201030106 六、發明說明： 【發明所屬之技術領域】 本發明之實施例係關於包含玻璃料及一或多種金屬有機 組份之導電墨水，及具有自包含玻璃料及一或多種金屬有 機組份之導電墨水形成之導電格線的光電伏打電池。 【先前技術】 使用導電墨水或膏在諸如矽等基板表面上形成金屬接觸 點’例如，銀格線及母線。該等基板可用於太陽能電池或 鲁光電伏打電池中，該等電池在來自日光之光子將半導體中 之電子自價帶激發至導帶時可將太陽能轉化為電能。流嚮 導帶之電子係由金屬接觸點收集。在當今工業中結晶矽太 陽能電池通常塗佈有抗反射塗層來促進光吸附，從而增加 電池效率《然而，抗反射塗層亦可用作絕緣體來防止電子 自基板轉移至金屬接觸點。在施加導電墨水之前，太陽能 電池通常由抗反射塗層覆蓋。抗反射塗層通常包括氮化 矽、氧化鈦或氧化矽。 導電墨水通常包含玻璃料、導電物質及有機介質。通常 為金屬顆粒（例如，銀）之導電物質在形成金屬接觸點後可 提供導電性質且用作集電器。為形成金屬接觸點，將導電 墨水印刷至基板上。然後在介於約650°C至約950。(：間之溫 度下對基板進行燒製。在大多數情況下需要燒結助劑，此 乃因燒製溫度低於銀與矽之低共熔點且低於銀的熔點。此 外’在施加導電墨水之前，太陽能電池通常由抗反射塗層 覆蓋。導電墨水應可滲透抗佈置於基板上之抗反射塗層以 138415.doc 201030106 形成與基板具有電阻接觸之金屬接觸點》 導電墨水納入玻璃料以幫助將金屬顆粒燒結至基板上且 促進所形成之金屬接觸點與基板之間的黏著與電阻接觸。 端視配方而定，玻璃料可藉由在約300°C與600。(：間之溫度 下燒製來液化。當玻璃料液化時，其往往向金屬顆粒與佈 置於基板上之抗反射塗層間之介面流動》溶化之玻璃可溶 解抗反射塗層材料以及部分銀及基板。一旦溫度降低，熔 融銀及經熔化或溶解之基板可經由液相再結晶。因此，一 些銀微晶能夠滲透抗反射層並與基板形成電阻接觸。該製 程稱作"燒滲法"且便於形成低接觸電阻且增強銀與基板之 間的結合。若所選玻璃料侵入性過強，則可能因此污染基 板從而使太陽能電池之性能降格。選擇合適之玻璃料或玻 璃料-前體之混合物可幫助避免該污染且達成良好電池效 率。 因此，業内需要具有以下性質之導電墨水：其可改善光 電伏打電池中之串聯電阻、幫助燒結且亦能夠經由抗反射 塗層來促進金屬接觸點與基板之黏著及電阻接觸。 【發明内容】 本發明之一態樣提供導電墨水，該等導電墨水使用玻璃 料、導電物質、有機介質及一或多種可藉由燒製形成金屬 合金或金屬氧化物之金屬有機組份。本申請案通篇所用之 術語"膏••及"墨水"應可互換使用。 在一或多個實施例中，導電墨水之玻璃料及一或多種金 屬有機組份合併於適於施加至基板（例如，光電伏打電池） 138415.doc 201030106 上之膏中，此可將光電伏打電池之串聯電阻降低至與上面 施加有不包含金屬有機組份之膏之光電伏打電池相同或更 大的程度。當施加至佈置於基板上之抗反射塗層上時，另 一實施例之導電墨水能夠滲透該抗反射塗層而與基板形成 電阻接觸。 在其他實施例中，一或多種金屬有機組份在墨水中之存 在量應足以藉由燒製形成約1重量％之金屬氧化物。在一 些實施例中，導電墨水中之一或多種金屬有機組份之量小 於約40重量％。在具體實施例中，一或多種金屬有機組份 之存在量小於約1 5重量％。在另一具體實施例中，金屬有 機組份之存在量小於約8重量％。 本發明之另一實施例提供使用玻璃料之墨水，該玻璃料 包含氧化鉍、二氧化矽、氧化硼、二氧化碲、及其組合中 之一或多種。 根據一或多個實施例，導電墨水包含祕金屬有機組份。 在具體實施例中，鉍金屬有機組份在導電墨水中之存在量 為約4重量％ «在另一具體實施例中，導電墨水可包含鉍 金屬有機組份及含有氧化鉍、二氧化矽、氧化硼、二氧化 碑、及其組合中一或多種之玻璃料。 根據本發明之另一態樣，光電伏打電池包含半導體基 板、抗反射塗層及自包含玻璃料及一或多種金屬有機組份 之導電墨水形成的導電格線。對光電伏打電池之一實施例 中所用之導電墨水實施燒製以形成包括金屬氧化物相及導 電物質的格線。在一或多個實施例中，對導電墨水實施處 138415.doc 6 - 201030106 理以去除有機介質且燒結導電物質。根據本發明之一實施 例，導電墨水包含包括氧化銘、二氧化石夕、氧化蝴二氧 化碲、及其組合中一或多種之玻璃料。在另一實施例中， 一或多種金屬有機組份在墨水中之存在量應足以藉由燒製 形成至少約1重量。/❶之金屬氧化物。在具體實施例中一 或多種金屬有機組份之存在量小於約4〇重量％。另一具體 ' 實施例以小於約15重量％之量包含一或多種金屬有機組 份，而再一具體實施例以小於約8重量％之量具有一或多 ® 種金屬有機組份》 根據一或多個實施例，光電伏打電池包含包括鉍金屬有 機組份之導電墨水。其他具體實施例具有包括存在量為約 4重量％之鉍金屬有機組份之導電墨水。光電伏打電池之 其他具體實施例使用鉍金屬有機組份及包含氧化鉍、二氧 化矽、氧化硼、二氧化碲、及其組合中一或多種之玻璃 料。 . 上文概述了本發明之某些特徵及技術優點。彼等熟習此 項技術者應瞭解，可使用所揭示之具體實施例作為依據來 容易地改進或設計屬於本發明範圍内之其他結構或製程。 彼等熟習此項技術者亦應瞭解，該等等效構造並不背離隨 附申請專利範圍中所述之本發明之精神及範圍。 【實施方式】 在闡述本發明之若干實例性實施例之前，應理解，本發 明並不限於下文所述構造或製程步驟之細節。本發明能夠 具有其他實施例且以各種方式來實踐或實施。 138415.doc 201030106 本發明之態樣係關於具有一或多種金屬有機組份、至少 一種玻璃料、導電物質及其他組份之導電 墨水，現將更詳 細地論述該等導電墨水。此外，亦將更詳細地論述關於光 電伏打電池之本發明態樣。 金屬有機物 本發明之一或多個實施例包含具有一或多種金屬有機組 份之導電墨水^通常’金屬有機物係含有金屬原子的化合 物’其包含金屬羧酸鹽（例如，新癸酸鹽、乙酸鹽及丙酸 鹽）、金屬醇鹽及金屬錯合物，且其略溶或不溶於水。金 屬有機物亦可含有任何芳香族或脂肪族基團，且有時當有 機部分係由衍生自樹脂或其他天然產物之基團組成時金屬 有機物可稱為金屬樹脂酸鹽。其他適宜之金屬有機組份包 含金屬硫醇鹽。一或多個實施例中所用之金屬有機組份可 具有多於一種金屬原子。 一或多種導電墨水所用之金屬有機組份的實例包含硼金 屬有機組份、鋁金屬有機組份、矽金屬有機組份、鉍金屬 有機組份、辞金屬有機組份及釩金屬有機物組份之組合。 有時將金屬有機物及有機金屬定義為兩個類別。本申請案 通篇所用之術語"金屬有機物，，包含金屬有機物及有機金屬 ^一者。 不受限於理論，據信藉由燒製可分解金屬有機組份且自 導電墨水中去除有機部分。另外，可產生金屬或金屬合金 或金屬氧化物之混合物。燒製後產生之固體材料量稱作 "金屬有機組份之固體重量百分比含量·•。根據一或多個實 138415.doc 201030106 施例，金屬有機組份可具有至少〇 5重量％之固體含量。另 一實施例包含具有至少1-2重量％之固體含量的金屬有機組 份。不受限於理論，據信，與在導電墨水中使用玻璃料相 同，由金屬有機組份產生之固體材料之量會影響導電墨水 在基板上形成導電體或與基板形成電阻接觸之能力。因此 該能力可促進納入導電墨水之器件（例如，半導體、光電 伏打電池或汽車玻璃）之性能。 在本發明之一或多個實施例中，金屬有機組份包含鉍金 屬有機物組份、及/或銀金屬有機物組份。本發明之具體 實施例可包含鉍金屬有機組份、銀金屬有機組份或硼金屬 有機組份中之一或多種。本發明之另一實施例包含鉍金屬 有機組份、銀金屬有機組份、硼金屬有機組份、鋁金屬有 機組份、鋅金屬有機組份及/或釩金屬有機組份之一種或 其組合。 根據一個實施例，為達成期望性質，可將單一元素或金 屬氧化物或膠體金屬懸浮液添加至金屬有機組份中作為改 質劑來增強某一元素含量或獲得新的性質。舉例而言，可 添加磷、Ρζ〇5或其他類型之含磷化合物以製備用於太陽能 電池應用中之自摻雜膏。 可考慮調配金屬有機組份之其他因素以調節所得性質。 一考慮因素包含控制導電墨水對抗反射塗層之侵入性以避 免污染基板。另一考慮因素包含根據燒製曲線在介於約 200°C至約500°C間之範圍或另一範圍中選擇熱分解溫度， 以提供足夠時間及熱量來使自金屬有機組份分解之固髖混 138415.doc -9- 201030106 合物與導電物質及抗反射塗層反應。可考慮使用金屬羧酸 鹽或低溫化學蒸氣沈積（"CVD")前體來調節分解溫度。第 二個考慮因素包含選擇一或多種具有適於印刷之稠度或亦 可用作流變改質劑之金屬有機組份。 導電物質 在一或多個實施例中，導電墨水使用導電物質，例如， 呈粉末或顆粒形式之銀。適宜導電物質之其他非限制性實 例包含導電金屬，例如，呈粉末或顆粒形式之金、銅及 銘。 一或多個實施例中所用之銀物質可為呈一或多種精細粉 末形式之銀金屬或銀合金。在其他實施例令，銀可以諸如 硝酸銀（AgN〇3)等銀鹽形式添加。根據一或多個實施例， 導電物質應能夠在高於約5〇〇它之溫度下燒結。 ❹ ，一或多個實施例未使用$電物質，巾是使用可藉由燒製 形成或多種導電金屬元素之金屬有機組份。導電金屬元 素之實例包含銅、銀、金、銘及/或其他貴金屬及其組 合…或多個實施例使用導電物質及可藉由燒製形成導電 金屬元素之金屬有機組份二者。 玻瑀料 本發明之-❹個實施射所用之玻璃料粉末含有氧化 銘、二氧切、氧化爛、二氧化碑、及其組合中之 種。 一具體實施例包含納 玻璃料。在該等實施例 入一氧化碲且不含有意添加之鉛之 中’術語"不含有意添加之鉛••意指 1384I5.doc 201030106 玻璃料中之鉛量小於約1，000 ppm。在具體實施例中，玻 璃料所包含之二氧化碲之量介於約0.01重量％與10重量％ 之間。本發明所用之玻璃料之另一具體實施例包含二氧化 碲、ZnO、AbO3及其組合❶含二氧化碲之玻璃料之再一具 體實施例亦可包含其他組份，例如，Ag20、Sb203、 Ge02、Ιη203、P2〇5、v205、Nb205、及 Ta205。本發明之 其他實施例使用鹼金屬氧化物及/或鹼土金屬氧化物，分 別例如 Na20、Li2〇、及/ 或 K20 及 BaO、CaO、MgO及 / 或 SrO。 在一實施例中，本發明之導電墨水中所用之玻璃料包括 高於約20重量％且小於約60重量％之Bi203、約1 5重量❶/〇至 約30重量％iSi02、及約2重量％至約9重量°/〇之B2〇3，其中 該玻璃料基本不含Na2C^根據一或多個實施例，基本不含 NazO意指NazO在玻璃料中之存在量介於約〇重量％至〇.2重 量％之間。 本發明之一或多個實施例之導電墨水亦納入碲酸鉍及/ 或矽酸鉍粉末。已發現，添加碲酸鉍及/或矽酸鉍粉末可 藉由將結晶起點改變至較低溫度來控制玻璃料之結晶。 儘管本發明不受限於理論，但據信碲酸銘及/或矽酸鉍 粉末可為晶艘生長提供成核位點。在光電伏打應用中，玻 璃料應可滲透或溶解抗反射層以使銀能形成電阻接觸，然 而’期望控制玻璃料之侵入性以防止其滲透半導體之接點 而使器件分流。其他實施例使用可產生與碲酸鉍及/或矽 酸銘具有相同或相似效應之其他已知相，例如，氧化鈦、 138415.doc •11 201030106 氧化鍅、磷化合物及其他相。 其他組份 一或多個實施例之導電墨水亦可包含有機媒劑。有機媒 劑可分散顆粒組份且便於將墨水組合物轉移至表面上》在 至少一個實施例中，有機媒劑包含任何適宜惰性溶劑、樹 脂及通用表面活性劑。具艎而言，有機媒劑可溶解樹脂並 * 分散導電物質及金屬有機組份以形成具有適宜流變性之導 電墨水。各種含有或不含增稠劑、穩定劑及/或其他常用 添加劑之有機媒劑適用於製備本發明之實施例。溶劑之實 例包含醇（包含二醇）以及該等醇之酯、諸如松油等萜、莊 品醇及諸如此類。其他具體之溶劑包含鄰苯甲二酸二丁 酯、二乙二醇單丁醚、萜品醇、異丙醇、十三醇及單異丁 酸2,2,4-三甲基-1，3-戊二醇酯。一些實施例使用亦含有揮 發性液體之溶劑以在施加至基板後促進更快乾燥。 適宜樹脂之實例包含乙基纖維素、曱基纖維素、硝酸纖 維素、羧曱基纖維素及其他纖維素衍生物。其他實例包含 樹脂，例如丙烯酸酯、曱基丙烯酸酯、聚乙烯醇、聚酮及 聚乙烯醇縮丁醛》 在一具體實施例中，使用諸如低碳醇之聚甲基丙烯酸酯 等樹脂的溶液，而在另一具體實施例中，有機媒劑包含存 於諸如松油及二乙二醇單丁醚等溶劑中之乙基纖維素。 根據一或多個實施例，導電墨水中有機媒劑與固體之比 率可大幅度變化且由最終期望調配物流變性來決定，該最 終期望調配物流變性又由系統之印刷需要來決定。在一或 138415.doc -12- 201030106 多個實施例中，導電墨水可含有約50重量％至約95重量％ 之固體及約5重量％至約50重量％之有機媒劑。 導電墨水之一或多個實施例可另外包括其他業内已知之 添加劑’例如’著色劑及染色劑、流變改質劑、黏著增強 劑、燒結抑制劑、原始強度改質劑、表面活性劑及諸如此 類。 一或多個實施例之導電墨水可藉由適宜設備製得，例如 二輥研磨機》在至少一個實施例中，將一或多種金屬有機 組份、玻璃料、導電物質及有機媒劑於研磨機中預混合並 實施分散。 光電伏打電池 本發明之另一態樣提供光電伏打電池，其包括半導體基 板、位於該基板上之抗反射塗層及導電格線。根據一或多 個實施例，導電格線係由包括玻璃料、導電物質、有機介 質及一或多種金屬有機組份之導電墨水形成β本文所揭示 之導電墨水之一或多個實施例可用於形成導電格線。根據 一或多個實施例，期望使用一或多種金屬有機組份以便導 電墨水可滲透或溶解基板上之抗反射塗層並建立電阻接 觸。 在一或多個實施例中，半導艎基板可為矽。可使用業内 已知之其他適宜基板，例如經摻雜之半導體基板。根據一 或多個實施例，抗反射塗層可包括二氧化矽、氧化鈦、氮 化矽或業内已知之其他塗層。 半導體基板可包括單晶或多晶矽。可使用化學蒸氣沈積 1384l5.doc •13- 201030106 技術將抗反射塗層施加至基板上。在一些實施例中，可使 用經電漿增強之化學蒸氣沈積技術來將抗反射塗層施加至 基板上。亦可將一或多個實施例之半導體基板蝕刻或紋理 化以減少日光反射並提高吸收程度。根據一或多個實施 例’然後藉由絲網印刷或其他技術將導電墨水施加至基板 表面或抗反射塗層上。加熱或燒製基板至約650-950°C之 溫度以形成格線。在一實施例中，如本申請案中另外所 述，燒製製程使得玻璃料可熔化並滲透抗反射塗層。在一 或多個實施例中，導電物質可在導體與基板之介面處形成 微晶，此可增強導體與半導體基板間的電接觸或電阻接 觸。 並非意欲以任何方式限制本發明，下列實例將更全面地 闡述本發明之實施例。 實例 測試六種光電伏打電池（六種導電墨水（墨水Α-C及對比 墨水A-C)分別印刷在各電池上）之填充因數、電池效率及 串聯電阻以量測器件及其上所佈置墨水之性能。墨水A_c 包含銀導電物質且各自包含三種不同玻璃料。玻璃料包含 氧化鉍、二氧化矽、氧化硼及氧化鋅。對比墨水A_c包含 銀導電物質及鉍金屬有機組份。導電墨水A亦包含在墨水 A中所測試之玻璃料’而導電墨水b及c分別包含在墨水b 及C中所測試之玻璃料。量測每一光電伏打電池之性能且 將其再現於表1中。分別相對於相應之墨水A、B&C來標 準化使用對比墨水A、B及C之光電伏打電池之所得數值。 138415.doc 201030106 之導電墨水之太陽能電池 表1 :含有或不含金屬有機組份 測試結果 墨水~ 填充因數 電池效率 1.00 串聯電阻(ohm/cm2) 1.00 玻璃料1 墨水A ----- 1.00 對比墨水A 1.45 1.47 0.20 玻璃料2 墨水B 對比墨水B 1.00 1.00 1.00 1.14 1.14 0.39 玻填料3 墨水C 1.00 1.00 1.00 對比墨水C 1.08 1.10 0.60 "填充因數"及"效率 "係半導體性能之量 度。術語"填充因 數疋義為最大功率（VropxJmp)除卩太陽能電池之電流-電壓 (I-V)特，中短路電流密度⑹與開路電壓之乘積的比 率。開路電壓（V。。)係開路條件下所能獲得之最大電麼。短 路電流密度（Jsc)係短路無負載條件下之最大電流密度❶填 充因數（FF)由此定義為（VmpJmp)/(v〇cJsc)，其中Jmp與Vmp代 表最大功率點處之電流密度及電壓。 術语效率"係當太陽能電池與電路相連時經轉化（自所吸 收之光轉化為電能）及收集之功率的百分比。效率係在 "標準"測試條件下使用峰值功率（p m )除以總入射輻照度 (E，以Wm.2量測）與器件面積（A，以“量測）之乘積之比率 來計算’其中ri=Pm/(ExA)。 如表1中所示，對比墨水A、B及c分別展示較墨水A、B 及C更大之效率。因此，基於該數據，據信嚮導電墨水中 添加一或多種金屬有機組份可改善光電伏打電池之性能。 138415.doc •15· 201030106 該說明書通篇中凡提及"一實施例"、，，某些實施例”、"一 或多個實施例，，或"實施例"時皆意指結合該實施例所述之 具體特徵、結構、材料、或特性包含於本發明之至少一個 實施例中。因&，該說明書通篇中之不同地方所出現之諸 如"在一或多個實施例中"、"在某些實施例令"、”在一實施 例中”或”在實施例中"等片語皆不—定係指本發明之相同 實施例。另外’於-或多個實施例中，具體特徵結構、 材料、或特性可以任一適宜方式組合。 儘管本文已參照具體實施例闡述本發明，但應瞭解該 等實施例僅闡釋本發明之原理及應用。彼等熟習此項技: 者將明瞭’在不背離本發明之精神及範圍之情况下，可對 本發明之方法及裝置作出各種修改及改變。因&，本發明 意欲包含屬於隨附申請專利範圍及其等效内容範圍内之修 改及改變。201030106 VI. Description of the Invention: [Technical Field] The present invention relates to a conductive ink comprising a glass frit and one or more metal organic components, and a conductive ink having a self-containing glass frit and one or more metal organic components A photovoltaic cell formed by a conductive grid. [Prior Art] A conductive contact ink such as a silver grid line and a bus bar is formed on a surface of a substrate such as tantalum using a conductive ink or paste. The substrates can be used in solar cells or Lutovoltaic cells that convert solar energy into electrical energy when photons from sunlight excite electrons in the semiconductor to the conduction band. The electrons flowing to the conduction band are collected by metal contacts. In today's industry, crystalline solar cells are typically coated with an anti-reflective coating to promote light absorption, thereby increasing cell efficiency. However, anti-reflective coatings can also be used as insulators to prevent electron transfer from the substrate to the metal contacts. The solar cell is typically covered by an anti-reflective coating prior to application of the conductive ink. Antireflective coatings typically include tantalum nitride, titanium oxide or tantalum oxide. Conductive inks typically comprise a glass frit, a conductive material, and an organic medium. Conductive materials, typically metal particles (e.g., silver), provide electrical conductivity after forming metal contact points and function as current collectors. To form metal contact points, conductive ink is printed onto the substrate. It is then between about 650 ° C and about 950. The substrate is fired at a temperature of between: In most cases, a sintering aid is required because the firing temperature is lower than the low eutectic point of silver and antimony and lower than the melting point of silver. Previously, solar cells were usually covered by an anti-reflective coating. The conductive ink should be permeable to the anti-reflective coating disposed on the substrate to form a metal contact point with electrical resistance to the substrate at 138415.doc 201030106. Conductive ink is incorporated into the frit to aid Sintering the metal particles onto the substrate and promoting adhesion and electrical contact between the formed metal contact points and the substrate. Depending on the formulation, the frit can be at a temperature of between about 300 ° C and 600 ° C. Firing to liquefy. When the glass frit is liquefied, it tends to flow into the interface between the metal particles and the anti-reflective coating disposed on the substrate. The molten glass dissolves the anti-reflective coating material and a portion of the silver and the substrate. Once the temperature is lowered The molten silver and the melted or dissolved substrate may be recrystallized via the liquid phase. Therefore, some of the silver crystallites are capable of penetrating the antireflection layer and forming electrical resistance contact with the substrate. The process is called "burning method" and facilitates the formation of low contact resistance and enhances the bond between silver and the substrate. If the selected frit is too invasive, it may contaminate the substrate and degrade the performance of the solar cell. A suitable frit or frit-precursor mixture can help avoid this contamination and achieve good cell efficiency. Therefore, there is a need in the industry for conductive inks that improve the series resistance in photovoltaic cells, aid in sintering, and It is also possible to promote adhesion and electrical resistance of the metal contact point to the substrate via the anti-reflective coating. SUMMARY OF THE INVENTION One aspect of the present invention provides a conductive ink using a frit, a conductive material, an organic medium, and/or A variety of metal organic components that can be formed by firing to form metal alloys or metal oxides. The terms "paste"""ink" used throughout this application should be used interchangeably. In one or more embodiments The frit of the conductive ink and one or more metal organic components are combined for application to a substrate (eg, a photovoltaic cell) 138415 In the paste of .doc 201030106, this can reduce the series resistance of the photovoltaic cell to the same or greater extent as the photovoltaic cell to which the paste containing no metal organic component is applied. When applied to the substrate When the anti-reflective coating is applied, the conductive ink of another embodiment can penetrate the anti-reflective coating to form electrical contact with the substrate. In other embodiments, one or more of the metal organic components are present in the ink. Sufficient to form about 1% by weight of metal oxide by firing. In some embodiments, the amount of one or more metal organic components in the conductive ink is less than about 40% by weight. In a particular embodiment, one or more metals The organic component is present in an amount less than about 15% by weight. In another embodiment, the metal organic component is present in an amount less than about 8% by weight. Another embodiment of the present invention provides an ink using a frit comprising one or more of cerium oxide, cerium oxide, boron oxide, cerium oxide, and combinations thereof. According to one or more embodiments, the conductive ink comprises a secret metal organic component. In a specific embodiment, the base metal organic component is present in the conductive ink in an amount of about 4% by weight. In another embodiment, the conductive ink may comprise a base metal organic component and contain cerium oxide, cerium oxide, A frit of one or more of boron oxide, sulphur dioxide, and combinations thereof. In accordance with another aspect of the present invention, a photovoltaic cell comprises a semiconductor substrate, an antireflective coating, and a conductive grid formed from a conductive ink comprising a glass frit and one or more metal organic components. The conductive ink used in one embodiment of the photovoltaic cell is fired to form a grid line including a metal oxide phase and a conductive substance. In one or more embodiments, the conductive ink is applied to 138415.doc 6 - 201030106 to remove the organic medium and sinter the conductive material. In accordance with an embodiment of the present invention, the conductive ink comprises a frit comprising one or more of oxidized, oxidized, oxidized cerium oxide, and combinations thereof. In another embodiment, the one or more organometallic components are present in the ink in an amount sufficient to form at least about 1 weight by firing. / ❶ metal oxide. In a particular embodiment, the one or more metal organic components are present in an amount less than about 4% by weight. Another specific 'embodiment comprises one or more metal organic components in an amount less than about 15% by weight, and yet another embodiment has one or more metal organic components in an amount less than about 8% by weight" according to one Or in various embodiments, the photovoltaic cell comprises a conductive ink comprising a base metal organic component. Other embodiments have a conductive ink comprising a cerium metal organic component present in an amount of about 4% by weight. Other embodiments of photovoltaic cells use a base metal organic component and a glass material comprising one or more of cerium oxide, cerium oxide, boron oxide, cerium oxide, and combinations thereof. The foregoing summarizes certain features and technical advantages of the invention. Those skilled in the art will appreciate that other structures or processes within the scope of the invention can be readily modified or designed using the disclosed embodiments as a basis. Those skilled in the art should also understand that such equivalent constructions do not depart from the spirit and scope of the invention as described in the appended claims. [Embodiment] Before the several exemplary embodiments of the present invention are described, it should be understood that the present invention is not limited to the details of the construction or process steps described below. The invention is capable of other embodiments and of various embodiments. 138415.doc 201030106 Aspects of the invention pertain to conductive inks having one or more metal organic components, at least one glass frit, conductive materials, and other components, which will now be discussed in greater detail. In addition, aspects of the invention relating to photovoltaic cells will also be discussed in greater detail. Metal Organics One or more embodiments of the invention comprise a conductive ink having one or more metal organic components, typically a 'metal organic compound containing a metal atom' comprising a metal carboxylate (eg, neodecanoate, acetic acid) Salts and propionates), metal alkoxides and metal complexes, and which are slightly soluble or insoluble in water. The metal organic material may also contain any aromatic or aliphatic group, and sometimes the metal organic compound may be referred to as a metal resin acid salt when the organic portion is composed of a group derived from a resin or other natural product. Other suitable metal organic components include metal thiolates. The metal organic component used in one or more embodiments may have more than one metal atom. Examples of the metal organic component used for one or more conductive inks include a boron metal organic component, an aluminum metal organic component, a base metal organic component, a base metal organic component, a metal organic component, and a vanadium metal organic component. combination. Metal organics and organometallics are sometimes defined in two categories. The term "metal organic matter" as used throughout this application, includes metal organics and organometallics. Without being bound by theory, it is believed that the organic component can be decomposed by firing and the organic portion removed from the conductive ink. In addition, a metal or metal alloy or a mixture of metal oxides can be produced. The amount of solid material produced after firing is referred to as "solids content by weight of the organic component of the metal. According to one or more embodiments 138415.doc 201030106, the metal organic component may have a solids content of at least 5% by weight. Another embodiment comprises a metal organic component having a solids content of at least 1-2% by weight. Without being bound by theory, it is believed that, as with glass frits in conductive inks, the amount of solid material produced by the organometallic component can affect the ability of the conductive ink to form or form electrical contact with the substrate. This capability therefore facilitates the performance of devices incorporating conductive inks such as semiconductors, photovoltaic cells or automotive glass. In one or more embodiments of the invention, the metal organic component comprises a ruthenium metal component, and/or a silver metal organic component. Specific embodiments of the present invention may comprise one or more of a base metal organic component, a silver metal organic component, or a boron metal organic component. Another embodiment of the present invention comprises one or a combination of a base metal organic component, a silver metal organic component, a boron metal organic component, an aluminum metal organic component, a zinc metal organic component, and/or a vanadium metal organic component. . According to one embodiment, a single element or a metal oxide or colloidal metal suspension may be added to the metal organic component as a modifier to enhance a certain elemental content or to obtain new properties in order to achieve the desired properties. For example, phosphorus, cerium 5 or other types of phosphorus containing compounds can be added to prepare self-doping pastes for use in solar cell applications. Other factors of the metal organic component may be considered to adjust the properties obtained. One consideration involves controlling the intrusiveness of the conductive ink against the reflective coating to avoid contamination of the substrate. Another consideration includes selecting a thermal decomposition temperature in the range between about 200 ° C to about 500 ° C or another range depending on the firing curve to provide sufficient time and heat to decompose the solid component from the metal. Hip mix 138415.doc -9- 201030106 The compound reacts with conductive materials and anti-reflective coatings. It is conceivable to use a metal carboxylate or a low temperature chemical vapor deposition ("CVD") precursor to adjust the decomposition temperature. A second consideration involves the selection of one or more metal organic components having a consistency suitable for printing or also useful as a rheology modifier. Conductive Substance In one or more embodiments, the conductive ink uses a conductive material, for example, silver in the form of a powder or granules. Other non-limiting examples of suitable electrically conductive materials include electrically conductive metals, such as gold, copper, and in the form of powder or granules. The silver species used in one or more embodiments may be a silver metal or a silver alloy in the form of one or more fine powders. In other embodiments, silver may be added in the form of a silver salt such as silver nitrate (AgN〇3). In accordance with one or more embodiments, the electrically conductive material should be capable of sintering at temperatures above about 5 Torr. ❹ One or more embodiments do not use an electrical material, and the towel is a metal organic component that can be formed by firing or a plurality of conductive metal elements. Examples of conductive metal elements include copper, silver, gold, indium and/or other precious metals and combinations thereof... or a plurality of embodiments using conductive materials and metal organic components which can be formed by firing to form conductive metal elements. Glass Batteries The glass frit powders used in the present invention contain oxidized, dioxobic, oxidized, oxidized, and combinations thereof. A specific embodiment comprises a nano glass frit. In these examples, ruthenium oxide is present and does not contain intentionally added lead. The term "term" does not contain intentionally added lead. • means 1384I5.doc 201030106 The amount of lead in the glass frit is less than about 1,000 ppm. In a particular embodiment, the amount of cerium oxide contained in the glass frit is between about 0.01% and 10% by weight. Another embodiment of the glass frit used in the present invention comprises cerium oxide, ZnO, AbO3, and combinations thereof. The cerium oxide-containing glass frit may further comprise other components, for example, Ag20, Sb203, Ge02, Ιη203, P2〇5, v205, Nb205, and Ta205. Other embodiments of the invention use alkali metal oxides and/or alkaline earth metal oxides such as Na20, Li2, and/or K20 and BaO, CaO, MgO and/or SrO, respectively. In one embodiment, the glass frit used in the conductive ink of the present invention comprises greater than about 20% by weight and less than about 60% by weight of Bi203, from about 15 weights ❶/〇 to about 30% by weight of ITO, and about 2 weights. % to about 9 weight / B B2 〇 3, wherein the glass frit is substantially free of Na 2 C ^ according to one or more embodiments, substantially free of NazO means that NazO is present in the glass frit in an amount of about 〇 重量% Between .2% by weight. The conductive ink of one or more embodiments of the present invention is also incorporated into bismuth ruthenate and/or bismuth ruthenate powder. It has been found that the addition of bismuth ruthenate and/or bismuth ruthenate powder can control the crystallization of the frit by changing the crystallization starting point to a lower temperature. Although the invention is not limited by theory, it is believed that the tannic acid and/or bismuth ruthenate powder provides a nucleation site for crystal growth. In photovoltaic applications, the glass material should be permeable or soluble in the antireflective layer to allow the silver to form a resistive contact, however, it is desirable to control the invasiveness of the frit to prevent it from penetrating the junction of the semiconductor to shunt the device. Other embodiments use other known phases that produce the same or similar effects as bismuth citrate and/or citric acid, for example, titanium oxide, 138415.doc • 11 201030106 cerium oxide, phosphorus compounds, and other phases. Other Components The conductive ink of one or more embodiments may also comprise an organic vehicle. The organic vehicle can disperse the particulate component and facilitate transfer of the ink composition to the surface. In at least one embodiment, the organic vehicle comprises any suitable inert solvent, resin, and universal surfactant. In the case of hydrazine, the organic vehicle dissolves the resin and * disperses the conductive material and the metal organic component to form a conductive ink having a suitable rheology. Various organic vehicles with or without thickeners, stabilizers, and/or other conventional additives are suitable for use in preparing the embodiments of the present invention. Examples of the solvent include alcohols (including diols) and esters of such alcohols, hydrazines such as pine oil, exemplified alcohols, and the like. Other specific solvents include dibutyl phthalate, diethylene glycol monobutyl ether, terpineol, isopropanol, tridecyl alcohol and 2,2,4-trimethyl-1 monoisobutyrate. 3-pentanediol ester. Some embodiments use a solvent that also contains a volatile liquid to promote faster drying after application to the substrate. Examples of suitable resins include ethyl cellulose, mercapto cellulose, nitric cellulose, carboxymethyl cellulose, and other cellulose derivatives. Other examples include resins such as acrylates, methacrylates, polyvinyl alcohols, polyketones, and polyvinyl butyral. In one embodiment, a solution of a resin such as a lower methacrylic polymethacrylate is used. In another embodiment, the organic vehicle comprises ethylcellulose stored in a solvent such as pine oil and diethylene glycol monobutyl ether. In accordance with one or more embodiments, the ratio of organic vehicle to solids in the conductive ink can vary widely and is determined by the final desired formulation denaturation, which is ultimately determined by the printing needs of the system. In one or more of the embodiments, the conductive ink may contain from about 50% to about 95% by weight solids and from about 5% to about 50% by weight organic vehicle. One or more embodiments of the conductive ink may additionally include other additives known in the art such as 'colorants and colorants, rheology modifiers, adhesion enhancers, sintering inhibitors, virgin strength modifiers, surfactants And so on. The conductive ink of one or more embodiments can be made by suitable equipment, such as a two-roll mill. In at least one embodiment, one or more metal organic components, glass frits, conductive materials, and organic vehicles are ground. Premixed and dispersed in the machine. Photovoltaic cell Another aspect of the invention provides a photovoltaic cell comprising a semiconductor substrate, an anti-reflective coating on the substrate, and a conductive grid. In accordance with one or more embodiments, the conductive grid is formed from a conductive ink comprising a frit, a conductive material, an organic medium, and one or more metal organic components. One or more embodiments of the conductive ink disclosed herein can be used. A conductive grid is formed. In accordance with one or more embodiments, it is desirable to use one or more metal organic components such that the conductive ink can penetrate or dissolve the anti-reflective coating on the substrate and establish a resistive contact. In one or more embodiments, the semiconducting germanium substrate can be germanium. Other suitable substrates known in the art, such as doped semiconductor substrates, can be used. In accordance with one or more embodiments, the anti-reflective coating can include ceria, titanium oxide, niobium nitride or other coatings known in the art. The semiconductor substrate may comprise a single crystal or polycrystalline germanium. The anti-reflective coating can be applied to the substrate using chemical vapor deposition 1384l 5.doc • 13-201030106 technology. In some embodiments, a plasma enhanced chemical vapor deposition technique can be used to apply an anti-reflective coating to a substrate. The semiconductor substrate of one or more embodiments can also be etched or textured to reduce solar reflection and increase absorption. Conductive ink is then applied to the substrate surface or anti-reflective coating by screen printing or other techniques in accordance with one or more embodiments. The substrate is heated or fired to a temperature of about 650-950 ° C to form a grid line. In one embodiment, as further described in this application, the firing process allows the frit to melt and penetrate the anti-reflective coating. In one or more embodiments, the electrically conductive material can form crystallites at the interface of the conductor and the substrate, which enhances electrical or electrical contact between the conductor and the semiconductor substrate. It is not intended to limit the invention in any way, and the following examples will more fully illustrate the embodiments of the invention. The example tests the fill factor, battery efficiency and series resistance of six kinds of photoelectric voltaic cells (six conductive inks (ink Α-C and contrast ink AC) printed on each battery) to measure the device and the ink disposed thereon. performance. Ink A_c contains silver conductive material and each contains three different frits. The glass frit contains cerium oxide, cerium oxide, boron oxide and zinc oxide. The comparative ink A_c contains a silver conductive material and a base metal organic component. Conductive ink A also contains the frit tested in ink A, and conductive inks b and c contain the frit tested in inks b and C, respectively. The performance of each photovoltaic cell was measured and reproduced in Table 1. The resulting values of the photovoltaic cells using the comparative inks A, B, and C were normalized with respect to the respective inks A, B & C, respectively. 138415.doc 201030106 Conductive Ink Solar Cell Table 1: With or without Metallic Organic Component Test Results Ink ~ Fill Factor Battery Efficiency 1.00 Series Resistance (ohm/cm2) 1.00 Glass 1 Ink A ----- 1.00 Contrast Ink A 1.45 1.47 0.20 frit 2 ink B contrast ink B 1.00 1.00 1.00 1.14 1.14 0.39 glass filler 3 ink C 1.00 1.00 1.00 contrast ink C 1.08 1.10 0.60 "fill factor " &"efficiency" . The term "fill factor is the maximum power (VropxJmp) except the current-voltage (I-V) of the solar cell, the ratio of the medium short-circuit current density (6) to the product of the open circuit voltage. The open circuit voltage (V.) is the maximum power that can be obtained under open circuit conditions. Short-circuit current density (Jsc) is the maximum current density under short-circuit no-load conditions. The fill factor (FF) is thus defined as (VmpJmp) / (v〇cJsc), where Jmp and Vmp represent the current density and voltage at the maximum power point. . The term efficiency " is the percentage of power that is converted (from the absorbed light to electrical energy) and collected power when the solar cell is connected to the circuit. The efficiency is calculated by dividing the peak power (pm) by the total incident irradiance (E, measured in Wm.2) and the device area (A, measured by the product) under the "standard" test conditions. 'where ri=Pm/(ExA). As shown in Table 1, the comparative inks A, B, and c respectively exhibit greater efficiencies than the inks A, B, and C. Therefore, based on the data, it is believed to be in the conductive ink. The addition of one or more organometallic components improves the performance of the photovoltaic cell. 138415.doc •15· 201030106 This specification refers to "an embodiment", ", some embodiments", " One or more embodiments, or "embodiments" are intended to encompass a particular feature, structure, material, or characteristic described in connection with the embodiments. As used in "" in various places throughout the specification, "in some embodiments", "in some embodiments", "in an embodiment" In the embodiment, the phrase "a" or "an" is used to mean the same embodiment of the invention. In addition, the specific features, materials, or characteristics may be combined in any suitable manner. The present invention will be described with reference to the specific embodiments thereof, but it is understood that the invention is only to be construed as being limited by the scope of the invention. Various modifications and changes may be made to the method and apparatus of the invention. The invention is intended to cover modifications and variations within the scope of the appended claims.
138415.doc138415.doc