有p | |含有p | 1含有p 1 實例 實例ΙΑ 實例2A 實例3A 實例4A 實例5A 實例6A 實例7A 實例8A 比較例1A °°ε 201133512 _ . —r*i <評價> 所製作的光伏電池單元的評價是將作為模擬太陽光的 Wacom Electric (股份)製造的 WXS-155S-10、作為電流-電壓(I-V)評價測定器的][_v CURVE TRACER MP-160 (EKO INSTRUMENT公司製造)的測定裝置加以組合來 進行。將關於作為光伏電池的發電性能的各測定值設定為 將比較例1A的測定值作為1000的相對值而示於表2。再 者,表示作為光伏電池的發電性能的Eff (轉換效率)、FF (填充係數)、Voc (開路電壓)及jsc (短路電流)分別 為藉由依據 JIS-C-8912、JIS-C-8913、以及 JIS-C-8914 進 行測定而獲得的測定值。 [表2] 實例 實例1Α Eff(相*f值) 轉換效率 102.5 作為光伏電池的發電性能 FF (相對值) 填充係數 103 0 Voc (相對值) 開路電壓 99 3 Jsc (相對值) 短路電流 貧例2Α 實例3Α 104) 92.0 103.3 91.1 101.3 93.2 實例4Α 99.6 103.2 101.1 102.0 98.9 實例5Α ----- 90S-- 100.0 實例6Α 991 100.5 97.8 100,2 實例7Α -- 100.2 98.1 99.8 103.5 101.2 98.4 實例8A -- 102.3 比較例1A 1 ππ λ — 100.5 98.2 i〇i 7 — [-ο 「100,0 _ 100.0 <實例1B> 中’使用藉由以日本專利特開平14_100191 覆量::質二製備的銀包覆銅粒子(本公司製造,銀包 、、、里。’粒徑為5·8 M^m)而製備的被銀包覆的銅 39 201133512 外,實例-相同的 <實例邮望的電_献€池單元1B。 溫度:7:中J將電極形成時的加熱處理(煅燒)的 (锻燒代替赋,並進行10秒的加熱處理 所期望的電H外’以與實例18相_方式製成形成有 m的電極的光伏電池單元2B。 <實例3B> 經(=:進而添:磷酸1份’並將銀粒子的粒 太制士變更為1 μηι,除此以外,以與實例1B相同的 式製成喊有所射的電極的絲電池單元3Β。 〈實例4Β> 1心:二中’將作為,、y夕X _氟化鉀的添加量自 為2 &,並將含有4%的乙基纖維素(^ 匕以外,以與實例1B相同的方式製成形成有所 極的光伏電池單元4B。 3關望的電 <實例5B、實例7B> 於實例1B中,將助熔劑替換成表 以與細相同的方式製成形成=, 電極的光伏f池單元5B、統電池單元1 '月望的 <實例6B> 於實例1B中,使用上述玻璃粒子(Αγι) 子(⑽),除此以外,以與實例5Β相同的方式 201133512 有所期望的電極的光伏電池單元6B。 <比較例1B> 除於製備實例1B中的電極用膏狀組合物時不使用助 熔劑以外,以與實例1B相同的方式製成形成有所期望的 電極的用於比較的光伏電池單元1B。 41 201133512 J-a5l 寸卜 ε 鬥ε<】Processing temperature / processing time 850 ° C / 2 750 ° C / l sec 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C/2 seconds 850 ° C / 2 sec < 0 ¥ Rong content (parts) 〇Ο oooooo solvent type borofluoride potassium borofluoride potassium borofluoride potassium borofluoride potassium dodecanoic acid borofluoride Potassium sodium borate 1 content (parts) (N o BCA solution containing 4% EC (parts) CN rn CN rn CN <N 〇(S CO (N rn cs rn <N ΓΟ <s rn glass particle type〇 \ Ο 〇 \ O On 5 On 3 〇 \ o ON 〇〇 \ 〇 Os o Content (parts) r-; r-; Bubu silver particle size (D50%) (μπι) mmm CO cn m Content (parts) 〇\ 〇\ jri Os On JO 〇\ jo Os Os On »〇00 particle size of copper-containing particles (D50%) (μπι) in l〇 content (parts) <Ν σ; CO cs cK fS O'; m m CO m m m m m m m m m m 1 contains p 1 instance instance 实例 instance 2A instance 3A instance 4A instance 5A instance 6A Example 7A Example 8A Comparative Example 1A °°ε201133512 _ . —r*i <Evaluation> The fabricated photovoltaic cell unit was evaluated as WXS-155S-10 manufactured by Wacom Electric (share) which simulates sunlight. The measurement device of [_v CURVE TRACER MP-160 (manufactured by EKO INSTRUMENT Co., Ltd.) as a current-voltage (IV) evaluation device is combined and set. The respective measurement values as the photovoltaic power generation performance are set to be compared. The measured value of the example 1A is shown in Table 2 as a relative value of 1000. Further, Eff (conversion efficiency), FF (filling factor), Voc (open circuit voltage), and jsc (short circuit current) which are power generation performance of the photovoltaic cell are shown. The measured values obtained by measurement according to JIS-C-8912, JIS-C-8913, and JIS-C-8914, respectively. [Table 2] Example Example 1 Α Eff (phase * f value) Conversion efficiency 102.5 as photovoltaic cell power generation performance FF (relative value) Fill factor 103 0 Voc (relative value) Open circuit voltage 99 3 Jsc (relative value) Short circuit current 2Α Example 3Α 104) 92.0 103.3 91.1 101.3 93.2 Example 4Α 99.6 103.2 101.1 102.0 98.9 Example 5Α ----- 90S-- 100.0 Example 6Α 991 100.5 97.8 100,2 Example 7Α -- 100.2 98.1 99.8 103.5 101.2 98.4 Example 8A -- 102.3 Comparative Example 1A 1 ππ λ — 100.5 98.2 i〇i 7 — [-ο "100,0 _ 100.0 <Example 1B> In 'Use a silver bag prepared by Japanese Patent Laid-Open No. 14_100191 Cover:: Quality II Copper-clad particles (manufactured by our company, silver package, and lining. 'particle size is 5·8 M^m) prepared by silver-coated copper 39 201133512, except for the same example. _ pool unit 1B. Temperature: 7: Medium J heat treatment (calcination) at the time of electrode formation (calcining instead of assignment, and performing heat treatment for 10 seconds outside the desired electric H) to be compared with Example 18 The photovoltaic cell 2B in which the electrode of m is formed is formed in a manner. <Example 3B> (=: Further adding: 1 part of phosphoric acid' and changing the size of the silver particles to 1 μηι, except for the same method as in Example 1B, the silk battery unit 3Β was fabricated. Example 4Β> 1 heart: 2, 'will be, y X X _ potassium fluoride is added in an amount of 2 & and will contain 4% ethyl cellulose (other than ^ ,, the same as in Example 1B) The method was to form a photovoltaic cell 4B which was formed to be extremely polarized. 3 Electrical power to be seen <Example 5B, Example 7B> In Example 1B, the flux was replaced with a table to form a film in the same manner as the electrode. Photovoltaic f cell unit 5B, cell unit 1 'Exposure of the month> Example 6B> In Example 1B, the above glass particles (Αγι) sub ((10)) were used, except that in the same manner as Example 5, 201133512 Photovoltaic cell 6B of the desired electrode. <Comparative Example 1B> A desired electrode was formed in the same manner as in Example 1B except that the flux composition for the electrode in the preparation of Example 1B was not used. Photovoltaic cell 1B for comparison. 41 201133512 J-a5l Inch ε ε <]
處理溫度/ 處理時間 850°C/2 秒 750°C/l〇 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 <0 ¥蓉 替 含量 (份) 〇 o 〇 〇 Ο Ο Ο 助熔劑 種類 硼氟化鉀 硼氟化鉀 硼氟化鉀 硼氟化鉀 |十二酸| 1十二酸ι 硼氟化鈉 1 含量 (份) (N w-^ Ο 杯 CQ CS η ΓΊ ΓΠ 〇 <N fO CN CO CA fO (Ν cn 玻璃粒子 種類 0\ Ο σ> ο 〇\ 〇 〇\ Ο On o 〇\ ·—h O Os ϋ 含量 (份) 卜 卜 Γ-; 銀粒子 粒徑 (D50%) (μτη) m m m cn m CO m 含量 (份) ON 〇\ ON jrj 〇\ »〇 On JO Os ON 00 含有銅的粒子 粒徑 (D50%) (μηι) 00 00 ui 00 … 00 00 to 00 in 00 uS 00 含量 (份) CN 〇\ m CM On m (N 〇\ cn (N 〇\ m (N Os m (S ON cs αί m I 種類 被Ag包覆 被Ag包復 被Ag包覆 被Ag包覆 被Ag包覆 被Ag包復 被Ag包覆 被Ag包復 實例IB 1實例2B 1 實例3B 實例4B 實例5B 實例6B 實例7B 比較例IB 201133512 <評價> 所製作的光伏電池單元的評價是將作為模擬太陽光的 Wacom Electric (股份)製造的 WXS-155S-10、作為電流_ 電壓(I-V)評價測定器的pv CURVE TRACER MP-160 (EKO INSTRUMENT公司製造)的測定裴置加以組合來 進行。將關於作為光伏電池的發電性能的各測定值設定為 將比較例1B的測定值作為1〇〇 〇的相對值而示於表4 ^再 者,表示作為光伏電池的發電性能的Eff (轉換效率)、FF (,充係數)、V0C (開路電壓)及Jsc (短路電流)分別 為藉由依據 JIS-C-8912、JIS-C-8913、以及 JIS-C-8914 進 行測定而獲得的測定值。 [表4]Processing temperature / processing time 850 ° C / 2 750 ° C / l sec 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C/2 seconds <0 ¥ Rongdi content (parts) 〇o 〇〇Ο Ο 助 Flux type potassium borofluoride potassium fluoride potassium borofluoride potassium borofluoride potassium | dodecanoic acid | Sodium borofluoride 1 content (parts) (N w-^ Ο cup CQ CS η ΓΊ ΓΠ 〇 <N fO CN CO CA fO (Ν cn glass particle type 0\ Ο σ> ο 〇\ 〇〇\ Ο On o 〇\ ·—h O Os ϋ Content (parts) Bu BuΓ-; Silver particle size (D50%) (μτη) mmm cn m CO m Content (parts) ON 〇\ ON jrj 〇\ »〇On JO Os ON 00 Particle size of copper (D50%) (μηι) 00 00 ui 00 ... 00 00 to 00 in 00 uS 00 Content (parts) CN 〇\ m CM On m (N 〇\ cn (N 〇\ m (N Os m (S ON cs αί m I type is coated with Ag, covered with Ag, coated with Ag, coated with Ag, coated with Ag, covered with Ag, coated with Ag, covered with Ag, IB 1 Example 2B 1 Example 3B Example 4B Example 5B Example 6B Example 7B Comparative Example IB 201133512 <Evaluation> The measurement of the battery unit was carried out by using WXS-155S-10 manufactured by Wacom Electric Co., Ltd., which is a simulated sunlight, and pv CURVE TRACER MP-160 (manufactured by EKO INSTRUMENT Co., Ltd.) as a current_voltage (IV) evaluation tester. The measured values of the photovoltaic power generation performance are set as the relative values of the comparative example 1B as 1 而 and are shown in Table 4. The performance Eff (conversion efficiency), FF (, charge factor), V0C (open circuit voltage), and Jsc (short circuit current) are respectively performed by JIS-C-8912, JIS-C-8913, and JIS-C-8914. The measured value obtained by the measurement. [Table 4]
Eff (相對值) 轉換效率 102.3 作為光伏電池的發電性能 FF (相對值) 填充係數 Voc (相對值) 開路電壓 JSC (相對值) 短路電流Eff (relative value) Conversion efficiency 102.3 Power generation performance as photovoltaic cell FF (relative value) Fill factor Voc (relative value) Open circuit voltage JSC (relative value) Short-circuit current
實例Instance
實例1B 實例2B 實例3B 實例4B 實例5B 實例6B 實例7B 比較例1B 〈實例1C> 式製成形成有所期望的電 ς 將作為表面處理劑的笨并三 子代‘含磷的钿:」吏用下述所製備的經表面處理的銅粒 子代替3侧銅合金’除此^―― 1A相同的方 1C。 溶解於溶劑乙 43 201133512 醇中來製備50%的表面處理溶液。使銅粉末(福田金屬箔 粉公司製造,純度為99.9%,粒徑為5 μπ〇浸潰於該表面 處理溶液中5G分鐘後,進行乾燥,從而製成經表面處理的 銅粒子。5亥經表面處理的銅粒子中的表面處理劑的含量於 經表面處理的銅粒子的總質量中為1%。另外,粒徑(〇5〇%) 為 5 μιη。 <貫例2C> 於實例1C中,將電極形成時的加熱處理( 溫度變更為75G°C來代替赋,並進行1G秒的加熱處理 (般燒)’除此以外,以與實例似目同的方 所期望的的献電料元2C。 成形成有 〈實例3C> 於貫例1C + ’進而添加麟酸i份’並 徑(D50%)變f A ! a 瓜于的桩 方犬m 為卿’除外,以與實例1C相同的 ^成七成有所期望的電極的光伏電池單元3C。 〈實例4C> i 中’將輪,V ?久義_的添加量自 77,並將含有4%的乙基纖維素(£c)沾丁 二必:醇乙酸酯(BCA)③液的添加量變 、 極的光伏電池^4C相同的方式製成形成有所期望的電 〈貫例5C、實例7C> 於實例Ip ^ 除此以外,以H㈣炼劑替換成表5所示的助炫劑, /、實例1C相同的方式製成形成有所期望的 201133512 電極的光伏電池單元5C、光伏電 6〇 -f com' 矛、以外,以與貫例5C相同的方式製成形成 有所期望的電極的光伏電池單元6C。 、农风办攻 〈比較例1C > 除於製備實例1C中的電極用膏狀組合物時 熔劑以外’讀實例1C㈣的方式製成形成有所 電極的用於比較的光伏電池單元lc。 ’ 45 201133512 J-aSI 寸卜 eExample 1B Example 2B Example 3B Example 4B Example 5B Example 6B Example 7B Comparative Example 1B <Example 1C> The formula was formed to form a desired electric enthalpy. The stupid three-child 'phosphorus-containing hydrazine which will be used as a surface treating agent: 吏The surface-treated copper particles prepared as described below were used to replace the three-side copper alloy 'the same square 1C except 1 - 1A. Dissolve in Solvent B 43 201133512 Alcohol to prepare a 50% surface treatment solution. Copper powder (manufactured by Fukuda Metal Foil Co., Ltd., having a purity of 99.9% and a particle size of 5 μπ〇) was immersed in the surface treatment solution for 5 G minutes, and then dried to prepare surface-treated copper particles. The content of the surface treatment agent in the surface-treated copper particles was 1% in the total mass of the surface-treated copper particles. Further, the particle diameter (〇5〇%) was 5 μηη. <Example 2C> In Example 1C In the heat treatment at the time of electrode formation (the temperature is changed to 75 G ° C instead of the heat, and the heat treatment is performed for 1 G seconds), the power is expected to be the same as the example. Feeding element 2C. Formed with <Example 3C> in Example 1C + 'and then adding linic acid i part' and diameter (D50%) changed f A ! a melon in the pile square dog m is Qing's except for example 1C is the same photovoltaic cell 3C with 70% of the desired electrode. <Example 4C> i The 'round, V? long-term _ is added from 77 and will contain 4% ethyl cellulose (£ c) Ding Ding must: the addition of alcohol acetate (BCA) 3 liquid, the formation of the same type of photovoltaic cell ^4C The desired electricity was obtained in the same manner as in Example 1C except that the H(tetra) refining agent was replaced with the H (four) refining agent in the same manner as in Example 1C. The photovoltaic cell unit 6C of the 201133512 electrode photovoltaic cell 5C, photovoltaic 6〇-f com' spear, in the same manner as the example 5C to form a desired photovoltaic cell 6C. Example 1C > Photovoltaic cell lc for comparison was formed in the same manner as in the preparation of the paste composition for an electrode in Example 1C by reading the example 1C (4). ' 45 201133512 J-aSI e
處理溫度/ 處理時間 850°C/2 秒 750°C/10 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 850°C/2 秒 <0 替 含量 (份) 〇 〇 Ο Ο Ο Ο 〇 助熔劑 種類 硼氟化鉀 硼氟化鉀 硼氟化鉀 硼氟化鉀 1十二酸1 1十二酸ι 硼氟化鈉 1 含量 (份) »·Η CN 〇 ^ c . Τ' 4^ ΕΏ Vw^ <N CO ΓΠ CN rn CN Ο cs rn CN rn (Ν ΓΛ <s 玻璃粒子 種類 σ\ Ο 〇 ON Ο 〇\ Ο ON a 〇\ 〇 ON Ο 含量 (份) 卜 卜 •"Ν ο *> 卜 卜 卜· 1 銀粒子 粒徑(D50%) (μηι) ΓΟ m CO CO m ΓΛ 含量 (份) Os tri 〇\ Ον jn On 在 〇\ ON iri 〇\ •Η ir! 00 1 含有銅的粒子 粒徑(D50%) (μιη) W-) in m U-) 含量 (份) (S σί CN On CN Os ΓΛ (N Os Μ ON m CN 〇\ CN OS m 1 種類 1表面處理| 1表面處理 |表面處理1 表面處理 ,表面處理 表面處理 表面處理 表面處理 1實例1C 1 I實例2C 1 實例3C 厂實例4C 1 實例5C 「實例6C 1 I實例7C 1 比較例1C 9寸 201133512 <評價> 所製作的光伏電池單元的評價是將作為模擬太陽光的 Wacom Electric (股份)製造的 WXS-155S-10、作為電流-電壓(I-V)評價測定器的LV CURVE TRACER MP-160 (EKO INSTRUMENT公司製造)的測定裝置加以組合來 進行。將關於作為光伏電池的發電性能的各測定值設定為 將比較例1C的測定值作為100.0的相對值而示於表6。再 者,表示作為光伏電池的發電性能的Eff (轉換效率)、FF (填充係數)、Voc (開路電壓)及jsc (短路電流)分別 為藉由依據 JIS-C-8912、JIS-C-8913、以及 JIS_C_8914 進 行測定而獲得的測定值。 [表6] 實例Processing temperature / processing time 850 ° C / 2 750 ° C / 10 sec 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C /2 seconds <0 replacement content (parts) 〇〇Ο Ο Ο Ο 〇 flux type borofluoride potassium borofluoride potassium borofluoride potassium borofluoride potassium dodecanoic acid 1 1 12 acid il boron fluorination Sodium 1 content (parts) »·Η CN 〇^ c . Τ' 4^ ΕΏ Vw^ <N CO ΓΠ CN rn CN Ο cs rn CN rn (Ν ΓΛ <s glass particle type σ\ Ο 〇ON Ο 〇 \ Ο ON a 〇\ 〇ON Ο Content (parts) Bub&"Ν ο *> Bub·1 Silver particle size (D50%) (μηι) ΓΟ m CO CO m ΓΛ Content (parts) Os Tri 〇\ Ον jn On at 〇\ON iri 〇\ •Η ir! 00 1 particle size of copper-containing particles (D50%) (μιη) W-) in m U-) content (parts) (S σί CN On CN Os ΓΛ (N Os Μ ON m CN 〇\ CN OS m 1 Type 1 Surface Treatment | 1 Surface Treatment | Surface Treatment 1 Surface Treatment, Surface Treatment Surface Treatment Surface Treatment Surface Treatment 1 Example 1C 1 I Example 2C 1 Example 3C Factory Example 4C 1 Example 5C "Example 6C 1 I Example 7C 1 Comparative Example 1C 9 inch 201133512 <Evaluation> The photovoltaic cell produced was evaluated by using WXS-155S-10 manufactured by Wacom Electric (share) which simulates sunlight as a current-voltage (IV) evaluation tester. The measurement device of the LV CURVE TRACER MP-160 (manufactured by EKO INSTRUMENT Co., Ltd.) was combined and set. The measured value of the power generation performance of the photovoltaic cell was set to the relative value of the comparative example 1C as 100.0. 6. In addition, Eff (conversion efficiency), FF (fill factor), Voc (open circuit voltage), and jsc (short circuit current) which are power generation performances of photovoltaic cells are respectively based on JIS-C-8912 and JIS-C. -8913, and JIS_C_8914 The measured value obtained by measurement. [Table 6] Example
實例1CExample 1C
實例2CExample 2C
實例3CExample 3C
實例5CExample 5C
實例6CExample 6C
實例7CExample 7C
比較例1CComparative Example 1C
Eff (相對值) 轉換效率 101.2 84.6 102.3 100.3 100.1 101.8 103.5 Ίοοό" 扣為光伏電池 FF (相對值) 填充係數 100.2 92.2 101.2 100.0 99.9 99.3 102.7 100.0 v〇c (相對值) 開路 _97.6 Jsc (相對值) 短路電流Eff (relative value) Conversion efficiency 101.2 84.6 102.3 100.3 100.1 101.8 103.5 Ίοοό" Deduction for photovoltaic cell FF (relative value) Fill factor 100.2 92.2 101.2 100.0 99.9 99.3 102.7 100.0 v〇c (relative value) Open circuit _97.6 Jsc (relative value) Short circuit current
雖然本發明已以較佳實施例揭露如上 護 限定本發明’任域習此技藝者,在錢離本t 和範圍内’當可作些狀與轉,因 ^砷 範圍當視後專職_界定 u之保 【圖式簡單說明】 47 201133512 圖1是本發明的光伏電池的剖面圖。 圖2是表示本發明的光伏電池的受光面側的平面圖。 圖3是表示本發明的光伏電池的背面側的平面圖。 圖4a是表示本發明的七小a vυ >夕夕卜光伏電池 單元的ΑΑ剖面構成的立體圖。 圖4b是表示本發明的七yl/ / A、'J ” 37 卜光伏電池 單元的背面側電極構造的平面圖。 【主要元件符號說明】 1 :包含P型矽基板的單元晶圓 2:集電用栅電極 3 : η型半導體層 4 :通孔電極 5:高濃度摻雜層 6、7 :背面電極 130 :半導體基板 131 :擴散層 132 :抗反射層 133 :受光面電極 134 :集電電極 135 :功率取出電極 136 :電極成分擴散層 48Although the present invention has been disclosed in the preferred embodiments as defined above, it is intended that the present invention may be used in the context of the present invention. u Bao Bao [Simple Description of the Drawings] 47 201133512 FIG. 1 is a cross-sectional view of a photovoltaic cell of the present invention. Fig. 2 is a plan view showing the light-receiving surface side of the photovoltaic cell of the present invention. Figure 3 is a plan view showing the back side of the photovoltaic cell of the present invention. Fig. 4a is a perspective view showing a cross-sectional structure of a seven-dimensional avυ > photovoltaic cell unit of the present invention. Fig. 4b is a plan view showing the structure of the back side electrode of the seven yl/ / A, 'J " 37 photovoltaic cell of the present invention. [Description of main components] 1 : Unit wafer 2 including a P-type germanium substrate: current collection Gate electrode 3: n-type semiconductor layer 4: via electrode 5: high-concentration doped layer 6, 7: back surface electrode 130: semiconductor substrate 131: diffusion layer 132: anti-reflection layer 133: light-receiving surface electrode 134: collector electrode 135: power take-out electrode 136: electrode component diffusion layer 48
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MY173371A (en) * | 2011-07-21 | 2020-01-21 | Hitachi Chemical Co Ltd | Conductive material |
CN103688365B (en) | 2011-07-25 | 2016-09-28 | 日立化成株式会社 | Element and solaode |
CN103890960A (en) * | 2011-07-25 | 2014-06-25 | 日立化成株式会社 | Element and solar cell |
WO2013073478A1 (en) * | 2011-11-14 | 2013-05-23 | 日立化成株式会社 | Paste composition for electrode, and solar cell element and solar cell |
JP2013131698A (en) * | 2011-12-22 | 2013-07-04 | Sharp Corp | Solar cell with wiring sheet, solar cell module, and manufacturing method of solar cell |
US20130248777A1 (en) * | 2012-03-26 | 2013-09-26 | Heraeus Precious Metals North America Conshohocken Llc | Low silver content paste composition and method of making a conductive film therefrom |
JP5598739B2 (en) | 2012-05-18 | 2014-10-01 | 株式会社マテリアル・コンセプト | Conductive paste |
JP2013243045A (en) * | 2012-05-21 | 2013-12-05 | Kanto Gakuin | Conductive laminate and method for producing conductive laminate |
CN105934830B (en) * | 2014-01-31 | 2018-09-11 | 日立化成株式会社 | Composition for electrode formation, electrode, solar cell device and its manufacturing method and solar cell |
US10593439B2 (en) * | 2016-10-21 | 2020-03-17 | Dupont Electronics, Inc. | Conductive paste composition and semiconductor devices made therewith |
CN113889293A (en) * | 2021-09-24 | 2022-01-04 | 暄泰电子(苏州)有限公司 | Conductive paste for electronic element |
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US20100096014A1 (en) * | 2006-12-25 | 2010-04-22 | Hideyo Iida | Conductive paste for solar cell |
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