TWI702265B - 提供對半導體基材具增強之附著強度之導電漿組成物及其用途 - Google Patents
提供對半導體基材具增強之附著強度之導電漿組成物及其用途 Download PDFInfo
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- TWI702265B TWI702265B TW107112977A TW107112977A TWI702265B TW I702265 B TWI702265 B TW I702265B TW 107112977 A TW107112977 A TW 107112977A TW 107112977 A TW107112977 A TW 107112977A TW I702265 B TWI702265 B TW I702265B
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- conductive paste
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Classifications
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/006—Anti-reflective coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本發明係關於一導電漿，其藉由併入LiAlO2(鋁酸鋰)使所形成之電極對於半導體基材具增強之附著強度。本發明又係關於由導電漿形成之電極及包含所製得之電極之半導體，特別是太陽能電池。
Description
本發明係關於一導電漿，其藉由併入LiAlO2(鋁酸鋰)使所形成之電極對於半導體基材具增強之附著強度。本發明又係關於由該導電漿形成之電極及包含所製得之電極之半導體，特別是太陽能電池。
太陽能電池為藉由光電效應將光能直接轉換為電力之電子裝置。多數太陽能電池為已進行金屬化之矽晶片形式，亦即提供具導電性之金屬電極。通常將導電漿網印在基材上並燒結以形成電極，如正面及背面電極。燒結時，背面鋁與背面銀或銀/鋁間界面呈現合金狀態，藉此達到電連接。此外，正面銀漿燒結並在燒結時穿透抗反射層(如SiNx膜)，因而達到與半導體基材之電接觸。
習知用於形成電極之導電漿包含導電金屬、玻璃料及有機介質。然而，製自導電漿之電極對於基材之附著強度不足會造成所得太陽能電池性能不佳。因此，需要提供可使所製得之電極對基材具有較佳附著強度、相比擬或較佳光電轉換效率及相比擬或較佳填充因子之導電漿。
本案發明人發現藉由將LiAlO2併入導電漿中可提供所製得之電極對於基材增強之附著強度。因此，本發明提供一導電漿組成物，其 包含：(a)導電金屬、其衍生物或其組合；(b)玻璃料(glass frits)；(c)LiAlO2；及(d)有機介質。
另一方面，本發明提供製自上述導電漿之電極，與含有該電極之太陽能電池。
成分(a)：導電金屬
本發明之導電金屬只要可達到本發明之技術功效，並不受任何特殊限制。導電金屬可為單一選自下列群組之元素：銀、鋁及銅；且亦可為上述金屬與如金、鉑、鈀、鎳等其他金屬之合金或混合物。由導電性之角度來看，純銀較佳。
若使用銀作為導電金屬，其可為銀金屬、銀衍生物及/或其混合物形式。銀衍生物之例子包括銀氧化物(AgO2)、銀鹽(如氯化銀(AgCl)、硝酸銀(AgNO3)、醋酸銀(AgOOCCH3)、三氟醋酸銀(AgOOCCF3)或磷酸銀(Ag3PO4))、塗覆銀之複合物(其具塗覆在表面之銀層)或銀為主之合金等。
一具體例中，導電金屬可為粉末形式(例如球形、片狀、不規則形式及/或其混合物)或膠態懸浮體等。導電金屬之平均粒徑不受任何特別限制，但0.05至10微米較佳。亦可使用具不同平均粒徑、粒徑分布或形狀等之導電金屬混合物。
本發明一具體例中，導電金屬包括銀粉。
本發明所使用之導電金屬、其衍生物或其組合的量只要可達到本發明之技術功效並不受任何特殊限制。
本發明一具體例中，導電漿組成物含有以導電漿組成物總重量為基準，約65重量%至約95重量%之導電金屬、其衍生物或其組合。
本發明一具體例中，導電漿組成物含有以導電漿組成物總重量為基準，約70重量%至約85重量%之導電金屬、其衍生物或其組合。
成分(b)：玻璃料
本發明之玻璃料只要可達到本發明之技術功效並不受任何特殊限制。
玻璃料可為含鉛或不含鉛。玻璃料之例子包括，但不限於鉛氧化物、碲氧化物、鉍氧化物、矽氧化物、鎢氧化物、鎂氧化物等。
一具體例中，玻璃料可包括Pb-Te-氧化物、Pb-Te-Bi-氧化物、Pb-Te-Bi-Si-氧化物、Pb-Te-Bi-Mg-氧化物、Pb-Te-Bi-W-氧化物、Te-Bi-氧化物、Te-Bi-W-氧化物及其組合。
本發明一具體例中，玻璃料進一步包含一或多個選自下列組成之群組的元素或其氧化物：磷(P)、鋇(Ba)、鈉(Na)、鋅(Zn)、鈣(Ca)、鍶(Sr)、鋁(Al)、鋰(Li)、鉀(K)、鋯(Zr)、釩(V)、硒(Se)、鐵(Fe)、銦(In)、錳(Mn)、錫(Sn)、鎳(Ni)、銻(Sb)、銀(Ag)、硼(B)、銅(Cu)、鉈(Tl)、鉺(Er)、鍺(Ge)、鈦(Ti)、鎵(Ga)、鈰(Ce)、鈮(Nb)、釤(Sm)及鑭(La)或其氧化物，以玻璃料總重量為基準，量為約0.1重量%至約10重量。
本發明一具體例中，導電漿組成物含有以導電漿組成物總重量為基準，約0.1重量%至約10重量%之玻璃料。本發明另一具體例中，導電漿組成物含有以導電漿組成物總重量為基準，約0.5重量%至約6重量%之玻璃料。
成分(c)：LiAlO
2
一具體例中，導電漿組成物含有以導電漿組成物總重量為基準，約0.1重量%至約5重量%之LiAlO2。另一具體例中，導電漿組成物含有以導電漿組成物總重量為基準，約0.2重量%至約3重量%之LiAlO2。
成分(d)：有機介質
適當之有機介質可均勻分散導電漿組成物中所有成分於其 中並具適當黏度以藉由網印、模版印刷等傳送該等成分至抗反射塗層表面。
一具體例中，有機介質為不受特別限制且可選自用於導電漿之習知溶劑。溶劑之例子包括醇(例如，異丙醇)、酯(例如，丙酸酯、鄰苯二甲酸二丁酯)及醚(例如，丁卡必醇)等或其混合物。較佳，溶劑為沸點約120℃至約300℃之醚。最佳，溶劑為丁卡必醇。有機介質可進一步包含揮發性液體以在施用導電漿至半導體基材上後促進快速硬化。
另一具體例中，有機介質為包含聚合物與溶劑之溶液。聚合物之例子包括纖維素(例如，乙基纖維素)、硝基纖維素、乙基羥乙基纖維素、羧甲基纖維素、羥丙基纖維素或其他纖維素衍生物、低碳醇之聚(甲基)丙烯酸酯樹脂、酚系樹脂(例如，酚樹脂)、醇酸樹脂(例如，乙二醇單醋酸酯)等或其混合物。較佳，聚合物為纖維素。最佳，聚合物為乙基纖維素。
又，另一具體例中，有機介質包含溶於乙二醇丁基醚之乙基纖維素。
另一具體例中，有機介質進一步包含一或多種功能性添加劑。功能性添加劑之例子包括黏度調節劑、分散劑、觸變劑、濕潤劑及/或視情況之其他習添加劑(例如，著色劑、保存劑或氧化劑)等。功能性添加劑只要不負面影響本發明之技術功效並不受特別限制。
導電漿組成物中有機介質之最佳量依施用導電漿組成物之方法以及所用特定有機介質而定。又一具體例中，導電漿組成物含有以導電漿組成物之總重量為基準，約7重量%至約30重量%之有機介質。
導電漿組成物之製造與應用
本發明中，導電漿可藉由混合及分散導電金屬、玻璃料、LiAlO2及有機介質(亦即成分(a)~(d))於三輥研磨機中製備。導電漿組成物較佳具良好乾燥速率及優異燒穿特性。
本發明另一方面係提供一物件，其包含半導體基材及施用於半導體基材上之上述導電漿組成物。一具體例中，該物件為半導體裝置。另一具體例中，半導體裝置為太陽能電池。
本發明之導電漿組成物可先以格線或其他圖形印刷在抗反射塗層上，其中印刷步驟可藉由習知方法進行，如網印或模版印刷等。隨後，燒穿步驟係在含氧氛圍(如周邊空氣)下藉由設定溫度約800℃至約980℃達約0.05至約5分鐘進行以去除有機介質並燒結導電金屬，藉此使燒結後導電漿實質上不含任何有機物質及使燒結後導電漿穿過抗反射塗層以與半導體基材與其下方一或多個抗反射塗層形成接觸。此燒穿步驟使半導體基材與格線(或其他圖形)透過金屬接觸形成電接觸，因而形成電極。
一具體例中，成分(a)、成分(b)、成分(c)及成分(d)之比例視導電漿組成物之黏度而定，藉此使導電漿組成物在燒結後對基材有足夠之附著強度。
本發明之另一方面係關於一物件，較佳為用於製造半導體裝置之物件，更佳為用於製造太陽能電池之物件。本發明之一實施例中，提供半導體基材，其中該半導體基材包括適用於半導體積體晶片之基材、適用於形成太陽能電池等之玻璃基材。一或多個抗反射塗層可藉由習知方法施用於半導體基材上，如化學蒸汽沉積法、電漿強化之蒸汽沉積法等。本發明之導電漿組成物與抗反射塗層施用於半導體基材上。之後，進行燒穿步驟以取得該物件。
一具體例中，半導體基材包含非晶形、多晶或單晶矽，或多晶PERC、單晶PERC矽。本發明另一較佳實施例中，抗反射塗層包含二氧化矽、二氧化鈦、氮化矽或其他習知塗層。
上述已勾勒出本發明之技術特徵及技術功效。發明所屬技術領域中具有通常知識者應可理解所揭露之特定具體例可在本發明之精神下輕易被結合、修改、替換及/或轉換供其他物件、方法或用途使用。此均等範圍並未脫離如申請專利範圍所載本發明之保護範圍。
非意欲限制本發明，藉由下列實施例說明本發明。
實施例
導電漿之製備
用於製備導電漿之玻璃A、B、C及D列於表1。
比較例
比較例1~5
用於導電漿之有機介質藉由將5至25克乙基纖維素溶於5至75克乙二醇丁基醚並加入少量黏度調節劑、分散劑、觸變劑、濕潤劑等製得。之後，藉由在三輥研磨機中混合及分散80至99.5克工業級銀粉、2.5克玻璃A與10至30克有機介質製得導電漿。
比較例6
以比較例1~5所述方式製備導電漿，但添加2.5克玻璃B以取代玻璃A。
比較例7
以比較例1~5所述方式製備導電漿，但添加2.3克玻璃C以取代玻璃A。
比較例8
以比較例1~5所述方式製備導電漿，但添加2.25克玻璃D以取代玻璃A。
本發明之實施例
實施例1、4及7
以比較例1~5所述方式製備導電漿，但加入以導電漿總重量為基準之2重量% LiAlO2。
實施例2、5及8
以比較例1~5所述方式製備導電漿，但加入以導電漿總重量為基準之1重量% LiAlO2。
實施例3、6及9
以比較例1~5所述方式製備導電漿，但加入以導電漿總重量為基準之0.2重量% LiAlO2。
實施例10
以比較例1~5所述方式製備導電漿，但添加2.25重量%之玻璃A，而非2.5重量%之玻璃A，以及加入以導電漿總重量為基準之0.65重量% LiAlO2。
實施例11
以比較例1~5所述方式製備導電漿，但加入以導電漿總重量為基準之0.65重量% LiAlO2。
實施例12
以比較例6所述方式製備導電漿，但加入以導電漿總重量為基準之0.7重量% LiAlO2。
實施例13
以比較例6所述方式製備導電漿，但加入以導電漿總重量為基準之0.6重量% LiAlO2。
實施例14
以比較例7所述方式製備導電漿，但加入以導電漿總重量為基準之0.3重量% LiAlO2。
實施例15
以比較例8所述方式製備導電漿，但加入以導電漿總重量為基準之0.6重量% LiAlO2。
測試電極之製備
為測試由比較例1~8及實施例1~15之導電漿形成之電極的附著特性及所製得太陽能電池性能，將導電漿網印在單晶矽基材、多晶矽基材或單晶PERC矽基材上及隨後在約100℃至約250℃之溫度下乾燥約5至 約30分鐘。進一步藉由IR運送帶式爐將乾燥之導電漿在810℃至910℃之設定溫度下燒結。
焊接/附著強度試驗
藉由切割機將焊料帶切成適當長度，再施予焊劑(soldering flux)(模型：ANX3012，Asahi)以去除焊料帶上氧化物層。之後，在預定溫度下焊接焊料帶達預定時間。焊接可藉由非接觸加熱(例如，IR系列焊接或熱空氣焊接等)或接觸加熱(例如，藉由焊接鐵進行系列焊接等)進行。
試驗中採用IR系列焊接。焊接溫度為230℃且焊接時間訂為2秒。焊料帶之規格如下表2所示：
附著強度測試藉由將測試電極放置在附著強度測試機器(模型：MOGRL009，MOGRLTechnology,Co.,Ltd.)上、以夾具固定焊料帶一端及以180°角度及300mm/分鐘之速度拉焊料帶進行。附著值藉由所附電子測力計取得。
太陽能電池性能測試
使用太陽能電池性能測試裝置(Berger，Pulsed Solar Load PSL-SCD)在AM 1.5G陽光下測試所得太陽能電池之電特性以測得填充因子(FF，單位：%)及光電轉換效率(Ncell，單位：%)等。
測試結果
A部分
將實施例1~9之導電漿及比較例1~3之導電漿網印在單晶矽基材上。附著強度測試結果顯示於表3中。
表3顯示加入LiAlO2顯著增加由本發明導電漿製成之電極對單晶矽基材之附著強度。
將實施例10、實施例11、比較例4與比較例5之導電漿網印在單晶PERC基材上。所得電極對基材之附著強度與含有該電極之太陽能電池之電特性展示在表4。
表4證實導電漿中加入LiAlO2可增強所製得之電極對單晶PERC基材之附著強度。此外，含有該電極之太陽能電池相較於不含LiAlO2之導電漿所製得之電極展現可相比擬或甚至較佳之電特性(例如，高光電轉換效率與填充因子)。
B部分
將實施例12、實施例13與比較例6之導電漿網印在單晶矽基材上並在810℃燒結。表5展示附著強度與含所製得電極之太陽能電池之電特性的測試結果。
由表5明顯得知實施例12與實施例13之導電漿相較於比較例6不含LiAlO2之導電漿，可使所製得之電極不僅對單晶矽基材具有增強之附著強 度，也使含有該電極之所得太陽能電池具有較佳之光電轉換效率與較高之FF值。
C部分
將實施例14與比較例7之導電漿網印在多晶矽基材上並在830℃燒結。表6展示附著強度與含所製得電極之太陽能電池之電特性的測試結果。
由表6可得知實施例14之導電漿相較於比較例7不含LiAlO2之導電漿，可使所製得之電極不僅對多晶矽基材具有增強之附著強度，也使含有該電極之所得太陽能電池具有可相比擬之光電轉換效率與FF值。
D部分
將實施例15與比較例8之導電漿網印在單晶PERC基材上並在855℃燒結。表7展示附著強度與含所製得電極之太陽能電池之電特性的測試結果。
由表7可得知實施例15之導電漿相較於比較例8不含LiAlO2之導電漿，可使所製得之電極不僅對單晶PERC基材具有增強之附著強度，也使 含有該電極之所得太陽能電池具有可相比擬之光電轉換效率與FF值。
總體而言，表3至表7清楚顯示導電漿中加入LiAlO2可顯著增強所製得電極對單晶或多晶矽基材或單晶PERC基材之附著強度。此外，含有所製得電極之太陽能電池亦可展現可相比擬或較高之光電轉換效率及/或FF值。
上述實施例僅用以說明本發明之技術特徵與其技術功效。該等實施例之技術內容仍可藉由實質均等之組合、修改、置換及/或轉換實施。因此，本發明之保護範圍係以所附申請專利範圍定義之發明範圍為基準。
Claims (11)
- 一種導電漿組成物，其包含：(a)導電金屬、其衍生物或其組合；(b)玻璃料；(c)LiAlO 2；及(d)有機介質。
- 如請求項1之導電漿組成物，其中該導電金屬、其衍生物或其組合包含銀粉。
- 如請求項1之導電漿組成物，其含有以導電漿組成物之總重量為基準，約65重量%至約90重量%之導電金屬、其衍生物或其組合。
- 如請求項1之導電漿組成物，其含有以導電漿組成物之總重量為基準，約0.1重量%至約10重量%之玻璃料。
- 如請求項1之導電漿組成物，其含有以導電漿組成物之總重量為基準，約0.1重量%至約5重量%之LiAlO 2。
- 如請求項1之導電漿組成物，其含有以導電漿組成物之總重量為基準，約8重量%至約30重量%之有機介質。
- 如請求項6之導電漿組成物，其中該有機介質為包含聚合物與溶劑之溶液。
- 如請求項1之導電漿組成物，其中該有機介質又包含一或多種選自下列組成之群組的功能性添加劑：黏度調節劑、分散劑、觸變劑及濕潤劑。
- 一種物件，其包含半導體基材及如請求項1之導電漿組成物形成之電極。
- 如請求項9之物件，其又包含一或多個施用於半導體基材上之抗反射塗層；且其中導電漿接觸抗反射層及與半導體基材具電接觸。
- 如請求項9之物件，其為太陽能電池。
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