TW201135753A - Paste composition for electrode and photovoltaic cell - Google Patents
Paste composition for electrode and photovoltaic cell Download PDFInfo
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- TW201135753A TW201135753A TW100102720A TW100102720A TW201135753A TW 201135753 A TW201135753 A TW 201135753A TW 100102720 A TW100102720 A TW 100102720A TW 100102720 A TW100102720 A TW 100102720A TW 201135753 A TW201135753 A TW 201135753A
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- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 239000002245 particle Substances 0.000 claims abstract description 163
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- 239000004332 silver Substances 0.000 claims abstract description 88
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 10
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- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- H01L31/0682—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
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Abstract
Description
201135753 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】 一般於結晶矽系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，參照凟川圭弘著八 與系統」，CMC出版社，2001年，ρ26-ρ27)。 光伏電池的表面電極通常是以如下方式形成。即，於 藉由使礙等在高溫下熱擴散於ρ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组八 物’然後於寥C〜_。(：下對其進行锻燒，藉此形成^ 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 種理由，業界正研究使用銀粉末以外的金屬粉末。例如， 揭示有可形成包含銀與紹的光伏電池用電極的導電性组人 物（例如，參照日本專利特開2006-3U744號公報）。另外〇, 揭不有包含含有銀的金騎綠子她以 電極形成錄合物（例如，參日s 金屬粒子的 號公報）。 …日本料_2_-226816 一般用於電極形成的銀 以及原料金屬本身價格高， 疋貝金屬，由於資源的問題、 因此期望提出—卿代含有銀 201135753 的導電性組合物（含有銀的膏）的膏狀材料。 【發明内容】 因此’本發明的第一課題在於提供一種可形成減少銀 的使用量且抑制電阻率的上升的電極的電極用膏狀組合 物、以及具有使用該電極用膏狀組合物所形成的電極 伏電池。 元 、CP2CVV2〇5系玻璃）。藉由更含有五氧化二 進一步提昇，電極的電阻率進一步下降。可 如以下原因所造成的：藉由更含有五氧化二 另外’作為導電性組合物中所包含的玻璃粒子，若考 慮對於環境的影響，則較佳為使用實質上不含鉛的無鉛坡 壤-作為無錯玻璃，就低接觸電阻率的觀點而言，較佳為 包含含有五氧化二磷的玻璃（磷酸玻璃，P2〇5系玻璃）， ，佳為包含除五氧化二磷以外更含有五氧化二釩的玻螭 一飢，耐氧化性 可認為其是由例 二飢，玻璃的軟 化點下降。201135753 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 crystalline lanthanide 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 wire width or shape is incident on sunlight. Influence (for example, refer to 凟川圭弘八八系统), CMC Press, 2001, ρ26-ρ27). The surface electrodes of photovoltaic cells are typically formed in the following manner. In other words, the conductive group eight is coated on the n-type semiconductor layer formed by thermal diffusion on the light-receiving surface side of the p-type germanium substrate at a high temperature, and then the conductive group eight is applied. . (The electrode is formed by calcination to form an electrode. 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, the metal powder other than the silver powder is being studied in the industry. For example, a conductive group member capable of forming an electrode for a photovoltaic cell containing silver and silver is disclosed (for example, refer to Japanese Laid-Open Patent Publication No. 2006-3U744). In addition, it is not necessary to include a gold-bearing green child containing silver. She forms a composition with an electrode (for example, the Japanese version of the metal particles). ... Japanese material 2_-226816 Silver and raw materials generally used for electrode formation The metal itself is expensive, and the mussel metal, due to the problem of resources, is expected to be proposed - a paste-like material containing a conductive composition of silver 201135753 (a paste containing silver). [Summary of the invention] It is an object of the invention to provide a paste composition for an electrode which can form an electrode which reduces the amount of use of silver and suppresses an increase in electrical resistivity, and has Volt battery electrode of the electrode paste composition formed meta, CP2CVV2〇5 based glass). By further increasing the pentoxide, the resistivity of the electrode is further lowered. It may be caused by the fact that the glass particles contained in the conductive composition are further contained as the pentoxide and the lead-free slope substantially free of lead is considered in consideration of the influence on the environment. - As the error-free glass, it is preferable to contain a glass containing phosphorus pentoxide (phosphoric acid glass, P2〇5-based glass) from the viewpoint of low contact resistivity, and it is preferable to contain phosphorus in addition to phosphorus pentoxide. Vanadium pentoxide is a hunger, and its oxidation resistance can be considered to be caused by the hunger of the second hunger and the softening point of the glass.
一種電極用膏狀組合物Paste composition for electrode
201135753 31及人〃205的玻璃。另外，該電極用膏狀組合物較 〇/以卜金粒子及上述銀粒子的總含有率為70質量 :二士：量:以下，上述玻璃粒子的含有率為ο.1質 : 〇質里％以下，上述溶劑及上述 率為3質量％以上、29·9質量％以下。树月曰U有 銅第2型·歧—種電極用膏狀組合物，其包含 2子、銀或銀合錄子、含有桃* v205的玻璃粒子、 ϋ率，且銅粒子相對於上述銀或銀合金粒子的 3有率為9質量％〜88質量％。 極用ίΊ月的第3型態疋一種光伏電池，其具有將上述電 H 塗佈卿絲上後進行輯而成的電極。 I·發明的效果] 在ιφ據本^明’可k供—種可形成減少銀的使用量且抑 =的上升的電極的電極用膏狀組合物、 '1用膏狀組合物所形成的電極的光伏電池。 另外，根據本發明，可提供一種 ::形成電阻率低的電極的電極用膏狀組二，、=有 T電極料狀組合物卿成的電極的絲電池。 易僅:和其他目的、特徵和優點能更明顯 明如7^特舉祕實施例，並配合所關式，作詳細說 【實施方式】 本說「本發明的實施形態進行詳細說明。再者，於 5曰中，〜」表示分別包含其前後所記載的數值作為 ⑧ 6 201135753 最小值及最大值的範圍。 <第一型態的電極用膏狀組合物> 粒子本的電極用膏狀組合物包含:銀合金 f成能的為銀合金粒 極。 R町使用里且抑制電阻率的上升的電 進行詳細說明4絲㈣'的電極时狀組合細各成分 (銀合金粒子） 外的構銀二=子=包含銀的合金，作為銀以201135753 31 and the glass of the person 205. Further, the paste composition for the electrode has a total content of yttrium/platinum particles and the silver particles of 70 mass: two ounces: the amount of the glass particles is ο.1: enamel % or less, the solvent and the above ratio are 3% by mass or more and 29.9% by mass or less. Shuyue 曰U has a copper type 2-disambiguation-type electrode paste composition comprising 2, silver or silver conjugates, glass particles containing peach * v205, ruthenium, and copper particles relative to the above silver Or the ratio of the silver alloy particles is from 9% by mass to 88% by mass. A third type of photovoltaic cell, which has an electrode formed by arranging the above-mentioned electric H coated filaments. I. Effect of the invention] The paste composition for the electrode and the paste composition for the '1 can be formed by the electrode of the electrode which can reduce the amount of use of silver and increase the amount of silver. Photovoltaic cells for electrodes. Further, according to the present invention, it is possible to provide a paste group 2 for forming an electrode having a low resistivity and a wire battery having an electrode formed of a T electrode material composition. EMBODIMENT AND OTHER OBJECTIVES, FEATURES, AND ADVANTAGES OF THE INVENTION EMBODIMENT OF THE INVENTION EMBODIMENT OF THE INVENTION In "5", "" indicates that the numerical values described before and after are included as the range of the minimum and maximum values of 8 6 201135753. <Standard composition for electrode of the first type> The paste composition for an electrode of the particle includes a silver alloy f which is a silver alloy particle. In the R-cho, the electric power which suppresses the increase of the electric resistivity is described in detail. The electrode of the four-wire (four)' is combined in detail. (Silver alloy particles) The outer structure of the silver is two = sub- = alloy containing silver, and silver is used as the silver.
Zr、w、M。、T. r Zn、Μη、Mg、V、Sn、 -種，亦可板‘二HNl等，該些可分別單獨使用 為不可避卜免=:2::避= 也混入的其他原子。作 Na、Li、Ba、Sr、^:tr 例如可列舉:Sb、Si、K、 Sn、Al、Zr、w λ/ g、Be、Zn、Pb、Cd、Ή、V、 較佳的銀合金的組成為1以及Au#。Zr, w, M. T. r Zn, Μη, Mg, V, Sn, -, or plate ‘two HNl, etc., these can be used separately as inevitable =: 2:: avoid = other atoms that are also mixed. Examples of Na, Li, Ba, Sr, and ^:tr include Sb, Si, K, Sn, Al, Zr, w λ/g, Be, Zn, Pb, Cd, yttrium, V, and a preferred silver alloy. The composition is 1 and Au#.
Ag-Cu-Zn 'Ag Cd ]U Ag-Cu-P > Ag-Cu-Mn ' 骖CU-C〇 lgAg_CU-V、、Ag_Cu_Tl、Ag-Cu-Zn 'Ag Cd ]U Ag-Cu-P > Ag-Cu-Mn ' 骖CU-C〇 lgAg_CU-V, Ag_Cu_Tl,
Ag-Cu-P-Mg > Ag Cu P V ^ CU'P'Mn ' A^-Cu-P-Zn ' Ag-Cu-P-Co , Ag.Cu.p.Sb # 〇 8 CU'P-Sn ' Ag-Cu-P-T, ^ 質二it”合金時，較佳為知的含有率為12 質里/〇、CU的含有率為9質量％〜88質量％的 201135753 情况’更佳為Ag的含有率兔 的含有率”二質量“ 12質另量t〜AS:合二時，較佳為Ag的含有率為 量%-的含4二質，率為1質量。，°〜87·” 々的含有率為23質量％〜83 &賤 ==兄，更佳為 I，質-，含有 的總===質子二的銀的含有 量%〜幻質量Τ °，質量%，更佳為23質 可二=:有銀的使_減少欵果，且 銀合金可單獨使用一種，亦可組合使用兩種以上。 上述銀合餘子的粒#並無制 二為_時的粒經(以下，有時略記為「〇^^^ .4 μπι〜1〇 μιη，更佳為丨卿〜7哗。藉由設 =上’耐氧化性更有效地提昇。另外，藉由為ι〇帅 地^的銀合金粒子彼此的接觸面積變大，電阻率更有效 另外，上述銀合金粒子的形狀並無特別限 ^狀、扁平狀、塊狀、板狀、及鱗片狀等中的任; 扁平 1耐=與低電阻率的觀點而言’較佳為大致球狀、 201135753. 金粒的方法來製造。另外，银合 金，利用製備金屬粉末c含有率的方式製備的銀合 用水霧化法並以常規方的方法來製備’例如，可利 善（股份）岐事業部法於金屬便覽（丸 具體而言’例如使銀合 \ 末化後，對所獲得的粉支、P解錯嘴嘴噴務將其粉 期望的含磷_合錄子7乾燥、分級，航可製造所 可製造且:t所㈣j 外’藉由適宜選擇分級條件， U所期望陳_銀合金粒子。 金粒:的電極用膏狀组合物中所包含的上述銀人 率，另外，作為包含後述的銀粒子時的ί: 質量。/的總含有率，例如可設定為7〇質量％〜二 If 剌氧化性與低電阻率的觀點而言，較佳為72暂 量。/。:9咖，更佳為74質量%〜88質量:， 量銀合錄子及上述録子_含量為70質 二π極用纽組合物時可容易地達成較佳= =二可產更r抑制賦予電極用膏狀組合物 觀點s 中’就耐氧化性與電極的低電阻率的 觀點而吕’較佳為銀含有率* 12 f量％〜二二 ，子的含有率於電極用膏狀組合物中為7〇匕^銀二 :。量％ ’另外，當包含後述的絲子時，銀含有率為;2質4 里。〜91質量％的銀合金粒子與練子的總含有率於電極 201135753 J /H-lHpii 用膏狀組合物中為70質量％〜94質量％，更佳為銀含有率 為23質量％〜83質量％的銀合金粒子的含有率於電極用膏 狀組合物中為74質量％〜88質量％，另外，當包含後述的 銀粒子時’銀含有率為23質量％〜83質量％的銀合金粒子 與銀粒子的總含有率於電極用膏狀組合物中為74質量％ 〜88質量％。 另外，於本發明中，亦可組合使用上述銀合金粒子以 外的導電性的粒子。作為此種導電性粒子，可列舉後 銀粒子等。 (玻璃粒子） 本發明的第一型態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，藉由所謂的煅燒貫穿（fire through)來去除 ^為抗反射膜的氮化賴，並形成電極射基㈣歐姆接 上述玻璃粒子若為於電極形成溫度下軟化、熔融，使 所接觸的氮化石夕膜氧化，並使經氧化的二氧化石夕插入，藉 此可去除抗反射膜的玻璃粒子，則可無特別限制地使用^ 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6001：以下，結晶化起始溫 度超過_。〇的玻璃的玻璃粒子。進而，就電極的低電阻 率的觀點而言，玻璃軟化點更佳為45〇七以下。 再者，上述玻璃軟化點是利用熱機械分析裝置 201135753 /-TATLfll. (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 (Thermal Gravimetry-Differential Thermal Analyzer » TG-DTA)以通常的方法來測定。 就可高效地插入二氧化石夕而言，電極用膏狀組合物中 所包含的玻璃粒子一般由包含鉛的玻璃構成。作為此種包 含鉛的玻璃，例如可列舉日本專利第〇3〇5〇〇64號公報等中 所記載的玻璃，於本發明中亦可較佳地使用該些玻璃。 另外，於本發明中，若考慮對於環境的影響，則較佳 為使用實質上不含鉛的無鉛玻璃。作為無鉛玻璃，例如可 列舉：日本專利特開2006-313744號公報的段落編號〇〇24 〜段落編號0025中所記載的無鉛玻璃、或者日本專利特開 2009-188281號公報等中所記載的無鉛玻璃，自該些無鉛 玻璃中適宜選擇後應用於本發明中亦較佳。 另外，就低接觸電阻率的觀點而言，上述玻璃粒子較 佳為包含含有五氧化二磷的玻璃（磷酸玻璃，系玻 璃）’更佳為包含除五氧化二磷以外更含有五氧化二釩的玻 璃（P2〇5-V2〇5系玻璃）。藉由更含有五氧化二飢，耐氧化 性進一步提昇，電極的電阻率進一步下降。可認為其是由 例如以下制所造成的：II由更含有五氧化二飢，玻璃的 軟化點下降。 當上述玻/璃粒子包含五氧化二鱗_五氧化二銳系玻璃 (P2〇s-V2〇5系玻璃）時，作為五氡化二釩的含有率，於 玻璃的總質量中’較佳為1質量％以上，更佳為〗質量％ 11 201135753 〜70質量％。 另外’上述五氧化二磷_五氧化二銳系玻璃視需要可更 包含其他成分。作為其他成分，可列舉：氧化鋇㈤⑴、 二氧化猛（Mn〇2)、氧化鈉（Na20)、氧化鉀（K2〇)、二 氧化錯（Zr02)、三氧化鶴（w〇3)、氧化蹄（Te〇)、三氧 化銷（Mo03)、三氧化二録（_3) #。藉由更包含=他 成分’可更高效地插人源自氣化耗二氧切。 及溶解溫度進-步下降。進而，可抑制與含有銅的 粒子或視需要而包含的銀粒子的反應。 岸：含五氧化二鈒時’銀與飢進行反 步下降。另外，於以提昇製成光伏電池時= 效率為目的之電極形成絲板的氫氟酸水溶液處理 中，電極材料的财氫氟酸水溶液性（電極材料 酸水溶液而自矽基板剝離的性質）得到提昇。虱氟 =為上述玻雜子的含有率，於第1 m ’進而更佳為1質量%〜7質量 /〇。藉由以上述範圍的含有率包含玻璃粒子， 夏 成财氧化性、電極的低電阻率及低接觸電阻。，也達 於本發明中，較佳為於第一型態的電極用 的總質量中含有作為玻璃粒子的包含 "被:物 玻璃粒子Μ質量%〜10質量％，更佳為5含; 子的包含v2〇5的含量為cu質量％以上的Ρ2〇5·ν== 12 201135753 璃的玻璃粒子1質量％〜7質量％。 (溶劑及樹脂） ° 、”，丨的第一型態的電極用膏狀組合物包含至少-種 二:種樹脂。藉此’可對應於賦予至矽基板時的 如，釉许、主發明的電極用膏狀組合物的液體物性（例 面張力等）調整為所需的液體物性。 曱苯等無特別限制。例如可列舉:己烷、環己烷、 夺、容劑’四G太—' 二氣乙院、二氯苯等氣化煙 3 =三°惡烧等環_系溶劑；n，n•二甲基甲酿胺、 «等:=ΠΓί溶劑;二甲基亞硬'二乙基亞 等_溶劑^醇、2丙:乙基嗣、二乙基酮、環己_ 合物；2,2,4_: f Α ! 3 2 _謂、二_醇等醇系化 戊二醇單丙;I ;二戊;3乙_咖 三甲基-u-戊二醇，3-戊二醇單丁酸醋、2,2,4· 乙酸酯、乙、齩酉曰、2,2,4·三乙基-1，3-戊二醇單 多元醇的劑單丁扣酸酉旨等 醇的醚系溶劑；0[萜口嫌’、 一醇一乙醚等多元 烯、檸m、二公彿：_品醇、月桂油稀、別羅勒 _、羅勒錄μ戍稀、α_装稀、卜蔽稀、松脂醇、香旱芹 作為本稀系溶劑’以及該些的混合物。 多元醇的自旨的觀點而言，較佳為選自 糸〜卜4烯系溶劑、以及多元醇的醚系溶劑 13 201135753 …* 'r**· 中的至少一種，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。 另外，作為上述樹脂，只要是可藉由煅燒而熱分解的 樹脂’則可無特別限制地使用該技術領域中通常所使用的 樹脂。具體而言，例如可列舉：曱基纖維素、乙基纖維素、 敌基曱基纖維素、硝化纖維素等纖維素系樹脂；聚乙烯醇 類；聚乙烯吡咯啶酮類；丙稀酸樹脂；乙酸乙烯酯_丙烯酸 酯共聚物；聚乙烯丁醛等的丁醛樹脂；酚改性醇酸樹脂、 蓖麻油脂肪酸改性醇酸樹脂之類的醇酸樹脂；環氧樹脂； 酚樹脂；松香酯樹脂等。 作為本發明中的上述樹脂，就煅燒時的消失性的觀點 而言，較佳為選自纖維素系樹脂、以及丙烯酸樹脂中的至 少一種，更佳為選自纖維素系樹脂中的至少一種。 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。 於本發明的第-型態的電極用膏狀組合物中，上 劑與上述獅的含#可對應於所膽⑽難性使 的溶劑及職__適宜選擇。例如， 含量於第-_的電極时狀組合物的料量中'== 3質量％〜29.9質量％ ’更佳為5 f量％〜 更佳為7質量％〜20質量％。 里/。進而 ’將電極用膏 藉由溶劑與樹脂的總含量為上述範圍内 201135753 賦予至石夕基板時的賦予適應性變得f好T审 至少f 11㈣抑纽岭她料更包含 模組時的焊接性’亦可獲得製成先伏電池 原子構^純狀的其他 --Na, :：〇ΤμΓβ：：:Ag-Cu-P-Mg > Ag Cu PV ^ CU'P'Mn ' A^-Cu-P-Zn ' Ag-Cu-P-Co , Ag.Cu.p.Sb # 〇8 CU'P- In the case of Sn 'Ag-Cu-PT, ^ bis-it alloy, it is preferable that the content is 12 里 / 〇, and the content of CU is 9% by mass to 88% by mass. The content rate of the rabbit is "two masses". 12 masses of different amounts of t~AS: when combined, it is preferred that the content of Ag is in the amount of -4, and the rate is 1 mass., °~87·含有 The content of 々 is 23% by mass to 83 & 贱 = = brother, more preferably I, quality -, total === proton two silver content % ~ magic mass Τ °, mass %, more Good for 23 quality can be two =: There are silver to reduce the effect, and the silver alloy can be used alone or in combination of two or more. The granules of the above-mentioned silver yttrium have no granules when the y is y (the following may be abbreviated as "〇^^^.4 μπι~1〇μιη, more preferably 丨卿~7哗. By setting The oxidation resistance is improved more effectively. In addition, the contact area of the silver alloy particles for the 〇 〇 ^ is increased, and the resistivity is more effective. Further, the shape of the silver alloy particles is not particularly limited. Any one of a flat shape, a block shape, a plate shape, and a scaly shape; flat 1 resistance = preferably a substantially spherical shape, 201135753. Gold grain method is produced from the viewpoint of low resistivity. The alloy is prepared by a water atomization method using a method of preparing a metal powder c content and is prepared by a conventional method. For example, the Kelly (share) business division method is used for metal notes (for example, After the silvering is finalized, the obtained powder branch and the P-dissolved nozzle are sprayed to dry and classify the desired phosphorus-containing synthon 7 of the powder, which can be manufactured by the manufacturer and: t(4) 'Using the appropriate classification conditions, U expects Chen _ silver alloy particles. Gold particles: electrode paste combination In addition, the total content rate of ί: mass. / including the silver particles to be described later can be set to, for example, from 7 〇 mass % to two if 剌 oxidizing properties and low resistivity. It is better to have a temporary amount of 72. /:: 9 coffee, more preferably 74% by mass to 88 mass:, the amount of silver and the above-mentioned recordings _ content is 70 mass two π pole with the composition can be easily In view of the viewpoint of the oxidation resistance and the low resistivity of the electrode, the ratio of the oxidation resistance to the low resistivity of the electrode is preferable. In the paste composition for an electrode, the content of the sub-component is 7 〇匕 银 银 : 。 。 。 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The total content of the silver alloy particles and the trainer is 70% by mass to 94% by mass in the paste composition of the electrode 201135753 J /H-lHpii, and more preferably the silver content is 23% by mass to 83% by mass. The content of the alloy particles is 74% by mass to 88% by mass in the paste composition for an electrode, and when it contains silver particles to be described later' The total content of the silver alloy particles and the silver particles in the silver content of 23% by mass to 83% by mass is 74% by mass to 88% by mass in the paste composition for an electrode. Further, in the present invention, it may be used in combination. Conductive particles other than the above-mentioned silver alloy particles. Examples of such conductive particles include post-silver particles, etc. (Glass particles) The paste composition for an electrode of the first aspect of the present invention contains at least one type of glass particles. The paste composition for an electrode contains glass particles, and at a temperature at which an electrode is formed, a so-called fire through is used to remove the nitride of the antireflection film, and an electrode is formed (4) ohmically connected to the glass particles. If it is softened and melted at the electrode formation temperature, the contacted cerium nitride film is oxidized, and the oxidized cerium oxide is inserted, whereby the glass particles of the antireflection film can be removed, and it can be used without particular limitation. ^ Glass particles commonly used in the technical field. In the present invention, from the viewpoint of oxidation resistance and low resistivity of the electrode, it is preferable that the glass softening point is 6001: or less, and the crystallization starting temperature exceeds _. Glass particles of enamel glass. Further, from the viewpoint of the low electrical resistivity of the electrode, the glass softening point is more preferably 45 〇 or less. Further, the glass softening point is measured by a usual method using a thermomechanical analyzer 201135753 /-TATLfll. (Thermo Mechanical Analyzer 'TMA), and the crystallization starting temperature is a thermogravimetry-thermal difference analyzer ( Thermal Gravimetry-Differential Thermal Analyzer » TG-DTA) is measured in the usual way. In order to efficiently insert the silica, the glass particles contained in the paste composition for an electrode are generally composed of glass containing lead. For example, the glass described in Japanese Patent Publication No. 3〇5〇〇64, etc., can be preferably used in the present invention. Further, in the present invention, in consideration of the influence on the environment, it is preferable to use a lead-free glass which does not substantially contain lead. For example, the lead-free glass described in Paragraph No. 〇〇24 to Paragraph No. 0025 of JP-A-2006-313744, or the lead-free method described in Japanese Patent Laid-Open Publication No. 2009-188281, and the like. Glass, which is suitably selected from the lead-free glasses, is also preferred for use in the present invention. Further, from the viewpoint of low contact resistivity, the glass particles preferably contain glass containing phosphorus pentoxide (phosphoric acid glass, glass). More preferably, it contains vanadium pentoxide in addition to phosphorus pentoxide. Glass (P2〇5-V2〇5 series glass). By further containing pentoxide, the oxidation resistance is further improved, and the resistivity of the electrode is further lowered. It can be considered to be caused by, for example, the following system: II is further reduced by the pentoxide, and the softening point of the glass is lowered. When the glass/glass particles comprise pentoxide pentoxide-pentafluoride glass (P2〇s-V2〇5-based glass), the content of vanadium pentoxide is preferably in the total mass of the glass. It is 1 mass% or more, more preferably 〖mass% 11 201135753 to 70 mass%. Further, the above-mentioned phosphorus pentoxide-pentaoxide two sharp glass may further contain other components as needed. Examples of other components include cerium oxide (5) (1), oxidized manganese (Mn〇2), sodium oxide (Na20), potassium oxide (K2〇), dioxin (Zr02), trioxane (w〇3), and oxidation. Hoof (Te〇), trioxide pin (Mo03), and O3 (_3) #. By including more = other ingredients, it is more efficient to insert a gas-consuming dioxotomy. And the dissolution temperature is stepped down. Further, it is possible to suppress the reaction with the particles containing copper or the silver particles contained as needed. Shore: When bismuth pentoxide is included, silver and hunger decline in reverse. In addition, in the hydrofluoric acid aqueous solution treatment for forming the wire plate by the electrode for improving the efficiency of the photovoltaic cell, the aqueous solution of the electrode material is hydrofluoric acid aqueous solution (the property of the electrode material aqueous acid solution and the self-tanning substrate) Upgrade. The fluorinated fluorine = the content of the above-mentioned chlorophyll is 1 m ' and more preferably 1% by mass to 7 Å / 〇. By including glass particles in the above range, the oxidizing property of Xia Chengcai, the low resistivity of the electrode, and the low contact resistance. Further, in the present invention, it is preferable that the total mass for the electrode of the first type contains, as a glass particle, a mass% to 10% by mass, more preferably 5%; The content of v2〇5 containing cu mass% or more is 〇2〇5·ν== 12 201135753 The glass particles of the glass are 1% by mass to 7% by mass. (Solvent and Resin) °, ", the paste type composition for the electrode of the first type of ruthenium contains at least one kind of two kinds of resins. Thus, 'corresponding to the case of imparting to the ruthenium substrate, for example, glaze, main invention The liquid physical properties (such as surface tension) of the paste composition for the electrode are adjusted to the desired liquid physical properties. The benzene and the like are not particularly limited, and examples thereof include hexane, cyclohexane, and a solvent. —' 2 gas, hospital, dichlorobenzene and other gasification smoke 3 = three ° bad burn and other ring _ system solvent; n, n • dimethyl amide, «etc: = ΠΓ solvent; dimethyl subhard' Diethyl acethanide _ solvent ^ alcohol, 2 C: ethyl hydrazine, diethyl ketone, cyclohexyl compound; 2, 2, 4_: f Α ! 3 2 _, diol and other alcoholic pentane Alcohol monopropyl; I; dipentane; 3 B-ca-trimethyl-u-pentanediol, 3-pentanediol monobutyrate, 2,2,4· acetate, B, 齩酉曰, 2 , 2,4·triethyl-1,3-pentanediol monopolyol, an agent, an ether solvent of an alcohol, etc.; 0 [萜口嫌', monool monoethyl ether, etc. m, two public Buddha: _ alcohol, laurel oil, belle _, basil recorded μ 戍, α _ thin, b The aliphatic alcohol and the fragrant celery are used as the present rare solvent "and a mixture of the above. From the viewpoint of the purpose of the polyol, it is preferably an ether solvent selected from the group consisting of a hydrazine-tetrazene solvent and a polyol. 13 201135753 At least one of the above-mentioned 'r**' 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 solvent may be used singly or in combination of two. In addition, as the resin, a resin which can be thermally decomposed by calcination is used, and a resin which is generally used in the technical field can be used without particular limitation. Specifically, for example, mercapto cellulose is exemplified. , cellulose cellulose such as ethyl cellulose, thioglycolyl cellulose, nitrocellulose; polyvinyl alcohol; polyvinylpyrrolidone; acrylic resin; vinyl acetate acrylate copolymer; polyethylene Butanal resin such as butyraldehyde; alkyd resin such as phenol-modified alkyd resin or castor oil fatty acid-modified alkyd resin; epoxy resin; phenol resin; rosin ester resin, etc. As the above resin in the present invention, on From the viewpoint of the disappearance at the time of firing, at least one selected from the group consisting of a cellulose resin and an acrylic resin is preferable, and at least one selected from the group consisting of cellulose resins is more preferable. In the present invention, the above resin may be used. One type may be used alone or two or more types may be used in combination. In the paste composition for an electrode of the first type of the present invention, the upper agent and the lion's inclusion # may correspond to the solvent and the duty of the biliary (10) difficulty. __ suitably selected. For example, the content of the electrode-time composition of the first-_ is -==3 mass%~29.9 mass%, more preferably 5 f%%~ more preferably 7 mass%~20 mass %. In the case of the electrode paste, the total content of the solvent and the resin is within the above range, 201135753 is given to the Shixia substrate, and the adaptability becomes good. The T is at least f 11 (four). The solderability of the module can also be obtained as the other atom of the atomic structure of the precursor battery - Na, ::〇ΤμΓβ:::
Ti、v、sn、A1、Zr、w、Mo、Tig Zn、Pb，、 二發明中的銀粒子的粒徑並無特別限二 為50/。時的粒徑（D ) 重量 燒結的觀點而言，較佳為)二^^ 有效=銀 ==τ等金屬粒子彼此的接觸面積變大，、電1: 粒徑合㈣，上祕合金粒子的 胜2| 。〃上述銀粒子的粒彳i (D5G%)的關係並| :寺別限制，較佳為任一方的粒徑（ 的 更佳為任一方的粒軸另-二： 猎在電極的電阻率更有效地下降。可認為其 疋由例如以下原因所造成的：電極内的銀合金粒子及銀粒 15 201135753 子等金屬粒子彼此的接觸面積變大。 的銀二===的電極用膏狀組合物中 而古，於雪搞田暮/尤耐氧性與電極的低電阻率的觀點 質量％，、=^#合物中，較佳為8.4質量％〜85.5 °更佳為8.9質量％〜80.1質量％。 觀點: 今Γ:氧化性與電極的低電阻率的 100質量。/脖 1 °金粒子與上述銀粒子的總量設定為 88質量。/ # t金粒子的含有率較佳為達到9質量〇/。〜 如合金粒子的含有率達到9質量%以上，例 抑；，電極的d =氧:二鈒時’銀與飢的反應得到 r不會因氫氟酸水編自絲 τ 88 t4%w 就耐氧化性一型態的電極用膏狀組合物中， 入 。電極的低電阻率的觀點而言，較佳a上、 70 f 二述玻顿子的含有率為G1質量％〜 質一議，ί ’ ’ 上述銀粒子的總含有率為74質量 201135753 /〇 88質量％，上述玻璃粒子的含有率為^質量％〜7質量 t上述溶劑及上述樹脂的總含有率為7質量％〜2〇質量 (其他成分） 、八進而，本發明的第一型態的電極用膏狀組合物除上述 成为以外，視需要可更包含該技術領域中通常所使用的其 ，成分。作為其他成分’例如可列舉：塑化劑、分散劑、 化劑、無機結合劑、金屬氧化物、陶究、有機金屬 (電極用膏狀組合物的製造方法） 益特丨的第—型態的電極用膏狀組合物的製造方法並 的分散·混合方法對上述銀 。金粒子、麵粒子、溶劑、樹脂、以及 混合’藉此製造本發明的第： 狀組合物的電極的製造方法） 法，將狀組合物來_極的方 氣中)進行即使於氧的存在下(例如，大 具體而各，例如當使用上述電極 电， 伏電池用電極時，將電極用膏^且膏狀組合物形成光 狀的方式職予至石夕基板上 後成為所期望的形 乾各後進仃炮燒，藉此可將電 17 201135753 =低的光伏電池電極形成為所期望的形 ，用=述電極用膏狀組合物，即使於氧的存在下（例=由 大孔中）進行锻燒處理，亦可形成電阻率低極。 作為將電極用膏狀組合物賦予板 如可列舉則墨法、=’例 點而言，較佳為利用網版印刷的塗佈。生的觀 當利用網版印刷塗佈本發明 組合物時，較佳為具有80Pa.s〜= 再者，電極用膏狀組合物的黏度 :二 (Bnx>kfieldHBT)來測定。a疋於沉下利用黏度計 ^述電刻纽組合物的料量可職於要形成的電 量—選擇。例如’可將電極用膏狀組合物賦予 量"又疋為2 g/m〜1〇 g/m2，較佳為4咖2〜8咖2。 鮮=1為使用本發明的第—型態的電極用膏狀組合 件（炮燒條件），可應用該技術領 條件，，言’熱處理溫度(- 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】秒〜2〇秒。 ι且選 <第二型態的電極用膏狀組合物〉 本發明的第二型態的電極用膏狀組合物包含銅粒子、 銀或，合錄子、含有Ρ2〇5及稿的玻輕子、樹脂、 以及溶劑，賴粒子相對於上賴或銀合錄子的含有率 為9質量％〜88質量〇/〇。 18The particle diameters of the silver particles in Ti, v, sn, A1, Zr, w, Mo, Tig Zn, Pb, and the second invention are not particularly limited to 50/. When the particle diameter (D) is from the viewpoint of weight sintering, it is preferable that the contact area between the metal particles such as Mn = silver == τ becomes large, and the electric particle size is (4), and the fine alloy particles are Win 2|. 〃The relationship between the granules i (D5G%) of the above silver particles and the :| Temple limit, preferably the particle size of either side (more preferably one of the grain axes of the other - two: the resistivity of the hunting electrode is more It is considered that the ruthenium is caused by, for example, the following: the contact area between the silver alloy particles in the electrode and the metal particles such as the silver particles 15 201135753 becomes large. The paste composition for the electrode of silver=== In the Middle Ages, in the case of the snow, the high resistivity of the field and the low resistivity of the electrode is %, and the compound is preferably 8.4% by mass to 85.5 ° and more preferably 8.9% by mass to 80.1. Mass %. Viewpoint: Today: Oxidation and 100% of the low resistivity of the electrode. / The total amount of the 1° gold particles and the above silver particles is set to 88. / # t The content of gold particles is preferably achieved. 9 mass 〇 /. ~ If the content of alloy particles reaches 9% by mass or more, for example, the d = oxygen of the electrode: the reaction of silver and hunger is not obtained by hydrofluoric acid water from the wire τ 88 t4%w In the paste composition for an electrode of oxidation resistance type I, from the viewpoint of low resistivity of the electrode Preferably, the content of the above-mentioned, 70 f two-dimensional Boron is G1% by mass. The total content of the silver particles is 74 masses 201135753 / 〇 88% by mass, and the content of the above glass particles is The mass ratio of the above-mentioned solvent and the above-mentioned resin is 7 mass% to 2 〇 mass (other components), and the paste composition of the electrode of the first aspect of the present invention is in addition to the above. In addition, the components which are generally used in the technical field may be further included as needed. As other components, for example, plasticizers, dispersants, chemicals, inorganic binders, metal oxides, ceramics, and organometallics may be mentioned. (Manufacturing Method of Paste Composition for Electrode) The method for producing a paste composition of an electrode of the first type of the present invention, the method of dispersing and mixing the silver, the gold particles, the surface particles, the solvent, the resin, and Mixing 'the method for producing the electrode of the first composition of the present invention by the method of the present invention, the composition of the composition is in the square gas of the electrode), even in the presence of oxygen (for example, each is large, for example, when Use the above When the electrode is used to volt the battery electrode, the electrode paste is applied and the paste composition is formed into a light pattern, and then the desired shape is dried and then burned. 201135753 = low photovoltaic cell electrode is formed into a desired shape, and the paste composition for the electrode can be formed into a low resistivity even if it is calcined in the presence of oxygen (for example, from a large hole). As a sheet for applying the paste composition for an electrode, for example, an ink method or an example is preferably applied by screen printing. The composition of the present invention is applied by screen printing. Preferably, it has 80 Pa.s~=, and the viscosity of the electrode paste composition is measured by two (Bnx > kfieldHBT). A 疋 沉 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用For example, 'the amount of the paste composition for the electrode can be imparted to the amount of 2 g/m to 1 g/m2, preferably 4 to 2 to 2 coffee. Fresh = 1 is the paste-like assembly for the electrode of the first type of the present invention (boiled condition), and the technique can be applied. The heat treatment temperature (-the other heat treatment time can be adapted to the heat treatment temperature, etc.) The selection may be, for example, sec. to 2 sec. ι and select <second type electrode paste composition> The second type electrode paste composition of the present invention contains copper particles, silver or , a synthon, a chlorhexidine containing Ρ2〇5 and a manuscript, a resin, and a solvent, and the content of the lamella particles relative to the lysate or silver conjugate is 9 mass% to 88 mass 〇/〇.
201135753 / ~τ 1. -TL/1A 如上所述，當將含有ρ2〇5& V2〇5的無錯的 用於電極用膏狀組合物中時，該玻璃粒子中所含有的V2〇 (五氧化二飢）與作為導電性金屬粉末而含有的銀進行2反5 應=生成釩酸銀，因此所形成的電極的電阻率上升。因此， 研究銀以外的金屬作為導電性金屬粉末的結果，_地將 以特定的比率與銀（Ag)併騎於形成抑制電阻 率的上升的電極有效。 尤其，若設定為銅粒子相對於銀或銀合金粒子的含有 ^為9質量％〜88 f量％的電極用膏狀組合物，則 2的電㈣的上升。當銅粒子㈣於銀或銀合金粒子的 :率未滿9質量％時，抑制由v2〇5 (五氧化二釩）與 銀）進行反應而生成的飢酸銀所引起的高電阻率化的 "低另方面，當含有率超過88質量％時，電極因由 銅的氧化所生成的氧化銅而高電阻率化。 此處對藉由銅粒子與銀粒子的併用來抑制銅的氧化 的現象進行說明。 -般於作為電極形成溫度區域的6(m：至誓c的溫 域中，產生銀於銅中的少量的固溶、以及銅於銀中的 =的固溶’而在銅與銀的界面形成銅銀固溶體的層（固 =域)。可認為當將含有_粒子與絲子的混合物加熱 广皿後’緩祕冷卻至室溫時，不產生固溶區域，但因 ^成電極時以數秒自高溫域冷卻至常溫，故可認為高溫下 ^各體的層作為非平衡㈣雜相或_銀的共晶組織 蓋銀粒子及含有銅的粒子的表面。可認為此種銅銀固 19 201135753 r Ατριι =體層有助於電極形成溫度下的含有銅的粒子的耐氧化 另外，銅-銀固溶體層於3〇〇。〇至5〇〇ΐ以上 開始形成。因此，可認為藉由將熱重-熱差同時測定;G 最大面積的發熱波峰的波峰溫度為28〇ΐ以上的魅 =與銀粒子併用，可更有效地提昇含有鋼的粒子的耐氧 化f生，所形成的電極的電阻率進一步下降。 88皙當相對於銀或銀合金粒子的含有率超過 量。夺g粒子不足，Cu-Ag固溶體層盔法充八 埋於粒子間，Cu的氧化顯著地產生。盾…"务充刀地填 進行Ϊ二^成第二_的電極用膏狀組合物的各成分 (銅粒子） 本發明中的銅粒子可為除純銅以外，亦可於 =效===其他㈣實質㈣括銅的= 子。亦可為W銅及對銅料耐氧化性的成分的金屬粒 例二 =二包=金= 子中的其他原子， rrrT，v.a，IL；r；；；：；--；BN：； 而言，L為= 整耐氧化性、炫點等特性的觀點 ⑧ 20 201135753 就耐乳化性與低電阻率的觀點而 上述鋼粒子的粒徑並無特別限制為1質^以下。 50%時的粒獲（以下，有時略記為「D5〇〇/乍為^的重量為 〜师，更佳為i卿〜7卿。藉以交:圭為〇·4卿 耐氧化性更有效地提昇。另外，藉由為to 帅以上， 中的銅粒子彼此的接觸面積變A，，電極 再者，銅粒子的粒徑是藉由地下降。 (日機裝公司製造，MT3綱型）來測^度刀布測定裝置 ^卜，上述銅粒子的形狀並無特別限制， 狀、扁平狀、塊狀、板狀、及鱗片狀”、、表 就耐氧化性與低電阻率的觀點而言，較佳為：：，形狀’ 平狀、或板狀。 較佳為大致球狀、扁201135753 / ~τ 1. -TL/1A As described above, when the error-free paste composition containing ρ2〇5& V2〇5 is used, the V2 contained in the glass particles (five) The oxidized stagnation and the silver contained as the conductive metal powder are subjected to a reverse reaction to the formation of silver vanadate, and thus the resistivity of the formed electrode is increased. Therefore, as a result of investigating a metal other than silver as a conductive metal powder, it is effective to form a silver with a specific ratio of silver (Ag) and to form an electrode which suppresses an increase in resistivity. In particular, when the paste composition for the electrode containing the copper particles in the range of 9% by mass to 88% by weight of the silver or the silver alloy particles is set, the electric (four) of 2 is increased. When the ratio of the copper particles (4) to the silver or silver alloy particles is less than 9% by mass, the high resistivity caused by the silver formed by the reaction of v2〇5 (vanadium pentoxide) and silver) is suppressed. " On the other hand, when the content rate exceeds 88% by mass, the electrode is highly resistive due to copper oxide generated by oxidation of copper. Here, a phenomenon in which copper particles and silver particles are used together to suppress oxidation of copper will be described. - at the interface between copper and silver, in the temperature range of 6 (m: to v, c, which produces a small amount of solid solution of silver in copper and solid solution of copper in silver) A layer forming a copper-silver solid solution (solid = domain). It is considered that when the mixture containing the _particle and the filament is heated to a dish, the solid solution region is not generated when it is cooled to room temperature, but the electrode is formed into an electrode. When it is cooled from a high temperature range to a normal temperature in a few seconds, it is considered that the layer of each body at a high temperature is used as a non-equilibrium (tetra) heterophase or a eutectic structure of silver, and the surface of the particles containing copper. Solid 19 201135753 r Ατριι = Body layer contributes to oxidation resistance of copper-containing particles at electrode formation temperature. In addition, the copper-silver solid solution layer starts to form at 3 〇〇. 〇 to 5 〇〇ΐ or more. The thermogravimetry-thermal difference is simultaneously measured; the peak temperature of the heat peak of the G largest area is 28 〇ΐ or more and is used together with the silver particles, so that the oxidation resistance of the steel-containing particles can be more effectively enhanced. The resistivity of the electrode is further reduced. 88 皙 when compared to silver or silver alloy particles The content of the material exceeds the amount. The particles of the Cu-Ag solid solution are buried in the particles, and the oxidation of Cu is remarkably generated. The shield..." Each component of the paste composition for an electrode (copper particles) The copper particles in the present invention may be in addition to pure copper, or may be in the form of ===other (four) substantial (four) copper = or may be W copper and For the metal granules of the oxidation resistance of the copper material, the second granule = two packets = gold = other atoms in the sub, rrrT, va, IL; r;;;;;--; BN:; From the viewpoint of the emulsification resistance and the low electrical resistivity, the particle diameter of the steel particles is not particularly limited to 1 mass or less. The grain yield at 50% (hereinafter, there are When the weight is D5〇〇/乍 is ^, the weight is ~ division, and better is i Qing ~ 7 Qing. By paying: Gui is 〇 · 4 Qing oxidation resistance is more effectively improved. In addition, by to handsome In the above, the contact area of the copper particles is changed to A, and the particle diameter of the copper particles is decreased by the electrode. (Made in Japan, MT3) In the case of the above-mentioned copper particles, the shape of the copper particles is not particularly limited, and is in the form of a flat shape, a flat shape, a block shape, a plate shape, and a scale shape, and the surface is resistant to oxidation and low resistivity. Preferably, the shape is 'flat, or plate-shaped. It is preferably substantially spherical or flat.
本！明的第二型態的電極用膏狀組合物中所包含 =粒子、錄子及銀合錄子（含有銀的粒子）的^ 有率，例如可設定為70質量％〜94質量 I 為74質〜88質量％。 ，由上述銅粒子及上述含有銀的粒子的總含量為7〇 ^二以上，賦予電極用膏狀組合物時可容易地達成較佳 人^。另外’藉由上述銅粒子及上述含有銀的粒子的總 二=94質量％以下’可更有效地抑制賦予電極用膏狀組 ό物時的斑點的產生。 另外，於本發明中，亦可組合使用銅粒子銀粒子及 銀合金粒子以外的導電性的粒子。 21 201135753 (銀粒子或銀合金粒子） 銀二合物更包含至少-種銀粒子或 ^子（以下’有時稱為「含有銀的粒子」）。 不可僻j粒子及銀合金粒子，可為除純銀以外，亦包含 子，亦可原子的實質上僅由銀構成的金屬粒 地混:=====， Z；'w ua'M8'Be'Zn'Pb'Cd'T1'V'S-A.-、w : Mo、Tl、c〇、Ni、以及 Au 等。 作為銀合金粒子，可應用上述 組合=明的銀合金粒子，較佳的範圍= HD5〇:/3)tt?立子的粒徑，累計的質量為5〇%時的粒 更佳為一-。 外，ί由為/ 上，耐氧化性更有效地提昇。另 等金屬曰粒子彼此^下’電極中的含有銀的粒子及銅粒子 於本發明的第二地：子 := 心/，為_，量:子 (3有Ρ2〇5及的玻璃粒子） 本發明的第二型態的電極用膏狀組合 的影響，而㈣至少—_ P似 時稱為「队v2〇5系玻璃粒子」）。藉由電極； ⑧ 22 201135753 物包含玻璃粒子，於電極形成溫度 穿來去除作為抗反射膜的氮化额 ^所謂的锻燒貫 的歐姆接觸。 、^成電極與矽基板 由於本發明的玻璃粒子含有五氡 低接觸電阻率化。另外，除五氧化二碟 化一釩，因此玻璃的軟化點下降 亦： 且電極的電阻率進一步下降。 性進—步棱幵， 於本發明中，藉由銅粒子的添加來抑 化二釩）與Ag (銀）進行反應 2 5(軋 雷阳末WU m 飢酸銀所引起的高 率，因此P2〇5-V205系玻璃粒子中 含有率並無特別限定。Ρ2ο5_ν2()5 二釩的含有率較佳為1質量％〜7〇質量％ j 、五—化 作!! ’P2(VV2C>5玻璃粒子視f要可更包含其他成分。 ==，可列舉:氧化鋇、二氧化盆、氧化納^^ 氧化鐵等。』由；=他=化鶴、氧化碲、氧化録、 化石夕的成分’可更高效地插入源自氮 、一氧化矽。另外’可使軟化及溶解溫度進一步下降。 你I抑制與銅粒子或者銀粒子祕合錄子的反應。 上述P2〇5-V205系玻璃粒子的含有率，於第二型 1=暂旦，用膏狀組合物的總質量中，較佳為αι質量％〜 量〇/里更佳為〇.5質量％〜8質量〇/〇，進而更佳為1質 7貝量〇/〇。藉由以上述範圍的含有率包含玻璃粒子， 有效地達柄氧化性、電極的低餘率及低接觸電阻。 (樹脂及溶劑） 23 201135753 發明的第二型態的電_膏狀纟且合物包含至少一種 溶劑與至少—種樹 裡 糟此，可對應於賦予至矽基板時的 如：产ί明的電極用膏狀組合物的液體物性（例 可ί用於Si 整為所需的液體物性。 與第-型態“=:用膏狀組合物的溶劑及樹脂 ，牛亦相冋，因此省略說明。 與電極的低用膏狀組合物中，就财獅 含有銀的粒暫較，上述謝^ 相對於f量％，銅糾 述P。'7… 的有率為9質量％〜88質量％ ’上 0/0, 2μ二2 5系玻璃粒子的含有率為0·1質量％〜10質量 上返溶劑及上述樹脂的總含有率為3質量％〜29 9賀 為7°= ^為上述峰子及上述含有銀的粒子的總含有_ 質量％〜88 f量％，銅粒子相對於含有銀的粒子的令 的ί li7質量％〜77質量％ ’上述执-v2〇5系玻璃粒子 人1 Φ ^ 1 1 〜7 ’上述溶劑及上述樹脂的總 3虿率為7質量％〜2〇質量％。 (其他成分） 進而’本發_第二型態的電極用膏狀組合物除上述 刀以外，視需要可更包含該技術領域中通常所使用的其 =成分。作為其他成分，例如可列舉：塑化劑、分散劑、' =活性劑、無機結合劑、金屬氧化物、_、有機 化合物等。 两 ⑧ 24 201135753 (電極用膏狀組合物的製造方法） 益特祕電極騎岐合_製造方法並 銅粒子、銀粒子或銀合金粒子、破2十上述 而包含的銀粒子等進行分散及混Γ藉Γ:造 本發明的第二型態的電極时狀組合物。籍此衣k 膏狀組合物的電極的製造方法） 極的方法，將上述電 物來製造電 域，乾燥德推ηΓ: 職予至形錢極的區 藉由使用上述膏所=的區域形成電極。 如：”進行锻;處狀=可:^ 具體而言，例如當#用卜什带以扣*千低的電極。 伏電池用電極時，將電極用膏狀===成光 狀的方式賦予至石夕基板上，乾物期望的形 ::低的光伏電池電極形成為所期望的丁二：:可 使用上述電極用膏狀組合物，即使於氧的存在卜=由 大虱_)進行炮燒處理，亦可形成電阻率低的電極。 組合=用:==t發明㈣二型態的電極用膏狀 :㈣雛為具有8GPa.s~i_pa.s_ 再者，電極用纽組合物_度是於坑 又 (Brookfield HBT)來測定。 用點度§十 極的予量可對應於要形成的電 極的大小而適且選擇。例如，可將電極用膏狀組合物賦^ 25 201135753 量設定為2 g/m2〜i〇 g/m2，較佳為4咖2〜8咖2。 另外，作為使用本發明的第二型態的電極用膏狀組合 物形成電極_熱處理條件（域條件），可應用該技術領 域中通常所使用的熱處理條件。 ，一瓜而έ，熱處理溫度（煅燒溫度）為8〇〇。〇〜9〇〇。〇， 仁田使用本發明的電極用膏狀組合物時，可應用更低的溫 度下的熱處理條件，例如，可形成於6G(rc〜85Qt：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〜2〇秒。 <光伏電池> 本發明的光伏電池具有於氧的存在下對被賦予至石夕基 板上的上述電極用膏狀組合物進行锻燒而形成的電極。藉 此’可獲得具有良好的特性的光伏電池，⑽献電池的 生產性優異。 以下 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。 八 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。 通吊，於光伏電池元件的半導體基板13〇中使用單晶 或多晶別等。該半導體基板130中含有硼等，而構成p型 半導體父光面側為了抑制太陽光的反射，藉由蚀刻而形 成有凹凸（紋理，未圖示）。於該受光面側捧雜鱗等，並以 次微米級的厚度設置有n型半導體的擴散層m，並且在 ⑧ 26 201135753. j /-Ti.-rL/ii 與P 1塊狀部分的邊界形成有pn接合部。進而，於受光面 側，藉由蒸鍍法等在擴散層131上設置膜厚為1〇〇 nm左 右的氮化矽等的抗反射層132。 、^次，對設置於受光面側的受光面電極133、以及形 ^於方面的集電電極134及功率取出電極135進行說明。 文光面電極133與功率取出電極135是由上述電極用膏狀 ^合物形成。另外’集電電極134是由包含玻璃粉末的銘 極膏狀組合物形成。該些電極是_網版印刷等將上述 組合物塗佈成所·_ ，進行乾燥，然後於大 氣以600 C〜850 C左右進行烺燒而形成。 此時，於找齡卜形錢光面電極133的上述電極 ^狀組合物中所包含的玻璃粒子與抗反射層132進行反 :(烺燒貫穿），而使受光面f極133與擴散層m 接（歐姆接觸）。 成本明中’藉由使用上述電極时狀組合物來形成 i的=面含有銅作為導電性金屬，一面抑制 1幻。而以❹的生紐形成低1：阻率的受光面電極 邀隼電電成分擴散層136’藉此可在半導體基板130 3極134、功率取出電極135之間獲得歐姆接觸。 例的發明的其他型態的光伏電池元件的-、 ㈣面構造的立體圖（a)、以及背面侧電 27 201135753 / ~r * —r 上<τ* 上 極構造的平面圖（b)示於圖4(a)及圖4(b)。 如圖4(a)及圖4(b)所示，於包含p型半導體的矽基板 的單元晶圓1上，藉由雷射鑽孔或蝕刻等而形成有貫穿受 光面侧及背面侧兩面的通孔。另外，於受光面侧形成有提 昇光入射效率的紋理（未圖示）。進而，於受光面侧形成有 利用η型化擴散處理所形成的η型半導體層3，且於n型 半導體層3上形成有抗反射膜（未圖示）。該些是藉由與先 刖的結晶Si型光伏電池單元相同的步驟來製造。 、、邀而，藉由印刷法或喷墨法將本發明的電極用膏狀组 合物填充至先前所形成的通孔内部，進而，於受光面側同 樣地將本發明的電極用膏狀組合物印刷成栅狀，而形成如 下的組合物層’該組合物層形成通孔電極4及集電用橋電 極2。 此處，用於填充用與印刷用的膏較理想的是使用以黏 度為首的特性最適合於各個製程的組成的膏，亦可使用相 同組成的膏一次性地進行填充、印刷。 另-方面，於受光面的相反側（背面側）形成用於防 止載子複合的高濃度摻雜層5。此處，使用硼（B)或鋁（ai) 作為形成純度摻雜層5 元素來形成p+層。該高濃 度摻雜層5例如可藉由於上述抗反射卿絲的單元製造 步驟中實施將B作為擴散源的熱擴散處理來形成，或者當 使用A1時，可藉由於上述印刷步驟中將Al f*印刷在相反 面側來形成。 久 其後，於650。〇至850。〇下進行煅燒，被填充、印刷於 ⑧ 28 201135753 •J /*τι*τυι» 受光面侧所形成的抗反射膜上的上述電極 歐姆接觸。岐“穿超，而達成與下部n型層的 另外，於相？面側’如由圖4⑻的平面圖所示，將 X月的I極用膏狀組合物分別於η側、ρ側均印刷成條 狀，並進行煅燒，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形成通 極4、集電用柵電極2、背面電極6及背面電極7，藉此一 面含有銅作為導電性金屬，—面抑制銅的氧化，而以 的生產性形成低電阻率的通孔電極4、集電用柵電極厂 面電極6及背面電極7。 再者’本發明的電極用膏狀組合物並不限定於如上 述的光伏電池電極_途，例如，亦可較佳地用於電 不器的電極線及屏蔽線、陶竟電容器、天線電路、各種 測器電路、半導體元件的散熱材料等用途。 再者，日本申請案201〇_〇13515號及日本申請 2010-222204號_示的所有内容是作為參照而被引用於 本說明書中。 、 本說明書申所記載的全部文獻、曰本專利申請案、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、日本專财賴、以及技術規_相同的程度， 作為參照而被引用於本說明書中。 [實例] 以下，藉由貫例更具體地說明本發明，但本發明並不 29 201135753this! In the second paste electrode composition of the second type, the yield of the particles, the recording material, and the silver conjugate (particles containing silver) can be set, for example, from 70% by mass to 94% by mass. Quality ~ 88% by mass. The total content of the copper particles and the silver-containing particles is 7 〇 ^ 2 or more, and the paste composition for an electrode can be easily obtained. In addition, the occurrence of speckle when the paste-form composition for electrodes is applied can be more effectively suppressed by the total of two of the above-mentioned copper particles and the above-mentioned silver-containing particles = 94% by mass or less. Further, in the present invention, conductive particles other than the silver particles of the copper particles and the silver alloy particles may be used in combination. 21 201135753 (Silver particles or silver alloy particles) The silver dimer further contains at least one type of silver particles or ^ (hereinafter referred to as "particles containing silver"). Non-singular particles and silver alloy particles may be contained in addition to pure silver, or may be mixed with metal particles consisting essentially of only silver: =====, Z; 'w ua'M8'Be 'Zn'Pb'Cd'T1'V'S-A.-, w: Mo, Tl, c〇, Ni, and Au, and the like. As the silver alloy particles, the above-mentioned combination = bright silver alloy particles can be used, and the preferred range is HD5 〇: /3) tt? The particle size of the iridium, and the granule when the cumulative mass is 5 〇% is more preferably one-. In addition, ί is / /, oxidation resistance is more effectively improved. Further, the metal ruthenium particles are separated from each other by the silver-containing particles and the copper particles in the second region of the present invention: sub: = heart/, _, amount: sub-(3 玻璃2〇5 and glass particles) The electrode of the second type of the present invention is affected by the paste combination, and (4) is at least "team v2 〇 5 type glass particles" when at least _ P like. By means of an electrode; 8 22 201135753 The object contains glass particles which are worn at the electrode formation temperature to remove the nitriding amount as an anti-reflection film. Electrode and tantalum substrate The glass particles of the present invention contain five turns of low contact resistivity. In addition, in addition to vanadium oxide, the softening point of the glass is lowered: and the resistivity of the electrode is further lowered. In the present invention, the addition of copper particles suppresses the reaction of vanadium with Ag (silver) and the high rate caused by the silver The content of the P2〇5-V205-based glass particles is not particularly limited. The content of bismuth 2ο5_ν2()5 divanado is preferably 1% by mass to 7〇% by mass j, and the five-formation is made!! 'P2(VV2C>5 Glass particles can contain other components depending on f. ==, can be listed as: cerium oxide, dioxide basin, oxide oxide ^ ^ iron oxide, etc. 』 by; = he = crane, yttrium oxide, oxidation recorded, fossil eve The component ' can be more efficiently inserted from nitrogen and osmium oxide. In addition, the softening and dissolution temperature can be further lowered. You I inhibit the reaction with copper particles or silver particles. The above P2〇5-V205 glass The content of the particles is in the second type 1 = temporary, and in the total mass of the paste composition, it is preferably α% by mass to 〇/min more preferably 55 mass% to 8 mass 〇/〇, Further, it is more preferably a mass of 7 Å/min. By containing glass particles at a content ratio of the above range, the oxidative property and the electrode are effectively attained. Residual ratio and low contact resistance. (Resin and solvent) 23 201135753 The second type of electro-paste bismuth composition of the invention comprises at least one solvent and at least one kind of tree, which may correspond to the application to the ruthenium substrate. For example, the liquid properties of the paste composition for electrode production (for example, can be used for Si to obtain the desired liquid physical properties. With the first type "=: solvent and resin with paste composition, cattle Since the description is omitted, the low-paste paste composition with the electrode is temporarily compared with the grain containing silver, and the above-mentioned X is relative to the amount of f, and the copper is described as P. The probability of '7... 9% by mass to 88% by mass 'The upper 0/0, the content ratio of the 2μ2 2 series glass particles is 0.1% by mass to 10%, and the total content of the above solvent is 3% by mass. 7°=^ is the total content of the above-mentioned peaks and the above-mentioned silver-containing particles _% by mass to 88%, and the copper particles are 7% by mass to 77% by mass with respect to the particles containing silver. 〇5 series glass particles human 1 Φ ^ 1 1 ～7 'The total solvent ratio of the above solvent and the above resin is 7 mass% to 2 〇 mass% (Other components) Further, in addition to the above-mentioned knives, the paste composition for an electrode of the present invention may further include a component which is generally used in the technical field, and may be, for example, other components. Plasticizer, dispersant, '=active agent, inorganic binder, metal oxide, _, organic compound, etc. Two 8 24 201135753 (Manufacturing method of paste composition for electrode) 益特秘电极骑合合_制造In the method, copper particles, silver particles, or silver alloy particles, silver particles contained in the above-mentioned 20, and the like are dispersed and mixed. The electrode composition of the second aspect of the present invention is produced. The method for producing an electrode of the coating composition of the coating k) is a method of manufacturing the electric field by the above-mentioned electric substance, and drying the area of the yttrium: the area to the shape of the money is formed by using the area of the above-mentioned paste = electrode. Such as: "forging; singular = can: ^ Specifically, for example, when #布什带带扣* thousand low electrode. When volt battery electrode, the electrode is paste-like === light-like way The desired shape of the dry matter is given to the substrate of the Shixi:: the low photovoltaic cell electrode is formed into the desired diced:: the paste composition for the above electrode can be used, even in the presence of oxygen = by 虱_) Cannon-burning treatment can also form electrodes with low resistivity. Combination = use: ==t invention (4) Type 2 electrode for paste: (4) Young for 8GPa.s~i_pa.s_ Further, electrode composition The degree is measured by Brookfield HBT. The amount of § ten poles can be selected according to the size of the electrode to be formed. For example, the paste composition can be applied to the electrode. 25 201135753 The amount is set to 2 g/m2 to i〇g/m2, preferably 4 to 2 to 8 coffee 2. In addition, the electrode is formed as a paste composition for an electrode of the second aspect of the present invention. Condition), the heat treatment conditions generally used in the technical field can be applied, and the heat treatment temperature (calcination temperature) is 8 〇.〇〇~9〇〇.〇, when Renda uses the paste composition for an electrode of the present invention, heat treatment conditions at a lower temperature can be applied, for example, it can be formed at a heat treatment temperature of 6G (rc~85Qt: 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 2 seconds. <Photovoltaic Cell> The photovoltaic cell of the present invention has a pair in the presence of oxygen. An electrode formed by calcining the paste composition for the electrode on the substrate, thereby obtaining a photovoltaic cell having excellent characteristics, and (10) providing excellent battery productivity. A specific example of the photovoltaic cell of the present invention is not limited thereto. Eighth, an outline of a typical photovoltaic cell element, a light-receiving surface, and a back surface are shown in Figs. 1, 2, and 3. In the semiconductor substrate 13 of the photovoltaic cell element, a single crystal or a polycrystal is used, and the semiconductor substrate 130 contains boron or the like, and the p-type semiconductor parent side is formed to suppress too much. In the reflection of sunlight, irregularities (textures, not shown) are formed by etching, and a scale layer or the like is held on the light-receiving surface side, and a diffusion layer m of an n-type semiconductor is provided in a thickness of a submicron order, and at 8 26 201135753. j /-Ti.-rL/ii forms a pn junction portion at the boundary of the block portion of P1. Further, on the light-receiving surface side, the film thickness is set to 1 on the diffusion layer 131 by a vapor deposition method or the like. The anti-reflection layer 132 such as tantalum nitride of about nm is used for the light-receiving surface electrode 133 provided on the light-receiving surface side, and the collector electrode 134 and the power extraction electrode 135 in terms of the shape. The electrode 133 and the power take-out electrode 135 are formed of the above-described electrode paste. Further, the collector electrode 134 is formed of an ingot paste composition containing glass powder. These electrodes are formed by coating the above composition into a _-screen printing, drying, and then calcining at about 600 C to 850 C in the atmosphere. At this time, the glass particles contained in the electrode-shaped composition of the epoch-shaped smooth surface electrode 133 are opposite to the anti-reflection layer 132: (the smoldering penetration), and the light-receiving surface f-pole 133 and the diffusion layer m connection (ohmic contact). In the cost, the surface of the i formed by using the above-mentioned electrode-like composition contains copper as a conductive metal, and suppresses the illusion. On the other hand, the light-receiving surface electrode having a low resistance ratio of ❹ is formed to invite the electric-electrode component diffusion layer 136' to thereby obtain an ohmic contact between the semiconductor substrate 130 3 pole 134 and the power extraction electrode 135. The perspective view (a) of the (four) plane structure of the other types of photovoltaic cell elements of the invention, and the plan view (b) of the upper pole structure of the back side electric 27 201135753 / ~r * -r are shown in Figure 4 (a) and Figure 4 (b). As shown in FIG. 4(a) and FIG. 4(b), on the unit wafer 1 of the ruthenium substrate including the p-type semiconductor, both sides of the light-receiving surface side and the back surface side are formed by laser drilling or etching. Through hole. Further, a texture (not shown) for improving the light incident efficiency is formed on the light receiving surface side. Further, an n-type semiconductor layer 3 formed by an n-type diffusion treatment is formed on the light-receiving surface side, and an anti-reflection film (not shown) is formed on the n-type semiconductor layer 3. These are produced by the same steps as the prior art crystalline Si-type photovoltaic cells. In the meantime, the paste composition for an electrode of the present invention is filled into the inside of the through hole formed by the printing method or the inkjet method, and the paste of the electrode of the present invention is similarly applied to the light receiving surface side. The material is printed in a grid shape to form a composition layer which forms the via electrode 4 and the current collecting bridge electrode 2. Here, it is preferable that the paste for filling and printing is a paste which is most suitable for the composition of each process, and the paste of the same composition can be filled and printed at one time. On the other hand, a high-concentration doping layer 5 for preventing carrier recombination is formed on the opposite side (back side) of the light receiving surface. Here, boron (B) or aluminum (ai) is used as the impurity doping layer 5 element to form a p+ layer. The high-concentration doping layer 5 can be formed, for example, by performing a thermal diffusion treatment using B as a diffusion source in the unit manufacturing step of the anti-reflective filament, or when Al is used, by Al f in the above printing step *Printed on the opposite side to form. Long after that, at 650. 〇 to 850. The crucible is calcined, filled and printed on 8 28 201135753 • J /*τι*τυι» The ohmic contact of the above electrode on the antireflection film formed on the side of the light receiving surface.岐 "Wearing over, and achieving the lower n-type layer, on the side of the phase" as shown in the plan view of Fig. 4 (8), the paste-like composition of the I-pole for X month is printed on the η side and the ρ side, respectively. The strip electrodes are formed and calcined to form the back electrodes 6 and 7. In the present invention, the gate electrode 4, the collector gate electrode 2, the back electrode 6 and the back electrode 7 are formed using the paste composition for an electrode described above. On the other hand, copper is used as the conductive metal, and the surface is suppressed from oxidation of copper, and the low-resistivity via-hole electrode 4, the collector gate electrode surface electrode 6 and the back surface electrode 7 are formed in a productive manner. Further, the paste composition for an electrode of the present invention is not limited to the above-described photovoltaic cell electrode, and may be preferably used for an electrode wire and a shield wire, a ceramic capacitor, and an antenna circuit, for example. , various detector circuits, heat dissipation materials for semiconductor components, etc. Further, the contents of the Japanese Patent Application No. 201- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ All the documents, the patent application, and the technical specifications described in the specification are the same as the specific documents, the Japanese financial resources, and the technical specifications. Reference is made to this specification. [Examples] Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not 29 201135753
限定於該些實心再者，只要事先無制 及「％」為質量基準。 、份J <實例1 > (a) 銀合金粒子的準備 製備包含Ag 63%、Cu 35%、P 2%的銀合金 为 解後藉由水霧化法將其粉末化，然後進行乾燥、八'、各 合經分級的粉末，並進行脫氧及脫水分處理，製二銀合混 粒子。再者，銀合金粒子的粒徑（D5〇%) 、σ金 /,、 ' J J κΙΠ 〇 (b) 銀粒子的準備 準備粒徑（D50%)為0.4 μηι、1.1 μιη、丨7从历的市 的二種試劑（三井金屬製造）作為銀粒子。 (Ο玻璃粒子的準備 製作兩種玻璃粒子。 玻璃1的组成（Ρ19)為氧化釩（％〇5) 32重量份、 氧化磷（P2〇5) 26重量份、氧化鋇（Ba0) 1〇重量份、氧 化錳（Mn〇2) 8重量份、氧化鈉（Ν&2〇) i重量份、氧化 鉀（K2〇) 3重量份 '氧化鋅（Zn〇) 1〇重量份、氧化鎢 (WO3) ίο重量部。該玻璃的軟化點為44：rc，結晶化溫 度為600°C以上。 玻璃2的组成（AY1)包含氧化釩（v2〇5) 45份、氧 化鱗（P205 )24.2份、氧化鋇（Ba0 )2〇.8份、氧化録（Sb203) 5份、氧化鎢（W03) 5份，且粒徑（D50%)為1.7 μιη。 另外’該玻璃的軟化點為492。(：，結晶化溫度超過600〇C。 (d)電極用膏狀組合物的製備 201135753 =成為表丨的調配比的方銅及 金粒子、銀粒子、ίΙΙΓΐ的調配比的方式稱量銀合 乳绰中授拌20分==子^容齊i及樹脂，然後於瑪職 刀隹里，製成電極用膏狀組合物1。 你炎於如，使用二乙二醇單丁醚乙酸酯（以下，稱為BCA) 制借：：’f使用乙基纖維素(以下，稱為EC)作為樹脂， ΐ的!Γ的BCA ’且為了適合於網版印刷’以使 、广1 〇Pa’s〜20〇pa‘s的方式調整溶劑量。 (d)光伏電池單元的製作 以Γ!於受光面形成有n型半導體層、紋理及抗反射膜 ’石膜）的膜厚為㈣μιη的p型半導體基板，並切 t日I:mxU5 mm的大小。利用網版印刷法，將上述所 則貧狀組合物丨以成為如圖2所示的電極圖案 手於其受光面。電極的圖案是由150㈣寬度的 ^曰線（Fingerline) w.lmm 寬度的匯流條（Busbar) 構成，且以使锻燒後的膜厚達到2〇 μιη的方式適宜調 刷條件（筛板的篩孔、印刷速度、印刷壓力）。將所獲得 放入加熱至im:的㈣巾15分鐘，藉岭散來絲^劑。 繼而，同樣利用網版印刷將鋁電極膏印刷於整個 ，。以使锻燒後的膜厚達到4〇μιη的方式適宜調整印 件。將所獲得者放入加熱至150¾的烘箱中15分鐘，— 蒸散來去除溶劑。 、里错由 繼而，於紅外線急速加熱爐内，在大氣環境下以85〇 進行2秒的加熱處理（锻燒）’製成形成有所期望的電極的 31 201135753 光伏電池單元1。 <實例2〜實例13 > 於實例1中’將銀合金粒子及 =，(叫破壤粒子的種類二=所: _卜’叫實例1㈣的方式製成光伏電池 早兀2〜光伏電池單元13。 <比較例1> 人1 +，不含有銀合金粒子來製備電極用膏狀組 除此以外，以與實例i相同的方式製成 伏 電池單元1。 <光伏電池元件的評價> 所製作的献電池it件的評價是將作域擬太陽光的 Wacom Electric (股份）製造的 WXS-155S-10、作為電流· 電壓（I-V)評價測定器的 I-V CURVE TRACER MP-160 (EKO INSTRUMENT公司製造）的測定裝置加以組合來 進行。將實例與比較例中所製作的膏的作為光伏電池的發 電性能結果一併記載於表1中。 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1的測定值作為100·0的相對值而示於表卜再者， 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。 32 ⑧ 201135753 J-aH 寸卜Γη 鬥Id 作為光伏電池的發電性能 Jsc (相對值） 短路電流 卜 〇{ 〇\ Os Os cK Os 〇\ 〇\ 寸 〇\ 〇\ 104.2 103.1 in Os Os 100.0 CN σ\ 〇\ o o oo 〇\ 104.0 100.0 υ ^ 辆1 卜 On On VO On 〇\ 00 On m oo On m cK On 100.3 100.0 00 a\ 100.4 寸 Os ^T) oo On 卜 00 Os 100.4 100.0 寂 孝 & ™ Q ^ ^ ^ ^ 1 100.5 1 100.2 100.1 00 cK 卜 C\ G\ 102.4 | 102.3 101.2 102.3 ro cK 0's CN cn On cn Ch 〇\ 104.6 100.0 Eff (相對 值） 轉換效 率 100.2 | loo.o | 00 cK On On On VO 〇\ 103.0 102.3 101.5 103.5 寸 〇\ 〇\ 00 卜^ On VO oo 〇\ 104.3 100.0 含有4% EC 的BCA溶液 (份） <Ti <n H <Ti i〇 IT) <Ti vn r~H 玻璃粒子 含量 (份） <N CN CN <N CN (N (N 寸 CN <N CM 鄉戥 σ\ Os Ki 〇\ On On PU as 〇\ Os Os 〇\ K, 1-H On E 銀粒子 含量 (份） »η o tn m (N VO $ o 粒徑 (D50%) μιη 1-H H ^Η (> 1-H 1-^ 寸 d r·^ 銀合金粒子 1 1 含量 (份） (T) o in m JO IT) yr\ vn in o 粒徑 (D50%) μηι in in 1-H uo <T) cn in yn T—H in ϊ—H 1 實例 CN m 寸 卜 oo 〇\ O CN ΓΟ 比較例1 201135753 (結果與考察） 如表1的結果所示，於含有銀合金 的電極用膏狀組合物中，銀的使用量減少 雷 性顯著下降。 且並未使電特 貫例1〜實例13的電極用膏狀組合物 j銀粒子的總含有率為7G _以 ^^及 玻璃粒子的含有率為（U質量％以上、1G ^ 以 劑及_L P a 枭置％以下，溶 =及土述糾日的總含有率為3質量％以上 粒子的存在而板的接觸電阻下降。有可能因銀合金 下降。 1 205與Ag的反應，其結果，接觸電阻 發 ，因此亦可對縣降低做出貢獻。 使用於實例1〜實例13的電極騎狀組合物中所 由；、立子不含鉛成分，因此可降低對於環境的影燮。 獲得粒子的粒徑為〇.4 μιη較粒徑為u帅“ 性，$為其原因在於:藉由使銀粒子變 而促進燒結，且體積電阻率下降。 的軟據實例1、實例11的結果可明確，破璃粒子 軟化點越低，電特性越良好，較佳為·。c以下。 <實例14> 使用上述所獲得的電極用膏狀組合物9，製成具有如 ⑧ 34 201135753Limited to these solid ones, as long as there is no system in advance and "%" is the quality benchmark. , J <Example 1 > (a) Preparation of Silver Alloy Particles A silver alloy containing Ag 63%, Cu 35%, and P 2% was prepared and then pulverized by water atomization, followed by drying. , eight ', each of the classified powder, and deoxidation and dehydration treatment, to make two silver mixed particles. Further, the particle diameter (D5〇%) of the silver alloy particles, σ gold/, and 'JJ κΙΠ 〇(b) silver particle preparation particle diameter (D50%) are 0.4 μηι, 1.1 μηη, 丨7 Two kinds of reagents (manufactured by Mitsui Metals Co., Ltd.) are used as silver particles. (Preparation of the glass particles to prepare two kinds of glass particles. The composition of the glass 1 (Ρ19) is 32 parts by weight of vanadium oxide (%〇5), 26 parts by weight of phosphorus oxide (P2〇5), and the weight of barium oxide (Ba0) 1〇 Parts, manganese oxide (Mn〇2) 8 parts by weight, sodium oxide (Ν & 2 〇) i parts by weight, potassium oxide (K2 〇) 3 parts by weight 'zinc oxide (Zn 〇) 1 〇 parts by weight, tungsten oxide (WO3 Ίοweight. The glass has a softening point of 44: rc and a crystallization temperature of 600 ° C or higher. The composition of the glass 2 (AY1) includes 45 parts of vanadium oxide (v2〇5) and 24.2 parts of oxidized scale (P205). Barium oxide (Ba0) 2 〇. 8 parts, Oxidation record (Sb203) 5 parts, tungsten oxide (W03) 5 parts, and particle size (D50%) is 1.7 μηη. In addition, the glass has a softening point of 492. (: The crystallization temperature exceeds 600 〇C. (d) Preparation of Paste Composition for Electrode 201135753 = Weighing silver chyle by weighing the ratio of square copper and gold particles, silver particles, and ΙΙΓΐ 丨In the middle of the training, mix 20 points = = child ^ Rong Qi i and resin, and then in the Ma Knife, make a paste composition for the electrode 1. You are inflamed, using diethylene glycol monobutyl Ether acetate (hereinafter referred to as BCA) is manufactured by: 'f using ethyl cellulose (hereinafter referred to as EC) as a resin, ΐ Γ Γ BCA ' and in order to be suitable for screen printing ' The amount of solvent is adjusted by the method of wide 1 〇Pa's~20〇pa's. (d) The thickness of the photovoltaic cell is Γ! The thickness of the n-type semiconductor layer, the texture and the anti-reflective film 'stone film' formed on the light-receiving surface is (4) A p-type semiconductor substrate of μιη, and cut to a size of I: mxU 5 mm. The above-mentioned poorly-formed composition is kneaded by the screen printing method to form an electrode pattern hand as shown in Fig. 2 on the light receiving surface. The pattern is composed of a 150 (four) width of a Fingerline w.lmm width bus bar (Busbar), and the brushing condition is suitable for the film thickness after the calcination is 2〇μηη , printing speed, printing pressure). Put the obtained (four) towel heated to im: for 15 minutes, then use the ridge to loosen the wire. Then, the aluminum electrode paste is also printed by screen printing, so that the forging It is suitable to adjust the printing method after the film thickness of the film reaches 4 〇μιη. 15 minutes in an oven of 1503⁄4, evacuing to remove the solvent. In the infrared rapid heating furnace, it is heated in the atmosphere at 85 2 for 2 seconds (calcining). Desired electrode 31 201135753 Photovoltaic cell unit 1. <Example 2 to Example 13 > In Example 1, 'will be silver alloy particles and =, (called the type of broken soil particle ==: _b' is called instance 1 (four) The way to make the photovoltaic cell is early 2 ~ photovoltaic cell unit 13. <Comparative Example 1> Human 1 +, a silver paste group was not prepared to prepare a paste group for an electrode. Otherwise, a volt battery unit 1 was fabricated in the same manner as in Example i. <Evaluation of Photovoltaic Cell Element> The evaluation of the battery element produced was performed by WWS-155S-10 manufactured by Wacom Electric Co., Ltd., which is a field current, and used as a current/voltage (IV) evaluation tester. A measuring device of IV CURVE TRACER MP-160 (manufactured by EKO INSTRUMENT Co., Ltd.) was combined. The results of the photovoltaic performance of the photovoltaics produced in the examples and the comparative examples are shown in Table 1. The respective measured values of the power generation performance of the photovoltaic cell are set as the relative value of the comparative example 1 as a relative value of 100·0, and the Eff (conversion efficiency) which is the power generation performance of the photovoltaic cell, FF (fill factor), Voc (open circuit voltage), and Jsc (short circuit current) are measured values obtained by measurement in accordance with JIS-C-8912, JIS-C-8913, and JIS-C-8914, respectively. 32 8 201135753 J-aH Inch Γ 斗 Id as the photovoltaic power generation performance Jsc (relative value) Short-circuit current 〇 〇 〇 O O O O O O O O O O 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 \ 〇\ oo oo 〇\ 104.0 100.0 υ ^ 1 On On VO On 〇\ 00 On m oo On m cK On 100.3 100.0 00 a\ 100.4 inch Os ^T) oo On 00 Os 100.4 100.0 孝孝 & TM Q ^ ^ ^ ^ 1 100.5 1 100.2 100.1 00 cK 卜 C\ G\ 102.4 | 102.3 101.2 102.3 ro cK 0's CN cn On cn Ch 〇\ 104.6 100.0 Eff (relative value) Conversion efficiency 100.2 | loo.o | 00 cK On On On VO 〇 \ 103.0 102.3 101.5 103.5 inch 〇 \ 〇 \ 00 卜 ^ On VO oo 〇 \ 104.3 100.0 BCA solution containing 4% EC (parts) <Ti <n H <Ti i〇IT) < Ti vn r~H Glass particle content (parts) <N CN CN <N CN (N (N inch CN <N CM nostalgia σ\ Os Ki 〇\ On On PU as 〇\ Os Os 〇\ K , 1-H On E Silver particle content (parts) »η o tn m (N VO $ o Particle size (D50%) μιη 1-HH ^Η (> 1-H 1-^ inch dr·^ Silver alloy particles 1 1 content (parts) (T) o In m JO IT) yr\ vn in o particle size (D50%) μηι in in 1-H uo <T) cn in yn T—H in ϊ—H 1 example CN m inch oo 〇 O O O O O O O O Example 1 201135753 (Results and investigation) As shown in the results of Table 1, in the paste composition for an electrode containing a silver alloy, the amount of use of silver was remarkably reduced, and the electric property was not particularly improved. 13 electrode paste composition j total content of silver particles is 7G _ _ ^ and glass particles content rate (U mass% or more, 1G ^ agent and _LP a 枭% or less, dissolved = and The total content of the soil is 3% by mass or more, and the contact resistance of the sheet is lowered. It is possible that the silver alloy will fall. The reaction of 1 205 with Ag results in a contact resistance, which can contribute to the reduction of the county. It is used in the electrode riding composition of Examples 1 to 13; the column does not contain a lead component, so that the influence on the environment can be reduced. The particle size of the obtained particles is 〇.4 μιη, and the particle size is u handsome, and the reason for this is that the sintering is promoted by changing the silver particles, and the volume resistivity is lowered. As a result, it is clear that the lower the softening point of the glass frit, the better the electrical characteristics, and it is preferably c. or less. <Example 14> The paste composition 9 for an electrode obtained above was used to have a composition such as 8 34 201135753.
圖4(a)及圖4(b)所示的構造的光伏電池I 千 14。再 熱處理是於750°C下進行10秒。 1可’力口 以與上述相同的方式對所獲得的光伏電池單元 價的結果，可知與上述同樣地顯示良好的特性。 仃評 雖然本發明已以較佳實施例揭露如上，'然其並 限定本發明’任何熟習此技藝者，在不脫離本發明 和範圍内’當可作些許之更動與_，因此本發明之= 範圍當視後附之申請專利範圍所界定者為準。 ' 【圖式簡單說明】 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侧的平面圖。 圖3是表示本發明的光伏電池的背面側的平面圖。 仰圖氕幻是表示本發明的七小八^^夕口〜/夕夕卜光伏電 池單元的AA剖面構成的立體圖。 ” 。圖4(b)是表示本發明的七卜光伏 池單元的背面側電極構造的平面圖。 【主要元件符號說明】 2 4 6 包含p型矽基板的單元晶圓 集電用柵電極 n型半導體層 通孔電極 高濃度摻雜層 7:背面電極 130 :半導體基板 35 201135753 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 36 ⑧The photovoltaic cell I of the structure shown in Fig. 4 (a) and Fig. 4 (b) is 14 . The reheat treatment was carried out at 750 ° C for 10 seconds. 1 can be used as a result of the obtained photovoltaic cell unit price in the same manner as described above, and it is understood that good characteristics are exhibited in the same manner as described above. The present invention has been disclosed in its preferred embodiments as described above, and it is intended to be limited to the invention, and the invention may be modified and modified without departing from the scope of the invention. = Scope is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing 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. The bottom view illusion is a perspective view showing the AA cross-sectional configuration of the seven-fifth occupant-photovoltaic cell unit of the present invention. Fig. 4(b) is a plan view showing the structure of the back side electrode of the seven-dimensional photovoltaic cell unit of the present invention. [Description of main element symbols] 2 4 6 Gate electrode n-type for cell wafer collecting including p-type germanium substrate Semiconductor layer via electrode high concentration doping layer 7: back surface electrode 130: semiconductor substrate 35 201135753 131 : diffusion layer 132 : anti-reflection layer 133 : light-receiving surface electrode 134 : collector electrode 135 : power extraction electrode 136 : electrode component diffusion layer 36 8
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| Application Number | Priority Date | Filing Date | Title |
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| JP2010013515 | 2010-01-25 | ||
| JP2010222204A JP2011171273A (en) | 2010-01-25 | 2010-09-30 | Electrode paste composition and solar cell |
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| TW201135753A true TW201135753A (en) | 2011-10-16 |
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| TW100102720A TW201135753A (en) | 2010-01-25 | 2011-01-25 | Paste composition for electrode and photovoltaic cell |
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| JP (1) | JP2011171273A (en) |
| TW (1) | TW201135753A (en) |
| WO (1) | WO2011090213A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102568649A (en) * | 2011-12-29 | 2012-07-11 | 彩虹集团公司 | Method for preparing electrode paste for grid buried crystal silicon solar cells |
| CN106229026A (en) * | 2016-07-12 | 2016-12-14 | 常州聚和新材料股份有限公司 | Alloy argentum powder and preparation method thereof and solar energy electrocondution slurry prepared therefrom |
| CN105144305B (en) * | 2012-12-28 | 2018-10-26 | 赫劳斯德国有限两和公司 | Prepare the electrocondution slurry for including vanadium-containing compound and phosphorus containg substances in MWT electrode of solar battery |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5689773B2 (en) * | 2011-10-01 | 2015-03-25 | 株式会社フジクラ | Photoelectric conversion element electrode, photoelectric conversion element, and silver paste used for manufacturing photoelectric conversion element electrode |
| CN102368391B (en) * | 2011-10-26 | 2013-05-22 | 南昌大学 | High-conductivity lead-free silver paste used for crystalline silicon solar cell and preparation method thereof |
| WO2013069727A1 (en) * | 2011-11-10 | 2013-05-16 | 株式会社村田製作所 | Conductive paste and method for producing through electrode |
| FR2992466A1 (en) | 2012-06-22 | 2013-12-27 | Soitec Silicon On Insulator | Method for manufacturing e.g. LED device, involves forming insulating material portion on sides of p-type layer, active layer and portion of n-type layer, and exposing contact studs over another portion of n-type layer |
| EP2750139B1 (en) * | 2012-12-28 | 2019-02-27 | Heraeus Deutschland GmbH & Co. KG | An electro-conductive paste comprising a vanadium containing compound in the preparation of electrodes in MWT solar cells |
| EP2750141B1 (en) | 2012-12-28 | 2018-02-07 | Heraeus Deutschland GmbH & Co. KG | An electro-conductive paste comprising coarse inorganic oxide particles in the preparation of electrodes in MWT solar cells |
| EP2750142B1 (en) * | 2012-12-28 | 2017-05-24 | Heraeus Deutschland GmbH & Co. KG | An electro-conductive paste comprising an inorganic reaction system with a high glass transition temperature in the preparation of electrodes in mwt solar cells |
| JP6371099B2 (en) * | 2014-04-18 | 2018-08-08 | ナミックス株式会社 | Conductive paste and crystalline silicon solar cell |
| JP7190989B2 (en) * | 2019-09-17 | 2022-12-16 | 富士フイルム株式会社 | Conductive film, film sensor, touch panel, liquid crystal display device, method for producing conductive film, and composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0696988A (en) * | 1992-09-11 | 1994-04-08 | Asahi Chem Ind Co Ltd | Paste for forming internal electrode of multilayer ceramic capacitor and multilayer ceramic capacitor employing the paste |
| JPH08138969A (en) * | 1994-11-02 | 1996-05-31 | Murata Mfg Co Ltd | Manufacture of electronic component |
| JP5224722B2 (en) * | 2007-05-17 | 2013-07-03 | 積水化学工業株式会社 | Resin composition, conductive paste and ceramic paste |
| CN102318013B (en) * | 2009-03-27 | 2014-12-03 | 株式会社日立制作所 | Conductive paste and electronic part equipped with electrode wiring formed from same |
-
2010
- 2010-09-30 JP JP2010222204A patent/JP2011171273A/en not_active Withdrawn
-
2011
- 2011-01-25 TW TW100102720A patent/TW201135753A/en unknown
- 2011-01-25 WO PCT/JP2011/051363 patent/WO2011090213A1/en active Application Filing
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102568649A (en) * | 2011-12-29 | 2012-07-11 | 彩虹集团公司 | Method for preparing electrode paste for grid buried crystal silicon solar cells |
| CN105144305B (en) * | 2012-12-28 | 2018-10-26 | 赫劳斯德国有限两和公司 | Prepare the electrocondution slurry for including vanadium-containing compound and phosphorus containg substances in MWT electrode of solar battery |
| CN106229026A (en) * | 2016-07-12 | 2016-12-14 | 常州聚和新材料股份有限公司 | Alloy argentum powder and preparation method thereof and solar energy electrocondution slurry prepared therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011171273A (en) | 2011-09-01 |
| WO2011090213A1 (en) | 2011-07-28 |
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