201027617 六、發明說明： 【發明所屬之技術領域】 本發明係有關於如申請專利範圍第1項所說明的一種矽晶片 的氧化和清洗方法以及利用此方法所生產的太陽能電池。 【先前技術】 目前，太陽能電池製造大部份係涉及矽晶太陽能電池。製造 太陽能電池時，首先需生產矽晶片，即所謂的晶片（Wafer)。矽 晶片由於採用矽晶棒切割製造，在切割過程其晶體結構的表面容 易導致嚴重損傷，因而會影響所生產的太陽能電池的性能。因此 必須將所述的切割損傷層去除，一般係採用蝕刻法來進行矽晶片 的钱刻處理。在矽晶材料採用坩銷直拉法而加工理想的厚度的矽 晶片情形，則至少可以節省大部份的切割過程。然而，這些所謂 的梦晶材料其表面經常會遭受污染而影響以該材料生產的太陽能 電池的性能，因此，首先需進行触刻處理。 除了上述去除切割損傷或表面污染缺陷進行蝕刻外，一般在 砍晶片表面有必要進行額外的或選擇性的制絨製程（又稱表面結 構化製程）（surface texturizati〇n)，以減少直射到石夕晶片表 面的太陽能_傷以及增加所生產的太陽能電池的光麵合作用。 在工業生產上’其表面金字塔結構（又稱金字塔群組織） (texturing) —般係採用濕式化學蝕刻法製造。 ㈣表面衫6賴化稍金轉轉，供製造太陽 月1^的〜日片需進行額外的擴散制結處理（Diffuse)，並遍 採用树晶片⑽雜材料，其目的在於形成PN結〔該p是:p 201027617 型半導體（受體）’N是指N型半導體（施體）。PN結又稱為又稱 P-N接合’或稱耗盡區〕。由於擴散處理通常需要在7〇(rc以上的 ΛΠ·度進行，在如此尚溫下，石夕晶片表面或擴散設備上的污染遺留 也會擴散至發晶片上。因此，制絨處理（表面結構化製程）後所 產生的遺留雜質會嚴重影響所生產的太陽能電池的性能。所以在 擴散制結處理前’矽晶片的表面潔淨非常重要，要求矽晶片在制 絨處理後，送進擴散設備前，要進行清洗。一般是採用濕式化學 方法清洗’原則上業者有各種不同的清洗方法可以採用。 ® 工業生產矽晶太陽能電池，一般其清洗方式是，矽晶片在利 用酸性化學溶液進行金屬氧化處理前，首先採用一鹼性蝕刻液進 行飯刻處理。然後將矽晶片以氫氟酸（HF)水溶液進行飯刻處理。 清洗過程一般係利用水，通常使用去離子水來清洗。無論如何， 砍晶片在利用氫氟酸餘刻處理後需以去離子水清洗。其目的在於 去除石夕晶片上可能殘留的污染物質或酸液殘餘或至少能加以稀 釋。至於鹼性蝕刻液，一般係採用氫氧化鉀或氫氧化鈉（燒鹼） φ 溶液。矽晶片以氫氟酸亦或以含有氫氟酸的溶液蝕刻的主要目 的’在於去除矽晶片表面上存在的氧化矽層（silic〇n 〇xide layer)。該氧化矽層可以事先利用適當生產過程，例如濕式化學 氧化方法形成，或者該氧化矽層係所謂的天然氧化矽，通常係受 到空氣氧化作用的周圍環境條件而形成的。 利用風敗酸去除氧化石夕層後會有一層疏水性的梦晶表面。因 此’在接下來的以去離子水清洗過程，水份會自矽晶片表面去除， 以便石夕晶片只殘留極少量的去離子水或不含去離子水的殘留而允 許被送至擴散設備。因此，去離子水所產生的污染，例如上述的 201027617 溶解污染，可以在擴散設備内明顯地被避免，因而能夠明顯地不 致於影響所生產的太陽能電池的性能。因此，上述的利用氫氟酸 產生疏水性的矽晶表面在目前的工業生產矽晶太陽能電池是傳統 的技術。甚至於要免除一般以氫氟酸蚀刻的方法是不可能，因為 假設在此帶入擴散管的污染至少部份會抵達擴散設備，導致稍後 置入擴散設備的矽晶片雖然事先已使用氫氟酸清洗過，仍然會導 致矽晶片受到汙染而影響其正常的性能。然而此過程如果矽晶片 具有氡化⑦層而必須精擴減理時會有_，因為該氧化梦層 在清洗過程會被氫氟酸去除。因此，在擴散處理過程，如果氧化◎ 碎層存在有摻雜材㈣，麵散縣是非常有獅，例如在目前 經常被採用的現有的擴散過程，如果掺雜材料的擴散制結需利用 在梦晶絲面上所加卫峨化㈣來完成時，讀關產生具有 30至75 Ω/sq電阻率的發射極（ermitter)，使能實現介於 與200 Q/sq之間的電阻率。此類氧化⑦層的高度電阻率如果仍 I保證與太陽能電池的良好電氣接觸而且具有滿意的較低電阻值 時’則_有利於提升效率。目此，糊氧化⑦層來擴散摻雜材 料在生產選擇性發射極（selective emitters)時可以有利地❹ 被應用。 【發明内容】 有鑑於此，為了克服上述習用技藝的各種問題，本發明的主 要目的在於提供—種抑片的清洗方法，而且财晶片至少有一 部份係具有一層氧化矽層。 此目的可藉如本發明申請專利範圍第1項所述的方法來達 成0 201027617 此外本發明的標的係如申請專利範圍第14項所述的-種太陽 能電池。 其他有利的實施例分別係本發明附屬項申請專利範圍的標 的。 ^騎洗方法迄今—致認為，以氫魏舰（HF_sQluti〇n) 或含氫氟酸的溶液使產生一疏水性表面的一種梦晶片姓刻法是必 要$，轉證能充分地清洗㈣#。_令人驚舒的是 ’不必利 用氫紐來__日肢形成—疏樣表面也可以達成一充分的 清洗效果’使能夠生產具有優良性能的太陽能電池。 因此，依據本發明的方法，矽晶片在蝕刻前至少有一部份的 表面具有氧化發層。餘刻係進一步在含有能夠氧化金屬污染物的 酸性溶液中處理。在此，太陽能電池的氧化♦層至少有一部份係 未受保護地曝露於雜溶液中。_過織，〜$片需以去離子 水清洗。至少-部份的未受賴的氧化_層至少有，份會遺留 在梦晶片上。梦晶片在清洗處理後需進一步進行乾燥處理； ❹ 絲本發明之另—#_，珍晶片在叫離子水清洗前 需H驗性侧親行侧處理，而且氧化韻至少有一部份是 未經保護地曝露於該餘刻液。必要時，藉此可以改善清洗效果。 各別__程，其不纽重^在各綱_過程之間可 以進行期間的清洗過程。 為了㈣至少-雜的未受倾的氧化魏至少有一部份能 遺留树晶片上，至少該部份是親水性（hydr〇phiUc)而非疏水 性（hyd_Qbic〇。因此，_含氫氟酸液來完全去除氧化 ㈣，如同傳統的形成非疏水性表面的方法，是不可能的。因此， 201027617 在#刻過程要在驗性飯刻液中完全去除氧化矽層也是不可能的。 然而此危險性只是原則上存在’實際上使驗⑽贿在一般所 使用的腐餘時間内進行清洗石夕晶片時不會發生。依據本發明，無 論如何，鹼性蝕刻液的蝕刻率與腐蝕時間能保證不可能完全去^ 氧化碎層。因此，晶片至少部份佩在親水性條件下而且在以 去離子水清洗後需進行乾燥處理。在此，其乾燥處理能夠以目前 已知的任何方法來實現。 此外，使用氫氟酸進行蝕刻作業基本上可以完全免除，而且 不致於影響所生產的太陽能電池的性能。依據本發明之另一有利 實施例，可以氫氟酸雜，尤其是_錢__刻液來 進行梦晶片的蚀刻處理。 依據本發明之另-有利實施例，發晶片可利用氣相分離法形 成一層氧化矽層。在此可利用低壓化學氣相沉積法（LpcvD)，常 壓化學氣相沈積法（APCVD )亦或電漿辅助化學氣相沈積法（pECVD ) 等分離法來處理。依據本發明之另—_有歡補，該氧化發 層係利用濕式熱氧化法來形成。 如果树晶片上形成的氧化石夕層在清洗過程能被充分地姓刻 時’則該氧化销原則上可獲得理想的厚度。然:而，清洗過程的 時間越長晶#秘面損細大，尤其會受繼性侧練長 時間反應的影響。依據本發明之另-實補，該氧化#層理想的 與7Gnm之間，而且最理想的厚度係介於1〇 nm與70 nm之間（nm=奈米）。 依據本發明之另一實施例，氧化矽層的厚度在蝕刻過程係比 。驗性_液最好是使用驗性氫氧化物溶 201027617 液（alkaline hydroxide s〇luti〇n)，尤其是水溶性的鹼性氫氧 化物溶液’且最為有綱是錄颂或lL氧倾（祕）溶液。 依據本發明的另一實施例，該鹼性蝕刻液之氧化矽蝕刻率為 每分鐘< 25 nm。該蚀刻率在實際加工上證明是可靠而且有利的。 依據本發明的另-實施例，梦晶片在加工氧化料之前可藉濕式 化學方法去除蝴損傷。在輯有已知_襲傷侧法都可以 細’尤其是切觸傷可制-驗性氫氧化物溶液去除。此外， ❾也可以使用酸性侧液。依據本發明的另一有利實施例該石夕晶 片在加工氧化梦層之前，至少在石夕晶片的部份表面上是利用濕式 化學方法形成-金字塔結構（又稱金字塔群組織）（texturing)。 為了能夠以濕式化學方法形成金字塔結構，可以使用所有已知的 制絨蝕刻液，尤其是驗性或酸性制絨蝕刻液。以濕式化學方法去 除切割損傷後可以額外地亦或選擇性地以濕式化學方法形成一金 字塔結構。 "T以元王免除利用氫氟酸钱刻的另一種選擇方法是，將梦晶 © 片額外地在一高度稀釋或緩衝氫氟酸溶液中進行蝕刻處理，而且 其氧切伽彳率係每分鐘〈25 nm。例如在需避紐職性钱刻液 或在需去除各別部位所存在的很薄的氧化矽（例如天然氧化矽） 的情形’利用此方法有其優點。腐蝕時間在此顯然需配合蝕刻率。 上述的利用一高度稀釋或緩衝氳氟酸溶液的蝕刻處理可以單獨結 合一種能夠氧化金屬污染物的酸性溶液或結合鹼性蝕刻液進行蝕 刻處理。 矽晶片在一氫氟酸溶液中理想的腐蝕時間需少於丨分鐘，尤 其有利的是少於30秒，最好是少於15秒。 201027617 本發明的方法尤其有利於製造太陽能電池。 【實施方式】 請參照第一圖所示，係本發明的第一實施例的示意圖《依據 此實施例所述的方法’首先利用蝕刻法來去除切割損傷層（10)。 因此’本方法特別適合由晶圓棒所切割的矽晶片。然而此方法也 可以進一步應用在其他的矽晶材料上，例如應用在薄膜矽晶材料 上。在利用钱刻法來去除切割損傷層（1〇)後，可以利用常壓化學 氣相沈積法（APCVD)在矽晶片表面產生氧化矽層（12)或使用其他 的氧化矽分離法，尤其是可利用低壓化學氣相沉積法（LPCVD)或 電漿辅助化學氣相沈積法（P_)或—熱氧化作用（thermal oxidation)等分離法來處理。 此外’矽晶片在氫氧化鈉（Na〇H，俗稱燒鹼）水溶液中腐蝕 (14) ’然後在氣化氫（HCL)水溶液中腐餘（16)〔該氣化氩（HC1) 溶於水而成的水溶液即是鹽酸〕。在&氧化鈉（Na〇H，俗稱燒驗） 水溶液中腐#(14)過程、在氣化氫（Ηα)水溶液中·⑽過程 以及以下有_實_所述的_過程，該氧化㈣係未受保護 地曝露於侧液。在此不會形成任何_，例如细塗料或電介 質（dielectrics)以便在蝕刻液中保護氧化矽層。因此，氧化矽 層係完全未受賴。然祕要求特雜造方域在製程允許情 形’尤其是在符合清洗要求時’糊上有可能，該氧切層至少 部份能阻抗㈣m而受到保護，例如利用適當的電介質 (dielectrics)〇 除了碎晶片如上所述可以在氫氧化納（_ί，俗稱燒驗）水 溶液中細⑷，織在氣化氫（Ηα)水溶液中雜⑽的方法 201027617 外，它也可以先在氫氧化納（Na0H，俗稱燒驗）水溶液中進行蝕 刻處理。矽晶片經過蝕刻處理後，需以去離子水清洗（18)。本發 明可以免除傳統的利用氫氟酸蝕刻的方式，使至少有部份的氧化 矽層仍能遺留在矽晶片上。其理由是有可能在一鹼性蝕刻液的蝕 刻過程中去除氧化矽層，而且在此以及在以下所述的所有實施例 係利用調整驗性蝕刻液之蝕刻率與腐蝕時間，使它不致於發生。 在所有的實施例可以有利地使用一驗性餘刻液，尤其是使用氧化 矽蝕刻率在每分鐘<25 nm的一種水溶性氫氧化鈉（Na〇H，俗稱燒 驗）或氫氧化钟（Κ0Η)溶液。在以去離子水清洗（⑻過程後，需 將矽晶片進行乾燥處理(20)。因為該矽晶片依據本發明方法至少 部份係屬親水性，其乾燥處理(2〇)過程較目前的傳統清洗方法更 為困難。原則上可採用目前已知的所有傳統乾燥方法。例如可使 用一乾燥氣體譬如氮氣，最好是利用額外的熱效應。 第二圖係表示本發明的另一實施例的示意圖，該實施例與第 一圖所表示的本發明的實施例不同的是，首先在去除切割損傷層 ® (10)後，利用濕式化學餘刻法在石夕晶片表面產生金字塔結構 (22)。此方法一般被稱為制絨触刻（texture etching) ^其另一 差異在於，該氧化石夕層在此係利用熱氧化效應在石夕晶片表面產生 氧化矽層（24)。此外，在此方法腐蝕矽晶片所使用的鹼性蝕刻液 為可由虱氧化鈉（NaOH ’俗稱燒驗）水溶液改以在氫氧化卸（koh) 水/合液中腐餘(26)。如第二圖所表示的本發明的實施例，其最終 乾燥處理(20)過程係採用脫水處理(28)方法。在此，該矽晶片例 如可以吊掛在一可旋轉的支架上。脫水處理（28)可以加速後續的 乾燥處理時間。 201027617 第三圖係表示本發明的另一實施例的示意圖，該實施例免除 了首先利用蝕刻法來去除切割損傷層（10)的製程而且與第二圖所 表示的本發明的實施例其製程有所區別。其他的區別是，其在氫 氧化鉀（Κ0Η)水溶液中腐蝕(26)，在氣化氫（HCL)水溶液中腐 餘（16)，於後續的以去離子水清洗（18)過程之後，接著係在氫氣 酸（HF)緩衝液中進行腐蝕(30)。在免除首先的切割損傷蝕刻製 程情形’此額外的在氫氟酸（HF)緩衝液中進行腐蝕（30)可以被 應用，俾能確實去除矽晶片上非常嚴重的污染。利用緩衝液來處 理’可以保證必要時’能部份去除在氫氟酸（HF)緩衝液中進行 腐蝕(30)過程所形成的氧化矽層。在使用緩衝液時需選擇氧化矽 的餘刻率每分鐘為<25 nm。在此，也可以使用經常被選擇的一充 分稀釋之氫氟酸的緩衝液來達成.顯然地也需配合適當的腐蝕時 間，以避免氧化矽層完全被去除。在氫氟酸（HF)緩衝液中進行 腐蝕(30)過程之後，接著需進行額外的以去離子水清洗(32)來去 除殘餘之氫氟酸的緩衝液。 第二圖所表示的實施例，不採用如第二圖所表示的實施例中 後續的脫水處理(28)製程，而以吹淨（blQwing)處理(34)方式取 代。在此，水份係機械式地利用一氣流往矽晶片吹淨。接下來是 進行矽晶片的乾燥處理(2〇)製程。 如第四圖所表示的實施例所使用的方法係大部份與第二圖所 表示的實關_。僅將在氫氧购⑽）水溶液中雜⑽改 為在氫氟酸ΟΠΟ緩衝液中進行雜⑽來取代。如在第三圖之 簡述所說明，需選擇適當的緩衝液、侧率和腐辦間，以便先 前所形成的氧化梦層在缝酸（HF)緩衝液中進行腐細)過程 201027617 八有4伤能被去除。在此’其適合的氧化矽層蝕刻率是每分鐘 nm°如此也可⑽證只遺留下充分稀釋之氫氟酸緩衝液尤其是 水洛性氯敗酸緩衝液’以便該溶液經常可以被用來選擇充當氫氟 酸緩衝液。 利用一氫氟酸緩衝液或利用一適當稀釋的氫氟酸緩衝液進行 蝕刻處理，例如在必須轉換至另一鹼性餘刻液中處理情形，有其 優點。其他的製程與如第二圖所表示的實施例的其他的製程相 同’請參考上述有關的說明。 ❿ 【®式辟細】 第一圖：本發明的第一實施例的示意圖 第二圖：本發明的第二實施例的示意圖 第三圖：本發明的第三實施例的示意圖 第四圖：本發明的第四實施例的示意圖 【主要元件符號說明】 · 〔本發明〕 (10)利用蝕刻法來去除切割損傷層 (12)利用常壓化學氣相沈積法（APCVD)在矽晶片表面產生 氧化矽層 (14)在氫氡化納（NaOH，俗稱燒驗）水溶液中腐餘 (16)在氯化氫（HCL)水溶液中腐蝕 (18)以去離子水清洗 (20)乾燥處理 (22)利用濕式化學触刻法在砍晶片表面產生金字塔結構 (24)利用熱氧化效應在矽晶片表面產生氧化矽層 13 201027617 (26)在氫氧化鉀（Κ0Η)水溶液中腐蝕 (28)脫水處理 (30)在氫氟酸（HF)緩衝液中進行腐蝕 (32)以去離子水清洗 (34)吹淨（blowing)處理 (36)在氩氟酸（HF)緩衝液中進行腐蝕201027617 VI. Description of the Invention: [Technical Field] The present invention relates to a method for oxidizing and cleaning a tantalum wafer as described in claim 1 of the patent application, and a solar cell produced by the method. [Prior Art] At present, most of solar cell manufacturing involves twinned solar cells. When manufacturing a solar cell, it is first necessary to produce a germanium wafer, a so-called wafer (Wafer).矽 Since the wafer is manufactured by cutting with a twin rod, the surface of the crystal structure during the cutting process is liable to cause serious damage, which may affect the performance of the produced solar cell. Therefore, the cutting damage layer must be removed, and etching is generally performed by etching. In the case of a wafer having a desired thickness processed by a twin-drawing method, the cutting process can save at least most of the cutting process. However, the surface of these so-called dream crystal materials is often contaminated to affect the performance of the solar cell produced by the material, and therefore, the first step is required. In addition to the above-mentioned etching to remove cutting damage or surface contamination defects, it is generally necessary to perform an additional or selective texturing process (also known as surface texturing process) on the surface of the chip to reduce direct light to the stone. Solar energy on the surface of the wafer - damage and increased matte cooperation of the solar cells produced. In industrial production, its surface pyramid structure (also known as pyramidal structure) is generally manufactured by wet chemical etching. (4) The tops of the topcoats 6 are transferred to a little gold. For the production of the solar moon, the daily film needs to be additionally diffused and Diffuse, and the tree wafer (10) is used for the purpose of forming a PN junction. p is: p 201027617 type semiconductor (acceptor) 'N means an N-type semiconductor (donor). The PN junction is also known as the P-N junction 'or depletion zone'. Since the diffusion treatment usually needs to be carried out at a temperature of 7 〇 (rc or more), at this temperature, the contamination residue on the surface of the stone wafer or the diffusion device is also diffused onto the wafer. Therefore, the texturing process (surface structure) The residual impurities generated after the chemical process will seriously affect the performance of the solar cells produced. Therefore, it is very important to clean the surface of the wafer before the diffusion bonding process. It is required that the wafer is sent to the diffusion device after the texturing process. It is to be cleaned. It is usually cleaned by wet chemical method. 'In principle, there are various cleaning methods that can be used. ® Industrial production of twinned solar cells, generally in the form of ruthenium wafers using metal oxidizing with acidic chemical solutions Before the treatment, the alkaline etching solution is first used for the rice cutting process, and then the silicon wafer is subjected to the rice etching process with an aqueous solution of hydrofluoric acid (HF). The cleaning process is generally performed by using water, usually using deionized water. In any case, The chopped wafer needs to be washed with deionized water after being treated with hydrofluoric acid. The purpose is to remove the stone wafer. The residual contaminant or acid residue may be at least diluted. As for the alkaline etching solution, potassium hydroxide or sodium hydroxide (caustic soda) φ solution is generally used. The crucible wafer is hydrofluoric acid or hydrofluoric acid. The main purpose of the solution etching is to remove the silicium oxide layer present on the surface of the tantalum wafer. The tantalum oxide layer may be formed in advance by a suitable production process, such as a wet chemical oxidation method, or the tantalum oxide layer. The so-called natural cerium oxide layer is usually formed by the surrounding environmental conditions of air oxidation. After removing the oxidized stone layer by using the wind septic acid, there will be a layer of hydrophobic dream crystal surface. Therefore, the next step is During the ionized water cleaning process, the water is removed from the surface of the crucible wafer, so that the Shixi wafer only leaves a small amount of deionized water or no deionized water residue and is allowed to be sent to the diffusion device. Therefore, the deionized water is produced. Contamination, such as the above-mentioned 201027617 dissolved pollution, can be clearly avoided in the diffusion equipment and thus can clearly not affect the production The performance of the solar cell. Therefore, the above-mentioned hydrophobic surface which utilizes hydrofluoric acid to produce a hydrophobic crystal is a conventional technique in the current industrial production of a twinned solar cell. It is impossible to eliminate the method of etching with hydrofluoric acid. Because it is assumed that at least part of the contamination brought into the diffusion tube will reach the diffusion device, and the silicon wafer which is later placed in the diffusion device, although previously washed with hydrofluoric acid, will still cause the germanium wafer to be contaminated and affect its normality. However, if the germanium wafer has a deuterated 7 layer and must be finely expanded, there will be _ because the oxidized dream layer will be removed by hydrofluoric acid during the cleaning process. Therefore, if the oxidation process is oxidized ◎ There are doped materials in the broken layer (4), and there are many lions in the surface scattered county. For example, in the existing diffusion process that is often used at present, if the diffusion of the doped material is to be used, it is necessary to use the defensive on the surface of the dream crystal. (d) Upon completion, the read-off produces an emitter with an electrical resistivity of 30 to 75 Ω/sq, enabling a resistivity between 200 Q/sq. The high resistivity of such an oxidized 7 layer is advantageous in improving efficiency if it still ensures good electrical contact with the solar cell and has a satisfactory lower resistance value. To this end, the paste oxidizes 7 layers to diffuse the dopant material to be advantageously applied in the production of selective emitters. SUMMARY OF THE INVENTION In view of the above, in order to overcome various problems of the above-described conventional techniques, the main object of the present invention is to provide a method for cleaning a film, and at least a portion of the chip has a layer of ruthenium oxide. This object can be achieved by the method of claim 1 of the present invention to achieve 0 201027617. Further, the subject matter of the present invention is a solar cell of the type described in claim 14. Other advantageous embodiments are the subject matter of the patent application scope of the present invention, respectively. ^The method of riding and washing has so far been thought that it is necessary to use a hydrogen Wei ship (HF_sQluti〇n) or a solution containing hydrofluoric acid to produce a hydrophobic surface. The method of engraving is necessary, and the transfer can be fully cleaned (4)# . _ It is fascinating that 'do not have to use hydrogen to __Japanese limb formation - the surface can also achieve a sufficient cleaning effect' to enable the production of solar cells with excellent performance. Thus, in accordance with the method of the present invention, the germanium wafer has an oxidized layer on at least a portion of the surface prior to etching. The remainder is further treated in an acidic solution containing oxidizable metal contaminants. Here, at least a portion of the oxidized layer of the solar cell is exposed unprotected to the heterogeneous solution. _ woven, ~ $ tablets need to be washed with deionized water. At least some of the unaffected oxidized _ layer will remain on the dream wafer. The dream wafer needs to be further dried after the cleaning process; ❹ silk is another invention of the invention—#_, the rare wafer needs to be treated side by side before the ion water cleaning, and at least part of the oxidation rhyme is not The protective ground is exposed to the residual liquid. This can improve the cleaning effect if necessary. Each __程, its non-weight ^ can be used during the cleaning process of each stage _ process. In order to (at) at least a portion of the at least heterogeneous unpourified oxidized Wei can remain on the tree wafer, at least the portion is hydrophilic (hydr〇phiUc) rather than hydrophobic (hyd_Qbic〇. Therefore, _ hydrofluoric acid containing solution To completely remove the oxidation (4), as in the conventional method of forming a non-hydrophobic surface, it is impossible. Therefore, it is impossible for the 201027617 to completely remove the yttrium oxide layer in the characterization process. Sexuality only exists in principle. In fact, the inspection (10) bribe does not occur when the stone is cleaned in the usual time. In accordance with the present invention, the etching rate and corrosion time of the alkaline etching solution can be guaranteed. It is not possible to completely oxidize the layer. Therefore, the wafer is at least partially exposed to hydrophilic conditions and needs to be dried after being washed with deionized water. Here, the drying treatment can be carried out by any method known at present. In addition, the etching operation using hydrofluoric acid can be substantially completely eliminated, and does not affect the performance of the produced solar cell. According to another advantageous embodiment of the present invention For example, the etching process of the dream wafer can be performed by hydrofluoric acid, especially _ money__ etch. According to another advantageous embodiment of the invention, the wafer can be formed into a layer of ruthenium oxide by gas phase separation. It can be treated by a low pressure chemical vapor deposition (LpcvD), atmospheric pressure chemical vapor deposition (APCVD) or plasma assisted chemical vapor deposition (pECVD) separation method. In addition, the oxidized hair layer is formed by wet thermal oxidation. If the oxidized stone layer formed on the tree wafer can be sufficiently surnamed during the cleaning process, the oxidized pin can in principle obtain a desired thickness. However, the longer the cleaning process, the finer the surface of the crystal, especially the long-term reaction of the secondary side. According to the other embodiment of the present invention, the oxidation # layer is ideally between 7Gnm and Moreover, the most desirable thickness is between 1 〇 nm and 70 nm (nm = nanometer). According to another embodiment of the present invention, the thickness of the yttrium oxide layer is in the etching process ratio. Use an illustrative hydroxide solution 201027617 solution (alkaline hydroxi De s〇luti〇n), especially a water-soluble alkaline hydroxide solution 'and most importantly is a recording or lL oxygen tilting solution. According to another embodiment of the invention, the alkaline etching solution The cerium oxide etch rate is < 25 nm per minute. This etch rate has proven to be reliable and advantageous in practical processing. According to another embodiment of the present invention, the dream wafer can be removed by wet chemical methods prior to processing the oxidized material. Butterfly damage. In the case of the known _ attack side method can be fine 'especially cut contact can be made - test hydroxide solution removal. In addition, strontium can also use acidic side liquid. Another advantage according to the present invention EXAMPLES The Shixi wafer is formed by a wet chemical method--pyramid structure (also referred to as pyramidal structure) on at least part of the surface of the Shihua wafer before processing the oxidized dream layer. In order to be able to form the pyramid structure by wet chemical methods, it is possible to use all known texturing etching solutions, especially an anionic or acidic texturing etching solution. After the cutting damage is removed by wet chemical methods, a gold column structure can be additionally or selectively formed by wet chemical methods. Another option for exempting the use of hydrofluoric acid is to additionally etch the Dream Crystals in a highly diluted or buffered hydrofluoric acid solution, and the oxygen chelate rate is <25 nm per minute. For example, there are advantages to using this method in situations where it is necessary to avoid the in-situ money engraving or in the case where it is necessary to remove the very thin cerium oxide (e.g., natural cerium oxide) present in each part. The etching time here obviously needs to match the etching rate. The above etching treatment using a highly diluted or buffered hydrofluoric acid solution may be combined with an acidic solution capable of oxidizing metal contaminants or etched in combination with an alkaline etching solution. The desired etching time of the germanium wafer in a hydrofluoric acid solution is less than one minute, and more preferably less than 30 seconds, preferably less than 15 seconds. 201027617 The method of the invention is particularly advantageous for the manufacture of solar cells. [Embodiment] Referring to the first figure, a schematic view of a first embodiment of the present invention "method according to this embodiment" is first performed by etching to remove the damage layer (10). Therefore, the method is particularly suitable for wafers cut by wafer rods. However, this method can be further applied to other twinned materials, for example, to thin film twins. After the cutting of the damage layer (1〇) by the money engraving method, the ruthenium oxide layer (12) may be generated on the surface of the ruthenium wafer by atmospheric pressure chemical vapor deposition (APCVD) or other ruthenium oxide separation method may be used, especially It can be treated by low pressure chemical vapor deposition (LPCVD) or plasma assisted chemical vapor deposition (P_) or thermal oxidation. In addition, the crucible wafer is etched in an aqueous solution of sodium hydroxide (Na〇H, commonly known as caustic soda) (14) and then rotified in a hydrogenated hydrogen (HCL) aqueous solution (16). The vaporized argon (HC1) is soluble in water. The resulting aqueous solution is hydrochloric acid]. In the & sodium oxide (Na〇H, commonly known as burning) aqueous solution in the ash # (14) process, in the hydrogenated (Ηα) aqueous solution · (10) process and below the _ process described in the _, the oxidation (four) Unprotected exposure to the side fluid. No _, such as fine coatings or dielectrics, is formed here to protect the ruthenium oxide layer in the etchant. Therefore, the yttrium oxide layer is completely unaffected. However, it is possible to require a special manufacturing domain to be in a process permitting condition, especially when it meets the cleaning requirements. The oxygen cut layer can be at least partially protected by (4) m, for example, by using appropriate dielectrics. As described above, the broken wafer can be fine (4) in an aqueous solution of sodium hydroxide (commonly known as calcination), and weaved in a solution (10) of a vaporized hydrogen (Ηα) aqueous solution, which can also be first in sodium hydroxide (Na0H, The etching process is commonly performed in an aqueous solution. After the wafer has been etched, it is rinsed with deionized water (18). The present invention eliminates the traditional use of hydrofluoric acid etching so that at least a portion of the hafnium oxide layer remains on the germanium wafer. The reason for this is that it is possible to remove the ruthenium oxide layer during the etching of an alkaline etchant, and in all of the embodiments described below, the etch rate and the etch time of the etchant are adjusted so that it does not occur. An all-in-one residual solution can be advantageously used in all embodiments, in particular a water-soluble sodium hydroxide (Na〇H, commonly known as a burn) or a hydrazine clock with an etch rate of ruthenium oxide at a temperature of <25 nm per minute. (Κ0Η) solution. After washing with deionized water ((8) process, the tantalum wafer is subjected to a drying treatment (20). Since the tantalum wafer is at least partially hydrophilic according to the method of the present invention, the drying treatment (2〇) process is more conventional than the current one. The cleaning method is more difficult. In principle, all conventional drying methods known at present can be used, for example a dry gas such as nitrogen can be used, preferably with additional thermal effects. The second figure shows a schematic representation of another embodiment of the invention. This embodiment differs from the embodiment of the present invention represented in the first figure in that, after removing the damage layer® (10), a pyramid structure is generated on the surface of the stone wafer by wet chemical remnant method (22). This method is generally referred to as texturing etching. Another difference is that the oxidized stone layer utilizes a thermal oxidation effect to produce a ruthenium oxide layer (24) on the surface of the stone wafer. The alkaline etchant used in the etching of the ruthenium wafer by this method can be changed from the sodium bismuth oxide (NaOH 'commonly known as burn test) aqueous solution to the sulphur (koh) water/liquid mixture (26). Express In an embodiment of the present invention, the final drying process (20) is performed by a dehydration process (28). Here, the crucible wafer can be suspended, for example, on a rotatable support. The dehydration treatment (28) can accelerate the subsequent process. Drying treatment time. 201027617 The third drawing shows a schematic view of another embodiment of the present invention, which eliminates the process of first removing the damage layer (10) by etching and the invention of the present invention represented by the second figure. In the examples, the process is different. The other difference is that it is corroded in aqueous solution of potassium hydroxide (26), and is sulphurized in aqueous solution of hydrogenated hydrogen (HCL) (16), followed by deionized water. After the cleaning (18) process, etching is carried out in a hydrogen acid (HF) buffer (30). This is done in a hydrofluoric acid (HF) buffer in the absence of the first cutting damage etching process ( 30) can be applied, can indeed remove very serious pollution on the germanium wafer. Use buffer to treat 'can guarantee if necessary' partial removal of corrosion in hydrofluoric acid (HF) buffer (30) form The ruthenium oxide layer. The residual rate of yttrium oxide to be selected when using the buffer is <25 nm per minute. Here, it can also be achieved by using a buffer of a sufficiently diluted hydrofluoric acid which is often selected. Obviously It is also necessary to match the appropriate etching time to avoid complete removal of the yttrium oxide layer. After the etching (30) process in hydrofluoric acid (HF) buffer, additional deionized water cleaning (32) is required to remove Residual hydrofluoric acid buffer. The embodiment shown in the second figure does not use the subsequent dehydration treatment (28) process in the example shown in the second figure, but is blQwing (34). Instead of the method, the water is mechanically blown off the silicon wafer by a gas stream. Next is the drying process (2〇) of the tantalum wafer. The method used in the embodiment shown in the fourth figure is substantially the same as that shown in the second figure. Only the hetero (10) in the aqueous (10)) aqueous solution was replaced with a hetero (10) in a hydrofluoric acid buffer. As explained in the brief description of the third figure, it is necessary to select the appropriate buffer, side rate and rot, so that the previously formed oxidized dream layer is spoiled in the sulphonic acid (HF) buffer. 4 injuries can be removed. Here, the etch rate of the suitable ruthenium oxide layer is nm° per minute. (10) Only a sufficiently diluted hydrofluoric acid buffer, especially hydrolose chlorpyrifos buffer, is left behind so that the solution can often be used. To choose to act as a hydrofluoric acid buffer. The use of a hydrofluoric acid buffer or an etch treatment with a suitably diluted hydrofluoric acid buffer, for example in the case of having to switch to another alkaline retentate, has advantages. The other processes are the same as the other processes of the embodiment shown in the second figure. Please refer to the above related description.第一 ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® BRIEF DESCRIPTION OF THE FOURTH EMBODIMENT OF THE INVENTION [Description of Main Components] [Invention] (10) Removal of a dicing damage layer by etching (12) is produced on the surface of a ruthenium wafer by atmospheric pressure chemical vapor deposition (APCVD). The ruthenium oxide layer (14) is etched in an aqueous solution of hydroquinone (NaOH, commonly known as calcination) (16) in an aqueous solution of hydrogen chloride (HCL) (18) washed with deionized water (20) dried (22) utilized Wet chemical lithography produces a pyramidal structure on the surface of the chopped wafer (24) uses a thermal oxidation effect to produce a yttrium oxide layer on the surface of the ruthenium wafer. 201027617 (26) Corrosion in aqueous solution of potassium hydroxide (28 Å) (28) Dehydration treatment (30) Corrosion in hydrofluoric acid (HF) buffer (32) Deionized water cleaning (34) Blowing treatment (36) Corrosion in argon fluoride (HF) buffer