201245418 六、發明說明： 【發明所屬之技術領域】 .201245418 VI. Description of the invention: [Technical field to which the invention belongs].
[0001] 此申請案主張來自於2011年4月22日在韓國智慧財產局申 請的韓國專利申請案編號1 0-20 1 1 -0037990的優先權， 其全部揭露内容併入於本文中以作為參考。 本發明有關一種用於結晶矽晶圓的紋理蝕刻溶液組成物 ，以及一種紋理蝕刻方法，該紋理蝕刻溶液組成物能夠 控制該結晶矽晶圓表面上微金字塔的形狀，並最小化前 述表面上區域内的紋理品質偏差，以改進光吸收功效。 【先前技術】 [0002] 近年來，太陽能電池已快速普及，且熟知為下個世代的 能源以及直接轉換乾淨能量的電子裝置，也就是，將陽 光轉成電。這種太陽能電池原則上具有包含矽以及硼加 入於其中的P型矽半導體，且包含PN接面半導體基板，其 中原則上包含具有矽以及硼加入於其中的P型矽半導體， 以及藉由將磷（P)擴散入該P型矽半導體的表面而形成N 型矽半導體層。 當光（例如陽光）照射具有由PN接面提供的電場的基板時 ，半導體中的電子（-)以及電洞（+ )被激發，且這種 激發的電子（-）以及電洞（+ )可自由且隨機地在該半 導體内移動。在此情況中，由該P N接面形成的電場内的 電子（-）可移動至該N型半導體中，同時該電洞（+ )移 動至該P型半導體。如果在該P型半導體以及該N型半導體 的表面上都提供電極以將電子朝向外部電路流動，即產 生電流。基於這種原理，陽光被轉換成電能。因此，為 了改進陽光轉換效率，PN接面半導體基板的每單位區域 1013286431-0 第4頁/共21頁 201245418 Ο 1013286431-0 的電輸出應被盡可能地掩 心盗从门士 曰加，為了這種目的，在最大化 光吸收度的同時必須滅少 ^ ^ , 射率。考慮前述情況，構成 PN接面半導體基板的用於 '灰陽能電池的矽晶圓應具有形 成在其表面上的微金字挞姓 α、構’且可被提供有抗反射的 薄嫉。已被紋理化成微金 予％結構的矽晶圓表面可減少 具有廣範圍波長的入射光 W反射率，隨之增加吸收光的 量。因此’太陽能電池的 攻吨，也就是該太陽能電池的 效率4被提1¾。 用於财晶圓表面紋理化成微金字塔結構的方法已被揭 露’例如，美國專利編號4,137,123描述了 一種石夕紋理 蚀刻洛液’其中將0. 5至1〇重量％的矽溶解於非等向性蝕 刻（一般為「乾蝕刻」）溶液中，該等向性蝕刻溶液包 含0至75體積％的乙二醇、〇. 〇5至5〇重量％的氫氧化鉀 以及剩餘部分為水。然而，這種蝕刻溶液導致金字塔形 成的失敗’因此增加了光反射率，並造成光吸收功效的 降低。 此外’歐洲專利編號0477424提出了 一種將氧進料至紋理 钮刻溶液的紋理蝕刻方法，也就是執行通氣過程達數分 鐘，該紋理蝕刻溶液包括溶解於乙二醇、氫氧化鉀以及 該剩餘部分為水的混合物中的矽。然而，上述触刻方法 造成金字塔形成的失敗，隨之增加光反射率，同時降低 光吸收功效，且此外，具有進一步需要替代性的通氣裝 置的缺點。 此外，韓國專利註冊編號0 180621揭露了一種紋理蝕刻溶 液’該紋理钱刻溶液包含0.5至5%的氫氧化钾溶液、3至 20體積％的異丙醇以及75至96. 5體積％的去離子水的混 A0101 第5頁/共21頁 201245418 合物；美國專利編號6，4 51，21 8揭露了一種包括驗金屬 化合物、異丙醇、水性鹼性乙二醇以及水的紋理蝕刻溶 液。然而，由於每種上述i虫刻溶液包括具有相對低沸點 的異丙醇，且此材料必須在紋理化期間被額外導入，可 能造成關於生產力與成本上的經濟不利。此外，該額外 導入的異丙if·導致該钮刻溶液的溫度梯度’因此在碎晶 圓表面上的區域内增加了紋理品質的偏差，且最終降低 均勻性。 【發明内容】 [0003] 因此，本發明的目標是提供一種用於結晶矽晶圓的紋理 蝕刻溶液組成物，其能夠在該結晶矽晶圓表面上提供微 金字塔結構時控制關於矽結晶方向的蝕刻率，同時最小 化區域内紋理品質的偏差，因此改進光吸收功效。 本發明的另一個目標是提供一種用於結晶矽晶圓的紋理 蝕刻溶液組成物，而不需應用通氣過程以及在紋理化期 間導入額外的蝕刻溶液成分。 此外，本發明的又另一個目標是提供一種使用用於結晶 矽晶圓的前述紋理蝕刻溶液組成物的紋理蝕刻方法。 為了完成上述目標，本發明提供下述。 (1 ) 一種用於結晶矽晶圓的紋理蝕刻溶液組成物，包含 :0. 1至20重量％的鹼性化合物；10_6至10重量％的具有 含有C2至C6烯烴基的官能基的環狀化合物，其中該環狀 化合物包括氮子；以及作為剩餘部分的水。 (2 )根據上述第（1 )項所述的組成物，該鹼性化合物 是選自氫氧化鉀、氫氧化鈉、氫氧化銨、四羥曱基銨以 1013286431-0 第6頁/共21頁 201245418 及四羥乙基銨所組成的群組的至少一者。 (3) 根據上述第〇)項所述的組成物，該環狀化合物 是選自N-乙烯基哌嗪、N-乙烯基甲基哌嗪、N-乙烯基乙 基°底嗓、N -乙烯基- Ν’ -曱基旅°秦、N -丙稀醯基旅嗪、 Ν-丙烯醯基-Ν’ -甲基哌嗪、Ν-乙烯基嗎啉、Ν-乙烯基 曱基嗎琳、Ν_乙稀基乙基嗎嚇·、Ν_丙稀酿基嗎嚇·、Ν -乙 稀基旅咬酮、Ν -乙稀基甲基β底咬酮、Ν -乙烯基乙基π底咬 酮、Ν-丙烯醯基哌啶酮、Ν-乙烯基。比咯烷酮、Ν-乙烯基 曱基吡咯烷酮、Ν-乙烯基乙基-2-吡咯烷酮、Ν-丙烯醯基 吡咯烷酮、Ν-乙烯基咔唑以及Ν-丙烯醯基咔唑所組成的 群組的至少一者。 (4) 根據上述第（1)項所述的組成物，該組成物更包 含至少一多醣，該多醣選自聚葡萄糖化合物、聚果糖化 合物、聚甘露糖化合物、聚半乳糖化合物以及其金屬鹽 類所組成的群組。 (5) 根據上述第（4)項所述的組成物，該多醣為至少 一聚葡萄糖化合物，該聚葡萄糖化合物選自纖維素、二 曱基胺基乙基纖維素、二乙基胺基乙基纖維素、乙基羥 乙基纖維素、甲基羥乙基纖維素、4-胺基苄基纖維素、 三乙基胺基乙基纖維素、氰基乙基纖維素、乙基纖維素 、曱基纖維素、羧甲基纖維素、羥乙基纖維素、羥丙基 纖維素、藻酸、直鏈澱粉、支鏈澱粉、果膠、澱粉、糊 精、α-環糊精、万-環糊精、環糊精、羥丙基-yS-環 糊精、曱基環糊精、類糊精、類糊精硫酸鈉、皂素 、肝糖、酵母聚糖、香菇多糖、裂褶菌多糖以及其金屬 鹽類所組成的群組。 1〇11Π68ί單編號腿01 第7頁/共21頁 1013286431-0 201245418 (6) 根據上述第（4)項所述的組成物，相對於用於結 晶矽晶圓的紋理蝕刻溶液組成物的100重量％，以10 一9 至10重量％的量來包括該多醣。 (7) —種結晶矽晶圓的紋理蝕刻方法，包含：將該結晶 矽晶圓浸沒於根據上述第（1)至（6)項任一所述的紋 理餘刻溶液組成物中、0;麗該組成物、或將該結晶碎晶 圓浸沒該組成物中，同時將該組成物喷灑於該晶圓上。 (8) 根據上述第（7)項所述的方法，該浸沒、喷灑或 浸沒與喷灑是在50至100°C下進行30秒至60分鐘。 根據本發明用於結晶矽晶圓的紋理蝕刻溶液組成物以及 紋理蝕刻方法，可能藉由控制關於矽結晶方向的蝕刻率 差異，而更密集地形成以及配置較小的微金字塔，該微 金字塔具有與本相關技術領域中已知不同的形狀的各個 面，其中每個面從該微金字塔的單峰至底面做出曲線。 此外，本發明可最小化該結晶矽晶圓表面上區域内的紋 理品質偏差，因此改進紋理均勻性。經由此，可最大化 陽光吸收的量，同時大大地減少光反射率，藉此大大地 增加光吸收功效。 此外，本發明既不需要導入額外的蝕刻溶液成分，也不 需在紋理化期間應用通氣設備，因此提高了品質以及生 產力。 【實施方式】 [0004] 本發明提供一種用於結晶矽晶圓的紋理蝕刻溶液組成物 ，以及此外，一種使用該紋理蝕刻溶液組成物的結晶矽 晶圓紋理蝕刻方法。 單編號删1 第8頁/共21頁 1013286431-0 201245418 在下文中，將給出下述描述以更具體地解釋本發明。 根據本發明用於結晶矽晶圓的紋理蝕刻溶液組成物可包 含：鹼性化合物；與含有C2至C6烯烴基的官能基鍵結的 環狀化合物，其中該環狀化合物包括氮原子以及水作為 剩餘部分。 更特別的是，前述組成物包括0. 1至20重量％的鹼性化合 物；10_6至10重量％的具有含有C2至C6烯烴基的官能基 的環狀化合物，其中該環狀化合物包括氮原子以及水作 為剩餘部分。 該鹼性化合物是蝕刻結晶矽晶圓表面的成分，且該成分 的種類不特別受限制。例如，使用了氫氧化钟、氫氧化 鈉、氫氧化銨、四羥曱基銨、四羥乙基銨，等等，且在 這些之中，較佳使用氫氧化鉀或氫氧化納。這些化合物 被單獨或以其二或更多個的組合而使用。 相對於用於結晶矽晶圓的理蝕刻溶液化合物之總10 0重量 %，可使用0.1至20重量％的量來包括驗性化合物，且較 佳為1至5重量％。當該鹼性化合物的含量在前述範圍内 時，可進行蝕刻該矽晶圓的表面。 本發明包括環狀化合物，且具體是，與具有C2至C6烯烴 基的官能基鍵結的環狀化合物，其中該環狀化合物包括 氮原子。特別是，該官能基可含有至少一烯烴基、只有 烯烴基或加上烯烴基的其他取代基。此外，至少一官能 基鍵結至該環狀化合物，且可鍵結至氮原子或除了該環 狀化合物的氮之外的任何其他原子。 環狀化合物可控制分別如同矽的結晶方向的在Si 110方 向以及Si 111方向的蝕刻率差異，以提供與相關技術領 1011116#單編號厕01 第9頁/共21頁 1013286431-0 201245418 域已知不同形態的微金字塔。更特別的是，對於根據相 關技術領域而形成的任何微金字塔，形成該微金字塔的 各別面從其單峰至底面為線性的（第la圖）。另一方面 ’使用本發明環狀化合物而形成的微金字塔包含各自的 面’其每個變成曲線，也就是形成平滑的曲線（第丨匕圖 )°此外’具有小尺寸的微金字塔被更密集地配置。經 由此’可藉由減少光反射率而改進光吸收功效。此外， 該環狀化合物可快速地減少由蝕刻產生的氫氣泡的量， 因此預防氣泡洞的發生。 環狀化合物可包括，例如；N_乙烯基哌嗪、N-乙烯基甲 基0底嗪、N-乙烯基乙基哌嗪、N-乙烯基-N，-甲基哌嗪、 N-丙烯醯基哌嗪、N-丙烯醯基-N，_曱基哌嗪、N-乙烯 基嗎啉、N-乙烯基曱基嗎啉、N-乙烯基乙基嗎啉、N-丙 烯醯基嗎啉、N-乙烯基哌啶酮、N-乙烯基甲基哌啶酮、 N -乙烯基乙基π底咬酿|、N -丙烯醢基u底咬_、N -乙烯基。比 咯烷酮、N-乙烯基曱基吡咯烷酮、N-乙烯基乙基-2-吡咯 烷酮、N-丙烯醯基吡咯烷酮、N-乙烯基咔唑、N-丙稀醯 基咔唑或諸如此類，其可被單獨或與其二或更多個組合 而使用。 相對於用於結晶矽晶圓的紋理蝕刻溶液組成物之1 00重量 % ’可使用10 6至10重量％的量來包括環狀化合物，且 較佳為1 0_3至1重量％。如果該環狀化合物的含量在前述 範圍内，可有效地改進該矽晶圓表面的濕潤性，以最小 化紋理品質的偏差，並因此提升均勻性。此外，可輕易 地形成具有與相關技術領域不同形狀的微金字塔。如果 該含量超過1 〇重量％ ’由於關於矽的結晶方向的蝕刻率 1013286431-0 1()111168f單編號A0101 第10頁/共21頁 201245418 差異難以控制，不能輕易地提供具有想要形態的微金字 塔。 根據本發明用於結晶矽晶圓的紋理蝕刻溶液組成物可進 一步包括多酷。 多醣是糖類（包含二或更多個單糖，以經由糖苷鍵結而形 成大分子），預防過度蝕刻以及藉由使用鹼性化合物的蝕 刻加速，以製備一致的微金字塔，同時快速地減少由蝕 刻掉矽晶圓表面而產生的氫氣泡，藉此改進其外部外觀 〇 多醣的範例可包括；聚葡萄糖化合物、聚果糖化合物、 聚甘露糖化合物、聚半乳糖化合物以及其金屬鹽類。在 這些之中，較佳使用聚葡萄糖化合物以及其金屬鹽類。 前述物質可單獨或與其二或更多個組合而使用。 聚葡萄糖化合物可包括，例如；纖維素、二甲基胺基纖 維素、二乙基胺基乙基纖維素、乙基羥乙基纖維素、曱 基羥乙基纖維素、4-胺基苄基纖維素、三乙基胺基乙基 纖維素、氰基乙基纖維素、乙基纖維素、曱基纖維素、 羧曱基纖維素、羥乙基纖維素、羥丙基纖維素、藻酸、 直鏈澱粉、支鏈澱粉、果膠、澱粉、糊精、α -環糊精、 環糊精、環糊精、經丙基_y5_環糊精、甲基_jS_ 環糊精、類糊精、類糊精硫酸鈉、皂素、肝糖、酵母聚 糖、香菇多糖、裂褶菌多糖以及其金屬鹽類。 多醣可具有5,000至1，000,000，以及較佳為50,000至 200, 000的分子量。 相對於用於結晶矽晶圓的紋理蝕刻溶液組成物的100重量 %，可使用10 —9至10重量％，以及較佳為1(Γ6至1重量％ 10111168#單編號 Α_ 第11頁/共21頁 1013286431-0 201245418 的含量來包括多醣。如果該多醣的含量在前述範圍内， 可預防過度蝕刻，並可有效地控制蝕刻加速。當該含量 超過ίο重量％時，蝕刻率在使用鹼性化合物時可能會突 然降低，導致形成想要微金字塔的困難。 此外，根據本發明用於結晶矽晶圓的紋理蝕刻溶液組成 物可進一步包括界面活性劑、脂肪酸以及其鹼金屬鹽類 的至少其中之一，以及含有二氧化矽的化合物。 用於結晶矽晶圓的紋理蝕刻溶液組成物可進一步包括水 作為的組成物的總100重量％的剩餘部分。 水的類型不受特別的限制，然而，較佳為去離子水以及 ，更佳為，用於半導體製程、具有18 ΜΩ/cm或更高特定 電阻的去離子水。 因此，根據本發明由前述成分組成的用於結晶矽晶圓的 紋理蝕刻溶液組成物大體上使用與具有C2至C6烯烴基的 官能基鍵結的特定環狀化合物，其中該環狀化合物包括 以最佳含量的在環狀化合物之間選擇的氮原子，以產生 小尺寸且更密集配置、與相關技術領域中已知微金字塔 不同的微金字塔，同時最小化結晶矽晶圓表面上區域内 的紋理品質偏差，藉此改進該紋理的均勻性。經由此， 陽光吸收的量被最大化，同時減少了光反射率，因此改 進了光吸收功效。 根據本發明用於結晶矽晶圓的 紋理蝕刻溶液組成物可被適當地使用在常用的蝕刻過程 中，例如浸潰、喷灑、嵌入類型的蝕刻，等等。 本發明提供一種結晶矽晶圓的紋理蝕刻方法，使用上述 用於結晶矽晶圓的紋理蝕刻溶液組成物。 結晶矽晶圓的紋理蝕刻方法可包括將該結晶矽晶圓浸沒 umms#單編號 A0101 第12頁/共21頁 1013286431-0 201245418 於用於結晶矽晶圓的蝕刻溶液組成物中、喷灑該組成物 、或將該結晶矽晶圓浸沒於其中同時喷灑。 可不特別限制浸沒及/或喷灑的次數，在該浸沒以及喷灑 同時執行的例子中，也可不限制其操作順序。 浸沒、喷灑或浸沒以及喷灑可在50至100°C進行30秒至 6 0分鐘。 如上所述，根據本發明的結晶矽晶圓紋理蝕刻方法不需 導入額外的通氣設備以供應氧，因此，在開始生產以及 處理成本方面為經濟的，且藉由簡單的過程能夠形成一 致的微金字塔結構。 在下文中，將描述較佳的具體實施例，以參照範例以及 比較性範例而更具體地了解本發明。然而，對於本領域 的技術人員而言，將清楚的是，這種具體實施例是提供 用於示例的目的，且各種修飾以及改變是可能的，而不 悖離本發明的範圍以及精神，且如附帶申請專利範圍所 定義的，這種修飾以及改變充分地包括在本發明中。 範例 範例1 藉由混合2重量％的氫氧化鉀（KOH)、0.1重量％的卜 乙烯基吡咯烷酮、0. 02重量％的藻酸鈉（AANa)以及作 為剩餘部分的去離子水而製備用於結晶矽晶圓的紋理蝕 刻溶液組成物。 範例2至4以及比較性範例1至5 除了使用列於下述表1中的基本成分以及其含量之外，執 行與範例1中所描述的相同程序。這裡，該含量意指重量 %。 1〇m16rf單編號 A0101 第13頁/共21頁 1013286431-0 201245418 [表1][0001] This application claims priority from Korean Patent Application No. 1 0-20 1 1 -0037990, filed on Apr. 22, 2011 in the Korean Intellectual Property Office, the entire disclosure of which is incorporated herein reference. The present invention relates to a texture etching solution composition for a crystalline germanium wafer, and a texture etching method capable of controlling the shape of the micropyramid on the surface of the crystalline germanium wafer and minimizing the area on the surface Texture quality deviation within to improve light absorption. [Prior Art] [0002] In recent years, solar cells have rapidly spread, and are well known as energy sources for the next generation and electronic devices that directly convert clean energy, that is, convert sunlight into electricity. Such a solar cell has in principle a P-type germanium semiconductor comprising germanium and boron added thereto, and comprises a PN junction semiconductor substrate, which in principle comprises a p-type germanium semiconductor having germanium and boron added thereto, and by phosphorus (P) diffusing into the surface of the P-type germanium semiconductor to form an N-type germanium semiconductor layer. When light (such as sunlight) illuminates a substrate having an electric field provided by a PN junction, electrons (-) and holes (+) in the semiconductor are excited, and such excited electrons (-) and holes (+) It can move freely and randomly within the semiconductor. In this case, electrons (-) in the electric field formed by the P N junction can be moved into the N-type semiconductor while the hole (+) is moved to the P-type semiconductor. If an electrode is provided on the surface of the P-type semiconductor and the N-type semiconductor to flow electrons toward an external circuit, an electric current is generated. Based on this principle, sunlight is converted into electrical energy. Therefore, in order to improve the solar conversion efficiency, the electrical output per unit area of the PN junction semiconductor substrate 1013286431-0 page 4 / 21 pages 201245418 Ο 1013286431-0 should be concealed as much as possible from the gates, in order to For this purpose, in order to maximize the light absorption, it is necessary to eliminate the ^ ^, the rate. In view of the foregoing, the germanium wafer for the 'gray solar cell' constituting the PN junction semiconductor substrate should have a micro-gold-like name α, structure formed on the surface thereof and can be provided with an anti-reflection thin crucible. The surface of the germanium wafer that has been textured to a micro-gold structure can reduce the reflectance of incident light W with a wide range of wavelengths, which in turn increases the amount of light absorbed. Therefore, the attack on the solar cell, that is, the efficiency of the solar cell 4 is raised. A method for texturing a surface of a wafer into a micro-pyramid structure has been disclosed. For example, U.S. Patent No. 4,137,123 describes a lithograph texture etching solution in which 0.5 to 1% by weight of lanthanum is dissolved in an anisotropic manner. In an etched (typically "dry etch") solution, the isotropic etch solution comprises from 0 to 75% by volume of ethylene glycol, 〇. 〇5 to 5% by weight of potassium hydroxide and the balance being water. However, such an etching solution causes a failure of the pyramid formation' thus increasing the light reflectance and causing a decrease in light absorbing efficiency. Furthermore, 'European Patent No. 0477424 proposes a texture etching method for feeding oxygen to a textured button engraving solution, that is, performing aeration process for several minutes, the texture etching solution comprising dissolving in ethylene glycol, potassium hydroxide and the remainder It is a mixture of water in a mixture. However, the above-described etch method causes failure of pyramid formation, which in turn increases light reflectivity while reducing light absorbing efficiency, and furthermore has the disadvantage of further requiring an venting device. In addition, Korean Patent Registration No. 0 180621 discloses a texture etching solution. The texture etching solution comprises 0.5 to 5% potassium hydroxide solution, 3 to 20% by volume of isopropanol, and 75 to 96.5% by volume. Ionized water mixed A0101 page 5 / 21 pages 201245418 compound; US Patent No. 6, 4 51, 21 8 discloses a texture etching solution including a metal compound, isopropyl alcohol, aqueous alkaline glycol and water . However, since each of the above-mentioned i-etching solutions includes isopropanol having a relatively low boiling point, and this material must be additionally introduced during texturing, it may cause economic disadvantages in terms of productivity and cost. In addition, the additional introduced isopropylif· results in a temperature gradient of the button solution' thus increasing the texture quality deviation in the region on the surface of the pulverized crystal and ultimately reducing the uniformity. SUMMARY OF THE INVENTION [0003] Accordingly, it is an object of the present invention to provide a texture etching solution composition for a crystalline germanium wafer that is capable of controlling the direction of germanium crystals when a micropyramid structure is provided on the surface of the crystalline germanium wafer. The etch rate, while minimizing variations in texture quality within the region, thus improving light absorption efficiency. Another object of the present invention is to provide a textured etching solution composition for crystallizing tantalum wafers without the application of aeration processes and the introduction of additional etching solution components during texturing. Furthermore, it is still another object of the present invention to provide a texture etching method using the foregoing texture etching solution composition for crystallizing a germanium wafer. In order to accomplish the above object, the present invention provides the following. (1) A texture etching solution composition for crystallizing a germanium wafer, comprising: 0.1 to 20% by weight of a basic compound; and 10 to 6 to 10% by weight of a ring having a functional group having a C2 to C6 alkene group a compound wherein the cyclic compound comprises nitrogen; and water as the remainder. (2) The composition according to the above item (1), which is selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, and tetrahydrocarbylammonium to 1013286431-0 page 6 of 21 At least one of the group consisting of 201245418 and tetrahydroxyethylammonium. (3) The composition according to the above item (), wherein the cyclic compound is selected from the group consisting of N-vinylpiperazine, N-vinylmethylpiperazine, N-vinylethyl, and N- Vinyl-Ν'-曱基旅°Qin, N-propyl sulfhydryl-pilin, hydrazine-acryloyl-yl-p-methyl piperazine, hydrazine-vinylmorpholine, hydrazine-vinyl hydrazine , Ν _ 乙 基 乙基 吗 吗 Ν Ν 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙Bottom ketone, hydrazine-acrylopylpiperidone, hydrazine-vinyl. a group consisting of pyrrolidone, fluorenyl-vinylpyrrolidone, fluorene-vinylethyl-2-pyrrolidone, anthracene-acryloylpyrrolidone, anthracene-vinylcarbazole, and anthracene-acryloylcarbazole At least one of them. (4) The composition according to the above item (1), further comprising at least one polysaccharide selected from the group consisting of polydextrose compounds, polyfructose compounds, polymannose compounds, polygalactose compounds, and metals thereof A group of salts. (5) The composition according to the above item (4), wherein the polysaccharide is at least one polydextrose compound selected from the group consisting of cellulose, dimethylaminoethyl cellulose, and diethylaminoethyl Cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, 4-aminobenzyl cellulose, triethylaminoethyl cellulose, cyanoethyl cellulose, ethyl cellulose , mercapto cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin, α-cyclodextrin, 10,000 -cyclodextrin, cyclodextrin, hydroxypropyl-yS-cyclodextrin, decyl cyclodextrin, dextrin, sodium dextrin, saponin, glycogen, zymosan, lentinan, crease A group consisting of polysaccharides and their metal salts. 1〇11Π68ί单号腿01 Page 7 of 21 1013286431-0 201245418 (6) The composition according to the above item (4), relative to the composition of the texture etching solution for crystallizing the germanium wafer The weight %, the polysaccharide is included in an amount of 10 to 9 to 10% by weight. (7) A method for etching a crystallization of a wafer, comprising: immersing the crystallization wafer in a texture remnant solution composition according to any one of the above items (1) to (6), 0; The composition is immersed in the composition, or the composition is immersed in the composition while the composition is sprayed onto the wafer. (8) The immersion, spraying or immersion and spraying are carried out at 50 to 100 ° C for 30 seconds to 60 minutes according to the method described in the above item (7). According to the texture etching solution composition and the texture etching method for a crystalline germanium wafer according to the present invention, it is possible to form and configure a smaller micropyramid more densely by controlling the difference in etching rate with respect to the crystal orientation of the germanium, the micropyramid having Each face of a different shape than known in the related art, wherein each face curves from a single peak to a bottom face of the micropyramid. In addition, the present invention minimizes texture quality variations in the area on the surface of the crystalline germanium wafer, thereby improving texture uniformity. Thereby, the amount of sunlight absorption can be maximized while greatly reducing the light reflectance, thereby greatly increasing the light absorption efficiency. In addition, the present invention does not require the introduction of additional etching solution components, nor does it require the application of aeration equipment during texturing, thereby improving quality and productivity. [Embodiment] The present invention provides a texture etching solution composition for a crystalline germanium wafer, and further, a crystalline germanium wafer texture etching method using the texture etching solution composition. Single Number Delete 1 Page 8 of 21 1013286431-0 201245418 Hereinafter, the following description will be given to explain the present invention more specifically. The texture etching solution composition for a crystalline germanium wafer according to the present invention may comprise: a basic compound; a cyclic compound bonded to a functional group containing a C2 to C6 alkene group, wherein the cyclic compound includes a nitrogen atom and water as The remaining part. More specifically, the foregoing composition includes 0.1 to 20% by weight of a basic compound; 10 to 6 to 10% by weight of a cyclic compound having a functional group containing a C2 to C6 alkene group, wherein the cyclic compound includes a nitrogen atom And water as the rest. The basic compound is a component which etches the surface of the crystallized wafer, and the kind of the component is not particularly limited. For example, a hydrazine hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydrocarbylammonium, tetrahydroxyethylammonium or the like is used, and among them, potassium hydroxide or sodium hydroxide is preferably used. These compounds are used singly or in combination of two or more thereof. An amount of 0.1 to 20% by weight may be used to include the test compound, and preferably 1 to 5% by weight, based on the total 100% by weight of the etch solution compound used for the crystallization of the ruthenium wafer. When the content of the basic compound is within the above range, the surface of the tantalum wafer can be etched. The present invention includes a cyclic compound, and specifically, a cyclic compound bonded to a functional group having a C2 to C6 olefin group, wherein the cyclic compound includes a nitrogen atom. In particular, the functional group may contain at least one olefin group, only an olefin group or other substituents added to the olefin group. Further, at least a functional group is bonded to the cyclic compound, and may be bonded to a nitrogen atom or any other atom than the nitrogen of the cyclic compound. The cyclic compound can control the difference in etching rate in the Si 110 direction and the Si 111 direction, respectively, like the crystal orientation of the crucible, to provide the related art collar 1011116# single number toilet 01 page 9 / total 21 page 1013286431-0 201245418 domain has been Know the micro-pyramids of different forms. More specifically, for any micropyramid formed according to the relevant technical field, the individual faces forming the micropyramid are linear from their unimodal to bottom surface (Fig. la). On the other hand, 'the micro-pyramid formed using the cyclic compound of the present invention contains the respective faces', each of which becomes a curve, that is, forms a smooth curve (Fig.). Further, the micro-pyramid having a small size is denser. Ground configuration. By this, the light absorption efficiency can be improved by reducing the light reflectance. Further, the cyclic compound can rapidly reduce the amount of hydrogen bubbles generated by etching, thus preventing the occurrence of bubble holes. The cyclic compound may include, for example, N-vinylpiperazine, N-vinylmethyloxazide, N-vinylethylpiperazine, N-vinyl-N,-methylpiperazine, N-propylene Mercaptopazine, N-propenyl-N,-mercaptopiperazine, N-vinylmorpholine, N-vinylmorphylmorpholine, N-vinylethylmorpholine, N-propenyl fluorenyl Porphyrin, N-vinylpiperidone, N-vinylmethylpiperidone, N-vinylethyl π bottom bite, N-propenyl sulfonate, N-vinyl. Pyrrolidone, N-vinylpyridylpyrrolidone, N-vinylethyl-2-pyrrolidone, N-propenylpyrrolidone, N-vinylcarbazole, N-propylcarbenylcarbazole or the like, It can be used alone or in combination of two or more thereof. The cyclic compound may be used in an amount of 10 6 to 10% by weight based on 100 parts by weight of the texture etching solution composition for crystallizing the germanium wafer, and is preferably from 10 3 to 1% by weight. If the content of the cyclic compound is within the above range, the wettability of the surface of the tantalum wafer can be effectively improved to minimize variations in texture quality and thus improve uniformity. Further, a micro pyramid having a shape different from the related art can be easily formed. If the content exceeds 1 〇% by weight 'Because the etching rate with respect to the crystal orientation of bismuth 1013286431-0 1 () 111168f single number A0101 page 10 / 21 pages 201245418 The difference is difficult to control, can not easily provide the micro with the desired shape pyramid. The texture etching solution composition for crystallizing germanium wafers according to the present invention may further include how cool. Polysaccharides are sugars (containing two or more monosaccharides to form macromolecules via glycosidation), preventing over-etching and etch acceleration by using basic compounds to prepare a consistent micro-pyramid while rapidly reducing Hydrogen bubbles generated by etching away the surface of the wafer, thereby improving its external appearance. Examples of the polysaccharide may include polydextrose compounds, polyfructose compounds, polymannose compounds, polygalactose compounds, and metal salts thereof. Among these, polydextrose compounds and metal salts thereof are preferably used. The foregoing substances may be used singly or in combination of two or more thereof. The polydextrose compound may include, for example, cellulose, dimethylamino cellulose, diethylaminoethyl cellulose, ethyl hydroxyethyl cellulose, mercapto hydroxyethyl cellulose, 4-aminobenzyl chloride. Cellulose, triethylaminoethylcellulose, cyanoethylcellulose, ethylcellulose, mercaptocellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, algae Acid, amylose, amylopectin, pectin, starch, dextrin, α-cyclodextrin, cyclodextrin, cyclodextrin, propyl _y5_cyclodextrin, methyl _jS_cyclodextrin, Dextrin, sodium dextrin, saponin, glycogen, zymosan, lentinan, Schizophyllum polysaccharides and metal salts thereof. The polysaccharide may have a molecular weight of 5,000 to 1,000,000, and preferably 50,000 to 2,000,000. 10 to 9 to 10% by weight, and preferably 1 (Γ6 to 1% by weight, 10111168# single number Α_第11页/total) may be used with respect to 100% by weight of the texture etching solution composition for crystallizing the germanium wafer. The content of 21 pages 1013286431-0 201245418 includes polysaccharides. If the content of the polysaccharide is within the foregoing range, excessive etching can be prevented, and the etching acceleration can be effectively controlled. When the content exceeds ίο% by weight, the etching rate is alkaline. The compound may suddenly decrease, resulting in difficulty in forming a desired micropyramid. Further, the texture etching solution composition for crystallizing a germanium wafer according to the present invention may further include at least one of a surfactant, a fatty acid, and an alkali metal salt thereof. One, and a compound containing cerium oxide. The texture etching solution composition for crystallizing the cerium wafer may further include water as a remainder of the total 100% by weight of the composition. The type of water is not particularly limited, however Preferably, it is deionized water and, more preferably, deionized water for a semiconductor process having a specific resistance of 18 Μ Ω/cm or higher. The texture etching solution composition for a crystalline germanium wafer composed of the foregoing components according to the present invention generally uses a specific cyclic compound bonded to a functional group having a C2 to C6 alkene group, wherein the cyclic compound is included in an optimum The content of the nitrogen atoms selected between the cyclic compounds to produce a micro-pyramid of a small size and denser configuration, different from the micro-pyramids known in the related art, while minimizing the texture quality in the region on the surface of the crystalline germanium wafer. Deviation, thereby improving the uniformity of the texture. By this, the amount of sunlight absorption is maximized while reducing the light reflectivity, thus improving the light absorption efficiency. The composition of the texture etching solution for crystallizing the germanium wafer according to the present invention The material can be suitably used in a common etching process such as dipping, spraying, embedding type etching, etc. The present invention provides a texture etching method for a crystalline germanium wafer using the above-described method for crystallizing germanium wafers. Texture etching solution composition. The texture etching method of the crystalline germanium wafer may include immersing the crystalline germanium wafer umms# single number A0101 first 2 pages/total 21 pages 1013286431-0 201245418 In the etching solution composition for crystallizing the germanium wafer, spraying the composition, or immersing the crystal germanium wafer therein while spraying. The immersion and/or may not be particularly limited. Or the number of spraying, in the example of the simultaneous immersion and spraying, the operation sequence may not be limited. Immersion, spraying or immersion and spraying may be carried out at 50 to 100 ° C for 30 seconds to 60 minutes. According to the crystallization wafer texture etching method of the present invention, it is not necessary to introduce an additional venting device to supply oxygen, and therefore, it is economical in terms of starting production and processing cost, and a uniform micro pyramid can be formed by a simple process. In the following, preferred embodiments will be described, and the present invention will be more specifically understood by reference to examples and comparative examples. However, it will be apparent to those skilled in the art that the present invention may be Such modifications and variations are fully encompassed by the invention as defined by the scope of the appended claims. EXAMPLES Example 1 was prepared by mixing 2% by weight of potassium hydroxide (KOH), 0.1% by weight of vinylpyrrolidone, 0.02% by weight of sodium alginate (AANa), and as the remainder of deionized water. A textured etching solution composition of a crystalline germanium wafer. Examples 2 to 4 and Comparative Examples 1 to 5 The same procedures as those described in Example 1 were carried out except that the essential components listed in Table 1 below and their contents were used. Here, the content means % by weight. 1〇m16rf单号 A0101 Page 13 of 21 1013286431-0 201245418 [Table 1]
酬：氫氧傭 NVP : N-乙烯基吡略院_ NVC : N-乙烯基啊 EG :乙二醇 DPG :二丙二醇 BDG : 丁二醇 NMP : N-甲基耻咯院酮 AANa :藻酸納 CMCNa :羧甲基纖維素鈉 項目 鹼性化合物 環狀化雜 多酿 去離子水 嚴型 含量 類型 含量 類型 含量 範例1 KOH 2 NVP O.i AANa 0.02 97.8S 範例2 KOH 2 NVP 0.1 CMCNa 0.02 97.88 範例3 KOH 2 NVC 0.05 AAnA 0.01 97.94 範例4 KOH 2 NVC 0.05 CMCNa Ο.Οί 97.94 比較性範例1 KOH 1 - AANa 0.02 97.98 比較性範例2 KOH 2 EG Ο.ί AAna 0.02 97.88 比較性範例3 KOH 2 DPG 0.1 AANa 0.02 97.88 比較性範例4 KOH 2 BDG 0.1 AANa 0.03 97.88 比較性範例5 KOH 2 NMP 0.1 AANa 0.02 97.88 示範性範例 藉由下述程序，將根據上述範例以及比較性範例的用於 結晶矽晶圓的每個製備的紋理蝕刻溶液組成物進行紋理 蝕刻效果的評估，其結果示於表2中： 將單晶矽晶圓基板浸沒在8 0°C用於單晶矽晶圓的製備紋 理蝕刻溶液組成物達20分鐘。 (1 )紋理均勻性 經由數位相機、3D光學顯微鏡以及掃瞄電子顯微 鏡（SEM)來視覺觀察在紋理蝕刻之後獲得的單晶矽晶圓 1013286431-0 第14頁/共21頁 201245418 並根據 基板表面上形成的紋理偏差，也就是，均勻性， 下述標準來評估。 〈評估標準〉 ◎-金字塔形成在整個晶圓基板。 〇-金字塔不形成在部分的晶圓基板上（沒有金 字塔的部分少於5%)。 △-金字塔不形成在部分的晶圓基板上（沒有金 字塔的部分範圍為5至50%)。 X -金字塔不形成在大體上大部分的晶圓基板上 (沒有金字塔的部分為90%或更多）。 (2)反射率（％) 在具有波長帶寬約600 nm的光射照在紋理蝕刻之 後獲得的單晶矽晶圓基板表面上的例子中，使用UV光譜 儀測量反射率。 [表2 ] 項目 紋理均勻性 平均反射率（600nm，％) 範例1 ◎ 9.31 範例2 ◎ 9.28 範例3 ◎ 9.34 範例4 ◎ 9.34 比較性範例1 〇 10.54 比較性範例2 〇 10.89 比較性範例3 △ 21.12 比較性範例4 △ 20.64 比較性範例5 ◎ 10.96 如表2中所示，在使用根據本發明範例1至4中製備的所任 一紋理蝕刻溶液組成物進行紋理蝕刻的例子中，展示了 單晶矽晶圓表面上微金字塔區域内的品質偏差被減低， 因此確保極佳的均勻性，並減少光反射率，隨之改進光 10111168产單編& A0101 第15頁/共21頁 1013286431-0 201245418 吸收功效，該紋理餘刻溶液組成物包括驗性化合物；與 含有C2至C6烯烴基的官能基鍵結的環狀化合物，其中該 環狀化合物包括氮原子；以及作為剩餘部分的水。 另一方面，當使用比較性範例1中所製備不含環狀化合物 的紋理蝕刻溶液組成物時，紋理均勻性比前述範例中的 還低。同樣地，發現在比較性範例2至4中含有環狀化合 物之外的化合物的產物顯示了降低的均勻性或大大減少 的光反射率。此外，對於比較性範例5中含有含量在根據 本發明預定範圍之外的環狀化合物的產物，可看到的是 ，雖然紋理均勻性極佳，具有與本發明中所描述不同形 狀的微金字塔已產生，並展現比前述範例還高的反射率 〇 第2以及3圖為描繪在使用範例1以及比較性範例5中所製 備的每個紋理蝕刻溶液組成物來紋理蝕刻之後獲得的結 晶矽晶圓基板表面的SEM照片。從這些圖式中，可確認的 是，使用範例5中的組成物而形成在該矽晶圓基板上的微 金字塔具有從該金字塔的單峰至底面完全為線性的各自 的面，且顯示出第la圖中所描繪的形態。另一方面，如 第lb圖中所描繪，使用範例1中的組成物而形成在該矽晶 圓基板上的微金字塔展現了從該金字塔的單峰至底面為 曲線形狀的各自的面。此外，相較於比較性範例5，展現 了根據本發明範例1中所獲得的微金字塔具有較高的均勻 性以及減小的尺寸。因此，由於微金字塔形狀的不同， 可最大化陽光吸收，同時大大地減少光反射率。 雖然已參照較佳的具體實施例描述了本發明，相關技術 領域的技術人員將了解的是，其中可做出各種修飾以及 1011116#單編號纽01 第16頁/共21頁 1013286431-0 201245418 變化，而不悖離如附帶申請專利範圍所定義的本發明範 [0005] 〇 圍。 【圖式簡單說明】 從下述詳細的描述並結合伴隨的圖式，本發明的上述以 及其他目標、特徵以及其他優勢將更清楚地被了解，其 中： 第1圖是描繪（a)根據相關技術而藉由紋理蝕刻 矽晶圓所形成的微金字塔以及（b)根據本發明所形成的 微金字塔的橫截面圖； 第2圖是描繪（a)使用本發明範例1中所製備用 於結晶矽晶圓的紋理蝕刻溶液組成物來紋理蝕刻的單晶 矽晶圓的表面，以及（b)橫截面的掃瞄電子顯微鏡（ SEM)照片；以及 第3圖是描繪（a)使用比較性範例5中所製備用 於結晶矽晶圓的紋理蝕刻溶液組成物來紋理蝕刻的單晶 矽晶圓的表面，以及（b)橫截面的SEM照片。 〇 [0006] 【主要元件符號說明】 無0 101111680 編號應01 第17頁/共21頁 1013286431-0Remuneration: Hydrogen Oxygen NVP : N-Vinyl Pyroline _ NVC : N-Vinyl EG : Ethylene Glycol DPG : Dipropylene Glycol BDG : Butane Glycol NMP : N-Methylpyrrolidone AANa : Alginic Acid Nano CMCNa : Carboxymethyl Cellulose Sodium Item Basic Compound Cyclized Heteropoly Deionized Water Severe Content Type Content Type Example 1 KOH 2 NVP Oi AANa 0.02 97.8S Example 2 KOH 2 NVP 0.1 CMCNa 0.02 97.88 Example 3 KOH 2 NVC 0.05 AAnA 0.01 97.94 Example 4 KOH 2 NVC 0.05 CMCNa Ο.Οί 97.94 Comparative Example 1 KOH 1 - AANa 0.02 97.98 Comparative Example 2 KOH 2 EG Ο. ί AAna 0.02 97.88 Comparative Example 3 KOH 2 DPG 0.1 AANa 0.02 97.88 Comparative Example 4 KOH 2 BDG 0.1 AANa 0.03 97.88 Comparative Example 5 KOH 2 NMP 0.1 AANa 0.02 97.88 Exemplary Example Each of the wafers for crystallization according to the above examples and comparative examples was used by the following procedure. The prepared texture etching solution composition was evaluated for the texture etching effect, and the results are shown in Table 2: The single crystal germanium wafer substrate was immersed at 80 ° C for the single crystal germanium wafer to prepare the texture etching solution composition. Up to 20 points bell. (1) Texture uniformity A single crystal germanium wafer 1013286431-0 obtained after texture etching was visually observed by a digital camera, a 3D optical microscope, and a scanning electron microscope (SEM), and was based on the surface of the substrate. The texture deviation formed on the surface, that is, uniformity, is evaluated by the following criteria. <Evaluation Criteria> ◎ - Pyramid is formed on the entire wafer substrate. The 〇-pyramid is not formed on a portion of the wafer substrate (less than 5% of the portion of the pyramid). The Δ-pyramid is not formed on a part of the wafer substrate (the portion without the pyramid is 5 to 50%). The X-pyramid is not formed on a substantial portion of the wafer substrate (90% or more without the pyramid). (2) Reflectance (%) In the example of the surface of the single crystal germanium wafer substrate obtained after the light irradiation having a wavelength band of about 600 nm was obtained after the texture etching, the reflectance was measured using a UV spectrometer. [Table 2] Item Texture Uniformity Average Reflectance (600 nm, %) Example 1 ◎ 9.31 Example 2 ◎ 9.28 Example 3 ◎ 9.34 Example 4 ◎ 9.34 Comparative Example 1 〇 10.54 Comparative Example 2 〇 10.89 Comparative Example 3 △ 21.12 Comparative Example 4 Δ 20.64 Comparative Example 5 ◎ 10.96 As shown in Table 2, in the example of performing texture etching using any of the texture etching solution compositions prepared in Examples 1 to 4 of the present invention, single crystals were exhibited. The quality deviation in the micro-pyramid region on the surface of the wafer is reduced, thus ensuring excellent uniformity and reducing the light reflectivity, and subsequently improving the light 10111168 production single & A0101 page 15 / 21 pages 1013286431-0 201245418 Absorption efficacy, the texture remnant solution composition comprising an inspective compound; a cyclic compound bonded to a functional group containing a C2 to C6 olefin group, wherein the cyclic compound includes a nitrogen atom; and water as a remainder. On the other hand, when the texture etching solution composition containing no cyclic compound prepared in Comparative Example 1 was used, the texture uniformity was lower than that in the foregoing examples. Also, it was found that the products containing the compounds other than the cyclic compounds in Comparative Examples 2 to 4 showed reduced uniformity or greatly reduced light reflectance. Further, with respect to the product of Comparative Example 5 containing a cyclic compound having a content outside the predetermined range according to the present invention, it can be seen that although the texture uniformity is excellent, the micropyramid having a shape different from that described in the present invention is obtained. Has been produced and exhibits a higher reflectance than the foregoing examples. Figs. 2 and 3 are crystal twins obtained after texture etching using each of the texture etching solution compositions prepared in Example 1 and Comparative Example 5. SEM photograph of the surface of the circular substrate. From these drawings, it can be confirmed that the micropyramids formed on the tantalum wafer substrate using the composition in Example 5 have respective faces which are completely linear from the single peak to the bottom surface of the pyramid, and are displayed. The form depicted in Figure la. On the other hand, as depicted in Fig. 1b, the micropyramid formed on the twin circular substrate using the composition of Example 1 exhibits respective faces from a single peak to a bottom surface of the pyramid. Further, compared with Comparative Example 5, it was revealed that the micropyramid obtained in Example 1 of the present invention has higher uniformity and reduced size. Therefore, due to the difference in the shape of the micro-pyramid, the absorption of sunlight can be maximized while greatly reducing the light reflectance. Although the present invention has been described with reference to the preferred embodiments, those skilled in the relevant art will understand that various modifications can be made therein as well as 1011116#单号纽01第16页/共21页1013286431-0 201245418 Without departing from the scope of the invention as defined by the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and other advantages of the present invention will become more <RTIgt; a micro-pyramid formed by texture etching a germanium wafer and (b) a cross-sectional view of a micro-pyramid formed according to the present invention; and FIG. 2 is a drawing (a) used for crystallization prepared using Example 1 of the present invention a textured etching solution composition of the wafer to texture the surface of the etched single crystal germanium wafer, and (b) a scanning electron microscope (SEM) photograph of the cross section; and Fig. 3 depicts (a) a comparative example using A texture etching solution composition for crystallization of a germanium wafer is prepared in 5 to texture the surface of the etched single crystal germanium wafer, and (b) a SEM photograph of the cross section. 〇 [0006] [Main component symbol description] No 0 101111680 No. 01 Page 17 of 21 1013286431-0