201135956 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種太陽能電池，特別是太陽能電池之矽基板 的表面處理方法及太陽能電池之製造方法。 【先前技術】 通常’太陽能電池可透過將一種光伏特效應，即光電動勢效 應而產生電動勢。 其中，可按基板的材料將太陽能電池分為：矽基太陽能電 池、化合物半導體太陽能電池及化合物/層疊式太陽能電池。此 處，可將矽基太陽能電池分為：晶態矽太陽能電池，如：單晶矽 太陽能電池與多晶矽太陽能電池；以及非晶矽太陽能電池。 其中’可透過基板之反射率等一些因素確定太陽能電池之能 效’同時透過使光入射面上的光反射，即反射率達到最小化而使 太陽能電池之能效達到最大。 在具有較低製造成本的晶態矽太陽能電池的方面，人們已經 提出了許多用於使光的反射達到最小化之方法，藉以提高太陽能 電池之效能。 【發明内容】 因此’本發明之目的在於提供一種太陽能電池之矽基板的表 面處理方法及一種太陽能電池的製造方法，藉以最大化地減小太 陽能電池之表面上的光反射。 為了達到本發明的目的，這裡對本發明進行具體而概括地敘 述，本發明之一方面提供了一種太陽能電池之矽基板的表面處理 201135956 方法’ &種方法包含有：第一表面處理步驟，係對用酸性溶液從 石夕鑄塊上切#]下之錄板飾_，藉以在魏板之外表面上形 成複數個第-蛛部分；以及第二表面處理步驟，伽於在將要 形成抗反射臈之處透過乾式_於絲板之外表面上，即在具有 透過第-表面處理步驟在上面形成了第—凸起部分之魏板^外 表面中形成尺寸小於第一凸起部分的複_第二凸起部分。 在此第-表面處理步驟中，酸性溶液包含有硝酸與氣敦酸， 在這種酸性溶液中硝酸與氫氟酸的重量比為1:1〜5.5:1。 其中’可透過滾筒將此石夕基板傳送至包含有酸性溶液的藉濕 台’藉以透過對此雜板進行侧來執行第—表面處理步驟 '，、、此 處在可6°c〜10°c的溫度中執行1〜10分鐘的蝕刻製程。 同時’還可以透過將基板浸泡於包含有酸性溶液的熊濕台而 對此石夕基板進行侧的浸泡法執行此第—表面處理步驟，其中可 在6°C〜10°C的溫度中執行20分鐘蝕刻製程。 在第-表面處理步驟之前，此方法還可包含：基板損傷處理 步驟，藉以ϋ過雜驗或雜溶液絲從《續塊上切割下之石夕 基板上的損傷。 在第一表面處理步驟之後，這種方法還可包含：第一第一清 洗步驟，係用於移除在第一表面處理步驟中所產生的雜質；第一 蝕刻步驟，係用於透過鹼性化合物部分地對殘留在矽基板之外表 面上的多孔石夕氧化物進行蝕刻；第二清洗步驟，係用於在第二勉 刻步驟之後移除殘留在矽基板之外表面上的雜質；以及乾燥步 驟，藉以在第二清洗步驟之後對石夕基板進行乾燥。 201135956 β而在此第-表面處理步驟之後與第二表面處理步驟之前，或 是僅在第二表面處理步驟之後，這種方法還可包含有·石夕基板中 凸起部分之背面的移除步驟，藉以透過對石夕基板之背面進行乾式 钱刻，移除形成於石夕基板之背面的第一凸起部分以及形成於在第 -表面處理步驟中所形成之第一凸起部分的外表面中形成由抗反 射膜之表面的相對面上的第一凸起部分。 其中第二凸起部分具有三角形橫截面，同時，第二凸起部分 朝向第-凸起部分之頂部的側面比第二凸柳分之另—側面短。 其中，矽基板係為單晶矽基板或多晶矽基板。 其中’在進行第-表面處理步驟之後，當雜板之外表面中 將要形成抗反射膜之外表面的面積為理想面積時，在第一表面處 理步驟中接受蝕刻之表面的實際面積與理想面積間之比率介於 1-2:1〜3·2:1的範圍内。 為了獲得本發明的這些目的和其他特徵，現依照本發明之目 的對本發明作具體化和概括性地描述，此處還提供了一種太陽能 電池的製造方法，係包含上述太陽能電池之雜板的表面處理^ 法。 因此，本發明具有下列優點： 首先，可透過濕式姓刻在第一表面處理步驟中形成多個第一 凸起部分，並透過乾式触刻在第二表面處理步驟中形成多個第二 凸起部分。因此，可顯著地減小矽基板之反射率，進而提供太陽 月t*電池的能效。 具體而言，可在低溫下透過酸性溶液執行第一表面處理步 201135956 驟，而不是在高溫下透過鹼性溶液執行此第 此，可提高製㈣產率及可靠性。 ❹步驟。因 面處理最大化地減小反神。 透過&種表 理4三並:=式_進行用於形成凸出部分的第-表面處 處=間條透過她顺行_形成恤起部分的 理步：因:透：式：Γ用於形成凸出部分的第，處 之狀对，谢位 本發明之前述及其他的目的、特徵、 部分在如下的她娜瓣蝴細戰f 【實施方式】 =，將接合關對本發明實施例進行詳盡的描述。 基====_軸_電池々 頂為第厂1第圖= 本發明實施例之太陽能電池之結構的剖面圖，「第 」如「第i n 7"之太陽能電池之製造方法的流程圖。 帛圖」所示，本發明實施例之太陽能電池包含有、 基板I係具㈣捿面結構；正面電極 電成=有·石夕 :的上表面(即，光— 電極3’係形成於底面（下文簡稱.基板的背面，）上，_以及抗^面 201135956 射膜4 ’係形成於矽基板1之表面上。 其中，石夕基板1係由晶態石夕材料形成，具體而言是由多晶 矽形成的。為了增大光接收面積，可不在太陽能電池之光接收面 上形成電極，而是僅在基板的背面上形成電極。 如「第2圖」所示，這種太陽能電池的製造方法包含有下列 步驟：基板處理步，驟（S10)，透過線鑛對石夕鑄塊進行切割，藉以 對石夕基板1進行處理；表面處理步驟（S20)，藉以在基板處理步 驟（S10)之後’執行在石夕基板！之表面上形成凸出部分；推雜步 驟（S30)，藉以在表面處理步驟（S2〇)後形成？^^接面結構；抗 反射膜形成步驟（40)，藉以在摻雜步驟（S3〇)後，在矽基板i 之表面上形成抗反射膜4 ;以及電極形成步驟（S5〇)，藉以分別於 矽基板1之正面與背面形成正面電極2與背面電極3。 同時，依照本發明實施例之太陽能電池的製造方法，也可於 摻雜步驟（S30)之别執行電極形成步驟（g5〇)。同時，可單獨地 執行基板處理步驟（sio)’或是與包含有表面處理步驟（S2〇)之 多個後續步驟一同執行此基板處理步驟。 同時，還可按其它方式執行這種太陽能的製造方法，下文不 再進行贅述。此處，將參照表面處理步驟（S2〇)對本發明實施例 中用於太陽能電池之石夕基板的表面處理方法進行描述。 「第3圖」為本發明實施例之太陽能電池之矽基板的表面處 理方法的流程圖。 如「第3圖」所示’這種太陽能電池之矽基板的表面處理方 法包含有：第一表面處理步驟（S21〇)，透過對用酸的水溶液對從 201135956 矽鑄塊上切下的基板進行蝕刻，藉以於矽基板1之外表面上形成 複數個第一凸起部分;以及第二表面處理步驟（S230)，藉以在 透k第表面處理步驟（S210)在其上形成第一凸起部分的石夕 基板1之外表面中對將要形成抗反射膜4之處的表面進行侧， 藉以形成複數個第二凸起部分。 在第一表面處理步驟（S210)中，可透過酸性溶液對從矽鑄 塊上切下的基板進行侧，藉以於此石夕基板1之外表面上形成複 數個第一凸起部分10。具體而言，如「第4A圖」所示，執行此 第一表面處理步驟（咖），_於雜板1之外表面上形成複數 個第一凸起部分。 在於此第—表面處理步驟（S21G)中使用酸性水溶液之狀況 下’將要形成抗反射膜4處絲板1之表_反射率低於使驗 性水溶液之狀況。因此，可增从的接收量，進而提高太陽能電 池的性能。 當於此第—表面處理步驟（S21G)中使紐性溶液時，第一 f面處理步驟（S21G)在很大程度上依賴於絲板1的材料。但 疋在使用n液時’會減小對⑦基板〗之材料的依賴性。 在第一表面處理步驟（奶〇)巾，最好在石夕基板1的光接收 面（即’表面）上形成第—凸起部分1G。為了防止在光接收面（即， 基板的背面)之相對表面上形成第—凸起部分H)，可在雜板！ 的背面上胁形縣罩的光罩職倾，藉⑽止财基板i 的背面形成這些第一凸起部分。 田在第表面處理步驟（S210)巾使用酸性溶液時，可使 201135956 用包含有硝酸與氫紐的水溶液。此處，這種溶液之重量配比與 濃度等參數取決於蝕刻溫度、蝕刻深度等條件。 在第-表面處理步驟（S210)巾，最好透過重量比為i】〜5 $] 的硝酸與氫驗混合成這魏性雜。同時，這魏性溶也可還 包含有表面活性劑與催化劑。 當使用酸性溶液時，可使用包含有：石肖酸、氣氣酸基乙酸（或 去離子水）的水溶液。 同時’在第一表面處理步驟（S21〇)巾，_深度（侧高 度）最好是1微米至10微米。 同時’還可透過内聯法（inlinemeth〇d)執行第一表面處理步 驟（S210)，藉以透過由滾筒將石夕基板1轉移至包含:t酸性溶液的 藉濕台’進而财基板1進行侧，而此侧製程可在6t：〜lot： 的溫度中執行1〜10分鐘。 匕卜還了透過使梦基板1浸泡於包含有酸性溶液之藉濕台 中對此石夕基板1進行侧，進而執行第-表面處理步驟（S210)， 而此敍刻製程可在忙〜1(TC的溫度中執行15〜25分鐘。 在這種第一表面處理步驟（S21〇)中，可透過酸性溶液執行 濕式钱刻。因此，這種太陽能f池的製造綠還包含有至少一種 後續製程，如：用於對經蝕刻處理後之矽基板丨之表面進行乾燥 的製程。 具體而言’在第一表面處理步驟（S210)後，這種太陽能電 池的製造方法還包含：第-清洗步驟（sm)，藉以歸在第一表 面處理步驟（S21G)巾所產生的顆粒；第二触刻步驟（S213)，藉 201135956 以透過驗性化合物（氫氧化納或氫氧化鉀）來分部分地對殘留於 石夕基板1之外表面上之多孔二氧化石夕（Si02)進行敍刻；第二清 洗步驟（S214) ’藉以在第二姓刻步驟（S213)之後移除殘留在石夕 基板1之外表面上的雜質；以及乾燥步驟（S215)，藉以在第二清 洗步驟（S214)之後對矽基板1進行乾燥處理。 其中’可執行第-清洗步驟（S212)與第二清洗步驟（S214) 藉以移除石夕基板1之表面上所殘留的雜質。此外，還可依據雜質 的麵及特性在-個階段或多個階段中執行第一清洗步驟（s2i2) 與第二清洗步驟（S214)。 「第4A圖」為透過「第3圖」所示之表面處理中第一表面處 理步驟進行首次處理之基板的部分剖面圖，「第4B圖」與「第4C 圖」分別示出了接受第-表面處理步驟之基板面積比率小於u 或大於3.2的部分剖面圖。此處，「第4A圖」至「第5圖」為簡 單示出。了基板的示意圖。因此，侧深度、頂端高度與尺寸都會 出現誤差。大體上，此截面可具有不規則形狀以及各種形狀。 此處’假設絲板1的核財將要形餅射的抗反麵4 之面積為實際面積Sr，其中可透過第__表面處理步驟（s2i〇)中 對石夕基板丨所進行之侧，藉以使絲板i之外表面上具有複數 個第一凸起部分1〇。同時，還假設完全平坦的表面面積為理想面 積Si在上述每些假设的前提下，如「第圖」與「第$圖」所 不，在執行了第—表面處理步驟（咖）之後鱗基板工之實 際面積Sr與理想面積Si間之比率位於12:1〜3 2:1範圍内。 如第4B圖」所不，當面積比率小於12時，第一表面處理 11 201135956 步驟（測）所形成較少的第—凸起部分ω，會使之反射率降低。 如「第4C圖」所示，當面積比率大於3.2時，此時，在第二 表面處理⑽0)步驟中透過電聚進行之反應並不劇烈，因此會 削弱表面處理效果。此外，當此面積比率大於3 2時，在太陽能電 池的製造方法之後續製程中，會阻礙電極形成步驟（S50)中用於 形成電極的金屬材料之擴散。進而，會對後續製程產生不利影響， 如：會形成空氣間隙。 在第-表面處理步驟（S21G)之前，這種製造方法還包含： 基板損傷處理步驟（S11)’係用於透過酸性溶液或臉性溶液去除 從矽鑄塊上切下的矽基板1之損傷。 在使用酸性溶液時，可用硝酸與氫氟酸、猶、氫氟酸及乙 酸（或去軒水）的混合水雜。鱗，俩錢_的重量比 為7:1 ’同時這種混合水溶液中水的重量比是由本技術領域中具有 通常知識者所確定的。 而在使紐性錢讀对，可在8叱〜贼的溫度中執行 15〜25分鐘之條件下執行基板損傷處理步驟（su)。當使用驗性 溶液時’可使用氫氧化納或氫氧化鉀，同時還可額外地加入2_異 丙醇(2-isopropyl-alcohol)。 在基板損傷處理步驟（S11)中，最好在石夕基板為單晶石夕時使 用驗性溶液。但是，當此石夕基板為多晶石夕時，最好使用酸性溶液。 此處，可以聯合使用基板損傷處理步驟（su)與第一表面處 理步驟（S210)。 第6圖」為經本發明實施例之第一表面處理步驟與第二表 12 201135956 面處理步驟處理後之基板的剖面圖。 此處，第二表面處理步驟（S230)係為用於形成微小凸起部 W紋理），即第二凸起部分2G之步驟’其中可對具有經第 面處理步驟（_處理表面並將要形成抗反射膜4的石夕基板！ 之外表面進行乾式侧。特別的是，如「第6圖」所示，第 面處理步驟⑽0)係用於在石夕基板i之表面上形成複數個;二 凸起部分2〇 (紋理）。此處，第二凸起部分20係為尺寸小於第一 凸起部分1G _、凸起。射，第—凸起部分10的寬度約為2 微水至20微米’而其高度約為i微米至1〇微米，最好為球狀（理 想狀況）。因此，此第—凸起部分之寬度可對應於餘，而其高度 (侧深度）可對應於半徑。另—方面，此第二凸起部分之^ 寸大約為100微米至800微米。 &其中’透過反應離子侧歧透過_可爾職真空壓力 狀態的真空㈣導搞合賴在第二表面處理步驟（咖）中執行 乾式钱刻。 同時，在進行乾式蝕刻時，可使用cl2/CF4/〇2、sf6/〇2、 CHF3/SF6/02、刚、F2及上述氣體之混合氣體作為侧氣體。 其中’執行_乾式爛的咖為幾秒至幾分鐘。 a為了透過反應離子_執行乾式⑽，可於轉板丨的上方 文裝具有複數個孔洞的平板，藉以協助形成微小凸起，即第 起部分20。 同時，可透過乾式_設備之基板支撐板上賴有複數個石夕 土板1的托盤對基板進行轉移，藉以執行乾式钮刻。 13 201135956 砂某Γ二Γ透過第二表面處理步驟_)使經過表面處理的 石夕基板1具有如「第6圖」所示之表面。 在第二表面處理步驟（咖）中可卿基板丨上 個第二凸起部分2〇,而这 硬数 ^ 起卩分2G小於賴第—表面處 , )所形成的第一凸起部分10之尺寸。 並且=6圖」所7^ ’此第二凸起部分2G具有三角形的橫截面， 面的相=起部分㈣之㈣侧面比這個側 在第-表面處理步驟（S21)中，可純含有形成了抗反射膜 的全部外表面、與外表__絲板之背_及勤上形成第 一凸起部分10。 其中’形成於石夕基板i之外表面上的第一凸起部分10可透過 降低光反射率而·光接㈣。但是m凸起部分1〇會在 電極形成步驟（S5G) ’即在形成此第一凸起部分1()以後的後續製 ^中造成不便’具體而言，這些第一凸起部分10會在製造具有較 π忐效的太陽能電池之基板時造成不便。 ，因此’最好僅細基板丨之外表面巾的表面（光接收面）上 域第ΰ；起部分1〇。此處，可於其它表面上形成此第一凸起部 分10 ’而需要移除的光接收面上形成此第一凸起部分1〇。 為了使透過屏蔽圖案於石夕基板之外表面上形成電極的電極圖 案形成過程更為簡便，需要對石夕基板1之外表面進行反餘刻。因 此’在執行第-表面處理步驟（S210)錢與第二表面處理步驟 (S230)之剛，或是僅在執行第二表面處理步驟（S230)之後， 201135956 步驟⑽ο) / 法還包含有：基板凸转分之背面移除 盆中移除形成於石夕基板背面上的第一凸起部分10， 二面進凸起部分1G之相對面上將要透過對石夕基板之 二订W刻而於第一表面處理步驟⑽0)中形成抗反射 膜4。 ^板凸起刀之背面移除步驟（S220)中，可在石夕基板！ 之背面處於向上的狀態下在第—表面處理步驟（咖）後透過將 石夕基板1裝餅乾式_識财對此錄板i進行反侧，而後 使用反應離子餘刻或感應耦合電漿钱刻對石夕基板1進行钱刻，藉 以使其厚度為3微米至1G微米。此處，可透過树基板1上方安 裝具有複數個孔洞的平板來執行這一製程。 在基板凸起部分之背面移除步驟（S22〇)中所使用的侧氣 體，含有：SF6/02、SF6/N2、刚、⑽、順、Clp3、ρ2或者上 述氣體的混合氣體。此處，執行_的時_域秒鐘至幾分鐘。 由於可透過乾式侧執行基板凸起部分之背面移除步驟 (S220 ) ’所以當進行濕式侧時，無須分麟此絲板之背面進 行乾式侧步驟、圖案形成步财及移除步驟。此處，可執行圖 案形成過程鄕除過程，藉以防止树基板之背面上形成凸起部 分。進而，可縮短矽基板的表面處理時間。 具體而言，若執行圖案形成過程與移除過程，則當製造矽基 板之背面沒有凸起部分的魏板丨時’需防止在第_表面處理之 前於石夕基板1之背面形成凸起部分。接下來，可對此雜板進行 蝕刻，進而可移除矽基板1之背面上所形成的圖案。因此，可僅 ΙΓ 15 201135956 於石夕基板1之表面上形成凸出部分。 由於在使用乾式蝕刻之本發明實施例的製造方法中無須透過 濕式钱刻執行醜製程與移除製程，所以由於當透過乾式餘刻執 行基板凸起部分之背面移除步驟（S22〇)時，可降低成本並縮短 製造時間’ _獲财基板之經侧後的背表面。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solar cell, particularly a surface treatment method for a tantalum substrate of a solar cell, and a method of manufacturing the solar cell. [Prior Art] Generally, a solar cell can generate an electromotive force by transmitting a photovoltaic special effect, that is, a photoelectromotive force effect. Among them, solar cells can be classified into materials based on substrates: germanium-based solar cells, compound semiconductor solar cells, and compound/stacked solar cells. Here, the ruthenium-based solar cells can be classified into: crystalline germanium solar cells, such as: single crystal germanium solar cells and polycrystalline germanium solar cells; and amorphous germanium solar cells. Among them, the energy efficiency of the solar cell can be determined by some factors such as the reflectivity of the substrate. At the same time, the energy efficiency of the solar cell is maximized by reflecting the light on the light incident surface, that is, the reflectance is minimized. In the aspect of crystalline germanium solar cells having lower manufacturing costs, many methods for minimizing reflection of light have been proposed to improve the performance of solar cells. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a surface treatment method for a tantalum substrate of a solar cell and a method of manufacturing the solar cell, thereby minimizing light reflection on the surface of the solar cell. In order to achieve the object of the present invention, the present invention is specifically and generally described herein. One aspect of the present invention provides a surface treatment of a tantalum substrate for a solar cell. 201135956 Method '& method includes: a first surface treatment step, For the use of an acidic solution from the Shixi ingot block, under the cutting board _, to form a plurality of first-spider parts on the outer surface of the Wei board; and a second surface treatment step, gazing at the formation of anti-reflection Where the 臈 is formed by the dry _ on the outer surface of the silk plate, that is, in the outer surface of the slab having the first convex portion formed thereon through the first surface treatment step, the size is smaller than that of the first convex portion _ The second raised portion. In this first surface treatment step, the acidic solution contains nitric acid and gas acid, and the weight ratio of nitric acid to hydrofluoric acid in the acidic solution is 1:1 to 5.5:1. Wherein 'the through-drum can be conveyed to the wet platform containing the acidic solution' to perform the first surface treatment step through the side of the miscellaneous sheet, where it can be 6 ° c ~ 10 ° An etching process of 1 to 10 minutes is performed in the temperature of c. At the same time, the first surface treatment step can be performed by immersing the substrate in a bear wet platform containing an acidic solution, and the surface treatment step can be performed at a temperature of 6 ° C to 10 ° C. 20 minute etching process. Prior to the first surface treatment step, the method may further comprise: a substrate damage treatment step whereby the damage on the substrate is cut from the slab by the miscellaneous or miscellaneous solution. After the first surface treatment step, the method may further include: a first first cleaning step for removing impurities generated in the first surface treatment step; and a first etching step for transmitting alkaline The compound partially etches the porous stellite oxide remaining on the outer surface of the ruthenium substrate; the second cleaning step is for removing impurities remaining on the outer surface of the ruthenium substrate after the second etch step; a drying step whereby the Shixi substrate is dried after the second washing step. 201135956 β and after the first surface treatment step and before the second surface treatment step, or only after the second surface treatment step, the method may further comprise removing the back side of the convex portion of the substrate. a step of removing the first convex portion formed on the back surface of the stone substrate and the first convex portion formed in the first surface treatment step by performing dry etching on the back surface of the stone substrate A first convex portion on the opposite side of the surface of the anti-reflection film is formed in the surface. Wherein the second convex portion has a triangular cross section, and at the same time, the side of the second convex portion facing the top of the first convex portion is shorter than the other side of the second convex portion. The germanium substrate is a single crystal germanium substrate or a polycrystalline germanium substrate. Wherein 'after the first surface treatment step, when the area of the outer surface of the anti-reflection film to be formed in the outer surface of the miscellaneous sheet is a desired area, the actual area and the ideal area of the surface subjected to the etching in the first surface treatment step The ratio between the two is in the range of 1-2:1 to 3·2:1. In order to obtain the objects and other features of the present invention, the present invention will be specifically and broadly described in accordance with the purpose of the present invention, and a method of manufacturing a solar cell comprising the surface of the solar cell of the above solar cell is also provided. Processing ^ method. Therefore, the present invention has the following advantages: First, a plurality of first convex portions can be formed in the first surface treatment step through the wet type, and a plurality of second convex portions can be formed in the second surface treatment step by dry-touching Part. Therefore, the reflectance of the germanium substrate can be remarkably reduced, thereby providing the solar cell t* battery energy efficiency. Specifically, the first surface treatment step 201135956 can be performed by passing the acidic solution at a low temperature, instead of performing the first step through the alkaline solution at a high temperature, and the yield and reliability can be improved. ❹ Steps. The surface treatment minimizes anti-god. Through & kind of symmetry 4: and = = _ for the first surface where the convex portion is formed = the strip is passed through her _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The above-mentioned and other objects, features, and parts of the present invention are formed in the following aspects. [Embodiment] =, the joint is closed to the embodiment of the present invention. Detailed description. Base ====_Axis_Battery dome is the first plant 1 FIG. 1 is a cross-sectional view showing the structure of a solar cell according to an embodiment of the present invention, and a flow chart of a method for manufacturing a solar cell according to "in 7th". As shown in the figure, the solar cell of the embodiment of the present invention comprises: a substrate I (four) facet structure; the front surface is electrically formed = the upper surface of the stone (ie, the light electrode 3' is formed on the bottom surface) (hereinafter referred to as the back surface of the substrate), _ and the anti-surface 201135956 film 4' are formed on the surface of the ruthenium substrate 1. Among them, the shixi substrate 1 is formed of a crystalline shi shi material, specifically In order to increase the light receiving area, electrodes may not be formed on the light receiving surface of the solar cell, but electrodes may be formed only on the back surface of the substrate. As shown in Fig. 2, the solar cell is manufactured. The method comprises the following steps: a substrate processing step, a step (S10), cutting a Shixi ingot through a line ore, thereby processing the Shixi substrate 1; and a surface treatment step (S20), thereby performing a substrate processing step (S10) After 'executing in Shi Xiji Forming a convex portion on the surface of the plate!; pushing the step (S30), thereby forming a junction structure after the surface treatment step (S2〇); and forming an anti-reflection film forming step (40), thereby performing the doping step ( After S3), an anti-reflection film 4 is formed on the surface of the ruthenium substrate i; and an electrode formation step (S5 〇), whereby the front surface electrode 2 and the back surface electrode 3 are formed on the front and back surfaces of the ruthenium substrate 1, respectively. In the method of manufacturing a solar cell according to the embodiment of the invention, the electrode forming step (g5〇) may be performed in the doping step (S30). Meanwhile, the substrate processing step (sio) may be performed separately or may include surface treatment. The substrate processing step is performed together with a plurality of subsequent steps of the step (S2). Meanwhile, the solar energy manufacturing method can also be performed in other manners, which will not be described below. Here, reference will be made to the surface treatment step (S2〇). A surface treatment method for a solar cell substrate for a solar cell according to an embodiment of the present invention is described. FIG. 3 is a flow chart of a surface treatment method for a tantalum substrate of a solar cell according to an embodiment of the present invention. As shown in the "Fig. 3", the surface treatment method of the tantalum substrate of the solar cell includes: a first surface treatment step (S21〇), which is cut from the 201135956 矽 ingot by an aqueous solution of acid. The substrate is etched to form a plurality of first convex portions on the outer surface of the ruthenium substrate 1; and a second surface treatment step (S230), whereby the first convex is formed thereon at the k-surface treatment step (S210) The surface of the outer portion of the stone substrate 1 is side to the surface where the anti-reflection film 4 is to be formed, thereby forming a plurality of second convex portions. In the first surface treatment step (S210), the acidic solution is permeable. The side of the substrate cut from the crucible ingot is subjected to a side, whereby a plurality of first convex portions 10 are formed on the outer surface of the substrate. Specifically, as shown in Fig. 4A, the first surface treatment step (coffee) is performed, and a plurality of first convex portions are formed on the outer surface of the miscellaneous sheet 1. In the case where an acidic aqueous solution is used in the first surface treatment step (S21G), the surface reflectance of the wire sheet 1 at which the antireflection film 4 is to be formed is lower than that of the test aqueous solution. Therefore, the amount of reception can be increased, thereby improving the performance of the solar battery. When the neodymium solution is used in this first surface treatment step (S21G), the first f-face treatment step (S21G) largely depends on the material of the silk plate 1. However, when using n liquid, the dependence on the material of the 7 substrate is reduced. In the first surface treatment step (milk), it is preferable to form the first convex portion 1G on the light receiving surface (i.e., the 'surface) of the stone substrate 1. In order to prevent the formation of the first convex portion H) on the opposite surface of the light receiving surface (i.e., the back surface of the substrate), it may be in the miscellaneous plate! On the back side of the damper-shaped hood, the reticle is tilted, and the first raised portion is formed by the back of the substrate 10i. In the first surface treatment step (S210), when the acid solution is used, the 201135956 can be used as an aqueous solution containing nitric acid and hydrogen. Here, the weight ratio and concentration of such a solution depend on conditions such as etching temperature, etching depth, and the like. In the first surface treatment step (S210), it is preferred to mix the nitric acid and hydrogen with a weight ratio of i]~5 $] to form the Wei hetero. At the same time, this Wei-smelting solution may also contain a surfactant and a catalyst. When an acidic solution is used, an aqueous solution containing: oxalic acid, gas-acid acetic acid (or deionized water) can be used. At the same time, in the first surface treatment step (S21), the depth (side height) is preferably from 1 micrometer to 10 micrometers. At the same time, the first surface treatment step (S210) can also be performed by an inline method (S210), whereby the substrate is transferred to the wet platform comprising: t acidic solution by the drum, and the side of the financial substrate 1 is further This side process can be performed for 1 to 10 minutes at a temperature of 6t:~lot:. Further, by immersing the dream substrate 1 in the wet platform containing the acidic solution, the side of the stone substrate 1 is subjected to the first surface treatment step (S210), and the etching process can be busy ~1 ( The temperature of the TC is performed for 15 to 25 minutes. In this first surface treatment step (S21〇), the wet etching can be performed through the acidic solution. Therefore, the manufacturing green of the solar energy f pool also includes at least one subsequent The process, for example, is a process for drying the surface of the etched substrate 。. Specifically, after the first surface treatment step (S210), the method for manufacturing the solar cell further includes: Step (sm), whereby the particles produced by the first surface treatment step (S21G) are collected; the second etch step (S213), by means of 201135956, by means of an organic compound (sodium hydroxide or potassium hydroxide) The porous silica dioxide (SiO 2 ) remaining on the outer surface of the Shi Xi substrate 1 is etched; the second cleaning step (S214) 'by removing the residue remaining in Shi Xi after the second surging step (S213) On the outer surface of the substrate 1 And a drying step (S215), whereby the crucible substrate 1 is subjected to a drying treatment after the second cleaning step (S214). wherein 'the first cleaning step (S212) and the second cleaning step (S214) may be performed to remove the stone The impurities remaining on the surface of the substrate 1. Further, the first cleaning step (s2i2) and the second cleaning step (S214) may be performed in one stage or in multiple stages depending on the surface and characteristics of the impurities. FIG. 4 is a partial cross-sectional view of the substrate subjected to the first surface treatment step in the surface treatment shown in FIG. 3, and FIG. 4B and FIG. 4C respectively show the acceptance of the first surface treatment. The substrate area ratio of the step is less than u or a partial cross-sectional view of more than 3.2. Here, "4A" to "5th" are simply shown. The schematic view of the substrate. Therefore, the side depth, the tip height and the size will appear. In general, the cross section may have an irregular shape and various shapes. Here, it is assumed that the area of the anti-reverse surface 4 of the core board 1 is the actual area Sr, which is permeable to the __ surface treatment. Step (s2i 〇) the side of the 夕 丨 substrate 丨, so that the outer surface of the silk plate i has a plurality of first convex portions 1 〇. Meanwhile, it is also assumed that the completely flat surface area is the ideal area Si in each of the above Under the premise of hypothesis, such as "figure" and "figure $", after the first surface treatment step (coffee) is executed, the ratio between the actual area Sr of the scale substrate and the ideal area Si is 12:1~ 3 2:1. As shown in Fig. 4B, when the area ratio is less than 12, the first surface treatment 11 201135956 step (measurement) forms fewer first convex portions ω, which reduces the reflectance. As shown in "Fig. 4C", when the area ratio is larger than 3.2, at this time, the reaction by electropolymerization in the second surface treatment (10) 0) is not severe, and thus the surface treatment effect is impaired. Further, when the area ratio is larger than 3 2, the diffusion of the metal material for forming the electrode in the electrode forming step (S50) is hindered in the subsequent process of the solar cell manufacturing method. In turn, it will have an adverse effect on subsequent processes, such as an air gap. Prior to the first surface treatment step (S21G), the manufacturing method further comprises: the substrate damage treatment step (S11)' is for removing the damage of the tantalum substrate 1 cut from the tantalum ingot through the acidic solution or the facial solution. . When an acidic solution is used, a mixed water of nitric acid and hydrofluoric acid, hepta, hydrofluoric acid, and acetic acid (or decanter) may be used. The weight ratio of the scales to the money is 7:1' while the weight ratio of water in the mixed aqueous solution is determined by those of ordinary skill in the art. In the case of reading the new money, the substrate damage processing step (su) can be performed under the condition of 15 to 25 minutes in the temperature of 8 叱 to thief. When an inert solution is used, sodium hydroxide or potassium hydroxide can be used, and 2-isopropyl-alcohol can be additionally added. In the substrate damage treatment step (S11), it is preferable to use an assay solution when the stone substrate is a single crystal. However, when the Shishi substrate is polycrystalline, it is preferable to use an acidic solution. Here, the substrate damage processing step (su) and the first surface treatment step (S210) may be used in combination. Figure 6 is a cross-sectional view of the substrate after the first surface treatment step of the embodiment of the present invention and the surface treatment of the second table 12 201135956. Here, the second surface treatment step (S230) is a step for forming a fine convex portion W texture, that is, the second convex portion 2G, wherein the second surface portion 2G may have a first processing step (the processing surface is to be formed) The outer surface of the anti-reflection film 4 is on the dry side. Specifically, as shown in FIG. 6, the first surface treatment step (10) 0) is for forming a plurality of surfaces on the surface of the stone substrate i; Two raised portions 2〇 (texture). Here, the second convex portion 20 is smaller in size than the first convex portion 1G_, the projection. The first raised portion 10 has a width of about 2 micrometers to 20 micrometers and a height of about 1 micrometer to 1 micrometer, preferably spherical (ideal condition). Therefore, the width of the first convex portion may correspond to the remainder, and the height (side depth) thereof may correspond to the radius. On the other hand, the second raised portion has a size of about 100 micrometers to 800 micrometers. & where 'through the reactive ion side 透过 _ _ er vacuum pressure state of the vacuum (four) guide to perform the dry money engraving in the second surface treatment step (coffee). Meanwhile, in the dry etching, a mixed gas of cl2/CF4/〇2, sf6/〇2, CHF3/SF6/02, just, F2, and the above gas may be used as the side gas. Among them, the 'executive_dry rotten coffee is a few seconds to a few minutes. a In order to perform the dry type (10) through the reactive ions, a flat plate having a plurality of holes may be installed above the transfer plate to assist in forming minute projections, i.e., the first portion 20. At the same time, the substrate can be transferred through the tray of the plurality of stone slabs 1 on the substrate support plate of the dry type device, thereby performing dry button engraving. 13 201135956 The second surface treatment step _) causes the surface treated stone substrate 1 to have a surface as shown in Fig. 6. In the second surface treatment step (coffee), the first convex portion 2 is formed on the substrate, and the first convex portion 2 is formed by the second convex portion 2, and the hard portion is 2G smaller than the Lai-surface. The size. And the second convex portion 2G has a triangular cross section, and the phase of the surface = the portion (4) of the side (four) is more purely formed than the side in the first surface treatment step (S21). The entire outer surface of the anti-reflection film, the back of the outer surface of the silk plate, and the first convex portion 10 are formed on the surface. Wherein the first convex portion 10 formed on the outer surface of the stone substrate i is permeable to reduce the light reflectance and the light is connected (four). However, the m convex portion 1〇 may cause inconvenience in the electrode forming step (S5G)', that is, in the subsequent process after forming the first convex portion 1(), specifically, the first convex portions 10 will It is inconvenient to manufacture a substrate having a solar cell of a more π effect. Therefore, it is preferable that only the surface of the surface towel (light receiving surface) other than the fine substrate ΰ is in the upper side; Here, the first convex portion 10' may be formed on the other surface and the first convex portion 1'' is formed on the light receiving surface which needs to be removed. In order to make the electrode pattern forming process by forming the electrode on the outer surface of the stone substrate through the shielding pattern, the outer surface of the stone substrate 1 needs to be reversed. Therefore, after performing the first surface treatment step (S210) and the second surface treatment step (S230), or only after performing the second surface treatment step (S230), the 201135956 step (10) ο) / method further includes: The first convex portion 10 formed on the back surface of the stone substrate is removed from the back surface removing basin of the substrate convex portion, and the opposite surface of the two-sided convex portion 1G is to be etched through the second surface of the stone substrate. The anti-reflection film 4 is formed in the first surface treatment step (10) 0). ^ The back of the plate knives removal step (S220) can be used in the Shixi substrate! The back side is in an upward state, after the first surface treatment step (coffee), the stone substrate 1 is loaded with a biscuit type _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The Shishi substrate 1 is engraved to have a thickness of 3 micrometers to 1 micrometer. Here, the process can be performed by mounting a plate having a plurality of holes above the tree substrate 1. The side gas used in the step (S22) of the back surface removal portion of the substrate convex portion contains: SF6/02, SF6/N2, just, (10), cis, Clp3, ρ2 or a mixed gas of the above gases. Here, the time_ field of _ is executed to a few seconds. Since the back side removal step (S220) of the raised portion of the substrate can be performed through the dry side, when the wet side is performed, the dry side step, the pattern forming step, and the removing step are not required to be performed on the back side of the screen. Here, the pattern forming process erasing process can be performed to prevent the formation of the convex portion on the back surface of the tree substrate. Further, the surface treatment time of the tantalum substrate can be shortened. Specifically, if the pattern forming process and the removing process are performed, when the back surface of the germanium substrate is not provided with the convex portion, the convex portion of the back surface of the stone substrate 1 is prevented from being formed before the first surface treatment. . Next, the dope can be etched to remove the pattern formed on the back side of the substrate 1. Therefore, a convex portion can be formed on the surface of the Shishi substrate 1 only on 2011 15 201135956. Since the ugly process and the removal process are not required to be performed by wet etching in the manufacturing method of the embodiment of the present invention using dry etching, since the back surface removing step (S22 〇) of the convex portion of the substrate is performed by the dry process , can reduce the cost and shorten the manufacturing time ' _ get the back surface of the substrate after the side.
tM A. 第一表面處理 以2.1的比例對硝酸與氫氟酸進行混合，藉以獲得酸性溶液。 蝕刻時間：内聯法（inlinemethod)持續1到10分鐘 姓刻溫度：約為6。〇〜1〇。〇 B. 第二表面處理（乾式侧：反應離子侧） 在5〇毫托之反應氣壓下，CHF3約為12標準立方米/分鐘， C12約為72鮮立方米/分鐘，約為標準立方米/分鐘， SF6為65標準立方米/分鐘。而第二表面處理係在，瓦特之射 頻功率之電聚中執行5秒至1〇秒。 C. 較佳實施例與比較實施例間之比較 女^ 厂矣· 1 」所不，透過本發明之方法進行處理的矽基板1所體 現的反射率遠遇小於透過習知方法進行處理的基板表面之反射 率。 16 201135956 「表1」 實例 反射率 (%，350奈米〜1〇50奈米） 僅執行基板損壞處理 28.96 執行基板損壞處理及反應離子姓 刻處理 10.51 執行第一表面處理與第二表面處 理（本發明） 7.79 其中’依據本發明實施例，在進行了第一表面處理與第二表 面處理之後透過電漿輔助化學氣相沈積（PECVD)所形成的具有 抗反射膜4之;5夕基板的反射率為140。 此處，本發明之前述實施例及優點僅是示範性的並且不對本 發明之揭露構成限制。而本發明所教示之内容也可便利地用於其 它類型的設備。同時，以上描述旨在對本發明進行說明，而無意 於限疋本發明清求保護之主題的範圍。同時，本技術領域中具有 通常知識者可⑽解本㈣之雜手段、實雛變化方式。 此外’當結合任意-個實施例對指定特徵、結構或特性進行描述 時，經由本領域之技術人員結合另外—些實侧也可輯到相同 之效果。 雖然本發日狀前软實施觸露如上，祕並_以限定本 發明。在不脫離本發明之精神和範圍内，所為之更動與潤飾，均 17 201135956 X月之專梅魏圍。關財發明所界定之保護範圍請參考 所附之申請專利範圍。 【圖式簡單說明】 第1圖為太陽能電池之結構的剖面圖； 第2圖為胁朗第〗圖卿之太電紅製造方法的流 程圖； 第3圖為胁說明本發明實施例之太陽能電池_基板之表 面處理方法的流程圖； 第4A圖為透過第3圖所示的表面處理方法之第一表面處理 步驟對其表面進行處理之基板的部分剖面圖； 第4B圖至第4C圖分別為經過第一表面處理後基板之面積比 率小於1.2及大於3.2的部分剖面圖； 第5圖為透過第3圖所示之表面處理方法形成凸起部分之狀 態的原理圖；以及 第6圖為經過本發明實施例之表面處理方法之第一表面處理 與第二表面處理的石夕基板之部分剖面圖。 【主要元件符號說明】 1 ...........................石夕基板 2 ...........................正面電極 3 ...........................面電極 4 ...........................抗反射膜 18 201135956 ίο ...........................第一凸起部分tM A. First surface treatment Nitric acid and hydrofluoric acid were mixed at a ratio of 2.1 to obtain an acidic solution. Etching time: Inline method (inlinemethod) lasts 1 to 10 minutes. Name engraved temperature: about 6. 〇~1〇. 〇B. Second surface treatment (dry side: reactive ion side) Under a reaction pressure of 5 Torr, CHF3 is about 12 standard cubic meters per minute, and C12 is about 72 fresh cubic meters per minute, which is about standard cubic meters. /min, SF6 is 65 standard cubic meters / minute. The second surface treatment is performed for 5 seconds to 1 second in the electropolymerization of the Watt frequency power. C. Comparison between the preferred embodiment and the comparative example. The substrate 1 processed by the method of the present invention exhibits a reflectance that is less than that of the substrate processed by the conventional method. The reflectivity of the surface. 16 201135956 "Table 1" Example reflectance (%, 350 nm ~ 1 〇 50 nm) Only substrate damage treatment is performed 28.96 Performing substrate damage treatment and reactive ion etch processing 10.51 Performing the first surface treatment and the second surface treatment ( The present invention] 7.79 wherein: according to an embodiment of the present invention, after the first surface treatment and the second surface treatment, the anti-reflection film 4 is formed by plasma-assisted chemical vapor deposition (PECVD); The reflectance is 140. The foregoing embodiments and advantages of the invention are intended to be illustrative and not restrictive. The teachings of the present invention are also convenient for use with other types of devices. In the meantime, the above description is intended to be illustrative of the present invention and is not intended to limit the scope of the claimed subject matter. At the same time, those skilled in the art can (10) solve the miscellaneous means of this (4), and change the mode of the actual chick. Further, when a specified feature, structure, or characteristic is described in combination with any of the embodiments, the same effect can be obtained by a person skilled in the art in combination with another solid side. Although the soft implementation of the present invention is as described above, it is intended to limit the invention. Without changing the spirit and scope of the present invention, the changes and retouchings are all made by the Meiwei Weiwei of 2011. Please refer to the attached patent application scope for the scope of protection defined by Guancai Invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing the structure of a solar cell; Fig. 2 is a flow chart showing a method for manufacturing a galvanic red of the scorpion; and Fig. 3 is a view showing the solar energy of the embodiment of the present invention FIG. 4A is a partial cross-sectional view of the substrate subjected to the surface treatment process by the first surface treatment step of the surface treatment method shown in FIG. 3; FIGS. 4B to 4C a partial cross-sectional view of the area ratio of the substrate after the first surface treatment is less than 1.2 and greater than 3.2; and FIG. 5 is a schematic diagram showing a state in which the convex portion is formed by the surface treatment method shown in FIG. 3; and FIG. It is a partial cross-sectional view of the first surface treatment and the second surface treatment of the surface treatment substrate according to the surface treatment method of the embodiment of the present invention. [Main component symbol description] 1 ...........................Shi Xi substrate 2 ............ ...............front electrode 3 ...........................face electrode 4 .. .........................Anti-reflection film 18 201135956 ίο ................... ........the first raised part
Sr ...........................實際面積Sr ...........................real area
Si ...........................理想面積 19Si ...........................Ideal area 19