201135955 六、發明說明： 【發明所屬技術領城】 著作權聲明 本專利文件的部分揭示包含受著作權保護的素材。當 本專利文件的揭示出現在專利商標局的專利檔案或記錄 時，著作權擁有者不反對任何人透過傳真複製專利文件或 專利揭示，但保有全部著作權權利。 發明領域 本發明大致上係有關裝置製造之領域，及更明確言 之’係有關諸如二氡化矽及矽等材料的紋理化用以增進薄 膜太陽能電池裝置的光钟。 C先前冬舒;3 發明背景 多種近代光伏（太陽能）電池典型地本質上為薄膜，藉此 若干感光材料薄膜沈積在基板上，然後用作為太陽能電池 的前表面或太陽表面。最常用的基板為各種形式的玻璃成 二氧化矽’但也可使用其它基板。因薄膜太陽能電池的感 光層太薄（典型地約為1-2微米），高度較佳將光捕陷於裝置 内部來獲得最大吸光。傳統上，矽晶圓太陽能電池採用紋 理化石夕表面來獲得光之捕陷於電池内最大化。此項紋理化 作用係藉由將矽晶圓沈浸於反應性化學品浴槽内來優先於 —個晶體方向触刻石夕，如此留下已被圖案化的電池表面而 達成。經圖案化表面藉由增加自表面反射的光被轉向返回 至裝置表面上’而非射入周圍空氣’來減少光之反射出電 201135955 池之外。 目前並無任何用以紋理化感光材料諸如結晶矽之薄膜 的常用方法。無法如同使用矽晶圓太陽能電池般達成化學 触刻石夕薄膜，原因在於石夕層太薄之故。典型地，係於感光 層薄膜沈積之前，藉經修飾或紋理化基板而達成光的捕陷 於此等薄膜。然後，當沈積感光材料時，所形成的薄骐隨 形於下方基板之已紋理化輪廓，因而允許以覆晶基板配置 組態形成太陽能電池。 目前用於紋理化薄膜太陽能電池所使用的基板之方法 包括但非限於鋁感應紋理化、溶膠-凝膠處理、於化學蝕刻 劑浸塗、及喷砂處理。 紹感應紋理化處理涉及於玻璃基板上沈積典型地於4 〇 奈米至230奈米範圍之鋁薄層。接著為於約610°C溫度將錄 鋁玻璃進行熱退火典型地歷時4〇分鐘。於退火處理期間， 鋁被玻璃氧化而導致氧化鋁及矽形成於玻璃表面上其隨後 係使用濕蝕刻技術去除而留下已紋理化的表面。雖然此種 方法適合用於薄膜光伏製程所使用的大型基板且相當簡 單，但一般認為太過昂貴而無法於商業上實施。 另一種業已發展用於紋理化薄膜結晶矽太陽能電池之 方法涉及使用二氧化矽粒子被覆玻璃表面。此種加成紋理 化方法係經由將玻璃基板浸塗於溶膠凝膠浴内。包含〇1 微米至2微来範圍的二氧化矽粒子之粒狀珠粒沈積在基板 表面上形成已紋理化的表面。於若干情況下，溶膠凝膠溶 液也含有0.5微米至3微米範圍之粉碎石英來改良紋理化結 201135955 果。但此種浸塗法可能導致玻璃表面上不均勻的紋理4 未經紋理化區除了光阱減少外，也可能形成應力集中點。 藉此方式的浸塗法也涉及隨後的帶材烤乾而可< 月t*托！终漆 品的成本。 藉將玻璃片材浸泡入酸浴（諸如氫氟酸）或以其它 均勻施用蚀刻劑而進行玻璃的直接化學|虫刻屬於扣成纟气 化法的一個實例。眾所周知由於需要大量蝕刻劑材料故理 該方法駭人地昂貴。此外，廢棄大量已用過的蝕刻劑斜戸 境造成危害。直接蝕刻玻璃也容易形成均勻触刻而缺乏2 面變化用以成功的捕陷光線。 另一項用以紋理化玻璃的技術是噴砂法，但此種方去 據報告於玻璃形成裂痕，可能藉分路而對太陽能電池的义 能產生不良影響。 ’ 【發明内容】 發明概要 提供一種紋理化選定材料之表面之方法，該方法包含： a. 施用基底蝕刻組分作為伸展於該選定材料之表面上 方的一層； b. 於該欲紋理化表面之一預定區上方依離散式沈積點 的圖案而沈積流體蝕刻組分， 藉此該所沈積的流體触刻組分於被沈積後朝向橫向展 開，且該基底蝕刻組分與該所沈積的流體蝕刻組分組合而 形成蝕刻組成物來蝕刻位在該所沈積的流體蝕刻組分被沈 積且展開的該等區域中之該選定材料之表面，造成於該所 201135955 選定材料之表面上經蝕刻的紋理圖案，該圖案乃該離散式 沈積點的圖案之二維空間調變。 紋理化方法之實施例可蝕刻9 0 %或以上欲紋理化表面 之預定區。離散式沈積點的圖案之空間調變可具有至少50 奈米的調幅。藉由調整組成物、水含量及基底蝕刻組分該 層的厚度，可改變流體蝕刻組分的展開程度。當沈積流體 蝕刻組分時，於若干相鄰沈積點的展開可能造成沈積組分 的重叠。 流體蝕刻組分可使用印刷法沈積。印刷法可使用沈積 裝置，諸如網版印表機、應需滴落(drop-〇n-demand)喷墨印 表機、連續式印表機，或電水力印表機，該種情況下，離 散式沈積點的圖案為預定圖案。另外，印刷法可使用沈積 裝置，諸如氣溶膠喷射印表機，該種情況下’離散式沈積 點的圖案為任意圖案（至少就沈積點的尺寸等級而言）。触刻 在表面上的圖案可具有主定向方向，該方向係與印刷法的 印刷方向配向。 基底蝕刻組分層之厚度可由用來形成該基底独刻組分 層的溶液黏度決定，及該基底蝕刻組分層可包含聚合物薄 膜。又，基底蝕刻組分層可含有已配向的分子組分’而該 等分子組分的配向可使用偏極化(poling)達成。 聚合物薄膜可使用作為液晶分子的聚合物製成’該等 聚合物諸如聚丙烯酸正烷酯類、聚甲基丙烯酸正炫酷類、 聚正烷基乙烯基醚類、聚正烷基乙烯基醚類或聚正炫基苯 乙烯類。另外，聚合物薄膜可使用含有小分子添加劑的作 201135955 用聚合物製成，該種情況下，該等添加劑可包含聚 ^ 心 八有▼電何支鏈的聚乙二醇衍生物 =者。該聚合物薄膜也可換混小型分子液晶進入酸性 ㈣而對結果所得之聚合物相賦與液㈣性。該 =:可於聚合物相中，藉施加電場㈣偏極化（或配向） ::方向。如此聚合物薄膜可用於對所得紋理化表面賦 度或節距。 4低所得紋理化圖案之解析 _組分沈積於其中的圖案典型地為數位圖案。流體 蚀刻組分較佳為液體，但也可為氣體。 ^個實;5』％仃餘刻而形成，及所得紋理化表面 係用來提供光的龍人裝置諸如光伏裝㈣。所選材料可 為多種材料中之任—者諸如發，但於較佳實施例為玻璃(二 氧化石夕）。該裝置較佳為形成於藉本方法所紋理化的半導體 或形成於基板諸如坡璃之已触刻表面上的半導體 薄膜層之光伏裝置。 Γ刻圖案之最大深度係不超過咖奈米，而所形成的 ==案Γ有經由將該紋理化表面浸沒於溶液而形成的 :姑攻、°構，4溶液係各向同性祕職物質。當該物201135955 VI. Description of Invention: [Technical Territory of Invention] Copyright Notice Part of this patent document discloses material that is protected by copyright. When the disclosure of this patent document appears in the patent file or record of the Patent and Trademark Office, the copyright owner does not object to anyone reproducing the patent document or patent disclosure by fax, but retains all copyright rights. FIELD OF THE INVENTION The present invention is generally in the field of device fabrication, and more specifically, the texturing of materials such as tantalum niobium and tantalum to enhance the optical clock of thin film solar cell devices. BACKGROUND OF THE INVENTION A variety of modern photovoltaic (solar) cells are typically essentially thin films whereby a plurality of photosensitive material films are deposited on a substrate and then used as the front or solar surface of a solar cell. The most commonly used substrates are various forms of glass into cerium oxide. However, other substrates may also be used. Since the photosensitive layer of the thin film solar cell is too thin (typically about 1-2 microns), it is preferable to trap light inside the device to obtain maximum light absorption. Traditionally, tantalum wafer solar cells have been textured with a fossilized surface to maximize the trapping of light within the cell. This texturing is achieved by immersing the germanium wafer in a bath of reactive chemicals in preference to the direction of the crystal, thus leaving the surface of the patterned cell. The patterned surface reduces the reflection of light by augmenting the light reflected from the surface and returning it to the surface of the device instead of injecting ambient air. 201135955 Outside the pool. There are currently no common methods for texturing thin films of photosensitive materials such as crystalline germanium. It is impossible to achieve a chemical touch-lithe film as with a silicon wafer solar cell because the stone layer is too thin. Typically, light is trapped on the film by modifying or texturing the substrate prior to deposition of the photosensitive layer film. Then, when the photosensitive material is deposited, the formed thin ridges follow the textured contour of the underlying substrate, thereby allowing the solar cell to be formed in a flip-chip substrate configuration. Current methods for texturing substrates used in thin film solar cells include, but are not limited to, aluminum induced texturing, sol-gel processing, chemical etchant dip coating, and sand blasting. Inductive texturing involves depositing a thin layer of aluminum typically on the glass substrate ranging from 4 Å to 230 nm. The thermal annealing of the aluminum-alloyed glass is then carried out at a temperature of about 610 ° C for typically 4 minutes. During the annealing process, the aluminum is oxidized by the glass causing the alumina and tantalum to form on the glass surface which is subsequently removed using wet etching techniques to leave a textured surface. Although this method is suitable for large substrates used in thin film photovoltaic processes and is relatively simple, it is generally considered too expensive to be commercially implemented. Another method that has been developed for texturing thin film crystalline germanium solar cells involves coating the glass surface with cerium oxide particles. This addition texturing method is carried out by dip coating a glass substrate in a sol gel bath. Granular beads comprising cerium oxide particles ranging from 1 micron to 2 micrometers are deposited on the surface of the substrate to form a textured surface. In some cases, the sol-gel solution also contains pulverized quartz in the range of 0.5 microns to 3 microns to improve the texture of the knot. However, such dip coating may result in uneven texture on the surface of the glass. 4 The untextured area may form a stress concentration point in addition to the reduction of the optical trap. The dip coating method in this way also involves the subsequent strip drying and can be <month t*! The cost of the final paint. Direct chemistry of the glass by soaking the glass sheet in an acid bath (such as hydrofluoric acid) or other uniform application of an etchant is an example of a gasification process. It is well known that this method is surprisingly expensive due to the large amount of etchant material required. In addition, it is a hazard to discard a large amount of used etchant. Direct etching of the glass also tends to form a uniform touch and lacks a 2-sided variation for successful trapping of the light. Another technique used to texture glass is sandblasting, but it has been reported to form cracks in the glass, which may adversely affect the solar cell's performance by shunting. SUMMARY OF THE INVENTION SUMMARY OF THE INVENTION A method of texturing a surface of a selected material is provided, the method comprising: a. applying a substrate etch component as a layer extending over a surface of the selected material; b. forming a surface to be textured Depositing a fluid etch component over a predetermined pattern in accordance with a pattern of discrete deposition points, whereby the deposited fluid etch component is developed laterally after being deposited, and the substrate etch component is etched with the deposited fluid The components are combined to form an etch composition to etch the surface of the selected material in the regions where the deposited fluid etch component is deposited and unfolded, resulting in an etched texture on the surface of the selected material of the 201135955 A pattern that is a two-dimensional spatial modulation of the pattern of discrete deposition points. Embodiments of the texturing method can etch 90% or more of the predetermined area of the surface to be textured. The spatial modulation of the pattern of discrete deposition points can have an amplitude modulation of at least 50 nanometers. The degree of development of the fluid etch component can be varied by adjusting the composition, water content, and thickness of the layer of the substrate etch component. When depositing a fluid etch component, the unfolding at several adjacent deposition points may result in an overlap of deposition components. The fluid etch component can be deposited using a printing process. The printing method may use a deposition device such as a screen printer, a drop-〇n-demand inkjet printer, a continuous printer, or an electro-hydraulic printer, in which case The pattern of discrete deposition dots is a predetermined pattern. Alternatively, the printing method may use a deposition apparatus such as an aerosol jet printer, in which case the pattern of the 'discrete deposition dots is an arbitrary pattern (at least in terms of the size level of the deposition dots). The pattern that is inscribed on the surface may have a main orientation direction that is aligned with the printing direction of the printing process. The thickness of the substrate etch component layer can be determined by the viscosity of the solution used to form the layer of the substrate singular component, and the substrate etch component layer can comprise a polymer film. Further, the underlying etching composition layer may contain the aligned molecular components ' and the alignment of the molecular components may be achieved using poling. Polymer films can be made using polymers that are liquid crystal molecules such as polyalkyl acrylates, polymethacrylic acids, poly-n-alkyl vinyl ethers, poly-n-alkyl vinyls. Ether or polysqualyl styrene. Alternatively, the polymer film may be made of a polymer containing a small molecule additive for use in 201135955, in which case the additive may comprise a polyglycol derivative of poly(ethylene). The polymer film can also be mixed with a small molecular liquid crystal to enter an acidity (4) and impart a liquid (tetra) property to the resulting polymer phase. The =: can be applied to the polymer phase by applying an electric field (4) to the polarization (or alignment) :: direction. Such polymeric films can be used to impart or pitch the resulting textured surface. 4 Analysis of Low-Related Textured Patterns The pattern in which the components are deposited is typically a digital pattern. The fluid etch component is preferably a liquid, but may also be a gas. ^ Reality; 5"% 仃 仃 formed, and the resulting textured surface is used to provide light to the Dragon Man device such as photovoltaic installation (four). The material selected may be any of a variety of materials such as hair, but in the preferred embodiment is glass (ruthenium dioxide). Preferably, the device is a photovoltaic device formed on a semiconductor textured by the method or a semiconductor film layer formed on a surface of a substrate such as a etched surface of a glass. The maximum depth of the engraved pattern is no more than the coffee, and the formed == case is formed by immersing the textured surface in the solution: auspicious, °, 4 solution isotropic secret material . When the thing
二 寺各向同性餘刻劑可具有包含HF或HF與NH4F 氳化物液而於較佳實施例可為包含觸：1緩衝 氧化物蝕刻劑之溶液。 圖式簡單說明 現在將參考附圖舉例該明本發明之實施例，附圓中： 201135955 第1A圖為示意圖以剖面圖顯示被覆以表面酸性聚合物 層之玻璃基板； 第1Β圖為示意圖顯示兩滴含有蝕刻組分的溶液沈積在 酸性聚合物層上，兩滴配送成彼此緊鄰； 第1C圖為示意圖顯示在玻璃基板表面上重疊蝕刻區的 形成； 第1D圖為示意圖顯示蝕刻殘餘物及酸性聚合物層已經 移除後的玻璃基板； 第2圖顯示酸性聚合物亦即聚丙烯酸之實例結構式； 第3圖為使用較佳配置所形成的紋理化區之原子力顯 微鏡(AFM)輪廓圖； 第4圖為貫穿第3圖的AFM輪廓圖之剖面圖，而該剖面 圖係以垂直於所蝕刻的溝槽的角度記錄； 第5圖為大面積氣溶膠喷霧單元之示意圖，該單元可用 來喷霧含氟化物溶液而達成較高的紋理化產出量；及 第6圖為第5圖大面積氣溶膠喷霧單元之示意圖，該單 元具有配向設置的線性喷霧單元，而於喷霧含氟化物溶液 前，在欲紋理化表面上形成聚合物層。 C實施方式]1 較佳實施例之詳細說明 典型地薄膜太陽能電池係形成在諸如玻璃等基板上來 對機械性質脆弱的薄膜材料提供機械支撐。因薄膜裝置的 活性層通常太薄而無法直接紋理化，故常在薄膜裝置形成 於基板上之前先將基板紋理化。現在將說明對表面包括基 201135955 板諸如玻璃表面，施用紋理化之改良方法，典型地係用來 提升薄膜太陽能電池裝置的光阱。此等方法係使用流體沈 積裝置來將流體圖案遞送至基板表面，於該基板表面可反 應而造成表面區域的蝕刻，如此在基板上形成已紋理化表 面。於太％能電池基板的情況下，所得紋理化表面較佳具 有週期性結構，此處該紋理圖案的週期幅度係類似於隨後 沈積在紋理化基板上的感光材料薄臈厚度。紋理化表面的 週期性結構較佳係藉負責基板表面蝕刻的分子類別之濃度 的精細解析度空間分布而達成。 流體沈積裝置允許小量欲沈積在基板上的功能性流體 呈圖案形式遞送。裝置可為應需㈣裝置諸如喷墨印表機 或電水力印表機。另外，也可使用連續流裝置，諸如連續 式喷墨或氣溶膠噴射印表 於採用喷墨印表機之應 用，功能流體軸配成―種減體，沈積裝置對沈積液體的 性質(例如表面張力及純)加料殊要求。科功能流體 可藉諸如氣溶㈣射印表機等裝置而沈積為氣溶膠。於額 外變化例’魏流體也可呈氣體遞送至基板，但於此等情 況下’更難以控制流體遞送至基板表面上的精準及離散位 置所在。可使用二組分式似彳劑，其中第—組分係呈凝膠 或更黏稍的流體施用於表面上，及第二組分係呈圖案施用 來於施用第二組分的位置形纽應點。另外，可施用液體 組分或凝膠組分的圖案，第二_組分的氣態氣氛係用來 活化施用圖案該區的蝕刻。 現行流體沈積裝置諸如前述裝置精準沈積小量流體體 201135955 積的能力有限’因此典型地無法達成具有小於約20微米尺 寸的特徵結構之蝕刻。業已發現具有較小尺寸的紋理化可 藉由沈積重疊流體流或小滴至功能聚合物層上而達成。使 用此種方法，可達成具有約為ίο微米週期性的紋理化圖 案。經由將功能流體小滴或液流重疊在反應性表面上，可 在該表面上獲得不等區域濃度之負責蝕刻的分子類別的離 散式圖案，如此造成經蝕刻的圖案形成，而該圖案可具有 特徵結構尺寸顯著小於所沈積的小滴或流體流的尺寸。此 外，小滴或液纽積在表面上的順序可用來在所㈣的（紋 理化的）表面形成特殊週期性特徵結構。 所述紋理化基板之方法並非僅限料膜太陽能 電池的 广絡而该方ΐ可應用於需要紋理化表面的其它用途。此 化㈣Γ佳貫施例敘述二氧切（亦即玻璃）基板的紋理 化，仁顯然該方法也可用來紋理化盆它 非限於各型摻雜玻璃、氮 土板匕括仁 物、有機樹脂及其它聚合石^碳化石夕、透明傳導性氧化 由改變較佳配置所使用的^括圖案遮罩材料。此外，藉 理化半導體材料，諸如t 液’該方法也可應用於紋 類諸如妙H坤化㈣、鍺，化鎵、舰銦，或合金 化鎵(CIGS)，及確實可用於，化銦、砸化鎵 '蹄化録或硒 金、錫及錯或合金。；、’文理化金屬，諸如！S、銅、銀、 但須’主思用於光解應用， 少9〇%表面須經㈣至某種。不期望顯著平坦區，因此至 化的全部面積，則吹籍+祆度。如果蝕刻劑覆蓋欲紋理 ^積在如上的㈣編部濃度須有顯 10 201135955 著變化，來於欲紋理化該區的不同位置所在達成可變的蝕 刻深度。 將說明較佳配置，其中玻璃（二氧化矽）基板係經紋理 化，用於採用結晶矽(於玻璃上）之感光層之薄膜太陽能電池 的光阱目的。此等太陽能電池典型地涉及於玻璃基板上沈 積1.2微米至1.5微米厚度的石夕層。較佳用於基板的玻璃為侧 矽玻璃且約3.3毫米厚。在單側上使用本揭示所述紋理化方 法而紋理化，及然後矽沈積在玻璃基板的紋理化表面上至 1.2微米至1.5微米，及更理想地1.4微米厚度。較佳使用電 漿增進化學氣相沈積(PECVD)沈積，但也可使用其它沈積 技術，諸如濺鍍或蒸鍍技術。然後所沈積的非晶矽係在烤 爐内結晶化，此處（載有矽的玻璃基板的）片材係加熱至約 600 C溫度。然後使用帶式爐或轉爐，藉快速加熱退火進行 退火來減少在較高溫度所耗時間。若有所需，各片材然後 藉雷射刻劃而切成具有期望大小的離散式電池。然後背面 較佳係被覆以白色絕緣樹脂，該樹脂係作為反光器，及自 背面分離金屬接點，但於需要接點位置除外。然後，藉由 通過樹脂層上的開口沈積金屬而形成金屬接點至薄膜太陽 能電池的兩極。最後，電池囊封成為模組及積層。 二氧化料已知濕㈣法，涉及將二氧化⑦表面暴露 於含氫氟哪F)之錢’而㈣料錄決#刻溶液的组 成、氧化物類別及溫度。舉例言之，（濃)49%氫氟酸溶液於 室溫將以23GG奈米/分鐘之速率_熱二氧化碎層。二氧化 石夕的_也可使用經緩衝的氧化物触刻溶液達成。此等溶 201135955 液乃氟化链與氟化氫之混合物，而敍離子係將触刻溶液維 持於恆;tPH，如此隨著_的進行，獲得恆定_速率。 業已對不同的氟化銨與IU匕氫之比報告不同的餘刻速率。 例如’ 5: m緩衝之氧化物姓刻劑（此乃5份4〇%說化敍扪 份49% I化氫之混合物读有約⑽奈米/分鐘之钮刻速率。 於經緩衝之氧化物触刻劑發生的總二氧化石夕触刻反應為： Si〇2(s) + 4HF(aq) + 2NH4F(aq) (NH4)2SiF6(aq) + 2h2〇 (1) 先則技術的一氧化石夕蚀刻配方存在有多項變化。 此處所述用於較佳配置對二氧化石夕進行圖案化钮刻之 方法係仰賴分開提供氟陰離子及酸，將兩種主要前驅组分 共同置於期望的姓刻位置。較佳，該組分係呈酸性質子提 供於水溶性酸性聚合物薄膜，該薄膜係提供於欲姓刻的玻 璃基板表面上呈表層。於另一種配置，表層可包含 =外的材料(例如藉諸如騎、濺鍍或化學氣相沈積或物理 氣相沈積等方法沈積的無機材料）。 氟陰離子較佳係配方於水溶液，然後藉流體沈積裳置 依照圖案而沈積。於沈積流體接觸聚合物薄膜的位置所 t ’聚合物係局部溶解，氣陰離子自該聚合物提取出酸性 為子而域氟化氫。錢在沈積位置溶解於溶㈣所形成 的氣化氫_暴露出的氧切。如此麵含HF的腐錄敍 山合液备’非直接處置。雖然含氣溶液被歸類為有毒，但仍 比處理HF溶液更安全^此外，較佳配置方法只使用小量氣 陰離子’ Μ陰離子係舰成具有合理稀釋濃度之溶液。 此外’利用含氟化物溶液的較佳配置所使用的沈積方法可 12 201135955 減少操作員接觸溶液。一曰 '，交 一 /合夜載何入例如噴墨印表機的 流體貯槽’賴驗不再f要進_步處置。 含HF之触刻流體直接沈積係難以達成，原因在於一般 極:有列印頭或更常見為喷射裝置能夠财受該流體的腐蚀 性本質。聽酸將攻擊與隸A部分絲㈣、不输鋼及 石夕的列印頭。無法㈣基於料列印頭，原因在於纽型 地含有被氟化氫所_的二氧切組分。_產物除^造 成列印頭的長時間腐料，也迅速引發間歇的嘴嘴堵夷， 因而導致難以可靠地噴射溶液。此外，沒有操作員會二為 透過喷墨來沈積含HF的溶液或其它祕沈積法為安全原 因在於當流體洩漏時，操作員有接觸含HF&溶液之風險。 此點對此處提示之方法不成問題，原因在於含氟陰離子溶 液不具腐蝕性。如此也表示該溶液可使用矽及陶瓷列印頭 喷射。 現在將參考第1A圖至第1D圖說明用於玻璃基板之紋 理化的較佳配置。水溶性酸性聚合物薄膜11〇係旋塗在厚約 3.3毫米的玻璃基板105表面上，如第1A圖所示。較佳係以 7000 rpm的離心速度自25%(w/v)聚丙烯酸(PAA)於水溶液 旋塗薄膜歷經30秒時間。聚丙烯酸PAA之分子量較佳係於 20,000至200,000克/莫耳(g m〇i_i)之範圍，及更佳約為9〇 〇〇〇 克/莫耳。聚丙烯酸乃丙烯酸之均聚物。丙烯酸單體單元為 如第2圖的化學結構式所示酸性質子來源。聚丙烯酸paa的 pKa約為 4.3。 已經旋塗的聚合物薄膜係經風乾歷經約3小時時間，獲 13 201135955 得厚約2·5微米的薄臈。用來形成酸性來 丨王1合物薄膜之溶液的 固體含量可自約5%變化至35%而未顯 不嶺者影響聚合物薄膜品 質，但較佳固體含量為2Q%至鄕。使用㈣㈣含量及/ 或較快速離心速度’結果獲得㈣㈣膜1有聚合物薄 膜110的玻璃基板105較佳係於氣下健存直至需用時來減 少聚合物薄膜的不均勻濕化。 於另-種配置，也可使用含有酸性基的其它水溶性聚 合物或樹脂(渺龜料吩絲笨胺魅物、聚苯乙稀項 酸醋、聚樹脂）。也可㈣聚合物混合物或換合物 來形成酸性薄膜。舉例言之，聚丙烯酸paa可摻混其它水 溶性聚合物，諸如^鱗(PVA)，依所⑽_度決定， 至自η 1至！ ： 4之範圍的PAA ; PVA比。聚丙稀酸也可換混 較非親水性聚合物諸如聚f基丙烯酸獲得具有較佳臨界表 面張力之乾膜。當需要較小的蝕刻特徵結構時以此項變 化為較佳，原因在於所沈積的小滴較少展開於具有較高斥 水性表面上。酸性聚合物(例如聚_酸PA A)之共聚物也可 用來製成聚合物薄膜。使用共聚物或聚合物摻合物來製成 薄膜乃可控制所形成的薄膜酸度之—種方式。此外，聚合 物薄膜可含有添加劑，料添加劑可直接提供額外酸性 基，或間接增強薄膜的酸度。此等添加劑可溶解於或分散 於(例如奈米粒子）用纟製成酸性聚合物層的溶液内。此等添 加劑也可用來修改聚合物薄膜之表面性質。 聚合物薄膜也可含有界面活性劑。較佳使用濃度小於 1 .〇%的此等界面活性劑(例如得自3M公司的諾維克㈣㈣ 201135955 4200)。此等界面活性劑藉由允許所沈積的溶液可均勻濕潤 欲蝕刻表面而改良所得蝕刻的均勻度。所添加的界面活性 劑也可活性地減低聚合物薄膜的臨界表面張力，如此允許 獲得更小型蝕刻特徵結構。也可添加其它含氟聚合物添加 劑諸如FC-4432(也得自3M)特別係用來減低聚合物表面終 產物的臨界表面張力。但比較小型界面活性劑製劑諸如諾 維克4200，較長鏈含氟聚合物為較非有效的濕潤劑。也可 使用與氟陰離子化學可相容性的其它界面活性劑或表面張 力改性劑。 於較佳配置的額外變化例中，聚合物薄膜可使用聚合 物製成，該等聚合物可作為液晶分子（例如聚正烷基丙烯酸 酯類及甲基丙烯酸酯類、聚正烷基乙烯基醚類及酯類、及 聚正烷基苯乙烯類），或含有可作為液晶的小分子添加劑[例 如聚二丙烯酸酯（乙二醇）酯及具有帶電荷支鏈之其它聚乙 二醇衍生物]。另外，小分子液晶可摻混入支鏈來對所得聚 合物相提供液晶特性。液晶可藉施加電場而於聚合物相於 規定方向偏極化（或配向）。如此所形成的薄膜可用來對所得 紋理化圖案提供期望的方向性，以及進一步減低所得紋理 化圖案的解析度或節距。 玻璃基板105表面的圖案化蝕刻係藉依據預定圖案而 於該表面上沈積含氟陰離子來源之流體而達成。於較佳配 置，流體係作為含氟陰離子溶液，藉應需滴落喷墨印表機 而沈積。第1B圖所示喷墨裝置120含有一個或多個列印頭 125，其可自喷嘴陣列喷射溶液130小滴。個別喷嘴的發射 15 201135955 可處在熱控制或壓電控制之下。欲噴射的溶夜可儲存在列 印頭上或附近，或儲存在較為遠離列印頭的聍槽内。於， 較佳配置，喷墨裝置120的列印頭於掃描中視需要跨聚人物 表面沈積溶液。玻璃基板105係位在一平台上，談平a俾； 垂直掃描軸的一軸線上相對於該列印頭移動。但於其它配 置，當列印頭於二方向掃描時，平台可維持固定；或卷展 板（亦即玻璃基板105)係於二方向移動時，列印頭可維持固 定。較好平台及因而玻璃基板1〇5可在進行列印時加熱。 於較佳配置，經壓電控制的矽列印頭係由富士軟片 (FUJIFILM)迪馬堤(Dimatix)製造，用來沈積含氟陰離子办 液。列印頭係結合於卡匣，具有16個噴嘴線性隔開254微米 距離而液滴大小為1皮升(pic〇liter)。也可使用可沈積其它小 滴體積的列印頭，但以較小的液滴體積為佳，原因在於其 可獲得具有較少蝕刻且具較精細解析度的紋理化圖案。個 別喷嘴的發射係在軟體控制之下，如此允許依據預定圖案 獲得經程式規劃的小滴沈積。使用標準影像格式諸如點陣 圖檔，可提供圖案。 依據沈積圖案的小滴位置之緊密程度而定，可能需要 沈積多層触刻圖案。須瞭解列印多層含氟陰離子溶液的需 求係來自於蝕刻化學計算學。對二氧化矽晶體層中的每個 經蝕刻的矽原子要求6氟陰離子。較佳配置所使用的噴墨裝 置之軟體允許多層選定圖案列印在選定位置。該等層係逐 一列印，而在連續二層間只有極短的延遲。選擇性地，延 遲可插置在連續二層的列印間。於又另一配置，替代列印 201135955 多層圖案’乡數沈積溶液]、滴可沈積在列印頭前方各個位 置所在，及/或平台可移動至下—個沈積位置。 於較佳配置’當黏度係為10 cP至14 cP間及表面張力介 於28至32毫牛頓/米（mN/m)間時，所使用的噴墨裝置可最佳 地喷射溶液。但使用該裝置也可喷射具有低抵2 cP黏度之 溶液。此項目的係藉妥善調整施加至壓電噴嘴的波形而達 成。改憂表面張力較難因應，但也可能。若溶液的表面張 力過高（例如對去離子水約為7 〇 mN/m)，難以打底引發列印 頭（亦即最初並無任何溶液可自喷嘴射出p另一方面，若溶 液的表面張力過低，則含有噴嘴孔口的表面（喷嘴孔板)典型 地將被喷射液所溢流，如此造成小液滴在聚合物表面上的 不規則排列。於較佳配置使用的喷墨裝置之喷嘴孔板具有 聚合物不會濡濕表面，但低表面張力流體的喷射仍然於該 表面上導致顯者濕潤區，如此導致不規則發射。 較好於沈積溶液的氟陰離子係提供為氟化銨水溶液， 而氟化銨濃度係在10%至15%(w/v)之範圍，及更佳約為 ll%(w/v)。也可使用其它氟陰離子來源（例如氟化鈉、氟化 鉀、氟化四烷基銨化合物），但須審慎考慮蝕刻終產物之溶 解度。舉例言之，氟矽酸鈉之溶解度（於2(rc約為4〇毫克/ 升)係运低於敗石夕酸敍之浴解度。如此較佳係喷射較為稀釋 的氟陰離子溶液來確保钱刻產物不會沈澱至欲触刻表面 上，及防止表面的進一步蝕刻。較為稀釋氟陰離子溶液的 沈積可能需要喷射更大量沈積溶液(換言之，將列印更多層 圖案）。 17 201135955 於其匕配置，當需要的飯刻深度極淺時，触刻阻擒沈 澱物的形成可用來控制蝴程度。因此例如，氣化納可使 用高平台溫度喷射來快速自沈積溶液中氣化水。於形成相 田小里的氟矽酸根陰離子後，氟矽酸鈉沈澱物將形成於表 面上而防止進一步蝕刻。較低的氟陰離子濃度也可用來形 成較佳的紋理化圖案。較淺的紋理化圖案可能優異，原因 在於其對形成於紋理化表面上的結晶性⑪薄膜造成較少應力。 於較佳配置，具有4〇〇克/莫耳分子量之2〇%(v/v)聚乙二 醇(PEG 400)也添加至喷射溶液來將黏度提高至約4 cp，如 此改良喷射效能。於另一種配置，PEG 4〇〇可自沈積溶液中 刪除，或以較低濃度含括於溶液。但要求較低的脈衝電壓、 較慢的脈衝升高時間、及較低的噴射頻率來可靠地喷射較 低黏度溶液。於其它配置，PEG 4〇〇可由提高溶液黏度的其 匕化合物（例如甘油、鹼性水溶性聚合化合物諸如聚乙烯基 °比咯啶酮，或其它二醇類）替代。 沈積溶液之pH可藉添加氫氧化銨而提高至8至1〇，及更 佳提高至8。以高pH為佳以免沈積溶液中有高濃度反應性蝕 刻劑類別，亦即HF及HF；f。於氟化銨溶液，於大於7之^^ 值’兩種蝕刻劑類別之濃度有效為零，結果並未導致二氧 化石夕的蝕刻’如此保護列印頭中的任何二氧化石夕組分。若 溶液太鹼(例如pH大於11)，則可能發生列印頭的若干姓刻。 所得較佳配置之沈積溶液的表面張力於28約為46 m N / m。雖然此數值超過所使用的富士軟片-迪馬堤列印頭 之最適表面張力範圍，但喷射波形可經調整來因應增高的 18 201135955 表張力 § >谷液接觸聚丙稀酸 表面具有約44 mN/m的臨界表面張面時，該聚丙烯酸 異地導致溶液的較少展開。沈積、_ ’增高的表面張力優 所沈積的錢狀更大展開，如此張力減低導致 徵結構。 ％更大型經蝕刻的特 最後，沈積溶液溫度較佳係維 較低溫度，但典型地溶液的表面 、C。也可使用 此使其更難以噴射溶液。 ：低溫升高’如 具有中高表面張力的溶液噴射 維克侧(得自3Μ)之聚合物表面上乃^㈣性劑諸如諾 特徵結構之有用策略。此種策 2型倒落触刻的 由田士軟片-迪馬堤列印頭所使用的發射波形。 於另—種配置’氟化界面活性劑諸如諾^克柳(得自 3M)可—添加至沈積溶液。此料面活性财有效減低表面張 至畜士軟片-迪馬堤列印頭的最適範圍的數值（參考約 圖）。對諾維克侧，α班α5%(ν/之濃度將沈積溶液 之表面張力減至38-32 mN/m範圍之表面張力，如此允許其 可靠地喷射。也可使職含氟陰離子溶液可相容性的其它 界面活性劑。 此外，也可使用可改變表面張力的其它添加劑。舉例 言之，添加二醇類諸如丙二醇也可方便地減低表面張力至 富士軟片-迪馬堤列印頭的最適範圍。於其它配置，使用其 它列印頭，可能需要改變表面張力及黏度來滿足列印頭的 操作需求。 201135955 於較佳配置’平台及如此玻璃基板105係於沈積溶液的 喷射d間加熱。平台的加熱，結果導致部分沈積溶液之溶 剡於喷射期間被氣化去除，造成較小的濕潤區及因而較小 型蝕刻開口。較佳用於紋理化圖案的蝕刻，平台溫度係維 持於55 C。平台的過度加熱可能導致溶劑的過度氣化，因 而導致在欲姓刻表面的水性環境減少。如此可能造成蝕刻 的減、’及也可能導致蝕刻產物氟石夕酸鈹的沈澱，其可能 造成跨欲紋理化區的蝕刻不均。如前文說明，蝕刻產物的 沈殿可用作為防止過度蝕刻與形成表淺蝕刻圖案的手段。 現在返回參考第1C圖，所沈積的小滴13〇溶解該聚合 物，於該處接觸表層11〇而形成已溶解的聚合物之一區 150。沈積溶液的氟陰離子係與已溶解的聚合物反應而形成 氟化氫’其可蝕刻玻璃基板1〇5的下表面而於玻璃基板1〇5 形成蝕刻區160及165。此等蝕刻區160及165之形狀及深度 係取決於沈積溶液的氟陰離子濃度、聚合物層11〇之性質及 厚度、用於玻璃基板105的玻璃類別、平台溫度、相鄰小滴 130的相對排列及列印速度。前述全部因素皆可改變來於玻 璃基板105區上方形成不同的紋理化圖案。 較佳於沈積圖案的光柵掃描中，隨後所沈積的小滴13〇 重疊而導致於全表面形成不等濃度的氟化氫。更明確言 之’當使用基於光栅的流體沈積裝置12〇諸如用於較佳配置 的富士軟片-迪馬堤印表機而沈積液滴時，小滴傾向於沈積 後合併而在玻璃基板105表面上形成高度紋理化的狹窄溝 槽，如第3圖所示。若表面係垂直所形成的溝槽而掃描時(參 20 201135955 考第4圖）’第3ϋ所示圖案之原子力顯微鏡(AFM)輪靡形成 週期性蚀刻圖案結果。藉由變更沈積圖案的液滴間隔，可 文又此等規貞IU;成溝槽間的間距。第3圖所示紋理化圖案可 於—軸線使用1G微米的液滴間隔形成。換言之，用來形成 第圖所示”.文理的沈積圖案為每毫米具有·像素的像素解 析度之像素格網。較小的液滴間隔，導致又更精細的圖案， 仁、、文理化特Μ:結構的細彳深度典型地為較大， 原因在於触 刻較大f氟化氫。另外’可藉由提高平台溫度及/或使用化 千手^又(例々減低氟陰離子濃度，或使用敗化納作為氟陰離 子源)加以控制蝕刻程度。 當紋理化係用於光阱目的時，要緊地須減少平坦區的 出現。第3圖及第4圖驗證使用本技術形成的紋理化圖案極 少有平坦區。即使對此等圖案，已經探勘光栅沈積順序來 達成淺層溝槽結構，但表面上仍然有某些紋理係在溝槽底 部。理想上，比較淺層紋理，具有較陡峭坡度的紋理將提 高此種紋理的光阱能力。 當流體沈積程序完成時，玻璃基板105係自流體沈積裝 置120之平台移開，及浸沒於流動中的去離子水歷經5至1〇 分鐘時間。此項最終清洗步驟去除捕陷在已姓刻區150的触 刻產物及水溶性聚合物薄膜二者而形成有開口 160的最終 已蝕刻基板100 ’如第1D圖所示。不似現行濕蝕刻法，於此 清洗步驟期間氟化廢液量為極小，唯有已經藉噴墨印表機 所沈積的氟化物。如此表示廢液極為稀釋而不具極大危害。 用於某些應用’可能期望形成具有較為圓化的特徵結 21 201135955 構之紋理化圖案。舉例言之，銳利緣可能於沈積在紋理化 表面頂上的薄膜造成較高應力。銳利緣的圓化可單純藉由 將已紋理化表面浸沒在溶液内而達成，該溶液係各向同性 地蝕刻玻璃（例如包含H F或H F與氟化銨之混合物的溶液）。 較佳使用包含10% 7 · 1經緩衝的氧化物钮刻劑之溶液，原 因在於其蝕刻玻璃極為緩慢，而方便藉浸沒時間長短來控 制圓化(平滑化)程度。 於另一配置，藉由使用大面積氣溶膠喷霧單元來沈積 含氟陰離子溶液之細霧或氣溶膠至聚合物層11〇上，可達成 較高紋理化產出量。較佳氣溶膠喷霧單元係排列作為大致 上線性單元，具有與欲紋理化的玻璃板之片材約略等寬， 如第5圖所示，該單元係延伸橫玻璃板。經以聚合物層11() 被覆的玻璃基板105係通過懸吊在結構$ 1 〇上的架空線性氣 溶膠單元520下方。帶有聚合物層11〇的玻璃基板1〇5係位在 帶材505上，該帶材5〇5係相對於固定式線性氣溶膠單元52〇 移動。較佳帶材5〇5係經加熱至3〇它至6〇它範圍之溫度及更 佳係於40°C至50°C之範圍。 藉此方式，玻璃基板105係在含線性氣溶膠單元52〇的 固定式結構510下方移動時，線性氣溶膠單元52〇可遞送氣 洛膠化氟化物溶液細霧至玻璃基板1〇5的聚合物層11(^線 性氣溶膠單元5 2 G難包含線性氣溶料.列，但也可使 用其它配置’其中也可使用二維氣溶膠噴嘴陣列。固定式 架空結構51G係連結至帶材5_邊上的單元，該單元係罩 住欲氣霧化的液體貯槽。於第5圖所示配置，包含組件5〇〇、 22 201135955 510及5 2 G之IU轉外殼單元係結構上連、结至用以移動玻璃 基板105的包含帶材驅動器5〇5之單元。 當來自氣溶膠氣霧的小粒子接觸聚合物層11〇的聚合 物時發生反應，主要係如對較佳配置說明。反應速率及因 而蝕刻程度係取決於氣霧化粒子剩餘的水量。粒子乾燥過 度導致極k的触刻速率。較佳氣溶膠氣霧係使用超音波霧 化器產生。其它霧化器或喷霧器（例如氣動霧化器、噴墨霧 化器）也可使用，但限制條件為其不會過度減低粒子的水含 量。為了減少氣溶膠粒子喪失至周圍環境，線性氣溶膠單 元之輸出噴嘴係設置距表面1厘米至5厘米距離，及更佳距 表面約2厘米。 於第5圖所示配置，藉由變更帶材速度及溫度、被氣霧 化的溶液中之氟陰離子濃度、氣溶膠濕度（有效控制個別粒 子大小）’及聚合物層之厚度及性質’可改變紋理化圖案的 性質。於玻璃基板105通過線性氣溶膠單元52〇下方後，其 繼續順著帶材505運輸直至反應完成，然後於清洗單元内移 動，此處去離子水自上方喷灑而洗掉聚合物層丨1〇及蝕刻殘 餘物。反應完成所需時間典型地為極短（較佳為3〇秒至60 秒）’但係取決於控制蚀刻速率等前文列舉的因素。 前述玻璃紋理化方法可藉由單純維持最低流體高度於 用來形成氣霧的液體貯槽，而連續地加工處理玻璃基板 105。由於大部分規定來自清洗站的廢液中的氟陰離子濃度 可控制於極低（低於5 ppm) ’故無需處理來自該製程的放流 水。因此，清洗單元可連續操作而廢液放流又係連續排放 23 201135955 來因應容納新的廢水。 於第5圖所示方法的額外變化例，聚合物層n〇也可藉 設置排齊於線性氣溶膠單元520的額外線性喷霧單元製 成。此項變化係以示意剖面圖顯示於第6圖。額外線性喷霧 單元610係位在距線性氣溶勝單元520上游的帶材505上 方’其配送已氣霧化的氟化物溶液。各玻璃基板1〇5首先通 過第一線性喷霧單元610下方，於該處理聚合物溶液喷霧係 配送至玻璃基板105表面上，導致聚合物層11〇形成在玻璃 基板105表面上。線性喷霧單元61 〇較佳係沈積聚合物溶液 噴霧’該喷霧實質上係與較佳配置中，用來旋塗玻璃基板 105表面的聚合物溶液相同。取決於帶材速度，該溶液係比 較佳配置中用來旋塗的溶液更稀薄或更不稀薄。不像氟陰 離子遞送至聚合物層11〇表面，無需氣霧化聚合物溶液，故 事使用跨玻璃基板105遞送均勻數量聚合物溶液的簡單噴 霧單元。 較佳然後加熱單元630設置在帶材505上方來在短時間 内執行聚合物層的乾燥。另外，聚合物層110可藉將氣體或 空氣流通過所沈積的聚合物表面上而乾燥。較佳已乾燥的 聚合物層110具有2-3微米的終乾厚度，及更佳約為25微 米。但較薄的聚合物層可用來允許極高的產出加工製程。 然後帶有已乾燥的聚合物層110的玻璃基板1〇5藉帶材 505移動至線性氣溶膠單元520位置，於該處，如前文說明’ 含敗陰離子550之氣霧係以線性方式沈積在移動中的基板 1〇〇表面上。 24 201135955 熟諳技藝人士也須瞭解可對特定實施例顯示之本發明 做出多項變化及修改而未悖離如廣義描述之本發明之範 圍。因此此等實施例就全部構面可視為說明性而非限制性。 c圖式簡單說明3 第1A圖為示意圖以剖面圖顯示被覆以表面酸性聚合物 層之玻璃基板； 第1B圖為示意圖顯示兩滴含有触刻組分的溶液沈積在 酸性聚合物層上，兩滴配送成彼此緊鄰； 第1C圖為不意圖顯不在玻璃基板表面上重豐钱刻區的 形成； 第1D圖為示意圖顯示蝕刻殘餘物及酸性聚合物層已經 移除後的玻璃基板； 第2圖顯示酸性聚合物亦即聚丙烯酸之實例結構式； 第3圖為使用較佳配置所形成的紋理化區之原子力顯 微鏡(AFM)輪廓圖； 第4圖為貫穿第3圖的AFM輪廓圖之剖面圖，而該剖面 圖係以垂直於所蝕刻的溝槽的角度記錄； 第5圖為大面積氣溶膠喷霧單元之示意圖，該單元可用 來喷霧含氟化物溶液而達成較高的紋理化產出量；及 第6圖為第5圖大面積氣溶膠喷霧單元之示意圖，該單 元具有配向設置的線性喷霧單元，而於喷霧含氟化物溶液 前，在欲紋理化表面上形成聚合物層。 25 201135955 【主要元件符號說明】 100.110.. .聚合物薄膜、聚合物層 105.. .玻璃基板 120.. .喷墨裝置、流體沈積裝置 125.. .列印頭 130.. .溶液小滴、沈積的小滴 150, 160, 165···蝕刻區、開口 500.. .帶材 505.. .帶材、帶材驅動器 510.. .基材、固定式架空結構 520.. .架空線性喷霧裝置 550, 620...墨滴 610…線性喷霧單元 630…加熱單元 26The two-isotropic isotropic agent may have a solution comprising HF or HF and NH4F telluride and in a preferred embodiment may be a solution comprising a touch: 1 buffered oxide etchant. BRIEF DESCRIPTION OF THE DRAWINGS Exemplary embodiments of the present invention will now be described with reference to the accompanying drawings, in which: 201135955 FIG. 1A is a schematic view showing a glass substrate coated with a surface acidic polymer layer in a cross-sectional view; The solution containing the etching component is deposited on the acidic polymer layer, and the two droplets are disposed in close proximity to each other; FIG. 1C is a schematic view showing the formation of an overlapping etching region on the surface of the glass substrate; FIG. 1D is a schematic view showing the etching residue and the acidity The glass substrate after the polymer layer has been removed; FIG. 2 shows an example structural formula of an acidic polymer, that is, polyacrylic acid; FIG. 3 is an atomic force microscope (AFM) profile view of a textured region formed using a preferred configuration; Figure 4 is a cross-sectional view through the AFM profile of Figure 3, which is recorded at an angle perpendicular to the groove being etched; Figure 5 is a schematic view of a large area aerosol spray unit available To spray a fluoride containing solution to achieve a higher textured yield; and Figure 6 is a schematic view of a large area aerosol spray unit of Figure 5, the unit has an alignment design A linear spray unit is placed to form a polymer layer on the surface to be textured prior to spraying the fluoride solution. C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A typical thin film solar cell is formed on a substrate such as glass to provide mechanical support to a film material that is mechanically weak. Since the active layer of the thin film device is generally too thin to be directly textured, the substrate is often textured prior to being formed on the substrate. An improved method of applying texturing to a surface including a base 201135955 panel such as a glass surface will now be described, typically to enhance the optical trap of a thin film solar cell device. These methods use a fluid deposition device to deliver a fluid pattern to the surface of the substrate, where the surface of the substrate can be reacted to cause etching of the surface region, thus forming a textured surface on the substrate. In the case of a solar cell substrate, the resulting textured surface preferably has a periodic structure where the periodicity of the texture pattern is similar to the thickness of the photosensitive material subsequently deposited on the textured substrate. The periodic structure of the textured surface is preferably achieved by a fine resolution spatial distribution of the concentration of the molecular species responsible for the etching of the substrate surface. The fluid deposition apparatus allows a small amount of functional fluid to be deposited on the substrate to be delivered in a pattern. The device can be an on-demand (4) device such as an inkjet printer or an electro-hydraulic printer. Alternatively, continuous flow devices such as continuous ink jet or aerosol jet printing can be used in applications employing ink jet printers, functional fluid shafts are formulated as a type of subtractive body, and deposition devices are useful for depositing liquids (eg, surfaces). Tension and pure) special requirements. The functional fluid can be deposited as an aerosol by means such as a gas-soluble (four) jet printer. For additional variations, the "Wei fluid can also be delivered to the substrate as a gas, but in such cases it is more difficult to control the precise and discrete position of fluid delivery onto the substrate surface. A two-component elixirs may be used, wherein the first component is applied to the surface as a gel or a more viscous fluid, and the second component is applied in a pattern to apply the position of the second component. Should be. Alternatively, a pattern of liquid components or gel components can be applied, and a gaseous atmosphere of the second component is used to activate the etching of the region in which the pattern is applied. Current fluid deposition devices, such as the aforementioned devices, have a limited ability to accurately deposit small amounts of fluid body 201135955 'and thus typically cannot achieve etching with features less than about 20 microns in size. It has been found that texturing with smaller dimensions can be achieved by depositing overlapping fluid streams or droplets onto the functional polymer layer. Using this method, a textured pattern with a periodicity of approximately ίο microns can be achieved. By superimposing a functional fluid droplet or stream on the reactive surface, a discrete pattern of molecular species responsible for etching at unequal region concentrations can be obtained on the surface, thus resulting in an etched pattern formation, and the pattern can have The feature size is significantly smaller than the size of the deposited droplet or fluid stream. In addition, the order of the droplets or liquids on the surface can be used to form special periodic features on the (textured) surface of (4). The method of texturing the substrate is not limited to the broadness of the film solar cell and the method can be applied to other applications requiring a textured surface. This method (4) describes the texturing of the dioxo (ie, glass) substrate. It is obvious that the method can also be used to texture the pot. It is not limited to various types of doped glass, slabs, and organic resins. And other polymeric stones, carbonized fossils, transparent conductive oxidation by changing the preferred configuration of the use of the pattern mask material. In addition, the use of physical and chemical semiconductor materials, such as t liquid 'this method can also be applied to patterns such as Miao H Kunhua (four), germanium, gallium, indium, or gallium alloy (CIGS), and indeed can be used, indium, Gallium bismuth 'hoof record or selenium gold, tin and wrong or alloy. ;, 'The arts and sciences, such as! S, copper, silver, but must be used for photolysis applications, less than 9% of the surface must pass (four) to some. A significantly flat zone is not desired, so the entire area to be used is blown + twist. If the etchant covers the desired texture, the concentration of the (4) part of the area must be changed to achieve a variable etch depth at different locations where the area is to be textured. A preferred arrangement will be described in which a glass (cerium oxide) substrate is textured for the purpose of a light trap of a thin film solar cell using a photosensitive layer of crystalline germanium (on glass). Such solar cells typically involve depositing a layer of a layer of 1.2 microns to 1.5 microns thick on a glass substrate. The glass preferably used for the substrate is a side enamel glass and is about 3.3 mm thick. The texturing is performed on one side using the texturing method of the present disclosure, and then deposited on the textured surface of the glass substrate to a thickness of 1.2 microns to 1.5 microns, and more desirably 1.4 microns. Plasma enhanced chemical vapor deposition (PECVD) deposition is preferred, but other deposition techniques such as sputtering or evaporation techniques can also be used. The deposited amorphous ruthenium is then crystallized in an oven where the sheet (of the glass substrate carrying the ruthenium) is heated to a temperature of about 600 C. The belt furnace or converter is then used to anneal by rapid heating annealing to reduce the time spent at higher temperatures. If desired, the sheets are then sliced by laser and cut into discrete batteries of the desired size. The back side is preferably coated with a white insulating resin which acts as a reflector and separates the metal contacts from the back side, except where contact points are required. Then, a metal contact is formed to the two poles of the thin film solar cell by depositing metal through the opening in the resin layer. Finally, the battery is encapsulated into a module and a laminate. The dioxide is known to be a wet (four) process involving the exposure of the surface of the dioxide 7 to the hydrogen containing fluorine (F) and (iv) the composition, oxide type and temperature of the solution. For example, a (concentrated) 49% hydrofluoric acid solution will be thermally oxidized at a rate of 23 GG nanometers per minute at room temperature. The cerium dioxide can also be achieved using a buffered oxide etch solution. These dissolved 201135955 liquids are a mixture of a fluorinated chain and hydrogen fluoride, and the Syrian ion system maintains the etchant solution constant; tPH, so that a constant _ rate is obtained as _ proceeds. Different recurring rates have been reported for different ratios of ammonium fluoride to IU 匕 hydrogen. For example, '5: m buffered oxide surrogate (this is 5 parts 4%% of the mixture of 49% I hydrogen mixture read about (10) nm / min button rate. The total cerebral tactile reaction of the etchant is: Si〇2(s) + 4HF(aq) + 2NH4F(aq)(NH4)2SiF6(aq) + 2h2〇(1) There are a number of variations in the oxidized oxide etch recipe. The method described herein for the preferred configuration of the patterned etched etched silica dioxide relies on providing a separate fluoride anion and acid, placing the two major precursor components together. Preferably, the component is provided as an acidic proton in a water-soluble acidic polymer film which is provided on the surface of the glass substrate to be surnamed as a surface layer. In another configuration, the surface layer may comprise = External material (for example, inorganic material deposited by methods such as riding, sputtering or chemical vapor deposition or physical vapor deposition). The fluorine anion is preferably formulated in an aqueous solution and then deposited by a fluid deposition pattern in accordance with the pattern. At the position where the deposition fluid contacts the polymer film, t 'polymer system The part is dissolved, the gas anion extracts acid from the polymer and the domain hydrogen fluoride. The money dissolves in the deposition position (4), and the vaporized hydrogen formed by the dissolution (IV) is exposed to oxygen. The HF-containing rust-reported mountain mixture 'Indirect treatment. Although the gas-containing solution is classified as toxic, it is still safer than the HF solution. In addition, the preferred configuration method uses only a small amount of gas anion' Μ anion to form a solution with a reasonable dilution concentration. In addition, the deposition method used in the preferred configuration of the fluoride-containing solution can reduce the operator's contact with the solution at the time of 2011. The same is true for the fluid storage tank of the inkjet printer. It is difficult to achieve direct deposition of HF-containing etchant fluids because of the general polarity: there is a print head or, more commonly, a spray device that can withstand the corrosive nature of the fluid. The printing head of part A (4), not steel and Shi Xi. It is impossible to (4) based on the head of the material, because the type contains the dioxo component of hydrogen fluoride. Long time rot It also quickly triggers intermittent mouth clogging, which makes it difficult to reliably eject the solution. In addition, no operator will deposit HF-containing solution or other secret deposition method by inkjet for safety reasons. There is a risk of exposure to the HF& solution. This is not a problem with the method suggested here because the fluorinated anion solution is not corrosive. This also means that the solution can be sprayed using enamel and ceramic print heads. A preferred configuration for texturing of a glass substrate is illustrated in Figures 1A through 1D. The water-soluble acidic polymer film 11 is spin-coated on the surface of a glass substrate 105 having a thickness of about 3.3 mm as shown in Figure 1A. The film was spin-coated from 25% (w/v) polyacrylic acid (PAA) in an aqueous solution at a centrifugal speed of 7000 rpm for 30 seconds. The molecular weight of the polyacrylic acid PAA is preferably in the range of 20,000 to 200,000 g/mol (g m〇i_i), and more preferably about 9 〇〇〇 g/mole. Polyacrylic acid is a homopolymer of acrylic acid. The acrylic monomer unit is a source of acid protons as shown in the chemical structural formula of Fig. 2. The polyacrylic acid paa has a pKa of about 4.3. The polymer film which has been spin-coated is air-dried over a period of about 3 hours to obtain a thin crucible having a thickness of about 2·5 μm from 13 201135955. The solids content of the solution used to form the acid film of the bismuth compound can vary from about 5% to about 35% without affecting the polymer film quality, but preferably has a solids content of from 2% to about 鄕. Using (4) (iv) content and/or faster centrifugal speed' results, (4) (iv) Film 1 The glass substrate 105 having the polymer film 110 is preferably kept under air until needed to reduce uneven wetting of the polymer film. In another configuration, other water-soluble polymers or resins containing an acidic group (such as a turtle, a polystyrene melamine, a polyresin) may also be used. The (4) polymer mixture or compound can also be used to form an acidic film. For example, polyacrylic acid paa can be blended with other water-soluble polymers, such as scales (PVA), depending on the degree of (10) _, from η 1 to! : A range of 4 PAA; PVA ratio. Polyacrylic acid can also be blended to obtain a dry film having a better critical surface tension than a non-hydrophilic polymer such as poly-f-acrylic acid. This variation is preferred when smaller etch features are desired because the deposited droplets are less developed on a higher water repellent surface. Copolymers of acidic polymers such as poly-acid PA A can also be used to form polymeric films. The use of copolymers or polymer blends to form films is a means of controlling the acidity of the formed film. In addition, the polymeric film may contain additives which may provide additional acid groups directly or indirectly enhance the acidity of the film. These additives may be dissolved or dispersed in a solution (e.g., nanoparticle) made of hydrazine to form an acidic polymer layer. These additives can also be used to modify the surface properties of the polymer film. The polymeric film may also contain a surfactant. It is preferred to use such surfactants at a concentration of less than 1% ( (for example, Novick (4) (4) 201135955 4200 from 3M Company). These surfactants improve the uniformity of the resulting etch by allowing the deposited solution to uniformly wet the surface to be etched. The added surfactant also actively reduces the critical surface tension of the polymer film, thus allowing for a smaller etched feature. Other fluoropolymer additives such as FC-4432 (also available from 3M) may also be added to specifically reduce the critical surface tension of the polymer surface end product. However, relatively small surfactant formulations such as Novik 4200, longer chain fluoropolymers are less effective wetting agents. Other surfactants or surface tension modifiers that are chemically compatible with the fluoride anion can also be used. In an additional variation of the preferred configuration, the polymeric film can be made using polymers that can act as liquid crystal molecules (eg, poly-n-alkyl acrylates and methacrylates, poly-n-alkyl vinyls). Ethers and esters, and poly-n-alkyl styrenes), or contain small molecule additives that can act as liquid crystals [eg, polydiacrylate (ethylene glycol) esters and other polyethylene glycols with charged branches) Object]. Alternatively, the small molecule liquid crystal may be incorporated into the branch to provide liquid crystal characteristics to the resulting polymer phase. The liquid crystal can be polarized (or aligned) in a predetermined direction in the polymer phase by application of an electric field. The film thus formed can be used to provide the desired directionality to the resulting textured pattern, as well as to further reduce the resolution or pitch of the resulting textured pattern. The patterned etching of the surface of the glass substrate 105 is achieved by depositing a fluid of a fluorine-containing anion source on the surface in accordance with a predetermined pattern. In a preferred configuration, the flow system is deposited as a fluorinated anion solution by dripping the ink jet printer. The ink jet device 120 shown in Fig. 1B contains one or more print heads 125 which eject droplets of solution 130 from the nozzle array. Individual nozzle emissions 15 201135955 can be under thermal or piezoelectric control. The night to be sprayed can be stored on or near the print head or in a gutter that is farther away from the print head. Preferably, the print head of the ink jet device 120 deposits a solution across the surface of the person as needed during scanning. The glass substrate 105 is tied to a platform, and is horizontally moved relative to the print head on an axis of the vertical scanning axis. However, in other configurations, the stage can remain fixed when the print head is scanned in both directions, or the print head (i.e., the glass substrate 105) can be held in a fixed position when the roll plate (i.e., the glass substrate 105) is moved in both directions. A better platform and thus a glass substrate 1〇5 can be heated while printing. In a preferred configuration, the piezoelectrically controlled 矽 print head is manufactured by Fujifilm (FUJIFILM) Dimatix for depositing a fluorinated anionic solution. The print head is bonded to the cassette with 16 nozzles linearly spaced apart by a distance of 254 microns and a droplet size of 1 picoliter. It is also possible to use a print head that can deposit other droplet volumes, but with a smaller droplet volume, because it provides a textured pattern with less etching and finer resolution. The emission of individual nozzles is under software control, which allows for the acquisition of programmed droplet deposition in accordance with a predetermined pattern. Patterns are available using standard image formats such as bitmap files. Depending on the tightness of the droplet position of the deposited pattern, it may be necessary to deposit a multi-layered etched pattern. It is important to understand that the need to print multiple layers of fluorinated anion solution comes from etch chemometrics. A 6-fluoride anion is required for each of the etched germanium atoms in the ceria crystal layer. The software of the ink jet device used in the preferred configuration allows multiple layers of selected patterns to be printed at selected locations. These layers are printed one by one, with only a very short delay between successive layers. Alternatively, the delay can be interposed between consecutive two layers of printing. In yet another configuration, instead of printing a 201135955 multi-layer pattern, the number of deposits can be deposited at various locations in front of the printhead, and/or the platform can be moved to the next deposition location. In a preferred configuration, the ink jet device used can optimally eject the solution when the viscosity is between 10 cP and 14 cP and the surface tension is between 28 and 32 millinewtons per meter (mN/m). However, it is also possible to spray a solution having a viscosity of less than 2 cP using the apparatus. This project was achieved by properly adjusting the waveform applied to the piezo nozzle. It is harder to change the surface tension, but it is also possible. If the surface tension of the solution is too high (for example, about 7 〇mN/m for deionized water), it is difficult to prime the print head (that is, there is initially no solution that can be ejected from the nozzle. On the other hand, if the surface of the solution If the tension is too low, the surface containing the nozzle orifice (nozzle orifice) will typically be overflowed by the spray liquid, thus causing irregular arrangement of small droplets on the polymer surface. The nozzle orifice plate has a polymer that does not wet the surface, but the ejection of the low surface tension fluid still causes a pronounced wetted zone on the surface, thus causing irregular emission. Preferably, the fluoride anion of the deposition solution is provided as ammonium fluoride. The aqueous solution, and the ammonium fluoride concentration is in the range of 10% to 15% (w/v), and more preferably about 11% (w/v). Other sources of fluoride anions (e.g., sodium fluoride, fluorination may also be used). Potassium, tetraalkylammonium fluoride), but the solubility of the final product of the etching must be carefully considered. For example, the solubility of sodium fluoroantimonate (at 2 (rc is about 4 〇 mg / liter) is lower than the failure of the stone The sour acid is the bath solution. So it is better to spray more diluted The anion solution ensures that the product does not precipitate onto the surface to be etched and prevents further etching of the surface. The deposition of the more diluted fluoride anion solution may require the injection of a larger amount of deposition solution (in other words, more layers will be printed). 17 201135955 In its configuration, when the required depth of the meal is extremely shallow, the formation of the engraved barrier can be used to control the degree of butterfly. Therefore, for example, gasification can use high platform temperature spray to rapidly self-deposit the solution gas. After the formation of the fluoroantimonate anion in the phase of the field, the sodium fluoroantimonate precipitate will be formed on the surface to prevent further etching. The lower fluoride anion concentration can also be used to form a better textured pattern. The textured pattern may be excellent because it causes less stress on the crystalline 11 film formed on the textured surface. In a preferred configuration, it has a 2 gram/mole molecular weight of 2% (v/v) Polyethylene glycol (PEG 400) was also added to the spray solution to increase the viscosity to about 4 cp, thus improving spray performance. In another configuration, PEG 4〇〇 can be self-deposited In addition, or included in the solution at a lower concentration, but requires a lower pulse voltage, a slower pulse rise time, and a lower injection frequency to reliably eject a lower viscosity solution. In other configurations, PEG 4〇 The ruthenium may be replaced by a ruthenium compound (for example, glycerin, an alkali water-soluble polymer compound such as polyvinylpyrrolidone, or other glycol) which increases the viscosity of the solution. The pH of the deposition solution can be increased by adding ammonium hydroxide to 8 to 1 〇, and more preferably increased to 8. High pH is preferred to avoid high concentration of reactive etchant in the deposition solution, namely HF and HF; f. In ammonium fluoride solution, greater than 7 ^^ The value 'the concentration of the two etchant classes is effectively zero, and as a result does not result in the etching of the dioxide dioxide' so as to protect any of the dioxide components in the print head. If the solution is too alkaline (e.g., pH is greater than 11), several surnames of the print head may occur. The resulting preferred deposition solution has a surface tension of about 46 m N / m at 28. Although this value exceeds the optimum surface tension range of the Fujifilm-Dimati print head used, the spray waveform can be adjusted to accommodate the increased 18 201135955 gauge tension § > Valley liquid contact with the polyacrylic acid surface has approximately 44 mN When the critical surface of the /m is superficial, the polyacrylic acid causes the solution to develop less. The surface tension of the deposition, _' is increased, and the deposited money is more developed, so that the tension is reduced to cause the structure. % Larger etched features Finally, the temperature of the deposition solution is preferably lower, but typically the surface of the solution, C. It can also be used to make it more difficult to spray the solution. : Low temperature rises, such as solution sprays with medium to high surface tensions. The surface of the polymer on the Vickers side (from 3 Å) is a useful strategy for the characterization of the properties. This type of strategy is a type of emission waveform used by the Tianshi film-Dimati print head. In another configuration, a fluorinated surfactant such as oxonol (from 3M) can be added to the deposition solution. This surface active is effective in reducing the optimum range of surface area to the film of the animal film-Dimati print head (refer to the figure). For the Novik side, α class α 5% (v / concentration reduces the surface tension of the deposition solution to a surface tension in the range of 38-32 mN / m, thus allowing it to be reliably sprayed. Other surfactants that are compatible. In addition, other additives that can change the surface tension can also be used. For example, the addition of glycols such as propylene glycol can also conveniently reduce the surface tension to the Fujifilm-Dimati print head. Optimum range. In other configurations, using other printheads, it may be necessary to change the surface tension and viscosity to meet the operational requirements of the printhead. 201135955 In a preferred configuration, the platform and such glass substrate 105 are heated between jets d of the deposition solution. The heating of the platform results in the dissolution of a portion of the deposition solution being vaporized during the ejection, resulting in a smaller wetted zone and thus a smaller etch opening. Preferred for etching of the textured pattern, the platform temperature is maintained at 55. C. Excessive heating of the platform may result in excessive vaporization of the solvent, resulting in a reduction in the aqueous environment at the surface of the desired surname. And may also cause precipitation of the etch product, fluorite, which may cause uneven etching across the textured regions. As explained above, the etched product can be used as a means of preventing overetching and forming superficial etched patterns. Referring back to Figure 1C, the deposited droplets 13〇 dissolve the polymer where it contacts the surface layer 11 to form a region 150 of dissolved polymer. The fluoride anion of the deposition solution reacts with the dissolved polymer. The hydrogen fluoride is formed to etch the lower surface of the glass substrate 1〇5 to form the etching regions 160 and 165 on the glass substrate 1〇5. The shapes and depths of the etching regions 160 and 165 depend on the concentration of the fluoride anion in the deposition solution, The nature and thickness of the polymer layer 11〇, the glass type used for the glass substrate 105, the platform temperature, the relative arrangement of the adjacent droplets 130, and the printing speed. All of the above factors can be changed to form different layers above the glass substrate 105. Textured pattern. In the raster scan of the deposited pattern, the subsequently deposited droplets 13〇 overlap, resulting in the formation of unequal concentrations of hydrogen fluoride on the entire surface. More specifically, when a droplet is deposited using a grating-based fluid deposition device 12 such as a Fujifilm-Dimajet printer for better configuration, the droplets tend to be deposited and combined on the surface of the glass substrate 105. A highly textured narrow groove is formed on the surface, as shown in Fig. 3. If the surface is perpendicular to the groove formed by scanning (see Figure 20, 201135955, Figure 4), the atomic force microscope (AFM) of the pattern shown in Figure 3 The rim forms a periodic etched pattern result. By changing the droplet spacing of the deposited pattern, the IU can be unequal; the spacing between the trenches. The textured pattern shown in Figure 3 can be used in the axis - 1G micron. The droplet spacing is formed. In other words, the deposition pattern used to form the image shown in the figure is a pixel grid having a pixel resolution per pixel. Smaller droplet spacing results in a finer pattern, kernel, and textual characteristics: the fine depth of the structure is typically larger due to the greater f-hydrogen fluoride. Alternatively, the degree of etching can be controlled by increasing the temperature of the stage and/or by using a thousand hands (e.g., reducing the concentration of fluoride anions, or using denaturization as a source of fluorine anion). When texturing is used for light trap purposes, it is important to reduce the occurrence of flat areas. Figures 3 and 4 verify that the textured pattern formed using the present technique has very few flat regions. Even with these patterns, the grating deposition sequence has been explored to achieve a shallow trench structure, but some texture remains on the surface at the bottom of the trench. Ideally, a shallower texture with a steeper slope will enhance the light trap capability of this texture. When the fluid deposition process is complete, the glass substrate 105 is removed from the platform of the fluid deposition apparatus 120, and the deionized water immersed in the flow is subjected to 5 to 1 minute. This final cleaning step removes the final etched substrate 100' having the opening 160 formed by both the etched product and the water-soluble polymer film trapped in the surnamed region 150 as shown in Fig. 1D. Unlike the current wet etching method, the amount of fluorinated waste liquid during this cleaning step is extremely small, and only the fluoride which has been deposited by the ink jet printer is used. This means that the waste liquid is extremely diluted without great harm. For some applications, it may be desirable to form a textured pattern with a relatively rounded feature knot 21 201135955. For example, sharp edges may cause higher stress on the film deposited on top of the textured surface. The rounding of the sharp edges can be achieved simply by immersing the textured surface in a solution that isotropically etches the glass (e.g., a solution comprising a mixture of HF or HF and ammonium fluoride). It is preferred to use a solution containing 10% 7.1 buffered oxide buttoning agent because the etched glass is extremely slow, and it is convenient to control the degree of rounding (smoothing) by the length of immersion. In another configuration, a higher texturing throughput can be achieved by using a large area aerosol spray unit to deposit a fine mist or aerosol of the fluoroanion solution onto the polymer layer 11〇. Preferably, the aerosol spray unit is arranged as a substantially linear unit having approximately the same width as the sheet of the glass sheet to be textured, as shown in Figure 5, which extends the transverse glass sheet. The glass substrate 105 coated with the polymer layer 11() is suspended below the overhead linear aerosol unit 520 suspended on the structure $1. The glass substrate 1〇5 with the polymer layer 11〇 is positioned on the strip 505, which is moved relative to the stationary linear aerosol unit 52〇. Preferably, the strip 5〇5 is heated to a temperature in the range of 3 Torr to 6 Torr and more preferably in the range of 40 ° C to 50 ° C. In this manner, when the glass substrate 105 is moved under the fixed structure 510 containing the linear aerosol unit 52A, the linear aerosol unit 52 can deliver a fine mist of the gas gelled fluoride solution to the polymerization of the glass substrate 1〇5. The layer 11 (the linear aerosol unit 5 2 G is difficult to contain a linear gas-soluble material. Columns, but other configurations may be used.) A two-dimensional aerosol nozzle array may also be used. The fixed overhead structure 51G is attached to the strip 5 a unit on the side that covers the liquid storage tank to be atomized. In the configuration shown in Figure 5, the IU-to-shell unit structure of the components 5〇〇, 22 201135955 510 and 5 2 G is connected. The junction to the unit comprising the strip driver 5〇5 for moving the glass substrate 105. The reaction occurs when small particles from the aerosol aerosol contact the polymer of the polymer layer 11〇, primarily as explained for the preferred configuration. The rate of reaction and thus the degree of etching depends on the amount of water remaining in the aerosolized particles. Excessive drying of the particles results in a etch rate of the pole k. Preferably, the aerosol aerosol is generated using an ultrasonic atomizer. Other nebulizers or sprays (eg pneumatic Nebulizers, inkjet nebulizers can also be used, but the limitation is that they do not excessively reduce the water content of the particles. In order to reduce the loss of aerosol particles to the surrounding environment, the output nozzle of the linear aerosol unit is set to the surface 1 Centimeter to 5 cm distance, and better about 2 cm from the surface. Configured in Figure 5, by changing the strip speed and temperature, the concentration of fluoride anions in the aerosolized solution, aerosol humidity (effective control The individual particle size 'and the thickness and nature of the polymer layer' can change the properties of the textured pattern. After the glass substrate 105 passes under the linear aerosol unit 52, it continues to travel along the strip 505 until the reaction is complete, then The cleaning unit moves, where the deionized water is sprayed from above to wash away the polymer layer and the etching residue. The time required for the reaction to complete is typically extremely short (preferably 3 to 60 seconds). However, it depends on the factors listed above, such as controlling the etching rate. The foregoing glass texturing method can be continuously added by simply maintaining the minimum fluid height in the liquid storage tank used to form the aerosol. The glass substrate 105 is treated. Since most of the fluorine anion concentration in the waste liquid from the cleaning station can be controlled to be extremely low (less than 5 ppm), it is not necessary to treat the discharged water from the process. Therefore, the cleaning unit can be operated continuously. The waste liquid discharge is continuously discharged 23 201135955 to accommodate new wastewater. In an additional variation of the method shown in Figure 5, the polymer layer n〇 can also be arranged by an additional linear spray aligned with the linear aerosol unit 520. The unit is made. This variation is shown in a schematic cross-sectional view in Figure 6. The additional linear spray unit 610 is positioned above the strip 505 upstream of the linear gas-melting unit 520, which dispenses aerosolized fluoride. The glass substrate 1〇5 is first passed under the first linear spray unit 610, and is sprayed onto the surface of the glass substrate 105 in the sprayed solution of the treated polymer solution, so that the polymer layer 11〇 is formed on the surface of the glass substrate 105. . Linear spray unit 61 is preferably a polymeric polymer solution spray. The spray is substantially the same as the polymer solution used to spin coat the surface of glass substrate 105 in a preferred configuration. Depending on the strip speed, the solution is thinner or less thin than the solution used for spin coating in the preferred configuration. Unlike the fluorine anion delivered to the surface of the polymer layer 11 without the need to aerosolize the polymer solution, a simple spray unit that delivers a uniform amount of polymer solution across the glass substrate 105 is used. Preferably, then the heating unit 630 is disposed above the strip 505 to perform drying of the polymer layer in a short period of time. Alternatively, polymer layer 110 can be dried by passing a stream of gas or air over the surface of the deposited polymer. Preferably, the dried polymer layer 110 has a final dry thickness of 2-3 microns, and more preferably about 25 microns. However, thinner polymer layers can be used to allow for extremely high throughput processing. The glass substrate 1〇5 with the dried polymer layer 110 is then moved by the strip 505 to the position of the linear aerosol unit 520 where it is described as previously described as 'the aerosol containing the anion 550 is deposited in a linear manner. The moving substrate is on the surface of the substrate. A person skilled in the art will recognize that the invention may be varied and modified without departing from the scope of the invention as broadly described. Therefore, the embodiments are to be considered as illustrative and not restrictive. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A is a schematic view showing a glass substrate covered with a surface acidic polymer layer in a sectional view; FIG. 1B is a schematic view showing two drops of a solution containing a tactile component deposited on an acidic polymer layer, The droplets are arranged in close proximity to each other; FIG. 1C is a formation of a heavy-grained area which is not intended to be apparent on the surface of the glass substrate; FIG. 1D is a schematic view showing the etching residue and the glass substrate after the acidic polymer layer has been removed; The figure shows an example structural formula of an acidic polymer, that is, polyacrylic acid; FIG. 3 is an atomic force microscope (AFM) profile view of a textured region formed using a preferred configuration; and FIG. 4 is an AFM profile view through FIG. A cross-sectional view, which is recorded at an angle perpendicular to the groove being etched; Figure 5 is a schematic view of a large-area aerosol spray unit that can be used to spray a fluoride-containing solution to achieve a higher texture. Figure 6 is a schematic diagram of the large-area aerosol spray unit of Figure 5, which has a linear spray unit with an alignment, and is to be textured before spraying the fluoride solution. A polymer layer is formed on the surface. 25 201135955 [Description of main component symbols] 100.110.. Polymer film, polymer layer 105.. Glass substrate 120.. Inkjet device, fluid deposition device 125.. Print head 130.. Solution droplet , deposited droplets 150, 160, 165···etching area, opening 500.. strip 505.. strip, strip drive 510.. substrate, fixed overhead structure 520.. overhead linear Spray device 550, 620... ink drop 610... linear spray unit 630... heating unit 26