201245417 六、發明說明： 【發明所屬戈^技術領域】 本發明係有關於用於製造經紋理化矽基板（更詳細地 說，矽晶圓（Si晶圓）)的方法。 L· 太陽能電池之前表面及後表面的光損耗為太陽能電池 内之主要損耗機制之一。一方面，該等損耗為起因於外施 金屬噴鍵的遮蔽損耗’而另一方面係為反射損耗。 然而’光彳貝耗不僅發生於該表面。於自光學上更稠密 介質（矽）至光學上較稀薄介質（EVA空氣）的過渡區，不需要 一電子-電洞對之激發，光可離開該太陽能電池。其尤其適 用於長波長光。因此，確保光在該後表面上反射而非使該 該光未經利用地逃逸是絕對必要的。本發明之一般目標為 減在該前表面上的反射損耗並增強在該後表面上的反射以 提供一可顯著降低製造成本之方法。自最新技術可知將石夕 基板紋理化可以使反射損耗減至最小。具有一大於3〇。的傾 角之表面結構可以使該反射光第二次撞擊該石夕表面。此等 結構通稱為紋理。 自最新技術已知有許多種用於產生紋理的方法。基本 上’自最新技術可知有4種用於產生紋理的其它可採用之方 法，亦即單晶矽的驗性紋理化、多晶矽的酸性紋理化、多 晶矽的電漿紋理化、及使用選擇性遮罩蝕刻磨耗所進行的 紋理化。而且’已知可借助於催化反應而增強上文列舉的 方法之其它可採用的方法。 201245417 在該驗性紋理化步驟中，係使單晶石夕進行驗性敍刻方 法。在本方法内，主要疋⑽相對於(_方向而傾斜5〇 的{111}表面。可藉驗(諸如氫氧化钟或氮氧化納）而進行對 於财表面的侵敍。更詳細地說，該等方法之缺點在單曰 很昂貴且由於該餘刻侵餘的異向性質，所以該驗性餘刻法 並不適用於多晶石夕。而且，該驗性纹理化需要很長的加工 時間（高至20分鐘）。 在該酸性紋理化步驟中，照例，係藉使用氫IL酸、石肖 酸、硫酸或填酸之水性溶液進行㈣。石夕與石肖酸及氮氣酸 之反應可形成氧化氮。本質上，本氣泡之形成會導致該表 面的粗縫化。高黏性鑛酸(尤其硫酸）的添加會促進小氣泡的 形成，並因此導致該Si表面變得更粗輕。此等钱刻混合物 之-主要缺點為在祕刻方法進行期間的快速消耗。本情 況會導致很高的供應及處理費用。另—缺點為如在，例如 DE 1〇3 20 212 A1内所述之在該砂晶圓之前及後表面上進 行的蚀刻紐。本情況會大大地降低該後表面上之反射 率，其會導致長波長光區域的光損耗。該等向性触刻劑可 侵襲該等多晶晶B)之尤其具有—結晶狀缺_部位。此等 謂鑛齒形損壞，亦即卿晶内之小裂痕及裂縫， 八專係藉5亥矽晶内之矽柱的拉鋸而產生。 ^真空氣氛内進行該f料刻法嘯據該另外可採用 吏用製程氣體，諸如响。該等 文、點為昂貴的真空技術及該系統的非腐钱構形。就 本文而卜該表面會藉該電毁的高能粒子而損壞且可產生 201245417 復&中心。έ亥復合中心會抵消該正性紋理化效應。 在該選擇性遮罩蝕刻法中，係產生類似一蜂巢或倒轉 金子塔的結構。通常，該等方法先後涵蓋一遮罩法、該遮 罩之似點的開啟、蝕刻及洗淨。已知使用一SiN層進行遮罩 且使用雷射開啟遮罩的方法。係等向性或異向性進行該後 、.-i触刻法。可藉強底触刻或第二飯刻法而移除該遮罩。 由於該附加製程步驟，所以該等方法亦具有以下缺 點.不能調和高有效紋理化作用及低製造成本。 最後，已知其中金屬顆粒係首先沈積在一矽晶圓的該 表面上’並接著進行該矽基板的表面之蝕刻的方法。因此， 該等沈積金屬顆粒可作為催化劑。 此種方法係描述在，例如De 1〇3 92 752 T5中。在這一 點上，金屬顆粒錢積在财基板上且接著使用氫氟酸及 過氧化氫進行_法。在進行料步驟前，自钟基板之 表面移除自然氧化物。藉將該㈣晶圓分職漬入該催化 劑溶液及_溶液Μ進行處置。描述在該文件内之該方 法有各種缺點。因此，更壯地說，藉浸潰人各該溶液内 而進行該等石夕晶圓之處置且因此在兩表上進行之姓刻侵蚀 會導致光彳祕。而且，該侧步驟的長製程時間為該等方 法之主要缺點。可移除自然氧化物之該表面的初洗淨之 額外製私步驟亦顯著增加成本及製程時間。 【韻^明内容^】 本心明之一目標為提供用於製造經紋理化石夕基板（更 詳細地，發晶ID)的方法，其可去除最難賴則的缺點。 201245417 本目標係藉於開始時所列舉的類型之方法而達成，該 方法包括以下製程步驟： a) 施加一含金屬離子之水性催化劑溶液至該矽基板之一表 面上； b) 以一含至少一氧化劑的酸性及/或鹼性蝕刻溶液處置該 碎基板。 與已知方法比較，本發明之方法具有各種優點。施加 該水性催化劑溶液至矽晶圓之一表面上的步驟，亦即該催 化劑溶液之空間上受限的選擇性施加可產生以下效應：在 後續蝕刻方法内，該矽晶圓之僅一表面經紋理化。即便該 蝕刻法内之矽晶圓完全浸潰在該蝕刻溶液内，亦僅蝕刻該 矽晶圓之一表面，因為蝕刻步驟僅在金屬顆粒已呈金屬團 簇的形式沈積的位置發生。在一表面上所進行之此種蝕刻 步驟可防止該晶圓之後表面上的反射率降低，因此亦可防 止該長波長光體系内的光損耗。 亦可使用局部受限方式將該催化劑溶液施加至一.表面 上。使用這種方法可確保，例如紋理化作用不會發生在匯 流排(busbar)/指形零件（finger)之下方。 本發明的方法因此可在一旦將該等矽片完全浸潰入該 I虫刻溶液内，在一表面上進行石夕晶圓的紋理化，且不需要 遮罩法及如有關於該钱刻系統之特殊需求。而且，不依賴 結晶學定向（包含該[111]晶體定向）且不管該表面是否有鋸 齒狀損壞，本發明可以使矽晶圓進行等向性紋理化。 該催化劑溶液内所含的該等金屬離子係呈元素金屬奈 201245417 米團簇的形式沈積在該矽表面上。可預期使用銀（例如 AgN〇3)、链（例如H^PtCl6)、絡、銅或金作為金屬離子。然 而，在一更特佳的其它可採用的方法中，該等金屬離子為 纪離子’其中所使用該鹽較佳為PdCl”本發明者已發現 PdCl2尤其能更有效地將纪離子沈積在一石夕表面上。亦已發 現把奈米團簇可顯著減少製程時間。而且，pd之使用可以 於環境溫度下進行蝕刻。 通常，該催化劑溶液含有HF。然而，亦可首先將該基 板浸入HF溶液内以移除自然氧化物，並接著在一表面上經 該催化劑溶液處置。 通常，在進行水清洗及乾燥程序後，該等金屬顆粒仍 然黏附於該基板表面。照例，在本發明内係使用非標準矽 材料’諸如線帶（String Ribbon)太陽能電池。 除了 HF外，該含金屬離子之催化劑溶液亦較佳包含 HC1。更詳細地說’該較佳的氣化把之使用需要hci，因為 氯化鈀僅難溶於水中。 該等把奈米團簇沈積後，可進行水清洗程序。該清洗 程序之目的為調節該矽基板上之該等鈀顆粒的濃度，因此 也可調節後續姓刻反應的強度。可藉改變該催化劑溶液内 之亂化I巴濃度而獲得一類似效應。 本發明方法之一特別優點為在製程步驟a)内，係兼進 行自該秒基板之表面移除自然氧化物的步驟（較佳藉該含 H F之催化劑溶液或藉一先前經η F處置的步驟）及使金屬奈 米顆粒（尤其把奈米顆粒）沈積在該矽基板之表面上的步 201245417 驟。該同時自矽基板之表面移除自然氧化物及使金屬顆粒 沈積的步驟可大大地簡化並縮短整個製程^已認為自然氧 化物可被視為該石夕基板一兰暴露於正常環境空氣時所形成 的氧化物。 有利的是，可藉噴塗、溢流、過度模製、滾輪塗佈法、 槽孔喷嘴塗佈法、滑動膜喷嘴塗佈法或刮刀塗佈法而將該 催化劑溶液施加至該矽基板之一表面上。該等列舉方法可 乾淨地將該催化劑溶液施加至矽晶圓之一表面上。 照例，該催化劑溶液含有約0.1至10% HF、約0.1至10% HC1及約1毫克至1〇〇毫克/升PdCl2。 有利的是，該酸性蝕刻溶液含有作為氧化劑之^11?及/ 或NHaF及H2〇2及/或NHO3。所列舉該等物質業經證明可特 別有效地用於該矽表面的蝕刻且尤其就清理而言，相對上 不成問題（與，例如硫酸及磷酸比較 自5玄催化劑溶液所沈積之該等金屬顆粒較佳具有0.5 奈米至100奈米的大小且較佳彼此以介於㈣米與5微米間 的距離經沈積。經㈣大小及距離之關係，最終可以使一 矽基板進行特別有利且有效的蝕刻。 ^幸乂佳的其它可採用方法之特徵為製程步驟C)，其中 ，以—鹼性溶液、較佳KOH溶液、詳細地說，10%濃K0H 冷液’處置财基板。經由所列舉製程步驟e)，可移除由 於非所欲製程條件所產生的多孔⑦。而且，歸性溶液可 在該矽材料内進行異向性蝕刻。 在該製程步驟c)之後，可接著進行中和步驟，其中係 201245417 使用酸(例如η α)進行處置。在這一點上，亦自該晶圓移除 金屬及有機雜質。 在一軚佳的其它可採用之方法中，係使該欲經處置的 石夕基板進行_步驟b)，f時至多45秒 '較佳約赚35秒。 與自最新技術所知的方法比較，該短_時間為另 一優點。 【實施方式】 實施及結果 1.紋理化 以氫氟酸、氫氯酸以及氯化把的水性溶液處置一具有 180+/-5微米之厚度及_5〇毫米之大小的線帶晶圓之一表 面其後在氫氟酸(50%濃度）：硝酸(69%濃度）：H20(體 積4 · 1 · 2)之酸性溶液内進行短⑽】程序，費時斯少以產 生〃有_4微米之厚度的多孔石夕層。事實上，雖然此種酸 性溶液的侵襲性报強，但是並不能似卜未具有作為催化 知丨之金屬顆粒且無鑛齒狀損壞的⑪表面。其可確認該把的 催化效力。 在濃氫氧化卸溶液内進行該石夕晶圓之最終處置步驟期 間’該表峨理_料切狀祕而形成。 發第1^圖表7F該具有5()至奈米之大小的把奈米顆粒 之掃描式電子彡像。經—含lUblG之催化劑溶液處置 30秒後’自該具有1〇8届半_2 __ 令 厘未之團簇密度的氣化鈀溶液，該 兀素鈀沈積在該線帶晶圓上。 ^ )圖表不先後在Pdcl2溶液内進行上述活化法及在 水性HF/HN〇3溶浓肉、任/ 夜内進仃蝕刻法(蝕刻時間：35秒)後的該線 201245417 帶晶圓。經由該姓刻法，可形成一具有小於1微米直徑之多 孔表面結構。如上文已揭示，該等把顆粒並不會直接與該 石夕基板或該钱刻溶液反應，但會下沈入藉該活化酸性溶液 而形成的大孔内。 第1 c)圖表示經數氧化奸最終處置後之最終紋理形 態。該氫氧化鉀首先會移除該多孔表面結構，然後藉異向 性蝕刻而形成具有1至3微米直徑的半球狀壓痕。 第2圖表示在波長λ[奈米]範圍内，線帶晶圓及經催化劑 協助蝕刻（“金屬協助性蝕刻”“MAE”)太陽能電池的表面反 射率R[%]降低。藉在自400奈米至1000奈米之波長區域内， 比較一 Α Μ 1，5 G太陽能照射之總反射率R ( Λ )與太陽能照射 通量(Nph)而計算有效反射率Reff。與具有3%之平 坦未紋理化晶圓的曲線01比較，在整個波長區域内，具有 曲線02之該等MAE紋理化晶圓可顯著地將該反射率降至 Reff=22‘7%。具有氮化石夕抗反射塗覆物之MAE紋理化晶圓的 有效反射率Reff=9.7%(曲線〇3)比具有Reff=11.6%之未紋理 化晶圓（曲線04)低很多。該MAE紋理化作用尤其可降低藍 色及紅色波長區域内的反射率。就波長；1>1〇〇〇奈米而言， 該較低的反射率表示該照射之較高的無規化等級，因此， 表示該材料内之一較長光程。 2.太陽能電池 所使用原料為具有180+/-5微米之厚度及80x150亳米2 之大小的p型雜摻線帶晶圓。就該催化性金屬沈積法而言， 亦使用氫氟酸、氫氣酸及氯化鈀溶液。在一最終步驟内， 10 201245417 係藉氫氧化鉀而移除最上之多孔矽層且重構該表面。紋理 化作用後，最後進行經HC1處置的步驟，繼而進行尺匸八清潔 步驟以移除金屬及有機雜質。最後，使該等晶圓進行標準 工業太陽能電池製造方法。使用P〇C13在一石英管内形成一 60歐姆/叫.之發射體。借助於PECVD施加一具有欲經最佳化 以成為不同表面形態之層厚度的氮化矽抗反射層。經由使 用該網板印刷法，施加該銀前金屬喷鍍法及該鋁後表面金 屬喷鍍法。藉共燒製及雷射邊緣分離而完成該等太陽能電 池的製造。 表1代表在各情況下，自2組（亦即一具有MAE紋理之組 及一未經紋理化之參考組）共8個電池的電流/電壓特徵（於 p。pt=loo毫瓦/厘米2及τ=25。c下之經校正為ISE值的内部測 定值)獲得之電值。與該參考組比較之該經紋理化電池的相 當減少之反射率可以使短路電流密度Jsc增加(△〗％=+〇 9毫 安培/厘米2)。平均開路電壓ν。。幾乎維持相同位準。 該開路電壓之小減少可被歸因於該等經紋理化電池的 增加之表面積，且鈀污染可導致VQC之強烈降低。該經紋理 化表面可以使該銀前金屬噴塗之更佳接點形成， 因此可以 使填充因數FF增加（AFF=+〇.7%abs)。總之，該MAE紋理可 以使平均效率η增加4abs)。 第3圖表示未經紋理化及MAE紋理化線帶太陽能電池 的量子效率。該幾乎相等的内部量子效率TqE表示該等太陽 能電池之類似的電子品質且顯示一類似的體積電荷載體壽 °P °就波長λ <6〇〇奈米而言，該等MAE紋理化電池之增加 201245417 的内部量子效率EQE係起因於該減少的前表面反射率且可以 使短路電流密度jsc增加(△JscwOS毫安培/厘米2)。在7〇〇奈 米<久<1200奈米之波長區域内的相等IQE顯示一相等的材 料品質，因此，表示鈀污染不存在。顯著的鈀污染之存在 可導致一增加的電荷載體污染，因此會惡化該電荷載體壽 命。 3. 太陽能模組 該等太陽能電池之增加的效率主要起因於在藍光波長 區域λ <600奈米内之光子的增加獲得。因此產生以下問 通·本增益在該等太陽能電池封裝入太陽能模組内之後， 是否可持續。 第4圖表示封裝在窗玻璃、EVA_箔、及泰德拉(Tedlar) 後v自内之線γ太1¼能電池、串焊(strjngs)及單電池模組的短 路電流岔度Jsc(於Ρ〇ιη=ι〇〇毫瓦/厘米2下之内部測定值太陽 能電池數據經校準至ISE值；串焊及模組··僅電池表面積照 明，Τ_ 25 C)。由於增強的光叙合，所以經紋理化太陽能 電池可得到一短路電流密度Jsc(AJsc=+〇 2毫安培/厘米2，而 未紋理化電池釋放!毫安培/厘来2。目此，該等經封 裝的MAE紋理化電池可另外得到Δη=+〇1%如，其可得到增 加的效率。 4. 結論 金屬協助的姓刻法可以使無鑛齒狀損壞結晶型石夕表面 不考慮結晶學定向而進行快速且均⑽紋理化。與未經紋 理化線電池比，由於短路電流密度增加(△〗％=+〇 9201245417 VI. Description of the Invention: [Technical Field] The present invention relates to a method for manufacturing a textured ruthenium substrate (more specifically, a ruthenium wafer (Si wafer)). The optical loss on the front and back surfaces of L· solar cells is one of the main loss mechanisms in solar cells. On the one hand, these losses are due to the shielding loss of the external metal spray bond and on the other hand the reflection loss. However, the light mussel consumption does not only occur on the surface. In the transition from an optically denser medium (矽) to an optically thinner medium (EVA air), an electron-hole pair excitation is not required and light can exit the solar cell. It is especially suitable for long wavelength light. Therefore, it is absolutely necessary to ensure that light is reflected on the rear surface rather than allowing the light to escape unutilized. A general object of the present invention is to reduce the reflection loss on the front surface and enhance the reflection on the back surface to provide a method that can significantly reduce manufacturing costs. From the latest technology, it is known that texturing the stone substrate can minimize reflection loss. Has a greater than 3 〇. The angled surface structure allows the reflected light to strike the surface of the stone for a second time. These structures are commonly referred to as textures. A variety of methods for producing textures are known from the latest technology. Basically, from the latest technology, there are four other methods that can be used to create textures, namely, the qualitative texturing of single crystal germanium, the acid texturing of polycrystalline germanium, the plasma texturing of polycrystalline germanium, and the use of selective masking. The mask is etched and the texture is textured. Moreover, other methods which are known to enhance the above-listed methods by means of catalytic reactions are known. 201245417 In this qualitative texturing step, a single crystal stone is subjected to an experimental characterization method. Within the method, the main enthalpy (10) is inclined to the {111} surface of 5 相对 with respect to the _ direction. The intrusion of the financial surface can be performed by a test (such as a hydrazine clock or a nitrogen oxynitride). In more detail, The disadvantages of these methods are that they are expensive and because of the anisotropic nature of the residual, the incumbent residual method is not suitable for polycrystalline stone. Moreover, this texture requires a long processing. Time (up to 20 minutes). In the acid texturing step, as usual, using an aqueous solution of hydrogen IL acid, salicia acid, sulfuric acid or acid (4). Reaction of Shixi with tartaric acid and nitrogen acid Nitric oxide can be formed. Essentially, the formation of the bubble causes coarsening of the surface. The addition of highly viscous mineral acid (especially sulfuric acid) promotes the formation of small bubbles and thus causes the Si surface to become thicker and lighter. The main disadvantage of such a mixture is the rapid consumption during the process of the secret engraving. This situation leads to high supply and handling costs. Another disadvantage is that, for example, in DE 1〇3 20 212 A1 Said on the front and back surfaces of the sand wafer Etching the enamel. This situation greatly reduces the reflectivity on the back surface, which can result in optical loss in the long wavelength light region. The isotropic etchant can attack the polycrystalline crystals B) especially having a crystalline Missing _ parts. These are the damage of the ore tooth shape, that is, the small cracks and cracks in the crystal, and the eight specialties are produced by the sawing of the mast in the 5 矽 矽 crystal. ^ The f-making method is carried out in a vacuum atmosphere, and it is additionally possible to use a process gas such as a ring. These articles, points are expensive vacuum techniques and the non-corruption configuration of the system. As far as this is concerned, the surface will be damaged by the electrically destroyed high energy particles and can produce the 201245417 Complex & Center. The έ海 composite center will offset this positive texturing effect. In the selective mask etching method, a structure similar to a honeycomb or an inverted gold tower is produced. Typically, such methods cover a masking method, the opening of the mask, the etching and cleaning. A method of masking with a SiN layer and using a laser to open the mask is known. The isotropic or anisotropic behavior is followed by the .-i lithography. The mask can be removed by strong bottom or second meal. Due to this additional process step, these methods also have the following disadvantages: they cannot reconcile high effective texturing and low manufacturing costs. Finally, a method is known in which metal particles are first deposited on the surface of a germanium wafer and then etching the surface of the germanium substrate. Therefore, the deposited metal particles can serve as a catalyst. Such a method is described, for example, in De 1 〇 3 92 752 T5. At this point, the metal particles are accumulated on the financial substrate and then subjected to hydrofluoric acid and hydrogen peroxide. The natural oxide is removed from the surface of the clock substrate before the material step. The (4) wafer is divided into the catalyst solution and the _ solution for disposal. The method described in this document has various drawbacks. Therefore, more strongly, the treatment of such a ray wafer by immersing each of the solutions in the solution and thus the erosion of the surname on the two tables can lead to light shackles. Moreover, the long process time of this side step is a major drawback of these methods. The extra-private steps of the initial wash of the surface from which the native oxide can be removed also significantly increase the cost and process time. [Rhyme content] One of the goals of the present invention is to provide a method for fabricating a textured fossil substrate (more specifically, a crystallographic ID) that removes the most difficult drawbacks. 201245417 The object is achieved by a method of the type listed at the outset, which comprises the following process steps: a) applying an aqueous catalyst solution containing metal ions to one surface of the crucible substrate; b) containing at least one An acidic and/or alkaline etching solution of an oxidizing agent treats the broken substrate. The method of the present invention has various advantages as compared to known methods. The step of applying the aqueous catalyst solution to one surface of the tantalum wafer, that is, the spatially limited selective application of the catalyst solution, can have the effect that, in a subsequent etching method, only one surface of the tantalum wafer passes through Textured. Even if the germanium wafer in the etching process is completely immersed in the etching solution, only one surface of the germanium wafer is etched because the etching step occurs only at a position where the metal particles have been deposited in the form of metal clusters. Such an etching step performed on a surface prevents a decrease in reflectance on the surface of the wafer, and thus also prevents light loss in the long-wavelength light system. The catalyst solution can also be applied to a surface using a locally limited manner. Using this method ensures that, for example, texturing does not occur below the busbar/finger. The method of the present invention can therefore perform the texturing of the Shixi wafer on a surface once the ruthenium sheets are completely immersed into the I-spotting solution, and no masking method is required and if the money is engraved The special needs of the system. Moreover, the present invention allows the germanium wafer to be isotropically textured without relying on crystallographic orientation (including the [111] crystal orientation) and regardless of whether the surface is sawtoothed. The metal ions contained in the catalyst solution are deposited on the surface of the crucible in the form of an elemental metal naphthalene 201245417 m cluster. It is expected to use silver (for example, AgN〇3), a chain (for example, H^PtCl6), a complex, copper or gold as a metal ion. However, in a more preferred alternative method, the metal ions are selected as the PdCl in which the salt is used. The inventors have found that PdCl2 is particularly effective in depositing ions into a stone. On the surface of the eve, it has also been found that nano-clusters can significantly reduce the process time. Moreover, the use of pd can be etched at ambient temperature. Typically, the catalyst solution contains HF. However, the substrate can be first immersed in an HF solution. Internally removing the natural oxide and then disposing it over the surface of the catalyst solution. Typically, after the water washing and drying process, the metal particles still adhere to the surface of the substrate. Non-standard tantalum material 'such as String Ribbon solar cell. In addition to HF, the metal ion-containing catalyst solution preferably also contains HC1. More specifically, the preferred gasification requires hci because it is used because Palladium chloride is only difficult to dissolve in water. After depositing the nanoclusters, a water cleaning procedure can be performed. The purpose of the cleaning procedure is to adjust the substrate on the substrate. The concentration of the palladium particles, and thus the intensity of the subsequent surname reaction, can be adjusted by changing the concentration of the chaotic I bar in the catalyst solution. One of the particular advantages of the method of the invention is that in process step a) And the step of removing the natural oxide from the surface of the substrate (preferably by the HF-containing catalyst solution or by a step previously treated by η F) and the metal nanoparticles (especially the nano particles) Step 201245417 deposited on the surface of the tantalum substrate. The step of simultaneously removing the native oxide from the surface of the tantalum substrate and depositing the metal particles can greatly simplify and shorten the entire process ^ It is considered that the natural oxide can be regarded as The oxide formed by exposure of the ambient light to the normal ambient air. Advantageously, it can be applied by spraying, overflowing, overmolding, roller coating, slot nozzle coating, and sliding film nozzle coating. The catalyst solution is applied to one surface of the tantalum substrate by a method or a doctor blade coating method. The enumerated methods can cleanly apply the catalyst solution to one surface of the tantalum wafer. For example, the catalyst solution contains from about 0.1 to 10% HF, from about 0.1 to 10% HCl, and from about 1 mg to about 1 mg/L PdCl2. Advantageously, the acidic etching solution contains oxidant as an oxidizing agent and/or NHaF and H2〇2 and/or NHO3. The listed materials have proven to be particularly effective for the etching of the surface of the crucible and, in particular, for cleaning, are relatively unproblematic (compared with, for example, sulfuric acid and phosphoric acid from 5 Xuan The metal particles deposited by the catalyst solution preferably have a size of from 0.5 nm to 100 nm and are preferably deposited with each other at a distance of between (4) and 5 microns. The relationship between (4) size and distance can ultimately A particularly advantageous and effective etching of the substrate is carried out. ^Other good methods are characterized by a process step C) in which an alkaline solution, preferably a KOH solution, in detail, a 10% thick K0H cold Liquid 'disposal of the financial substrate. Via the enumerated process step e), the porous 7 produced by the undesired process conditions can be removed. Moreover, the homeostatic solution can be anisotropically etched within the tantalum material. Following the process step c), a neutralization step can then be carried out in which the system 201245417 is treated with an acid such as η α. At this point, metals and organic impurities are also removed from the wafer. In a preferred alternative method, the stone substrate to be treated is subjected to _step b), and f is at most 45 seconds, preferably about 35 seconds. This short_time is another advantage compared to the method known from the latest technology. [Embodiment] Implementation and Results 1. Textured with a hydrofluoric acid, hydrochloric acid and chlorinated aqueous solution to treat a wire wafer having a thickness of 180 +/- 5 microns and a size of _5 〇 mm A surface is then subjected to a short (10) procedure in an acidic solution of hydrofluoric acid (50% concentration): nitric acid (69% concentration): H20 (volume 4 · 1 · 2), with less time to produce 〃4 μm The thickness of the porous stone layer. In fact, although the invasiveness of such an acidic solution is strong, it does not seem to have an 11 surface which is a metal particle which is catalytically known and has no orthodontic damage. It confirms the catalytic efficiency of the catalyst. During the final treatment step of the Shihua wafer in the concentrated hydrogeno-decomposition solution, the surface is formed. The first image 7F shows a scanning electron image of nanoparticle having a size of 5 () to nanometer. After 30 seconds of treatment with a catalyst solution containing lUblG, the vaporized palladium solution having a cluster density of 1 〇 8 1/2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ^) The chart was not subjected to the above activation method in the PdCl2 solution and the line 201245417 with wafer after the aqueous HF/HN〇3 dissolved meat and the overnight/night etching method (etching time: 35 seconds). By this surname method, a porous surface structure having a diameter of less than 1 micrometer can be formed. As has been disclosed above, the particles do not directly react with the slab or the solution, but sink into the macropores formed by the activated acidic solution. Figure 1 c) shows the final texture state after the final disposal of the oxidized rape. The potassium hydroxide first removes the porous surface structure and then forms an hemispherical indentation having a diameter of 1 to 3 microns by anisotropic etching. Figure 2 shows the reduction in the surface reflectance R [%] of the tape wafer and the catalyst assisted etching ("metal assisted etching" "MAE") solar cell in the wavelength λ [nano] range. The effective reflectance Reff is calculated by comparing the total reflectance R ( Λ ) of a solar radiation of 1 5 1, 5 G with the solar radiation flux (Nph) in a wavelength range from 400 nm to 1000 nm. Compared to curve 01 having 3% of flat untextured wafers, such MAE textured wafers having curve 02 can significantly reduce the reflectance to Reff = 22 ' 7% over the entire wavelength region. The effective reflectance of the MAE textured wafer with the nitrided anti-reflective coating was Reff = 9.7% (curve 〇 3) much lower than the untextured wafer (curve 04) with Reff = 11.6%. This MAE texturing particularly reduces the reflectance in the blue and red wavelength regions. In the case of wavelengths; 1 > 1 nanometer, the lower reflectivity indicates a higher degree of randomization of the illumination and, therefore, represents a longer optical path within the material. 2. Solar Cell The raw material used was a p-type hybrid wire wafer having a thickness of 180 +/- 5 microns and a size of 80 x 150 mm 2 . For the catalytic metal deposition method, hydrofluoric acid, hydrogen acid and palladium chloride solution are also used. In a final step, 10 201245417 removes the uppermost porous layer by potassium hydroxide and reconstructs the surface. After the texturing, the HC1 treatment step is finally performed, followed by a ruler cleaning step to remove metal and organic impurities. Finally, the wafers are subjected to standard industrial solar cell manufacturing methods. A 60 ohm/called emitter was formed in a quartz tube using P〇C13. A tantalum nitride antireflection layer having a layer thickness to be optimized to be a different surface morphology is applied by means of PECVD. The silver front metallization method and the aluminum back surface metallization method are applied by using the screen printing method. The manufacture of such solar cells is accomplished by co-firing and laser edge separation. Table 1 represents the current/voltage characteristics of a total of 8 cells from 2 groups (i.e., a group with MAE texture and an untextured reference group) in each case (at p.pt = loo milliwatts/cm) 2 and τ = 25. The internal value obtained by correcting the internal measured value of the ISE value under c). A substantially reduced reflectivity of the textured battery compared to the reference set can increase the short circuit current density Jsc (Δ]% = + 〇 9 mA/cm 2 ). Average open circuit voltage ν. . Almost the same level is maintained. This small reduction in open circuit voltage can be attributed to the increased surface area of the textured cells, and palladium contamination can result in a strong decrease in VQC. The textured surface allows for better joint formation of the silver front metal spray, thereby increasing the fill factor FF (AFF = + 〇. 7% abs). In summary, the MAE texture can increase the average efficiency η by 4 abs). Figure 3 shows the quantum efficiency of untextured and MAE textured line solar cells. The nearly equal internal quantum efficiency TqE represents a similar electronic quality of the solar cells and exhibits a similar volumetric charge carrier lifetime. The wavelength of λ < 6 nanometers, the MAE textured battery Increasing the internal quantum efficiency EQE of 201245417 is due to the reduced front surface reflectance and can increase the short circuit current density jsc (ΔJscwOS milliamperes/cm 2 ). An equivalent IQE in the wavelength range of 7 〇〇 nanometer <1 il<1200 nm shows an equal material quality, and therefore, indicates that palladium contamination does not exist. Significant palladium contamination can result in an increased charge carrier contamination, thus deteriorating the charge carrier lifetime. 3. Solar Modules The increased efficiency of these solar cells is mainly due to the increase in photons in the blue wavelength region λ < 600 nm. Therefore, it is believed that the following gains are sustainable after the solar cells are packaged in the solar module. Figure 4 shows the short-circuit current Jsc of the γ-too 11⁄4 battery, series welding (strjngs) and single-cell modules packaged in window glass, EVA_foil, and Tedlar. Ρ〇ιη=ι〇〇 milliwatts/cm2 of internal measured solar cell data calibrated to ISE value; series soldering and module ··only battery surface area illumination, Τ _ 25 C). Due to the enhanced light recombination, the textured solar cell can achieve a short circuit current density Jsc (AJsc = + 〇 2 mA / cm 2 , while the untextured battery is released! mA / PCT 2). The encapsulated MAE textured battery can additionally obtain Δη=+〇1%, for example, which can increase the efficiency. 4. Conclusion Metal-assisted surname engraving can make the mineral-free tooth-like damage crystallographic surface without considering crystallization. Fast and uniform (10) texturing by orientation, compared to untextured wire cells, due to increased short circuit current density (Δ〗%=+〇 9
12 201245417 毫安培/厘米2)，所以MAE紋理化線帶太陽能電池顯示效率η 增加(Δη==+〇·4% abs)，且由於在該經紋理化表面上之增強的 接點形成，所以填充因數FF增加(ΔΡΡ=〇·7%)。當封裝時， 5亥紋理化表面亦可得到一增強的光耦合。因此，與未經紋 理化電池比較，發現經封裝電池的短路密度可額外地增加 (/UsC=±〇·3毫安培/厘米2)。具有MAE紋理化線帶太陽能電池 的單電池模組顯示效率額外地增加(Δη=+〇.丨％ abs)。 藉標準酸性蝕刻法而進行多晶矽的表面紋理化對於無 錯齒狀損壞之表面具挑戰性。使用KOH進行單晶[in]表面 的紋理化亦具同等挑戰性。 除了該線帶技術外’有關於基板技術之Ribbon長晶技 術亦可得到無鋸齒狀損壞的多晶矽晶圓SLIVER及SI-GEN 技術可得到具有一 [111]表面定向的單晶矽晶圓。 由於該蝕刻溶液受到該等金屬顆粒之催化性活化，所 以該MAE紋理化方法完全未受結晶學定向的影響且因此可 得到一大簡化的製法。因此’該紋理化方法提供一可改良 所有上述晶圓製法的效率之大可能性。 表1 7sc[mA/cm2] ^octmV] FF[9〇] 〇[%] #電池 MAE紋理 中等1 31.9 ± 0.5 597.7 ±4 76.5 ± 0.4 14.5 ±0.2 8 最好2 32.0 599.1 76.7 14.7 1 無紋理 中等1 31.0 士 0-6 602.4 ± 5 75.8 ± 0.7 14.1 ± 0.4 8 最好2 31.4 604.9 77.0 14.6 1 1 經破認為ISE CalLab值。藉ISE CalLab，Freiburg, Germany而確認。 13 201245417 ϊ：圖式簡單說明i 第1圖顯示線帶（String Ribbon)晶圓紋理化表面的掃描 式電子顯微鏡影像。 第2圖顯示在波長λ[ηηι]範圍内，線帶晶圓及經催化劑 協助姓刻（金屬協助性I虫刻，MAE)之太陽能電池的表面反 射率R[%]降低。 第3圖顯示未經紋理化及經MAE紋理化之線帶太陽能 電池的量子效率。 第4圖顯示封裝在窗玻璃、EVA-箔以及泰德拉(Tedlar) 後箔内之線帶太陽能電池、串焊(strings)及單電池模組的短 路電流密度Jsc。 【主要元件符號說明】 (無） 1412 201245417 mA/cm 2), so the MAE textured line solar cell shows an increase in efficiency η (Δη==+〇·4% abs), and due to the enhanced joint formation on the textured surface, The fill factor FF is increased (ΔΡΡ=〇·7%). When packaged, a 5 Hz textured surface also provides an enhanced optical coupling. Therefore, it was found that the short-circuit density of the packaged battery was additionally increased (/UsC = ± 〇 · 3 mA / cm 2 ) as compared with the untreated battery. The single cell module with MAE textured wire solar cells has an additional display efficiency (Δη = +〇.丨% abs). Surface texturing of polysilicon by standard acid etching is challenging for surfaces that are free of dentate damage. The use of KOH for the texturing of single crystal [in] surfaces is equally challenging. In addition to the tape technology, the long-crystal technology of substrate technology can also obtain polycrystalline germanium wafers SLIVER and SI-GEN technology without zigzag damage to obtain a single crystal germanium wafer having a [111] surface orientation. Since the etching solution is catalytically activated by the metal particles, the MAE texturing method is completely unaffected by the crystallographic orientation and thus a greatly simplified process can be obtained. Thus, the texturing method provides a great possibility to improve the efficiency of all of the above wafer fabrication methods. Table 1 7sc[mA/cm2] ^octmV] FF[9〇] 〇[%] #电池MAE texture medium 1 31.9 ± 0.5 597.7 ±4 76.5 ± 0.4 14.5 ±0.2 8 Best 2 32.0 599.1 76.7 14.7 1 No texture medium 1 31.0 ± 0-6 602.4 ± 5 75.8 ± 0.7 14.1 ± 0.4 8 Best 2 31.4 604.9 77.0 14.6 1 1 The ISE CalLab value is considered broken. Confirmed by ISE CalLab, Freiburg, Germany. 13 201245417 ϊ: Simple description of the diagram i Figure 1 shows a scanning electron microscope image of the textured surface of the String Ribbon wafer. Fig. 2 shows that the surface reflectance R [%] of the solar cell of the tape wafer and the catalyst assisted surname (metal assisted insect insect, MAE) is reduced in the wavelength range λ [ηηι]. Figure 3 shows the quantum efficiency of a non-textured and MAE textured wireline solar cell. Figure 4 shows the short-circuit current density Jsc of a ribbon solar cell, strings, and cell modules packaged in window glass, EVA-foil, and Tedlar back foil. [Main component symbol description] (none) 14