201039385 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種形成一具有週期結構基板之方法， 尤指一種能快速製作、成本低廉、且可避免基板損傷之形 5 成一具有週期結構基板之方法。 / 【先前技術】 所謂的光子晶體是一種週期性結構，可使某些頻率的 光線侷限於一特定的方向傳播，並可防止其他頻率的光線 10之傳播；且因光子晶體其操作範圍是光的範圍，故光子晶 體之結構週期尺寸必須為次微米或奈米等級。目前，光子 晶體除可應用於光學通訊系統以及光計算機等領域外更 可將光子晶體應用在光電元件以增進光電元件之效能。 一般係以高能量雕刻成型或奈米壓印術等方式圖案化 15基板以形成光子晶體，如雷射、電子束、離子束雕琢成型、 雷射全像干涉、或以上述方法製作硬質光子晶體母板後再 將母板拓印於軟基材之技術。然而，高能量雕刻成型旦有 極面成本及低產能之缺點，而奈米壓印術雖較高能量雕刻 成型之成本低且產能較高，但仍無法滿足低成本及高產能 20 之需求。 目前’可採用乾蝕刻或濕蝕刻方法圖案化基板以形 成具有週期結構之基板。以乾㈣法為例，係如圖^至圖 不。百先’如圖1A所示，提供—基板1〇;而後於基板 姉面丨(H形成—光阻和，如圖1B所示。接著，於光阻層 201039385 11上覆蓋一光罩12 ’並進行曝光以圖案化光阻層u，如圖 ic所示。經顯影並移除光罩12後，可得一圖案化之光阻層 11 ’如圖1D所示。而後，以圖案化之光阻層u做為一蝕刻 遮罩，利用反應性離子氣體蝕刻基板1〇，以形成複數微凹 穴102，如圖1E所示。接著，移除圖案化之光阻層11(蝕刻 遮罩）後，可得一圖案化之基板1〇 ’如圖1F所示。其中，此 圖案化之基板1 〇其表面丨〇 i具有以複數微凹穴1 所排列形 成之週期性結構。201039385 VI. Description of the Invention: [Technical Field] The present invention relates to a method for forming a substrate having a periodic structure, and more particularly to a method for rapidly manufacturing, low cost, and avoiding damage of a substrate. The method. / [Prior Art] The so-called photonic crystal is a periodic structure that allows light of certain frequencies to be confined to a specific direction and prevents the propagation of light 10 of other frequencies; and because the operating range of the photonic crystal is light The range of the structure of the photonic crystal must be in the order of submicron or nanometer. At present, photonic crystals can be applied to photovoltaic elements in addition to optical communication systems and optical computers to enhance the performance of photovoltaic elements. Generally, the 15 substrate is patterned by high energy engraving or nanoimprinting to form a photonic crystal, such as laser, electron beam, ion beam engraving, laser holographic interference, or hard photonic crystal by the above method. The technique of printing the mother board on the soft substrate after the mother board. However, high-energy engraving has the disadvantages of extreme cost and low productivity, while nanoimprinting has low cost and high productivity due to its high energy engraving, but it still cannot meet the needs of low cost and high capacity. Currently, the substrate can be patterned by dry etching or wet etching to form a substrate having a periodic structure. Take the dry (four) method as an example, as shown in Figure ^ to Figure. As shown in FIG. 1A, a substrate 1 is provided; then, a substrate is formed on the substrate (H is formed as a photoresist, as shown in FIG. 1B. Then, a photomask 12 is covered on the photoresist layer 201039385 11 ' And exposing to pattern the photoresist layer u, as shown in Figure ic. After developing and removing the photomask 12, a patterned photoresist layer 11' can be obtained as shown in Fig. 1D. Then, patterned The photoresist layer u is used as an etch mask, and the substrate 1 is etched by reactive ion gas to form a plurality of micro-pits 102, as shown in Fig. 1E. Then, the patterned photoresist layer 11 is removed (etch mask) After that, a patterned substrate 1' is obtained as shown in FIG. 1F, wherein the patterned substrate 1 has a periodic structure formed by arranging a plurality of micro-pits 1.
ίο 15 〇 20 然而，以上述乾蝕刻法雖可製造出圖 =性結構之基板，然此方法之缺點為：因：行= 影製程’故成本高且產速低；若要形成奈米級週期性結構， 貝！所，用-人微米光罩昂貴，且如要彻⑽以下的圖形則成本 更加提高；反應離子氣體蝕刻機台昂貴且製程緩慢；易損 傷基板；且蝕刻面非自然晶格面。 為解決乾飯刻法之問題，目前發展出以㈣刻法形成 具有週期性結構之基板；如圖2A至圖2F所示，係以 晶向之單晶石夕基板為例。其中，形成具有週期性結構基板 ^方法，係與乾_法相似，除了以緩衝餘刻祕刻基板。 ^安如圖2A至2〇所示’先以曝光顯影方法（微影製程）形 ”化之光阻層n(請參見圖2D);而後以圖案化之光阻 曰1做為-㈣遮罩’以非等向性緩衝㈣液㈣基板 形成複數微凹穴1G2，如圖2E所示。接著，移除圖案 ^光阻刻遮罩）後，可得—圖案化之基板10，如圖 不/、中，此圖案化之基板10其表面101具有以複數微 5 201039385 凹八102㈣列形成之週期性結構。值得注 刻圖案化基板_形成之微凹穴1〇2，其形狀係為心 ::此倒四角錐的周圍斜面，亦為單…u>之自然晶袼 5 10 列面圖㈣基板可避免基板受到損傷且餘 ”，，w日日格面，然而，進行濕蝕刻時若參數控制不告， Γ成週期性結構的均勾性較差。同時因上述之製作過田程 需進仃微影製程’故仍面臨成本高且產速低等問題。 ，因此，目前虽需發展出-種圖案化基板之方法， =免基板受到損傷，並可快速且便宜形成具有週期結構 暴板。 【發明内容】 本發明之主要目的係在提供—種形成一具有週期結構 15 -板之方法’俾能減少製程時間、降低製作成本、並 時避免基板受到損傷。 、為達成上述目的，本發明之形成具有週期結構基板之 方法，係包括下列步驟：（A)提供一基板及複數奈米球宜 中複數奈米球係排列於該基板之表面；（B)形成一填充層ς 20基板之部分表面及複數奈米球之間隙；（c)移除複數奈米 求’（D)將填充層做為一蝕刻遮罩並蝕刻基板；以及（ε)移除 蝕刻遮罩，以形成一週期結構於基板之表面。 本發明係利用奈米球的「自組裝」特性，即這些奈米 求每自動且有序地排列於一基板的表面，取代黃光微影製 201039385 201039385 5 〇 ίο 15 ❹ 20 形之模板。同時，利用這些自動排列之 廉的成本來成:昂貴之次微米曝光遮罩，故可以較低 二 週期性結構，，本發明之形成具有週 =形成且:Γ續需之材料也非常容易取得:二 &大里形成週期結構之基板。 於本發明之形成具有週期結構基板之 面之週期結構係具有複數微凹穴 土板表 S ϋέ ^ ^ Μ X, 权佳為，馒數微凹穴係 此外，微凹穴之形狀係由蝕刻基板過程中 柱體的所圍繞形成’可為倒角錐、倒圓錐、圓 =:，：：倒截頭圓錐。不同材質之基板與不同 板採：氫氧化ί不同形狀之微凹穴。如為前述之單晶碎基 板私用㈣化㈣刻，則微凹穴為—細肖錐， 錐之底部係、位於基板表面，而四角錐之頂部係、自基 凹陷。若以氫氟㈣刻㈣刻玻璃基板，則微凹穴Ζ 為一倒截頭圓錐。 办狀 後更2發Γ之形成具有週期結構基板之方法_，步驟（Ε) 1包括-步驟（F)··再關該基板表面。於步驟⑻所形成 之，、週期結構之基板’其中相鄰之微凹穴間係具有一平 二而力：視為一凹板結構。而若再經過步驟(F)再-次钮刻， 貝1〜加微凹穴之寬度及深度，而使相鄰之微凹穴間不 一平面’而可視為一凸板結構。 v、 ，於本發明之形成具有週期結構基板之方?去中 之週期結構可為奈米級或微米級之週期結構；其中，週期 7 201039385 級、米及或人微米級之週期結構，且更佳為奈米 、，及匕期、、·。構。於本發明之形成具有週期結構基板之方法 中，步驟⑷之複數奈米球排列於基板表面之步驟 5 10 15 下列师⑷）提供基板、及容器中之膠體溶液， 且勝體溶液包括複數奈米球及一介面活性劑；（A2)放置基 板於容器中’且膠體溶液覆蓋於基板之表面；以及⑽加 入-具揮發性之溶液於容器t，以增加溶液揮發速率且 促使複數奈米球於基板之表面進行排列。其中，複數太米 球係形成-奈米球層，且較佳為—層之奈米球層。— 於本發明之形成具有週期結構基板之方法中，步驟⑼ 之㈣基板之方法可職_法或祕料，較佳為祕 刻法。其中’濕姓刻法係以一緩衝敍刻液银刻基板，而緩 衝蝕刻液可為根據基板及填充層之材質選擇一般常用之酸 性或鹼性蝕刻液。其中’酸性蝕刻液可包含一酸液、一醇 類、以及水，而鹼性蝕刻液則包含一鹼液、—醇類以及 水。酸液較佳為氫氟酸、8〇臥出7與1^^17混合溶液）、鹽酸、 硝酸、磷酸、硫酸、醋酸、或其混合溶液。或者，酸液亦 可為由乙醇胺（ethanolamine)、五倍子酸（gaUic acid)、水、 過氧化氫（hydrogen peroxide)、及表面活性劑所混合而成之 Amine Callates。此外，鹼液較佳為氫氧化鈉、氫氧化鉀、 氨水 '氫氧化鈽、氫氧化铷、氫氧化四甲銨、乙二胺、或 聯胺再者，醇類較佳為乙醇或異丙醇。由於本發明之方 法較佳係使用濕蝕刻法蝕刻基板，因此可達到避免基板損 傷之目的。 20 201039385 Ο ίο 15 Ο 20 =明之形成具有週期結構基板之方法中，奈米球 甲…特殊限制，較佳為氧化石夕（Si〇x) '陶曼、聚甲基 ⑽叫氧化鈦(T叫或聚笨乙烯阶此外， 不^之直徑可介於刚⑽至以心之間，較佳係介於_ ….2“m之間’且複數奈米球較佳係具有相同的直徑。 於本發明之形成具有週期結構基板之方法中，步驟⑻ 之形成填充層之方法並無特殊限制，較佳係期化學氣相 =積法或物理氣相沉積法，以於基板之部分表面及複數奈 2之間隙形成填充層°此外，填充層之厚度係根據所欲 =，之微凹穴尺寸來決定，較佳係小於該複數奈米球之直 徑。再者，填充層之材質並無特殊限制可為一般常用之 做為^丨遮罩之材料，且較佳為氧化$、氮化♦'氧氮化 矽、氧化銘、氧化鋅、氧化銦錫、氧化鋅摻銘、鉻、组、 鎢、釩、鎳、錫、鐵、銅、鉬、鈦、鋁、銀、金、鉑、鈀、 或光阻㈣、聚甲基丙稀酸甲_财)、聚笨乙烯(ps)。 於本發明之形成具有週期結構基板之方法中基板之 材質並無特殊限制’可依照所應用之領域做選擇。其中， 基板材質可為P型單晶石夕、N型單晶石夕、p型多晶石夕N型多 晶石夕、P型非晶石夕、N型非晶石夕' p型神化録、N型砂化錄、 P型鱗化銦、N型碟化_、p型魏鎵銦、N型碟化鎵姻、p 型氮化鎵、N型氮化鎵、”砸化銦銅、化銦銅、氧 化銦錫、碳化石夕、氮化石夕、石英、或氧化鋅及氧化辞推鋁 化合物。或者，本發明之方法所使用之基板亦可為藍寶石 9 201039385 基板（單晶氧化旬。較佳為，本發明之方法所使用之基板係 為p型矽基板或藍寶石基板。 此外’本發明之方法所使用之基板亦可為玻璃基板' 或表面具有透明導電膜（TC0)層之玻璃基板。若使用之基板 5為表面具有透明導電膜（TC0)層之玻璃基板，則週期結二係 形成在透明導電膜（TC〇)層；亦可反之。 本發明之形成具有週期結構基板之方法，除了利用奈 米球做為蝕刻遮罩之模板，以取代黃光微影製程，同時， 更利用濕式蝕刻圖案化基板，故可達到均勻之週期結構且 10避免基板損傷之目的。因此，本發明之形成具有週期結構 基板之方法，可以簡單、成本低、及高產能的方式圖案化 基板。 【實施方式】 15 如圖3A至圖3F所示，此為本發明一較佳實施例中’奈 米球排列於基板表面之步驟示意圖。首先，如圖所示， 提供—基板21及一位於一容器26中之膠體溶液25,其中此 膠體溶液25係由複數個奈米球（圖中未示）及一介面活性劑 (圖中未示）混合而成。接著，將此基板21放置於容器％中並 20 使得基板21完全浸入於膠體溶液25中，如圖3B所示。在靜 置數分鐘以後，奈米球22便逐漸有序地排列於基板21表 面’即形成所謂的「奈米球層」，如圖3C所示。而後，將 一揮發性溶液27倒入容器26中，以將前述之膠體溶液25揮 發掉’如圖3D所示。最後，如圖3E所示，等到前述之膠體 201039385 溶液25完全被揮發後，便將基板21從容器26中取出並得到 一具有複數個奈米球22有序地排列於其表面的基板21，如 圖3F 〇 ❹ 10 15 Ο 於本實施例中，奈米球22的材質係為聚苯乙烯（ps)， 但是在不同的應用場合中，這些奈米球22的材質亦可為陶 瓷、如氧化鈦（Ti〇x)之金屬氧化物、聚曱基丙烯酸甲酯 (PMMA)或玻璃（Si〇x)等材質。此外，於本實施例中奈米 球22之直徑係介於100 nm至2.5"m之間，且絕大多數奈米 球22係具有相同的直徑，但是在不同的應用場合時，這些 奈米球22之尺寸不僅限於前述之範圍。 此外，於本實施例中，基板之材質為單晶矽基板。然 而’基板之材質係依照不同的應用場合作選擇，可為p型單 晶矽、N型單晶矽、p型多晶矽、N型多晶矽、p型非晶矽、 N型非晶珍、P型碎化鎵、N型神化鎵、P型鱗化銦、N型麟 化銦、p型碟化_、N㈣⑽姻、” m w 鎵、p型硒化銦銅'N型硒化銦銅、氧化銦錫、碳化矽氮 化矽、石夬、或氧化鋅及氧化辞摻鋁化合物；且亦可為藍 寶石基板（單晶氧化旬、玻璃基板、表面具有透 (TCO)層之玻璃基板。 、 接下來，請參閱圖4A至圖4E，此為本發明—較佳實 例中’形成具有週期結構基板之剖面示意圖。此外，並同 時參考圖5A至圖5B，此為本發明—較佳實施财，形成二 有週期結構基板之SEM圖。 、 20 201039385 首先’如圖4A所示，提供一基板21及複數奈米球22， 並依照上述之方法’使複數奈米球22排列於基板21之表 面，而形成一奈米球層。其中，奈米球22可以多層堆疊於 基板21表面，而於本實施例中，奈米球22係以一層的方式 5排列於基板21表面。由圖5A之SEM圖顯示，奈米球的確可 以一層的方式排列於基板之表面。 接著’如圖4B所示，利用化學氣相沉積法形成一填充 層23於基板21之部分表面及複數奈米球22之間隙。其中， 填充層23之厚度係小於該複數奈米球之直徑，且填充層之 10材質為氮化矽。然而，除了可以化學氣相沉積法形成填充 層23外，更可以物理氣相沉積法形成，且填充層23之材質 亦可為其他常用於做為蝕刻遮罩之金屬，如氧化矽、氧氤 化石夕、氧化銘、氧化鋅、氧化銦錫、氧化鋅摻紹、鉻、组' 鎢、釩、鎳、錫、鐵、銅、鉬、鈦、鋁、銀、金、鉑、鈀、 15或光阻（PR)'聚曱基丙烯酸甲酯（PMMA)、聚苯乙烯（PS)。。 而後，使用四氫。弗喃溶液（THF)移除複數奈米球22，並 將填充層23係做為一蝕刻遮罩24，如圖4C所示。在此注意 的是，不同材質的奈米球需使用不同的溶液才能將這些奈 米球自基板移除。舉例來說，若使用聚曱基丙烯酸曱酯 2〇 (PMMA)材質的奈米球，則是使用甲酸（fomic add)移除奈 米球’·若使用玻璃（SiQx)材質的奈米球，収所❹含氫氟 酸（HF)溶液移除奈米球。 接著，如圖4D所示，將填充層做為一蝕刻遮罩24，以 濕蝕刻法蝕刻基板21。於本實施例中，濕蝕刻法所使用之 12 201039385 緩衝银刻液係包含氫氧化鈉、異丙醇、以及水。然而，依 照基板與填充層之材質，亦可選擇不同之緩衝姓刻液，如 鹼性緩衝蝕刻液或酸性緩衝蝕刻液。於鹼性緩衝蝕刻液 二可包含：如氫氧化鈉、氫氧化鉀、氨水、氫氧化鈽、 5氫氧化飯、氫氧化四曱錢、乙二胺或聯胺等驗液；如乙醇 或異丙醇等醇類；以及水。而於酸性緩衝姓刻液中，可包 含.如酸液為氫氟酸、BOE(HF與NH4F混合溶液卜鹽酸、 石肖酸、磷酸、硫酸、醋酸、或其混合溶液。或者，：液亦 〇 可為由乙醇胺（ethanolamine)、五倍子酸（gallic acid)、水、 10過氧化氫(hydrogen pen)xide)、及表面活性劑所混合而成之 AmineCaUates;以及如乙醇或異丙醇等醇類；以及水。此 外，可藉由調整緩衝蝕刻液之組成及濃度、蝕刻溫度、以 及時門則寻到不同之钱刻結構。同時，隨著勉刻溫度上 升，所需的時間隨之減少。 15 移除㈣遮罩24後，可於基板21表面2〇1形成複數微凹 穴202，即所謂之「週期結構」，如圖4E所示。其中’這些 〇 微凹穴202係呈陣列狀排列1因基板21之材f係為單晶: 基板，敍刻液為氫氧化納、異丙醇、以及水，故所形成之 微凹穴2〇2之形狀係為倒四角錐，即四角錐之底部係位於基 20板21表面2(H，而四角錐之頂部係自基板㈣面洲凹陷。 同時1參考圖5B，此為經姓刻並移除敍刻遮罩後，所得 之具有週期結構基板之SEM圓。由圖5B可明確得知’本實 施例所製得之基板其微凹穴之外形確實為倒四角錐形。 13 201039385 為更加清楚了解本實施例所製得之基板表面上之 結構’請參考圖6，此為本發明一較佳實施例之具有週期:士 構基板之示意圖m述方法所形成之具有 i 板，於基板21表面2〇1形成有以陣列狀排列之複二“ 5 202,且此些微凹穴2G2之形狀係為倒四角錐（倒金字塔形 狀）。 ^ 上述實施例係使用單晶石夕基板，故可形成形狀為倒四 角錐之微凹穴’其原因在於微凹穴之形狀係由敍刻基板過 程t產生的自然晶格面所圍繞形成。不同材質之基板與不 f 10 同钱刻液’會產生不同形狀之微凹穴。 接下來，本發明之另一較佳實_係使用上述相同製 作方法製作，除了使用藍寶石基板取代單晶石夕基板，其中， 係敍刻液係使用硫酸、磷酸混合溶液。經钮刻後，可形成 角錐形微凹穴，如圖7所示9其中，相鄰之微凹穴2〇2間係 15具有一表面201，且平面係位於同—高度上。在此，可製得 凹板之具有週期結構之藍寶石基板。經随量測後，角錐 頂部於底部之投影點至底邊的長度係約為31G⑽，而角錐 之長度係約為410 nm。故本實施例所製得之凹板藍寶石《 板其週期結構係為奈米級週期結構。 "° 此外，本發明更提供再一較佳實施例，其係將本發明 另-較佳實施例所製得之藍f石基板，進行再—次姓刻， 以凸顯藍寶石基板表面粗操度。經第二次餘刻後，可將微 凹穴202之範圍擴張、深度加深，相鄰微凹穴2〇2間平面也 藉由蝕刻而消除。故相鄰之微凹穴2〇2間則不再具有一平 14 201039385 面，因此，而可製得凸板之具有週期結構之藍寶石基板， 如圖8所示。 再者本么明之更一較佳實施例係使用上述相同製作 方法製作，除了使用玻璃基板取代單晶矽基板。其中，係 5蝕刻液係使用氫氟酸溶液，因氫氟酸蝕刻液本身是等向性 蝕刻，故可形成形狀為倒截頭圓錐體之微凹穴2〇2，如圖9 所示。 相較於以往使用頁光顯影加上濕姓刻法形成具週期結 © 構之石夕基板’無法達到奈米級的尺寸。雖然使用乾餘刻法 ίο I形成奈米級尺寸週期結構，然而花費相當昂貴且製程相 田複雜 片要價約30萬元。此外，以習知方法製作具週 期結構之藍寶石基板，往往無法形成奈米級尺寸週期結 構。反觀本發明之以奈米球製備具有週期結構之基板係 利用奈米球自組裝之特性，而可整齊排列於基板之表面。 15同時，藉由選擇不同直徑之奈米球，可輕易的形成且有任 何尺寸微凹穴之基板，以應用於不同領域；且藉由選用具 〇 纟米尺寸之奈米球，而可輕易達成具奈来尺寸微結構。此 外，相較於以往以電子束微影形成週期結構，本發明之方 法可大幅降低製作成本；且相較於以往以黃光微影製程（曝 20光及顯影）形成姓刻遮罩，由於本發明係以奈来球所排列而 成之奈米球層做為形成钱刻遮罩的模板，而不需使用次微 米曝光遮罩，故可大幅減少製作成本且提升製程速度。再 者，相較於乾㈣所使用之RIE或Icp機台昂貴且高危險， 本發明係使用價格較低且危險性低之祕刻槽進行濕独 15 201039385 刻；且相較於易損傷基板之章UM法，本發明使用濕_ 法形成週期結構’玎避免基板受到損傷。因此，藉由本發 明之方法，可以快速且便宜的方式，报士 、t成具有週期結構之 基板。 上述實施例僅係為了方便說明而舉例而已，本發明所 主張之權利範圍自應以申請專利範圍所述為準，而非僅限 於上述貫施例。 【圖式簡單說明】 H)圖1A至圖㈣習知以乾蝕刻法製作具有週期結構基板之 流程之剖面示意圖。 圖2A至圖2F係習知以非等向性濕蝕刻法製作具有週期結 構基板之流程之剖面示意圖。 圖3A至圖3F係、本發明—較佳實施例中，奈米球排列於基板 15 表面之步驟示意圖。 土 圖4A至圖4E係本發明一較佳實施例中，形成具有週期結構 基板之剖面示意圖。 圖5A係本發明—較佳實施例中，奈米球排列於單晶石夕基板 之SEM圖。 土 20 圖58係本發明一較#眘#办丨#目女.s & 权彳土霄;^例之具有週期結構之單晶石夕基 板之SEM圖。 圖6係本發明-較佳實施例之具有週期結構基板之示意圖。 圖7係本發明另—較佳實施例之具有週期結構基板示意圖。 圖8係本毛月再—較佳實施例之具有週期結構基板示意圖。 201039385 圖9係本發明更一較佳實施例之具有週期結構基板示意圖。 【主要元件符號說明】 10 基板 101 表面 102 微凹穴 11 光阻層 12 光罩 201 表面 202 微凹穴 21 基板 22 奈米球 23 填充層 24 名虫刻遮罩 25 膠體溶液 26 容器 27 揮發性溶液 〇 17ο 15 〇 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而 然而Periodic structure, Bay! The use of a human micro-mask is expensive, and the cost is further improved if the pattern is less than (10); the reactive ion gas etching machine is expensive and the process is slow; the substrate is easily damaged; and the etched surface is non-natural lattice surface. In order to solve the problem of the dry rice engraving method, a substrate having a periodic structure is formed by (4) engraving; as shown in Figs. 2A to 2F, a single crystal slab of a crystal orientation is taken as an example. Among them, the method of forming a substrate having a periodic structure is similar to the dry method except that the substrate is secreted by a buffer. ^A2A to 2〇's photoresist layer n (see Figure 2D) first formed by exposure development method (lithography process); then patterned photoresist 1 as (4) The cover 'forms the plurality of micro-pits 1G2 with the non-isotropic buffer (four) liquid (four) substrate, as shown in FIG. 2E. Then, after removing the pattern ^ photoresist mask, the patterned substrate 10 can be obtained, as shown in the figure. The surface 101 of the patterned substrate 10 has a periodic structure formed by a plurality of micrometers 5 201039385 concave eight 102 (four) columns. It is worth noting that the patterned substrate _ formed micro-pits 1 〇 2, the shape of which is Heart: The surrounding bevel of this inverted pyramid is also a single...u> natural crystal 5 10 column view (4) The substrate can avoid damage to the substrate and the rest of the surface, however, when wet etching If the parameter control is not reported, the uniformity of the periodic structure is poor. At the same time, due to the above-mentioned production of Tiancheng, it is necessary to enter the lithography process, so it still faces the problems of high cost and low production speed. Therefore, at present, there is a need to develop a method of patterning a substrate, and the substrate is damaged, and a periodic structure slab can be formed quickly and inexpensively. SUMMARY OF THE INVENTION The main object of the present invention is to provide a method for forming a periodic structure 15-plate, which can reduce the processing time, reduce the manufacturing cost, and avoid damage to the substrate. In order to achieve the above object, the method for forming a periodic structure substrate of the present invention comprises the following steps: (A) providing a substrate and a plurality of nanospheres, wherein the plurality of nanospheres are arranged on the surface of the substrate; (B) Forming a portion of the surface of the filling layer ς 20 substrate and the gap between the plurality of nanospheres; (c) removing the plurality of nanometers (D) using the filling layer as an etch mask and etching the substrate; and (ε) removing The mask is etched to form a periodic structure on the surface of the substrate. The present invention utilizes the "self-assembly" characteristics of nanospheres, i.e., these nanometers are arranged automatically and orderly on the surface of a substrate instead of the yellow light micro-shadow 201039385 201039385 5 〇 ί 15 15 ❹ 20-shaped template. At the same time, the cost of these automatic arrangements is used to form an expensive sub-micron exposure mask, so that a lower two-period structure can be formed, and the formation of the present invention has a weekly formation and a continuous material is also very easy to obtain. : Two & large to form the substrate of the periodic structure. The periodic structure of the surface of the present invention having a periodic structure substrate has a plurality of micro-cavity soil plate tables S ϋέ ^ ^ Μ X, the weight is good, the number of micro-cavities is further, and the shape of the micro-pits is etched. The surrounding formation of the cylinder during the substrate process may be a chamfer cone, an inverted cone, a circle =:,:: an inverted truncated cone. Substrates of different materials and different plates: Hydrogenated micro-cavities of different shapes. If the above-mentioned single crystal crushed substrate is privately used (four) (four), the micro-pit is a thin-shaped cone, the bottom of the cone is located on the surface of the substrate, and the top of the quadrangular pyramid is recessed from the base. If the glass substrate is engraved with hydrogen fluoride (four), the micro-pits are an inverted truncated cone. After the operation, the method of forming the substrate having the periodic structure is further performed, and the step (F) 1 includes - the step (F) · reclosing the surface of the substrate. In the step (8), the substrate of the periodic structure has a flat force between adjacent micro-pits: it is regarded as a concave plate structure. However, if the step (F) is repeated - the button is engraved, the width and depth of the micro-cavities are increased, and the adjacent micro-pits are not planar" and can be regarded as a convex plate structure. v, in the formation of the periodic structure of the substrate of the present invention, the periodic structure may be a nano- or micro-scale periodic structure; wherein, the period 7 201039385 grade, meters and or human micron-scale periodic structure, and More preferably, nano, and 匕, , ·. Structure. In the method for forming a substrate having a periodic structure according to the present invention, the step of arranging the plurality of nanospheres of the step (4) on the surface of the substrate 5 10 15 (4) provides the substrate and the colloidal solution in the container, and the winning solution includes the complex a ball of rice and an interface active agent; (A2) placing the substrate in the container' and the colloidal solution covering the surface of the substrate; and (10) adding a volatile solution to the container t to increase the rate of evaporation of the solution and causing the plurality of nanospheres Arranged on the surface of the substrate. Wherein, the plurality of meters of the ball form a nanosphere layer, and preferably a layer of nanospheres. - In the method of forming a substrate having a periodic structure of the present invention, the method of the substrate of the step (9) is a method or a secret, preferably a secret method. The 'wet surrogate method uses a buffering engraving liquid to engrave the substrate, and the buffering etching solution can select a generally used acid or alkaline etching solution according to the material of the substrate and the filling layer. The 'acidic etchant may contain an acid solution, an alcohol, and water, and the alkaline etchant contains a lye, an alcohol, and water. The acid solution is preferably hydrofluoric acid, 8 〇 lying 7 and 1 ^ 17 mixed solution), hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, or a mixed solution thereof. Alternatively, the acid solution may be Amine Callates which is a mixture of ethanolamine, gaUic acid, water, hydrogen peroxide, and a surfactant. Further, the alkali liquid is preferably sodium hydroxide, potassium hydroxide, ammonia water, barium hydroxide, barium hydroxide, tetramethylammonium hydroxide, ethylenediamine, or hydrazine. The alcohol is preferably ethanol or isopropyl. alcohol. Since the method of the present invention preferably etches the substrate by wet etching, the purpose of avoiding substrate damage can be achieved. 20 201039385 Ο ίο 15 Ο 20 = In the method of forming a substrate having a periodic structure, the nanosphere is ... a special limitation, preferably oxidized stone (Si〇x) 'Taoman, polymethyl (10) is called titanium oxide (T) In addition, the diameter may be between just (10) to the center of the core, preferably between _..2"m" and the plurality of nanospheres preferably have the same diameter. In the method for forming a substrate having a periodic structure according to the present invention, the method of forming the filling layer in the step (8) is not particularly limited, and is preferably a stage chemical vapor deposition method or a physical vapor deposition method for partially surface of the substrate and The gap between the plurality of layers 2 forms a filling layer. Further, the thickness of the filling layer is determined according to the size of the micro-cavities, which is preferably smaller than the diameter of the plurality of nanospheres. Further, the material of the filling layer is not The special limitation can be generally used as a material for the mask, and is preferably oxidized by $, nitriding ♦ ytterbium oxynitride, oxidized, zinc oxide, indium tin oxide, zinc oxide, chrome, group , tungsten, vanadium, nickel, tin, iron, copper, molybdenum, titanium, aluminum, silver, gold, platinum, Or the photoresist (4), polymethyl methacrylate, and polystyrene (ps). In the method for forming a substrate having a periodic structure of the present invention, the material of the substrate is not particularly limited 'according to the applied field The material of the substrate may be P-type single crystal stone, N-type single crystal stone, p-type polycrystalline stone, N-type polycrystalline stone, P-type amorphous stone eve, N-type amorphous stone eve ' P-type deuteration, N-type sand recording, P-type scalar indium, N-type dishing _, p-type Wei-gallium indium, N-type disc galvanic, p-type gallium nitride, N-type gallium nitride, "indium antimonide copper Indium copper, indium tin oxide, carbon carbide, nitriding, quartz, or zinc oxide and oxidized aluminum compound. Alternatively, the substrate used in the method of the present invention may be a sapphire 9 201039385 substrate (single crystal oxidation. Preferably, the substrate used in the method of the present invention is a p-type germanium substrate or a sapphire substrate. Further, 'the present invention The substrate used in the method may also be a glass substrate or a glass substrate having a transparent conductive film (TC0) layer on the surface. If the substrate 5 used is a glass substrate having a transparent conductive film (TC0) layer on the surface, the periodic junction is formed. In the transparent conductive film (TC〇) layer; or vice versa. The method for forming a periodic structure substrate of the present invention, in addition to using a nanosphere as a template for etching a mask, instead of a yellow light lithography process, and at the same time, using a wet type By etching the patterned substrate, a uniform periodic structure can be achieved and the substrate can be prevented from being damaged. Therefore, the method of forming a periodic structure substrate of the present invention can pattern the substrate in a simple, low-cost, and high-capacity manner. 15] FIG. 3A to FIG. 3F are schematic diagrams showing the steps of arranging the nanospheres on the surface of the substrate in a preferred embodiment of the present invention. As shown, a substrate 21 and a colloidal solution 25 in a container 26 are provided, wherein the colloidal solution 25 is composed of a plurality of nanospheres (not shown) and an surfactant (not shown). Then, the substrate 21 is placed in the container % and 20 so that the substrate 21 is completely immersed in the colloidal solution 25, as shown in Fig. 3B. After a few minutes of standing, the nanospheres 22 are gradually ordered. The surface of the substrate 21 is arranged to form a so-called "nanosphere layer" as shown in Fig. 3C. Then, a volatile solution 27 is poured into the container 26 to volatilize the aforementioned colloidal solution 25. 3D. Finally, as shown in FIG. 3E, after the colloid 201039385 solution 25 is completely volatilized, the substrate 21 is taken out from the container 26 and a plurality of nanospheres 22 are arranged in an orderly manner on the surface thereof. The substrate 21 is as shown in FIG. 3F 〇❹ 10 15 Ο In the embodiment, the material of the nanosphere 22 is polystyrene (ps), but in different applications, the materials of the nanospheres 22 can also be used. Is a ceramic, such as titanium oxide (Ti〇x) metal oxide, polyfluorenyl A material such as methyl olefinate (PMMA) or glass (Si〇x). In addition, in the present embodiment, the diameter of the nanosphere 22 is between 100 nm and 2.5 " m, and most of the nanospheres The 22 series have the same diameter, but the size of the nanospheres 22 is not limited to the above range in different applications. In addition, in the embodiment, the material of the substrate is a single crystal germanium substrate. According to different application field cooperation, it can be p-type single crystal germanium, N-type single crystal germanium, p-type polycrystalline germanium, N-type polycrystalline germanium, p-type amorphous germanium, N-type amorphous, P-type gallium gallium, N Type of deuterated gallium, P-type indium telluride, N-type indium arsenide, p-type dishing _, N (four) (10) marriage, "mw gallium, p-type indium selenide copper 'N type indium selenide copper, indium tin oxide, niobium carbide Huayu, Dendrobium, or zinc oxide and oxidized aluminum compound; and may also be a sapphire substrate (single crystal oxide, glass substrate, glass substrate with a transmissive (TCO) layer on the surface). Next, please refer to FIG. 4A to FIG. 4E, which is a schematic cross-sectional view showing the formation of a substrate having a periodic structure in the preferred embodiment of the present invention. Further, and referring to Figs. 5A to 5B at the same time, this is an SEM image of a substrate having a periodic structure formed by the present invention. 20 201039385 First, as shown in FIG. 4A, a substrate 21 and a plurality of nanospheres 22 are provided, and the plurality of nanospheres 22 are arranged on the surface of the substrate 21 in accordance with the above method to form a nanosphere layer. The nanospheres 22 may be stacked on the surface of the substrate 21 in multiple layers. In the present embodiment, the nanospheres 22 are arranged on the surface of the substrate 21 in a layer 5 manner. As shown in the SEM image of Fig. 5A, the nanospheres can be arranged in a layer on the surface of the substrate. Next, as shown in Fig. 4B, a portion of the surface of the filling layer 23 on the substrate 21 and the gap between the plurality of nanospheres 22 are formed by chemical vapor deposition. The thickness of the filling layer 23 is smaller than the diameter of the plurality of nanospheres, and the material of the filling layer is tantalum nitride. However, in addition to forming the filling layer 23 by chemical vapor deposition, it can be formed by physical vapor deposition, and the material of the filling layer 23 can also be other metals commonly used as etching masks, such as yttrium oxide and yttrium oxide. Fossil eve, oxidized, zinc oxide, indium tin oxide, zinc oxide doped, chromium, group 'tungsten, vanadium, nickel, tin, iron, copper, molybdenum, titanium, aluminum, silver, gold, platinum, palladium, 15 or Photoresist (PR) 'polymethyl methacrylate (PMMA), polystyrene (PS). . Then, tetrahydrogen is used. The flu solution (THF) removes the plurality of nanospheres 22, and the filling layer 23 is used as an etch mask 24, as shown in Fig. 4C. It is important to note that different materials of nanospheres require different solutions to remove these nanospheres from the substrate. For example, if a nanosphere made of phthalocyanine 2 〇 (PMMA) is used, the fossil is used to remove the nanosphere'. If a nanosphere of glass (SiQx) is used, The nanosphere is removed by a solution containing hydrofluoric acid (HF). Next, as shown in Fig. 4D, the filling layer is used as an etching mask 24, and the substrate 21 is etched by wet etching. In the present embodiment, the 12 201039385 buffered silver engraving system used in the wet etching method contains sodium hydroxide, isopropyl alcohol, and water. However, depending on the material of the substrate and the filling layer, a different buffering solution such as an alkaline buffering solution or an acidic buffering etching solution may be selected. The alkaline buffer etchant 2 may include: a test solution such as sodium hydroxide, potassium hydroxide, ammonia, barium hydroxide, 5 hydroxide rice, tetrahydrogen hydroxide, ethylenediamine or hydrazine; such as ethanol or different Alcohols such as propanol; and water. In the acid buffer surname solution, it may be included. For example, the acid solution is hydrofluoric acid, BOE (HF and NH4F mixed solution, hydrochloric acid, sulphuric acid, phosphoric acid, sulfuric acid, acetic acid, or a mixed solution thereof. 〇 may be AmineCaUates mixed with ethanolamine, gallic acid, water, hydrogen pen xide, and a surfactant; and an alcohol such as ethanol or isopropanol ; and water. In addition, by adjusting the composition and concentration of the buffer etchant, the etching temperature, and in time, the memory structure can be found. At the same time, as the engraving temperature rises, the time required decreases. After the (four) mask 24 is removed, a plurality of micro-pits 202, a so-called "periodic structure", can be formed on the surface 2〇1 of the substrate 21, as shown in Fig. 4E. Among them, 'these micro-cavities 202 are arranged in an array. 1 Because the material f of the substrate 21 is a single crystal: a substrate, the engraving liquid is sodium hydroxide, isopropyl alcohol, and water, so the micro-pit 2 is formed. The shape of 〇2 is an inverted quadrangular pyramid, that is, the bottom of the quadrangular pyramid is located on the surface 2 of the base 20 plate 21 (H, and the top of the quadrangular pyramid is recessed from the substrate (4) face. At the same time, referring to FIG. 5B, this is a surname After removing the mask, the SEM circle having the periodic structure substrate is obtained. It can be clearly seen from FIG. 5B that the substrate formed by the embodiment has a micro-cavity shape which is indeed an inverted quadrangular pyramid. 13 201039385 In order to more clearly understand the structure on the surface of the substrate prepared by the present embodiment, please refer to FIG. 6 , which is a schematic diagram of a method for forming a substrate of the present invention. On the surface 2〇1 of the substrate 21, a plurality of "2202" arranged in an array are formed, and the shape of the micro-pits 2G2 is an inverted quadrangular pyramid (inverted pyramid shape). ^ The above embodiment uses a single crystal substrate. Therefore, a micro-cavity shaped as an inverted quadrangular pyramid can be formed. The shape of the hole is formed by the natural lattice surface generated by the process of the substrate substrate t. The substrate of different materials and the micro-cavity of the same will produce different shapes of micro-pits. Next, another of the present invention Preferably, the method is the same as the above-mentioned production method, except that a sapphire substrate is used instead of the single crystal substrate, wherein the sulfuric acid and phosphoric acid mixed solution is used for the engraving, and the pyramidal micro-cavities can be formed by the button. As shown in Fig. 7, wherein the adjacent microcavity 2〇2 has a surface 201 and the plane is at the same level, a sapphire substrate having a periodic structure of the concave plate can be obtained. After the measurement, the length of the top of the pyramid from the projection point to the bottom of the bottom is about 31G (10), and the length of the pyramid is about 410 nm. Therefore, the concave sapphire "the periodic structure of the plate" obtained in this embodiment In addition, the present invention further provides a further preferred embodiment, which is a blue f stone substrate prepared by another preferred embodiment of the present invention. To highlight the surface roughness of the sapphire substrate After the second remnant, the range of the micro-pits 202 can be expanded and deepened, and the plane between the adjacent micro-pits 2〇2 is also eliminated by etching. Therefore, the adjacent micro-pits are between 2 and 2 There is no longer a flat 14 201039385 surface, so that a sapphire substrate having a periodic structure with a convex plate can be obtained, as shown in Fig. 8. Further, a preferred embodiment of the present invention is produced by the same manufacturing method as described above. A glass substrate is used in place of the single crystal germanium substrate. Among them, the system 5 etching liquid uses a hydrofluoric acid solution, and since the hydrofluoric acid etching liquid itself is isotropically etched, the micro recess 2 having an inverted truncated cone shape can be formed. 〇2, as shown in Fig. 9. Compared to the previous use of page light development plus wet-name lithography to form a periodic structure, the stone substrate can not reach the nanometer size. Although the use of the dry residual method ίο I forms a nanometer-scale periodic structure, it is quite expensive and the process is complicated by a sheet price of about 300,000 yuan. Further, it is often impossible to form a nano-scale periodic structure by fabricating a sapphire substrate having a periodic structure by a conventional method. In contrast, the substrate having a periodic structure prepared by the nanosphere of the present invention can be aligned on the surface of the substrate by utilizing the characteristics of self-assembly of the nanosphere. At the same time, by selecting nanospheres of different diameters, substrates of micro-cavities of any size can be easily formed for application in different fields; and it is easy to select nanometer balls of glutinous rice size. Achieve a nanostructure with a size. In addition, the method of the present invention can greatly reduce the manufacturing cost compared to the conventional formation of a periodic structure by electron beam lithography; and the present invention is formed by a yellow light lithography process (exposure 20 light and development). The nanosphere layer arranged by the Nailai ball is used as a template for forming a money mask without using a sub-micron exposure mask, thereby greatly reducing the manufacturing cost and increasing the processing speed. Furthermore, the present invention is more expensive and dangerous than the RIE or Icp machine used in the dry (four), and the present invention uses a low-cost and low-risk secret groove to perform wet-series 15 201039385; and compared to the easily damaged substrate In the UM method, the present invention uses a wet method to form a periodic structure '玎 to avoid damage to the substrate. Therefore, with the method of the present invention, the reporter can be made into a substrate having a periodic structure in a fast and inexpensive manner. The above-described embodiments are merely examples for the convenience of the description, and the scope of the claims is intended to be limited to the scope of the claims. BRIEF DESCRIPTION OF THE DRAWINGS H) Figs. 1A to 4(4) are schematic cross-sectional views showing a process of fabricating a substrate having a periodic structure by dry etching. 2A to 2F are schematic cross-sectional views showing a process of fabricating a substrate having a periodic structure by an anisotropic wet etching method. 3A to 3F are schematic views showing the steps of arranging the nanospheres on the surface of the substrate 15 in the preferred embodiment of the present invention. 4A to 4E are schematic cross-sectional views showing a substrate having a periodic structure in a preferred embodiment of the present invention. Figure 5A is a SEM image of a nanosphere aligned on a single crystal substrate in the preferred embodiment of the present invention. Soil 20 Fig. 58 is an SEM image of a single crystal stone base plate having a periodic structure of the present invention, which is a comparison of #慎#办丨#目女.s & Figure 6 is a schematic illustration of a substrate having a periodic structure in accordance with the preferred embodiment of the present invention. Figure 7 is a schematic view of a substrate having a periodic structure in accordance with another preferred embodiment of the present invention. Figure 8 is a schematic view of a periodic structure substrate of the present invention. 201039385 FIG. 9 is a schematic view of a substrate having a periodic structure according to a further preferred embodiment of the present invention. [Main component symbol description] 10 Substrate 101 Surface 102 Micro-pits 11 Photoresist layer 12 Photomask 201 Surface 202 Micro-pit 21 Substrate 22 Nanosphere 23 Filled layer 24 Insect mask 25 Colloidal solution 26 Container 27 Volatile Solution 〇17