201225175.f 六、發明說明： 【發明所屬之技術領域】 本發明是有關於-種 (wafe〇的表面處理方法及 製造方法，本發明尤其是有關於如下的晶圓的表面處理方 法及晶_製造方法，該晶®的表面處理方法可使成為太 陽電池的受光©的表面上的光的表面反射率減小，上述晶 圓具有已減小的光的表面反射率。 曰 【先前技術】 一般而言，使用以矽晶圓（siliconwafer)為代表的半 導體晶圓來形成太陽電池組㈤1)β關於適合用於太陽電 池的石夕晶圓’按照慣例’應用如下_晶圓， 對於對單㈣晶圓、多_晶圓雙方均進行蝴（slicef 加工所得的晶圓進行清洗處理’紐，實施⑽（etching) ，理以將由切割步驟引起的損傷（damage)予以除去所 得。然而’-般而言’實施用以將損傷予以除去的侧處 理之後的表面，會處於平滑性高的狀態，因此，太陽光合 被受光面反射，導致將光能（Qptieal _gy)轉換為電二 時的效率下降。因此’為了使此種太陽光的表面上的反射 率減小，按照慣例，對成為受光面的晶圓的表面實施被稱 為紋理化（texturing)處理的化學蝕刻處理，於晶圓表面 形成被稱為紋理構造的凹凸。該紋理化處理包 處理以及驗峨理，尤其當使用單 作為基板時，由於能夠有效果地活用晶圓的結晶面方位， 因此，在多數情形下使用鹼系蝕刻處理。 201225175』 然而，於鹼系蝕刻處理中，存在於晶圓表面的污染所 產生的影響大，具體而言，根據由切割加工或切割加工之 後的清洗步驟引起的油成分或者界面活性劑成分的殘留程 度’形成於晶圓表面的紋理構造的形成，會對應於殘存於 晶圓表面的有機物成分量而產生偏差。因此，存在如下的 問題，即’為了穩定地使表面反射率減小，必須設定與每 個晶圓相對應的條件。 又，於鹼系蝕刻中，一般使用混合溶液，該混合溶液 是將揮發性的異丙醇（Isopropyl Alcohol，IPA)混合於氫 氧化鉀等的鹼而成的溶液，存在如下的問題，即，於蝕刻 過程中，IPA會揮發，混合溶液中的jpA的濃度會發生變 化從而難以使IPA的濃度穩定化，當ιρΑ的濃度下降時， 難以形成紋理構造。 狖寻才j文默1宁已提出了如下的技術，即，於 粗，刻處理之前’使用網版（screen)印刷法來將玻璃 【枓』，paste)印刷至半導體晶圓的成為受光面的表 【矣接者實施鍛燒處理’藉此來形成掩模（mask)，於晶 固表面形成多個凹凸。 曰日 網 上 版專利文獻2 +已提出有如下的技術，即，藉由 P刷法等’將漿難佈至構成太陽· 上，接著進行煅燒，藉此來形成掩 土板 來形成包含微細的凹凸的抗由繼刻 具有耐驗性、耐酸性的素材的粒^上述漿料中混入有 先前技術文獻 201225175,』 專利文獻 專利文獻1 :曰本專利特開平5_136444號公報 專利文獻2 :日本專利特開2〇〇4_1〇3736號公報 然而，專利文獻1及專利文獻2所揭示的方法可不依 賴於基板的表©狀態㈣細凸，但問題在於：由於 網版印刷練鮮的繁_處理來形成掩模 、 性會下降。 &王座 【發明内容】 因此’本發_目的在於提供如下的晶_表面處理 方法及晶8]的製造方法，該晶圓的表面處理方法可使成為 太陽電池的受光面的表面上縣喊岐射麵小，上述 晶圓具有已減小的光的表面反射率。 本發明人針對解決上述問題的方法而進行了仔細研 究’結果發現：可_高分子來有效果轉決上述問題。 亦即，本發明人發現：藉由簡便的浸潰法等，將上述高分 子的溶液塗佈至成為太陽電池的受光面的半導體晶圓的表 面，藉此，於上述塗佈處理之後，無需實施燒結等的繁雜 的處理’塗佈的溶液中所含的高分子於糊處理中成為掩 模，從而完成了本發明。 亦即，本發明的晶圓的表面處理方法的特徵在於：將 高分子的溶液塗佈至成為太陽電池的受光面的半導體晶圓 的表面之後，對上述表面實施蝕刻處理。 又，本發明的晶圓的表面處理方法的特徵在於：上述 高分子的分子量為1000以上。 5 pif 201225175 於本發明的晶圓的表面處理方法令，上述古八工 的任音種古八3 ΐ 維素、以及十二燒基硫酸納中 以及十-严其 ' 人婦醇、經乙基纖維素、 _處理Μ會成為掩模。 本發明的晶圓的表面處理方法 鹼性浴液來進行上述蝕刻處理。藉此，可省^先^所 的脱等的有機溶劑的添加。猎了名略先別所添加 述塗^之^發明的晶^的表面處理方法的特徵在於：於上 过塗佈之後，且於上述敍刻處理 洗（rinse)處理。 耵上這表面貝施沖 ^發明的晶圓的製造方法的特徵在於·將高 i 陽電池Μ光面的半㈣晶_表面之 後對上迷表面貫施韻刻處理。 子丄ΓΓ的晶圓的製造方法的特徵在於:上述高分 子的分子量為1000以上。 4门刀 又’於本發_晶_製造方法巾，上述高 為聚乙烯醇、羥乙基纖維辛、 軏佳 ^種冋刀子。原因在於：聚乙烯醇、經乙基纖維素、以及 十一烷基硫酸鈉於蝕刻處理中均會成為掩模。 …本發明的晶_製造方法的特徵在於：使用驗性 溶液來進行上述姓刻處理。 =，本發明的晶_製造方法的特徵在於：於上述塗 :之後，且於上述_處理之前，對上述表面實施沖 i里0 201225175 [發明的效果] 根據本發明，可不對成為太陽電池的受光面的半導體 晶圓的表面實施繁雜的處理而形成掩模，因此，能夠以高 生產性來使上述晶圓表面形成紋理構造，從而可使成為太 陽電池的受光面的表面上的光的表面反射率減小。 【實施方式】 以下，參照圖式來對本發明的實施形態進行說明。 圖1 (a)〜圖1 (c)是表示本發明的晶圓的表面處理 方法的順序的圖。首先，如圖1 (a)所示，準備成為太陽 電池的基板的半導體晶圓1。可使用單晶晶圓及多晶晶圓 中的任意種晶圓作為上述半導體晶圓丨。例如，單晶石夕晶 圓可使用如下的矽晶圓，該矽晶圓是利用線鋸（wiresaw) 等，對由柴式法（CZ法（Czochralski method))或懸浮區 熔法（FZ法（Floating Zone method ))製成的單晶矽晶錠 (ingot)進行切割而成。又，關於晶圓表面的面方位，亦 可根據需要而選擇（〇〇1)或（111)等。 一接著，如圖1 (b)所示，將高分子的溶液塗佈至上述 半導體晶圓1的成為太陽電池的受光面的表面la。藉此， 附著於晶IB 1的表面la的高分子成為之後賴刻處理中的 掩模。如上所述’於先前技射，需要藉由網版印刷法等 將漿料印顧晶圓表面，接著進行職等繁_處理，但 於本發月中利用潰法或喷霧法（Spray meth〇(j)等的簡 便的^法來進行塗佈即可。原因在於：使晶圓表面與溶解 有附著於晶圓表面的高分子的溶液賴，藉此，可充分地 201225175 使所需量的高分子吸附於晶圓表面。 油性成分 ^處，所使㈣高分子無統定於切性及油溶性中 的任忍種〶分子，但根據如下的觀點，上述使用的高分子 ，佳為水溶性，上述觀點是指於油溶性的情形時，需要將 溶劑予以除去的轉’以及於後續的綱步财，不使用 又，所使用的高分子並無特別的限定，但較佳為使用 谷性的聚乙神祕乙基齡素、以及十二絲硫酸納 。而且，根據形成於晶圓表面的紋理構造的 (C⑻的觀點，具有3〇_左右的分子量的聚2 = 高分子的分子量設為1000以上。原因在於：當分子量 不足1000時，無法充分地形成紋理構造。又，根據形成紋 理，造的觀點，分子量的上限並無限定，但如上所述，由 於高分子較佳為水溶性高分子，因此，上述分子量的實質 性的上限為1000000左右。 高分子溶液的濃度設為0.0001 wt%以上且為20 wt% 以下。此處，將濃度的下限設為0 0001 wt%的理由在於： 無法轉保所需的高分子附著量，且無法形成良好的紋理構 造，另外’將濃度的上限設為20 wt%的理由在於：高分子 附著量大量地過剩，即便於後段處理的沖洗處理之後，仍 會殘留過剩的高分子，因此，會對紋理蝕刻本身產生阻礙。 又’高分子塗佈處理之後的晶圓表面的有機物量設為 1 ng/cm2以上且1000 ng/cm2以下（十六烷換算）。此處， 201225175..； 將I，設為lng/cm2的理由在於：無法確保所需的高分子 附著量，且無法形成良好的紋理構造；將上限設為1〇〇〇 ng/cm2的理由在於：高分子附著量大量地過剩，即便於後 段處理的沖洗處理之後，仍會殘留過剩的高分子，因此， 會對紋理化本身產生阻礙。 作為將如上所述的高分子溶液塗佈至半導體晶圓i的 表面la的方法，可使用浸潰法或噴霧法。 於使用浸潰法的情形時，將半導體晶圓丨的表面la 浸潰於高分子溶液之後’使用鼓風（airbl〇w)方式、旋轉 (spin)乾燥方式或提拉乾燥方式等的方法來使該半導體 晶圓1的表面la乾燥◊藉此，形成高分子層2。 此處，於進行乾燥之前，為了將過剩的高分子成分予 以除去，亦可對半導體晶圓1的表面la實施沖洗處理。具 體而s，將上述半導體晶圓1的表面la浸潰於水或溫水 中此時文漬的時間較佳設為1分鐘以上且分鐘以下。 又’於使用噴霧法的情形時，例如藉由喷搶（spmy gun) 來將高分子溶液喷霧至半導體晶圓丨的表面la，對晶圓i 進行旋轉乾燥處理而使該晶圓丨乾燥。藉此，形成高分子 層2。 如此，可藉由極簡便的方法，於晶圓表面上形成後續 的侧處財的掩模’上述極簡便的方法是㈣高分子溶 液塗佈至成為太陽電池的受光面的晶圓的表面。 接著，對塗佈有上述高分子溶液的半導體晶圓丨的表 面1實施蝕刻處理。該蝕刻處理的目的在於：將加工應變 9 201225175 予以除去，以及於半導體晶圓1的表面1&形成紋理構造， 上述加工應變是利用線鋸等來對已製成的矽晶錠進行切割 而製造矽晶圓時所產生的加工應變，可藉由將半導體晶圓 1的表面la浸潰於蝕刻液來進行上述蝕刻處理。 立此處，蝕刻液亦可使用酸系蝕刻液及鹼系蝕刻液中的 任意種蝕刻液，但根據易於形成紋理構造的理由，鹼系蝕 刻較佳。可使用氫氧化鉀水溶液、氫氧化納水溶液、以及 氫氧化四甲基銨（Tetr_thylammonium Hydroxide， TMAH)溶液等作為鹼蝕刻液。 ^上述蝕刻液的濃度設為〇丨wt%以上。此處，將 了限設為0.1 wt%的理由在於：若上述钮刻液的濃度不足 .wt/°’職法確保侧能力，難以雜所需的钮刻量， 特別的限定’可應用直至鹼成分的飽和濃度為止 例如於使贱氧化鉀溶__時’作為飽和 /晨度的48 wt%成為上限。 3八，f ^體日日圓1的表面la浸潰於姓刻液時的時間設為 由為6〇分鐘以下。此處，設為3分鐘以上的理 的韻刻孴H足3分鐘的短時間處理’則難以確保所需 鐘的長_；:為6〇分鐘以下的理由在於：若為超過60分 的，時間處理，則無法適用於工業處理。 如圖實^利用水等的沖洗處理以及乾燥處理，藉此， 造lla。 不，於半導體晶圓1的表面la形成紋理構 如此，此夠以高生產性來使成為太陽電池的受光面的 201225175、 _，*1· 半導體晶圓的表面形成紋理構造。 是如上=本發明的表面處理方法的半導體晶圓i 的成為受光面的表面上的光的表面 1 於太陽電池。亦即，對半導體晶圓 上述本發明的表面處理，藉此， :反體::已::導趙晶圓的成為受細表面上的：表 ，著’已實施上述處理的石夕晶圓經由pn接面形成步 池組抗反射膜形成步驟、及電極形成步驟等而成為太陽電 實例 (發明例A1〜發明例A3及比較例A1) 以下，對本發明的實例進行說明。 首^，準備3塊156 mm見方的太陽電池用的p型 (〇〇1)單晶石夕晶圓。使用0.002 wt%(發明例A1 )、〇 〇2 wt% 、（發明例A2)、及〇.2wt〇/0 (發明例A3)的聚乙婦醇水溶 液’對上述晶圓各自的成為太陽電池的受光面的表面實施 浸潰處理。在室溫進行上述浸潰處理，又，將浸潰的時間 設為5分鐘。 接著，利用水來對已實施上述處理的矽晶圓的表面實 施10分鐘的沖洗處理之後，進行鼓風乾燥，從而使晶圓表 面乾燥。 然後，使用包含1.5%的氫氧化卸的蝕刻液，對已實施 β潰處理的晶圓表面實施蚀刻處理。以8〇。〇，實施1〇分 11 201225175 鐘的上述蝕刻處理。然後，於實施水沖洗之後，使晶圓表 面乾燥，藉此來獲得如下的矽晶圓，該矽晶圓於成為太陽 電池的受光面的表面具有紋理構造。圖2(b)〜圖2(d) 分別表示藉由掃描型電子顯微鏡（Scanning Electr〇n201225175.f VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a surface treatment method and a manufacturing method of the wafer, and the present invention particularly relates to a surface treatment method and a wafer of the following wafers. In the manufacturing method, the surface treatment method of the crystal® can reduce the surface reflectance of light on the surface of the light receiving surface of the solar cell, and the wafer has a surface reflectance of the reduced light. [Prior Art] For example, a semiconductor wafer represented by a silicon wafer is used to form a solar cell group. (5) 1) About a Shihwa wafer suitable for use in a solar cell, 'as is customary', the following application is applied to the wafer (for the wafer). Both the wafer and the multi-wafer are subjected to a butterfly (slice-processed wafer for cleaning treatment), and (10) (etching) is performed to remove the damage caused by the cutting step. However, The surface after the side treatment for removing the damage is in a state of high smoothness, and therefore, the sun is combined by the light receiving surface, resulting in light energy (Qpt). Ieal _gy) is reduced in efficiency when converted to electricity 2. Therefore, in order to reduce the reflectance on the surface of such sunlight, the surface of the wafer to be the light-receiving surface is conventionally referred to as texturing. The chemical etching treatment of the process forms a concave and convex surface called a texture structure on the surface of the wafer. The texture processing package processing and inspection, especially when using a single substrate, can effectively utilize the crystal plane orientation of the wafer. Therefore, in many cases, an alkali etching treatment is used. 201225175" However, in the alkali etching treatment, the influence of contamination on the surface of the wafer is large, specifically, after the processing by cutting or cutting The degree of residue of the oil component or the surfactant component caused by the cleaning step is such that the formation of the texture structure formed on the surface of the wafer varies depending on the amount of the organic component remaining on the surface of the wafer. Therefore, there is a problem that 'In order to stably reduce the surface reflectance, it is necessary to set the conditions corresponding to each wafer. A mixed solution is generally used, which is a solution obtained by mixing volatile isopropanol (IPA) with a base such as potassium hydroxide, and has a problem that during the etching process, IPA will Volatile, the concentration of jpA in the mixed solution changes, making it difficult to stabilize the concentration of IPA. When the concentration of ιρΑ is lowered, it is difficult to form a texture structure. 狖寻才 j文默1宁 has proposed the following technique, namely, Before the roughing and engraving process, 'screen printing method is used to print the glass onto the surface of the semiconductor wafer to be the light-receiving surface. (mask), a plurality of irregularities are formed on the surface of the crystal solid. Japanese Laid-Open Patent Publication No. 2+ has proposed a technique in which a slurry is formed by a P-brush method or the like to form a solar panel, followed by calcination, thereby forming a green sheet to form a fine layer. In the above-mentioned slurry, the above-mentioned slurry is mixed with the above-mentioned slurry, and the above-mentioned slurry is mixed with the prior art document 201225175. Patent Document 1: Patent Publication No. 5-136444 Patent Document 2: Japan However, the methods disclosed in Patent Document 1 and Patent Document 2 can be made without depending on the state of the substrate (4), but the problem is that the processing is complicated due to the practice of screen printing. To form a mask, the performance will drop. & Throne [Explanation] Therefore, the present invention aims to provide a method for manufacturing a crystal surface treatment method and a crystal 8 as follows: the surface treatment method of the wafer can be used as a surface of the solar cell's light-receiving surface The radiant surface is small, and the wafer has a surface reflectance of reduced light. The present inventors conducted a detailed study on a method for solving the above problems. As a result, it has been found that the polymer can be effective in solving the above problems. In other words, the inventors have found that the solution of the above polymer is applied to the surface of the semiconductor wafer which is the light-receiving surface of the solar cell by a simple dipping method or the like, thereby eliminating the need for the coating process. A complicated process such as sintering is performed. The polymer contained in the applied solution is used as a mask in the paste treatment, and the present invention has been completed. That is, the surface treatment method of the wafer of the present invention is characterized in that after the solution of the polymer is applied onto the surface of the semiconductor wafer which is the light-receiving surface of the solar cell, the surface is etched. Further, in the surface treatment method of the wafer of the present invention, the polymer has a molecular weight of 1,000 or more. 5 pif 201225175 The surface treatment method of the wafer of the present invention is such that the above-mentioned ancient eight-worker's syllabus is octagonal, and the twelve-sodium sulphate sulphate and the sulphate sulphate The base cellulose, _ treated Μ will become a mask. The surface treatment method of the wafer of the present invention is performed by an alkaline bath to perform the above etching treatment. Thereby, the addition of the detached organic solvent can be saved. The surface treatment method of the invention is characterized in that after the coating is applied, the rinsing treatment is performed in the above-described characterization. The method of manufacturing the wafer of the invention is characterized in that the surface of the high-positive solar cell's semi- (tetra) crystal surface is subjected to a rhyme treatment. The method for producing a wafer of a child is characterized in that the molecular weight of the above polymer is 1000 or more. 4 knives and 'in the hair _ crystal _ manufacturing method towel, the above high is polyvinyl alcohol, hydroxyethyl fiber xin, 軏 good ^ 冋 knife. The reason is that polyvinyl alcohol, ethyl cellulose, and sodium undecy sulfate are masks in the etching process. The crystal_manufacturing method of the present invention is characterized in that the above-described surname treatment is carried out using an inert solution. The method for producing a crystal according to the present invention is characterized in that, after the above-mentioned coating, and before the above-mentioned treatment, the surface is subjected to a rushing period. 201225175 [Effects of the Invention] According to the present invention, it is possible to become a solar cell. The surface of the semiconductor wafer on the light-receiving surface is subjected to complicated processing to form a mask. Therefore, the surface of the wafer can be textured with high productivity, and the surface of the light on the surface of the light-receiving surface of the solar cell can be formed. The reflectance is reduced. [Embodiment] Hereinafter, embodiments of the present invention will be described with reference to the drawings. Fig. 1 (a) to Fig. 1 (c) are views showing the procedure of a surface treatment method of a wafer of the present invention. First, as shown in Fig. 1 (a), a semiconductor wafer 1 which is a substrate of a solar cell is prepared. Any of a single crystal wafer and a polycrystalline wafer can be used as the above semiconductor wafer cassette. For example, a single crystal wafer can use a germanium wafer using a wire saw or the like, or a CZ method (Czochralski method) or a suspension zone melting method (FZ method). (Floating Zone method)) The resulting single crystal twin ingot is cut. Further, regarding the surface orientation of the wafer surface, (〇〇1) or (111) or the like may be selected as needed. First, as shown in Fig. 1(b), a solution of a polymer is applied to the surface 1a of the semiconductor wafer 1 which is a light receiving surface of the solar cell. Thereby, the polymer adhered to the surface la of the crystal IB 1 becomes a mask in the subsequent etching process. As described above, in the prior art, it is necessary to print the slurry on the surface of the wafer by screen printing, etc., and then carry out the processing of the class, but in the present month, the method of using the method of spraying or spraying (Spray meth) The coating may be carried out by a simple method such as 〇(j), because the surface of the wafer and the solution of the polymer adhered to the surface of the wafer are dissolved, whereby the required amount can be sufficiently 201225175 The polymer is adsorbed on the surface of the wafer. The oily component is such that the polymer does not have any of the molecular properties of N. sinensis in the properties of cuttability and oil solubility. However, according to the following viewpoints, the polymer used above is preferably Water-soluble, the above-mentioned viewpoint means that in the case of oil-soluble property, it is necessary to remove the solvent, and in the subsequent step, the polymer to be used is not particularly limited, but it is preferably used. a glutamic acid, a mysterious ethyl sulphate, and a sodium sulphate. Further, according to the texture structure formed on the surface of the wafer (C(8), poly 2 having a molecular weight of about 3 〇 = molecular weight of the polymer Set to 1000 or higher. The reason is: When the amount is less than 1,000, the texture structure cannot be sufficiently formed. Further, the upper limit of the molecular weight is not limited in view of texture formation, but as described above, since the polymer is preferably a water-soluble polymer, the molecular weight is preferably The substantial upper limit is about 1,000,000. The concentration of the polymer solution is set to 0.0001 wt% or more and 20 wt% or less. Here, the reason why the lower limit of the concentration is set to 0 0001 wt% is: The reason why the amount of the polymer adhered was not able to form a good texture structure, and the reason why the upper limit of the concentration was 20 wt% was that the amount of the polymer adhered was excessively large, and even after the rinsing treatment of the subsequent treatment, excess remained. The polymer is impeded by the texture etching itself. The amount of organic matter on the surface of the wafer after the polymer coating treatment is 1 ng/cm 2 or more and 1000 ng/cm 2 or less (in terms of cetane). , 201225175..; The reason for setting I to lng/cm2 is that the required amount of polymer adhesion cannot be ensured, and a good texture structure cannot be formed; the upper limit is set to 1〇〇〇ng The reason of /cm2 is that the amount of the polymer adhered is excessively large, and even after the rinsing treatment in the subsequent stage treatment, the excess polymer remains, which hinders the texturing itself. As the polymer solution as described above The method of applying to the surface 1a of the semiconductor wafer i may be a dipping method or a spraying method. When the dipping method is used, the surface of the semiconductor wafer crucible is immersed in the polymer solution, and the blast is used. The surface of the semiconductor wafer 1 is dried by a method such as an air drying method, a spin drying method or a pulling drying method, thereby forming the polymer layer 2. Here, before drying, In order to remove excess polymer components, the surface 1a of the semiconductor wafer 1 may be subjected to a rinsing treatment. Specifically, the surface la of the semiconductor wafer 1 is immersed in water or warm water. The time of the stain is preferably 1 minute or more and minutes or less. Further, when the spray method is used, for example, a polymer solution is sprayed onto the surface 1a of the semiconductor wafer cassette by a spmy gun, and the wafer i is spin-dried to dry the wafer. . Thereby, the polymer layer 2 is formed. In this way, a mask for the subsequent side surface can be formed on the surface of the wafer by a very simple method. The above-described extremely simple method is that the (4) polymer solution is applied to the surface of the wafer which is the light receiving surface of the solar cell. Next, the surface 1 of the semiconductor wafer on which the polymer solution was applied was subjected to an etching treatment. The etching process is intended to remove the processing strain 9 201225175 and form a texture structure on the surface 1& of the semiconductor wafer 1, which is manufactured by cutting a prepared twin ingot by a wire saw or the like. The processing strain generated when the wafer is formed may be subjected to the above etching treatment by dipping the surface of the semiconductor wafer 1 to the etching liquid. Here, the etching liquid may be any etching liquid selected from an acid etching liquid and an alkali etching liquid. However, alkali etching is preferred because of the ease of forming a texture structure. As the alkali etching solution, an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, a tetramethylammonium hydroxide (TMAH) solution or the like can be used. The concentration of the above etching liquid is set to be 〇丨wt% or more. Here, the reason for setting the limit to 0.1 wt% is that if the concentration of the button engraving is less than .wt/°', the side ability is ensured, and it is difficult to mix the required button amount, and the special limitation is applicable until For example, when the saturated concentration of the alkali component is such that the potassium pentoxide is dissolved, the upper limit is 48% of the saturation/morning degree. 3, the time when the surface la of the Japanese yen 1 is immersed in the surname engraving is set to be less than 6 minutes. Here, it is assumed that the rhyme of 3 minutes or more and the short processing of 3 minutes of H is difficult to ensure the length of the required clock _; the reason for being 6 minutes or less is that if it is more than 60 minutes, Time processing cannot be applied to industrial processing. As shown in the figure, the rinsing treatment using water or the like and the drying treatment are carried out, whereby lla is produced. Therefore, the surface la of the semiconductor wafer 1 is textured, and the surface of the 201225175, _, *1· semiconductor wafer which is the light-receiving surface of the solar cell can be textured with high productivity. The surface of the semiconductor wafer i on the surface of the light-receiving surface of the semiconductor wafer i of the present invention is as described above in the solar cell. That is, the surface treatment of the above-described semiconductor wafer of the semiconductor wafer, whereby: the reverse body:: the guide wafer is on the thinned surface: the table, the 'Shi Xi wafer that has been subjected to the above processing is passed through pn Examples of solar power (Examples of Invention A1 to Inventive Example A3 and Comparative Example A1) are formed by forming a step group anti-reflection film forming step and an electrode forming step, etc. Hereinafter, an example of the present invention will be described. First, prepare three p-type (〇〇1) single crystal silicon wafers for 156 mm square solar cells. 0.002 wt% (Inventive Example A1), 〇〇2 wt%, (Inventive Example A2), and 2.2wt〇/0 (Inventive Example A3) Ethyl Ethyl Alcohol Solution' The surface of the light-receiving surface is subjected to an impregnation treatment. The above impregnation treatment was carried out at room temperature, and the time of the impregnation was set to 5 minutes. Next, the surface of the tantalum wafer subjected to the above-described treatment was subjected to a rinsing treatment for 10 minutes using water, and then air-dried to dry the wafer surface. Then, the surface of the wafer subjected to the ?-cracking treatment was subjected to an etching treatment using an etching solution containing 1.5% of hydrogen hydroxide. Take 8 〇. 〇, the above etching treatment was carried out for 1 minute and 11 201225175 hours. Then, after the water rinsing is performed, the surface of the wafer is dried, whereby a ruthenium wafer having a textured structure on the surface of the light receiving surface of the solar cell is obtained. Figure 2(b) to Figure 2(d) show the scanning electron microscope (Scanning Electr〇n)
Micr〇scope，SEM) ’對已實施發明例A1〜發明例A3的處 理的晶圓的表面進行觀察所得的圖像。為了進行比較，於 上述處理中，未使用聚乙烯醇水溶液來實施浸潰處理時（比 較例A1)的表面示於圖2 (a)。又，將已實施上述處理的 晶圓所接受的光的波長與表面反射率之間的關係歸納於表 1 ° 如圖2 (a)所示，已知：當未藉由聚乙烯醇水溶液來 實施次潰處理時，石夕的（〇〇1)表面因氫氧化钟溶液而被姓 亥1從而形成多個包含（Hi )面的錐體（Pyramid)構造。 相對於此，根據圖2 (b)〜圖2 (d)，已知··並未形成如 圖2 (a)中所觀察到的錐體構造般的依賴於晶圓的結晶構 造的構造’而是形成有隨機（random)的紋理構造。又， 已知：隨著聚乙烯醇水溶液的濃度增加，所形成的紋理構 造會自微細的凹凸變化為大溝槽。 (發明例A4〜發明例A6及比較例A2) 代替10分鐘’將蝕刻處理的時間設為20分鐘，除此 以外，在與發明例A1〜發明例A3及比較例A1相同的條 件下，實施蝕刻處理。 12 201225175 J-atNoo卜 6εMicr〇scope, SEM) 'An image obtained by observing the surface of the wafer subjected to the treatment of Inventive Example A1 to Inventive Example A3. For comparison, in the above treatment, the surface of the impregnation treatment (Comparative Example A1) was not shown in Fig. 2(a) without using a polyvinyl alcohol aqueous solution. Further, the relationship between the wavelength of light received by the wafer subjected to the above treatment and the surface reflectance is summarized in Table 1 ° as shown in Fig. 2 (a), and it is known that when not using an aqueous solution of polyvinyl alcohol When the secondary pulverization treatment is carried out, the surface of the 夕 ) (〇〇1) is named by the oxidized bell solution to form a plurality of Pyramid structures including the (Hi) plane. On the other hand, according to FIGS. 2(b) to 2(d), it is known that the structure of the wafer-dependent crystal structure like the pyramid structure observed in FIG. 2(a) is not formed. Instead, a random texture is formed. Further, it is known that as the concentration of the aqueous solution of polyvinyl alcohol increases, the texture structure formed changes from fine irregularities to large grooves. (Inventive Example A4 to Inventive Example A6 and Comparative Example A2) Except that the time of the etching treatment was changed to 20 minutes instead of 10 minutes, the same conditions as in the inventive example A1 to the inventive example A3 and the comparative example A1 were carried out. Etching treatment. 12 201225175 J-atNoo Bu 6ε
【II 表面反射率（％) ♦ 〇 g 故2 « 30.11 | 丨 22.21 I | 21.21 I | 17.50 I | 28.46 I 1 16.70 I 1 15.41 I I 11.62 I 29.61 21.51 20.58 16.82 28.09 16.44 14.87 11.19 24.61 17.21 14.59 13.02 12.23 波長 700 nm | 31.58 I | 22.71 | 丨 21.36 | | 17.76 ] 30.01 I 17.23 I I 16.23 I 1 12.61 I ! 31.07 ! 22.10 1 21.06 17.21 29.78 16.78 15.70 11.93 26.29 18.36 15.42 13.63 12.28 波長 600 nm 33.28 j 23.88 | 22.55 1 | 18.67 | 1 31.90 1 18.46 I I 17.24 I 13.98 | 32.89 1 1 23.19 1 22.01 18.17 31.53 17.83 16.61 12.94 28.05 19.55 16.35 14.56 13.00 波長 300 nm 57.49 : | 45.10 j | 42.66 I | 38.34 I | 53.99 I I 39.01 I 1 37.99 I [34.32 | | 55.92 1 ! 43.06 1 40.92 36.28 52.63 37.46 36.93 33.47 48.47 39.66 36.10 33.54 32.11 蝕刻條件 時間 (分） 〇 〇 〇 溫度 (0〇 g § g 蝕刻液（濃 度） KOH (1.5%) KOH (1.5% ) + IPA (3%) KOH (1.5%) 乾燥 條件 i 1 鼓風 鼓風 鼓風 鼓風 鼓風 沖洗條件 時間 (分） 1 〇 〇 ο 〇 〇 1 浸浸條件 時間 (分） 1 1 Η賴 {m 分子 量 1 1000 1000 1000 1000 〇 1000 5000 10000 30000 濃度 (wt%) 1 0.002 S 〇 d | 0.002 I 〇 d (N d 1 0.002 1 | 0.02 | (Ν d | 0.002 I CN q d (N 〇 <N 〇 d 高分子 溶液 1 聚乙烯 醇水溶 液 1 聚乙烯 醇水溶 液 聚乙烯 醇水溶 液 聚乙烯 醇水溶 液 聚乙烯 醇水溶 液 實例 比較例A1 發明例A1 |發明例A2 發明例A3 比較例A2 發明例A4 發明例A5 發明例A6 比較例B1 發明例Β1 發明例Β2 |發明例B3 | 比較例B2 發明例B4 發明例B5 發明例B6 發明例C1 發明例C2 發明例C3 發明例C4 發明例C5 201225175〆 (發明例B1〜發明例B3及比較例B1 ) 準備3塊與發明例A1〜發明例A3的情形相同的晶 圓，亦即’準備3塊156 mm見方的太陽電池用的p型（〇〇1) 單晶石夕晶圓’實施與發明例A1〜發明例A3的情形相同的 浸潰處理’亦即，使用0.002 wt% (發明例B1)、0.02 wt% (發明例B2)、及0.2 wt% (發明例B3)的聚乙烯醇水溶 液，對晶圓各自的成為太陽電池的受光面的表面實施浸潰 處理。以室溫來進行上述浸潰處理，又，對於全部的晶圓， 將戌潰的時間設為5分鐘。然後，利用水來對已實施上述 處理的石夕晶圓的表面實施分鐘的沖洗處理之後，進行鼓 風乾燥，從而使晶圓表面乾燥。 人接著，使用包含1.5%的氫氧化鉀及3%的異丙醇的混 合溶液的_液，對已實施浸潰處理的晶圓表面實施触刻 處理。在80 C實施1〇分鐘的上述钮刻處理。 然後’於實施水沖洗之後，使晶圓表面乾燥，藉此來 付如下的@晶圓’該碎？日圓於成為太陽電池的受光面的 發：2紋理構造。圖3⑴〜圖3 U)分別表示已實施 =例m〜發明例扮的處理的晶圓的表面的顧圖像。 行比較，圖3 (a)表示於上述處理中，未使用聚乙 德y谷液來實施浸潰處理時（比較例Bl)的表面的sem 矣而’將已實施上述處理的晶81所接受的光的波長與 表面，之間的關係歸納於表卜 行比di(a)〜？2⑷及圖3 (a)〜圖3⑷進 乂，，虽水溶性高分子水溶液的濃度相同時，蝕刻處 201225175..Γ 理時的蝕刻液中是否包含先前技術的以一般方式經混合的 揮發性的異丙醇，未對紋理構造產生太大的影響，而且根 據表1亦已知：未對表面反射率產生大影響。亦即，已知 於本發明中，無需使用異丙醇。 (發明例B4〜發明例B6及比較例B2) 代替10分鐘，將蝕刻處理的時間設為20分鐘，除此 以外’在與發明例B1〜發明例B3及比較例B1相同的條 件下’實施蝕刻處理。 (發明例C1〜發明例C5) 首先，準備5塊156 mm見方的太陽電池用的p型 (001)單晶矽晶圓。使用0.02 wt%的聚乙烯醇水溶液， 對上述晶圓各自的成為太陽電池的受光面的表面實施浸潰 處理。此時，將水溶液中的聚乙烯醇的分子量設為500(發 明例α)、1000 (發明例C2)、5_ (發明例C3)、1〇〇〇〇 ^明例C4)及30000 (發明例C5)。在室溫來進行上述 浸潰處理，又，將浸漬的時間設為5分鐘。 接著，利用水來對已實施上述處理的矽晶圓的表面實 施10刀鐘的沖洗處理之後，進行鼓風乾燥，從而使晶圓表 面乾燥。 @、^/、、;後，使用包含丨·5%的氫氧化鉀的蝕刻液，對已實施 ’文凊處理的晶圓表面實施姓刻處理。在8(TC，實施1〇分 述綱處理。然後’於實施水沖洗之後，使晶圓表 雷此來獲得如下的碎晶圓’财晶圓於成為太陽 、、夂光面的表面具有紋理構造。圖4 (a)〜圖4 (e) ,.f 201225175 不藉由SEM來對已實施發明例C1〜發明例C5的 二里2的表面進行觀察所得的圖像。又，將已實施上 圓所接受的光的波長與表面反射率之間的關係 可知：當聚乙稀醇的分子量小至500時 -\ ^ ’於晶圓表面形成有錐體構造，但如表1所 ί ’(:二未使用聚乙_的水溶液來實施浸潰處理的情 形（_例八0,表面反射率已減小。 ㈣ 醇的自4⑴〜®4 (e)可知：當聚乙稀 、、以上時，於晶圓表面形成紋理構造。 個、表1的表面反料進行贿，已^對於任一 絲制聚乙觸的水溶絲f (比較例A1)相比較，已實施發明例ci〜發明例 =的晶_絲反鮮減小，但絲乙辆的分子 =購0以上，斷便分子量增加，表面反射率亦不太會 於本實例中，使用聚乙_作為高分子，但即便 =乙基纖維素及十二絲硫酸納來代替聚乙稀醇:進 上述實驗相同的實驗時，亦獲得了與本實例相同的結 【圖式簡單說明】 方法=二圖1(c)是表示本發明的晶圓的表面處理 圖2(a)是比較例，圖2(b)〜圖2(d)是由本發 201225175.； 明的晶圓的表面處理方法獲得的矽晶圓表面的SEM圖像。 圖3 (a)是比較例，圖3 (b)〜圖3 (d)是由本發 明的晶圓的表面處理方法獲得的矽晶圓表面的SEM圖像。 圖4 (a)〜圖4 (e)是由本發明的晶圓的表面處理方 法獲得的矽晶圓表面的SEM圖像。 【主要元件符號說明】 1 :半導體晶圓 la :表面 2:高分子層 3 :蝕刻液 11a :紋理構造 17[II Surface reflectance (%) ♦ 〇g 2 2 30.11 | 丨22.21 I | 21.21 I | 17.50 I | 28.46 I 1 16.70 I 1 15.41 II 11.62 I 29.61 21.51 20.58 16.82 28.09 16.44 14.87 11.19 24.61 17.21 14.59 13.02 12.23 Wavelength 700 nm | 31.58 I | 22.71 | 丨21.36 | | 17.76 ] 30.01 I 17.23 II 16.23 I 1 12.61 I ! 31.07 ! 22.10 1 21.06 17.21 29.78 16.78 15.70 11.93 26.29 18.36 15.42 13.63 12.28 Wavelength 600 nm 33.28 j 23.88 | 22.55 1 | 1 31.90 1 18.46 II 17.24 I 13.98 | 32.89 1 1 23.19 1 22.01 18.17 31.53 17.83 16.61 12.94 28.05 19.55 16.35 14.56 13.00 Wavelength 300 nm 57.49 : | 45.10 j | 42.66 I | 38.34 I | 53.99 II 39.01 I 1 37.99 I [34.32 55.92 1 ! 43.06 1 40.92 36.28 52.63 37.46 36.93 33.47 48.47 39.66 36.10 33.54 32.11 Etching conditions Time (minutes) 〇〇〇 Temperature (0〇g § g Etching solution (concentration) KOH (1.5%) KOH (1.5%) + IPA (3%) KOH (1.5%) Drying conditions i 1 Blasting blasting blasting blasting conditions (minutes) 1 〇〇ο 〇〇1 Immersion conditions Between (minus) 1 1 Η { {m Molecular weight 1 1000 1000 1000 1000 〇1000 5000 10000 30000 Concentration (wt%) 1 0.002 S 〇d | 0.002 I 〇d (N d 1 0.002 1 | 0.02 | (Ν d | 0.002 I CN qd (N 〇 < N 〇d polymer solution 1 polyvinyl alcohol aqueous solution 1 polyvinyl alcohol aqueous solution polyvinyl alcohol aqueous solution polyvinyl alcohol aqueous solution polyvinyl alcohol aqueous solution Example Comparative Example A1 Inventive Example A1 | Inventive Example A2 Inventive Example A3 Comparative Example A2 Inventive Example A4 Inventive Example A5 Inventive Example A6 Comparative Example B1 Inventive Example Β 1 Inventive Example Β 2 | Inventive Example B3 | Comparative Example B2 Inventive Example B4 Inventive Example B5 Inventive Example B6 Inventive Example C1 Inventive Example C2 Inventive Example C3 Inventive Example C4 Inventive Example C5 201225175 (Inventive Example B1 - Inventive Example B3 and Comparative Example B1) Three wafers identical to those in the case of Inventive Example A1 to Inventive Example A3 were prepared, that is, "prepared for three solar cells of 156 mm square" The p-type (〇〇1) single crystal ray wafer was subjected to the same impregnation treatment as in the case of Inventive Example A1 to Invention Example A3, that is, 0.002 wt% (Inventive Example B1) and 0.02 wt% were used. B2), and 0.2 wt% (Inventive Example B3) Aqueous solution of polyvinyl alcohol, each of the wafer receiving surface becomes dipping process embodiment of the solar cell surface. The above-mentioned impregnation treatment was performed at room temperature, and the time of collapse was set to 5 minutes for all the wafers. Then, the surface of the Shiyue wafer subjected to the above-described treatment was subjected to a rinsing treatment for a minute by water, and then air-dried to dry the surface of the wafer. Then, the surface of the wafer subjected to the impregnation treatment was subjected to a etch treatment using a _ liquid containing a mixed solution of 1.5% potassium hydroxide and 3% isopropyl alcohol. The above-described button processing of 1 minute was performed at 80 C. Then, after performing the water rinse, the surface of the wafer is dried, thereby paying the following @wafer's shreds? The yen becomes the light-receiving surface of the solar cell: 2 texture structure. Fig. 3 (1) to Fig. 3 U) respectively show the images of the surface of the wafer on which the processing of the example m to the invention example was carried out. In comparison, Fig. 3 (a) shows the sem 表面 of the surface of the comparative treatment (Comparative Example B1) without using the polyethylene oxide y solution in the above treatment, and the acceptance of the crystal 81 which has been subjected to the above treatment is accepted. The relationship between the wavelength of light and the surface, is summarized in the table than the row di(a) ~? 2(4) and Fig. 3(a) to Fig. 3(4), in the case where the concentration of the water-soluble polymer aqueous solution is the same, whether the etchant at the etching point 201225175.. contains the volatility of the prior art mixed in the conventional manner. Isopropanol did not have a large effect on the texture structure, and it is also known from Table 1 that it does not have a large effect on the surface reflectance. That is, it is known that in the present invention, it is not necessary to use isopropyl alcohol. (Inventive Example B4 to Inventive Example B6 and Comparative Example B2) The same was carried out under the same conditions as in the inventive example B1 to the inventive example B3 and the comparative example B1 except that the etching treatment time was 20 minutes instead of 10 minutes. Etching treatment. (Inventive Example C1 to Inventive Example C5) First, five p-type (001) single crystal germanium wafers for solar cells of 156 mm square were prepared. The surface of each of the above-mentioned wafers to be the light-receiving surface of the solar cell was subjected to a dipping treatment using a 0.02 wt% aqueous solution of polyvinyl alcohol. In this case, the molecular weight of the polyvinyl alcohol in the aqueous solution is 500 (invention example α), 1000 (invention example C2), 5_ (invention example C3), 1 〇〇〇〇^example C4), and 30,000 (invention example) C5). The above impregnation treatment was carried out at room temperature, and the immersion time was set to 5 minutes. Next, the surface of the tantalum wafer subjected to the above-described treatment was subjected to a rinsing treatment for 10 knives by water, and then air-dried to dry the wafer surface. After @,^/,,;, the surface of the wafer subjected to the 'texture processing was subjected to a surname treatment using an etching solution containing 5% potassium hydroxide. At 8 (TC, the implementation of 1 〇 述 处理 。 。 。 。 。 于 于 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施Fig. 4 (a) to Fig. 4 (e), .f 201225175 An image obtained by observing the surface of the second embodiment 2 of the invention examples C1 to C5 without SEM. The relationship between the wavelength of the light received by the upper circle and the surface reflectance shows that when the molecular weight of the polyethylene glycol is as small as 500 - - ^ ', a cone structure is formed on the surface of the wafer, but as shown in Table 1 (: Two cases where the impregnation treatment is not carried out using an aqueous solution of polyethyl _ (_Example 80), the surface reflectance has been reduced. (4) From 4(1) to 4(e) of the alcohol, it is known that when polyethylene is used, At the time of the formation of the texture on the surface of the wafer, the surface of Table 1 was used to make a bribe, and the inventive example ci to the inventive example was compared with respect to the water-soluble filament f (Comparative Example A1) of any of the silk-colored polyethylene contacts. = crystal ray anti-fresh reduction, but the molecular weight of silk B = buy 0 or more, the molecular weight of the break increases, the surface reflectance is not too much In the example, polyethyl _ was used as the polymer, but even if ethyl cellulose and sodium dodecyl sulphate were used instead of polyethylene glycol: the same experiment as in the previous experiment was obtained in the same experiment as in the above experiment. Brief Description of the Method] Method = 2 Figure 1 (c) shows the surface treatment of the wafer of the present invention. Figure 2 (a) is a comparative example, and Figure 2 (b) ~ Figure 2 (d) is from the present 201225175. SEM image of the surface of the germanium wafer obtained by the surface treatment method of the wafer. Fig. 3 (a) is a comparative example, and Figs. 3 (b) to 3 (d) are obtained by the surface treatment method of the wafer of the present invention. SEM image of the wafer surface. Fig. 4 (a) to Fig. 4 (e) are SEM images of the surface of the germanium wafer obtained by the surface treatment method of the wafer of the present invention. [Description of main component symbols] 1: Semiconductor crystal Circle la: Surface 2: Polymer layer 3: Etching liquid 11a: Texture structure 17