201245353 41666pif 六、發明說明： 【發明所屬之技術領域】 本發明是有關於共形塗層及薄膜的製造’其可用於例 如是電子產品以及光學元件中。這些塗層及薄膜可以藉由 本申請案的方法來製造，其中將例如是矽氧烷樹脂的聚合 物材料的液體配方散佈在基板上。 【先前技術】 共形塗層對於電子工業及光學工業而言是相當重要 的。許多現有的互補金屬氧化物半導體（CMOS)影像感 測器將共形抗反射（antireflective，AR)塗層置於微透鏡 陣列的頂部上來增加透光率。在沒有AR-塗層的情況下， 有超過5%的光線會因微透鏡頂面處的反射而損失，在低 光線的環境下靈敏度降低及雜訊增加。反射光也會對眩光 (flare)及對比度（contrast)產生負面景多響。 一般地，儘管平坦面性（planarity)通常為所需的性 質且用來填充半導體工業中所製造之產品中的間隙及溝 渠，但好的抗反射塗層通常需要共形性。太過平面的AR 塗層反而會造成總反射率及相鄰感光單元（ph〇t〇site)之 間的交互干擾（cross-talk)增加。而且低角度效能（原本 使用Μ透鏡的一個原因）也會變差。此將導致周邊暗角 (vignetting )，且此現象隨著廣角透鏡的使用而更為顯著。 理想的抗反射塗層在微透鏡之頂部上具有均一的厚 度。在圖1至圖3中繪示適當(proper；^ AR塗層對微透鏡 之反射率的影響： 201245353 41666pif 圖1表示在90。的角度下，微透鏡材料（RI = 157) 上具有對白光最佳化厚度之AR塗層（RI=丨25，Τχ= 1〇9 5 nm)的模擬反射率。 圖2顯示在90。的角度下，微透鏡材料（RI = 1.57) 上具有對藍光最佳化厚度之AR塗層（RI=丨25，Τχ= 87 5 nm)的模擬反射率。 圖3福繪沒有AR塗層時微透鏡材料（RI = 157)的 模擬反射率。 根據經驗法則，當抗反射塗層的折射率（亦縮寫為 RI)約等於所使用之微透鏡材料之RI的平方根值時，即 得到反射率的最大降低量。例如，在大氣中為了得到最理 想效能’ RI為1.57的酚醛清漆型微透鏡材料（n〇v〇lac based microlens material)需要 RI 為 i 25 ( 1 55l/2)的抗反射塗 層另方面’可藉由和>圼耳方程（Fresnell equations )來 計算上述塗層的最佳化厚度。在此情況下，根據可由本質 上已知的方法而最佳化的波長，共形AR塗層之最佳厚度 為 80 nm 至 120 nm。 典坦的共形塗層是以化學氣相沈積（chemical vapor deposition，CVD)來形成。然而，CVD方法是一種相對 而言又貴又慢的製程。CVD方法需要昂貴的設備。此製程 可形成高度共形塗層，其RI的最小值通常大於14。在許 多情況下，此RI數值雖小於微透鏡材料的RI數值，但仍 高於最小反射率。CVD薄膜的RI並不易調整。 以聚合物溶液來塗佈薄膜提供了在材料的選擇範圍 201245353 muuupii 較廣的可能性。此類的薄膜可藉由例如浸塗（dip coating)、縫塗（slit coating)、嘴塗（spray c〇ating)或旋 塗（spin-on coating )來沈積。 浸塗法、缝塗法及喷塗法通常用於較大的物體，例如 LCD及太陽能板’而旋塗則常用於矽晶圓。旋塗材料沈積 在石夕晶圓上的方法通常是將已知量的聚合物溶液置於旋轉 中的晶圓上’再進行軟烤使溶劑蒸發，最後在加熱板或爐 管上藉由熱或是藉由UV光將薄膜固化。旋塗法所使用的 工具便宜且相對快速，特別是如果在可同時容納許多晶圓 的爐管中執行固化，則尤其快速。 一般來說，旋塗材料的最佳特性之一是其良好的平面 性，然而，平面性與共形性是對立的。此部分的原因在於 ✓谷劑的使用讓材料在沈積期間於晶圓上均勻的流動，而且 也因為於在最後固化其間聚合物未完全固化時通常發生的 聚合物回流（reflow)現象。 本發明的目的為提供一種製造電子及光學應用上之 共形薄膜的改善方法，其係將聚合物溶劑塗覆在待處理的 表面上。 【發明内容】 出奇的發現，旋塗材料確實也可得到極高度共形的塗 層。經過許多研究後發現，在固化期間不會回流的聚合物 或聚合物混合物能夠達到此效果。 本發明的概念是基於形成矽氧烷材料於塗覆組成物 中，所述塗覆組成物包括有好的低沸點溶劑與高沸點非溶 201245353 41666pif 劑（non_solvent)混合在一起的溶劑混合物。 特別地，本發明的目的是配製上述成分的組成物，使 得聚合物不會完全地從高沸點非溶劑中沉殿析出，而是在 塗覆期間與高沸點非溶劑形成透明且潔淨的凝膠。為了得 到適當的薄膜品質’並且為了可以在製造產物的最後過濾 時移除異物粒子，好的低沸點溶劑是必需的。 更具體地說’本發明之方法的主要特徵在於申請專利 範圍第1項之特徵部分中所陳述的内容。 本發明提供相當多的優點。因此’藉由使用具預定比 例的鹼及/或酸催化聚合物，可製造對微透鏡或其他光學材 料而言效能最佳之具有可調式幻的高度共形AR塗層。 亦可藉由光驗產生劑（photo base generator，PBG) 或光酸產生劑（photo acid generator，PAG )的使用將此材 料光圖案化。 以下，將參照一些非限制性的操作實例詳述實施方 式’以更仔細地探究本發明。 【實施方式】 ，在本發明之較佳實施财，高度共形塗層或薄膜是由 石夕氧烧樹驗錢所製造，所述魏_脂組成物包括在 有機化合物之混合物（在下文中亦稱為「溶劑混合物 (solvent blend)」）t的矽氧烷樹脂’所述有機化合物之混 合物包=至少-個彿點小於或等於145的低濟點溶劑 以及至-個雜大於或等於120C)C的高軸化合 下文中亦稱為「非溶劑(n〇n_s〇lven〇」)。高沸點溶劑與低 201245353 ^fiooopil 沸點溶劑的彿點差值至少為10 oc，較佳為大於15 oc，特 別為大於20。(：’通常約為25。(：至200。〇例如至多不超 過 160oC。 「低沸點溶劑」可為任何化合物。任何化合物通常在 室溫下為液體，且通常在製造石夕氧烧樹脂組成物的溫度範 圍内’對於聚合物而言可視為良溶劑。低彿點溶劑較佳的 是液體，且在矽氧烷樹脂組成物旋澆鑄（叩比⑵也叩）在 合適基板上的初始階段時亦為液體。 。低沸點溶劑一般在大氣壓力下的沸點約為3〇 至 145 °C，特別是約為4〇至145 〇c，較佳是約為5〇 % 至 145 0C。 所使用的低彿點溶劑較佳是在、塗覆石夕氧烧樹脂組成 ，之初始步驟期間或初始步驟之後的預選階段巾可完全或 實質上疋全蒸發掉，以留下由聚合物材料及溶劑混合物之 第二主要成分（高沸點化合物）所形成的濕凝膠（wet gd)。 —在較佳實施例中，與高沸點溶劑的沸點相比，低沸點 溶劑具有相當低的彿點，以使得薄膜在隨後的乾燥製程期 間有機會形成濕凝膠。 而且’較佳的是所使用的低沸點溶劑具有相對低的毒 |·生且不會過度力口迷聚合物老化（哗㈣）。 低彿點溶劑可例如是選自於由脂肪族酮類、芳香族酮 ，、醇類、酯類及醚類的有機化合物。較佳的溶劑的具體 實例包括1（bP· 56.5 °C)、曱基乙基_ (methyl ethyl ketone)(bp. 79.6。〇、異丙醇（iSOpr〇pan〇i)(bp. 82.5 0C)、 201245353 41666pif 二乙基酮（diethyl ketone)( bp_ 100 °C )、異丁醇（isobutanol) (bp. 108 C)、丙二醇甲基喊（pr〇pyiene giyC〇i methyl ether) (bp. 118 °C)以及丙二醇乙基喊（pr0pyiene giyC〇i ethyl ether) (bp. 133 °C)。所給定的沸點為參照標準狀態 (亦即’環境壓力）下的沸點，且僅表示純化合物的沸點。 雖然純化合物是較佳的’但並不排除在作為「低沸點溶劑」 之有機化合物中存在有可改變沸點或黏度或有機化合物之 其他特性的額外成分。 溶劑混合物之高沸點成分可為任何在低沸點溶劑蒸 發之後此與聚合物一起形成凝膠的化合物溶劑。而且，高 沸點化合物較佳的是從室溫至塗覆溫度的溫度範圍内為液 體。在較佳的實施例中’對於聚合物而言，高沸點溶劑行 為像非溶劑。 高沸點溶劑的沸點通常遠高於低沸點溶劑的沸點，以 使得在蒸發低沸點溶劑之後而沉澱的薄膜能夠在乾燥製程 期間形成濕凝膠。較佳的是所使用的高沸點溶劑的毒性相 對低且不會過度加速聚合物老化。 高沸點非溶劑可例如是，但其選擇並不限於，二異丙 基酮（di-iso-propyl ketone) (bp. 124 0C)、二正丙基酮 (di-n-propyl ketone) (bp. 145。〇、乙基異戊基酮（ethyl isoamyl ketone) (bp. 160。〇、二異 丁基酮（diisobutyl ketone) (bp. 169.4。〇、二正丁基酮（di-n-butyl ketone) (bp. 186 〇C)或二戊基酮（dipentyl ketone)(bp. 186 °C)。 上述沸點僅供參考。 9 201245353 4K)〇〇pit 溶劑混合物通常包含丨重量份至1〇〇重量份的低沸點 溶劑以及約1重量份至約100重量份的高沸點化合物，特 別是’兩個成分之間的重量比例約為1 : 2〇至20 : 1。莫 耳比例較佳約為1 : 50至50 : 1，特別是約為1 : 20至20 : 1 ;等莫耳比至比低沸點溶劑的化學計量稍高的狀況是特 別佳的。 當上述的聚合物溶劑旋轉塗佈在晶圓上時，溶劑起初 如同正常欲塗材料。也就是說’溶劑均勻地散佈在整個晶 圓上。 然而’當好的低沸點溶劑蒸發時，薄膜便成為流動特 性大幅降低的濕凝膠。接著，當高沸點非溶劑變乾後，凝 膠會乾縮在結構上而形成高度共形塗層。 因此，所得到的薄膜厚度通常約在5 nm至1〇〇 μιη範 圍内，較佳針對一些例如是微透鏡的應用，薄膜較佳的厚 度約為lOnm至500 nm’特別約為5〇11111至2〇〇nm。上 述之厚度值特別適用於矽氧烷薄膜。 組成物的聚合物可為一個矽氧烷聚合物或是兩個或 兩個以上矽氧烷聚合物的混合物。 根據-實施例，合適的石夕氧燒聚合物是藉由驗催化水 解或酸催化水解以及縮合絲魏單體魏氧基石夕烧單 t並選擇性加人改善黏著性的魏來製造。在絲石夕烧 氧基魏賴巾，含有低碳絲雌或低碳烧氧 基殘基（lower alkoxy residue )的單體為特別較佳的。因此， 燒基殘基通常選自Cl.6絲團，例如f基、正 201245353 41666pif 及異丙基、正丁基、第三丁基、異丁基以及正戊基 (n-amyl)。同樣地烷氧基較佳的是含有丨個碳原子至6個 碳原子（Cm烷氧基團），例如是曱氧基團、乙氧基團、正 丙氧基團及異丙氧基團、正丁氧基團、新丁氧基團及異丁 氧基團以及正戊氧基團。矽烷單體可包括丨至4的烷基團 以及1至4的烷氧基團及其組合，例如，4個烷氧基團， 或是3個烷氧基團及1個烷基團。 合適單體的具體實例為曱基三烷氧基矽烷 (methyltrialkoxysilane )及四烷氧基矽烷 (tetraalkoxysilane )。 尤其，以下的單體為特別有利的： —由曱基二曱氧基碎烧（methyltrimethoxysilane)及甲基 二乙氧基碎烧（methyltriethoxysilane )中所選出的甲 基二烧氧基石夕烧（methyltriethoxysilane)，以及 -由四乙氧基矽烷（tetraethoxysilane)或四甲氧基矽烷 (tetramethoxysilane)中所選出的四烷氧基矽烷。 根據一較佳實施例，為了根據本發明使用矽氧烷樹脂 組成物來製造高度共形塗層及薄膜，藉由控制或改變混合 物中之石夕氧院聚合物的混合比例，可以將所得石夕氧烧聚合 物之折射率調整至預定值（predetermined value)。 根據一較佳實施例，改善黏著性的石夕烧可由以下組成 的族群中選出：三甲基曱氧基矽燒 (trimethylmethoxysilane )、三曱基乙氧基石夕燒 (trimethylethoxysilane )、二曱基二曱氧基石夕燒 201245353, ^ιοοοριι (dimethyldimethoxysilane )、二曱基二乙氧基石夕烧 (dimethyldiethoxysilane )、三氟丙基三甲氧基石夕烧 (trifluoropropyltrimethoxysilane )、三氟丙基三乙氧基石夕 炫（trifhioropropyltriethoxysilane)、縮水甘油喊氧基丙基 三曱氧基矽烧（glycidyloxypropyltrimethoxysilane)、縮水 甘油醚氧基丙基三乙氧基矽烷 (glycidyloxypropyltriethoxysilane)、乙烯基三曱氧基矽烧 (vinyltrimethoxysilane )、乙烯基三乙氧基石夕烧 (vinyltriethoxysilane)、曱基丙烯醯氧基丙基三甲氧基石夕 烧（methacryloxypropyltrimethoxysilane )、曱基丙烯酿氧 基 丙基三 乙氧基 石夕烧 (methacryloxypropyltriethoxysilane)、丙烯酿氧基丙基三 甲氧基石夕烧（acryloxypropyltrimethoxysilane )、丙稀醯氧 基丙基三乙氧基石夕院（aeryloxypropyltriethoxysilane)、笨 基三曱氧基石夕烧（phenyltrimethoxysilane)、苯基三乙氧 基石夕烧（phenyltriethoxysilane)、苯基甲基二曱氧基石夕燒 (phenyl methyl dimettioxysilane)及苯基曱基二乙氧基石夕 烧（phenyl methyl diethoxysilane )。 一般三烷氧基矽烷或四烷氧基矽烷或是其混合物對 改善黏著性的矽烷的莫耳比為1000 : 1至1 : 1000，特另,J 是約為100 : 1至1 : 100 ’較佳約為100 : 1至1 : 1，以及 特別是約為75 : 1至5 : 1。 通常，如上文所討論，石夕烧單體藉由本質上已知的方 法來水解及預聚合（prepolymerize)，以製造分子量 12 201245353 41666pif 約為500 m〇1/g至100，_ m〇1/g，特別是約為5 〇〇〇咖… 至50，_m雨的預聚物（prepGlymer)，且在可能的溶劑 置換之後配製塗覆組成物。此組成物包含約佔Qi重量％ 至25重量％的聚合物材料，較佳約佔1重量％至加重量％ 的聚合物材料。 以上述組成物可藉由旋塗、浸塗、縫塗或喷塗來製造 高度共形塗層及薄膜。此塗層或薄膜可沈積在合適的基板 上。基板的實例包㈣材料，例如珍晶圓、三氧化石夕材料 (silica materials )’例如玻璃基板、其他金屬氧化物材料、 金屬及金屬合金、祕清漆及丙烯酸（aeiy 微透鏡材料。 ，、他 塗層可以藉由添加本領域已知的光酸產生劑 a:id generator，PAG)或光鹼產生劑（含量為i %至重 量％的固體）而使其感光。較佳實例為自由基型光起始劑 (free radical photoinitiator )，例如用於顯示器的自由基型 起始劑，特別是BASF供應的irgacure(g) 〇χΕ〇2型光驗產 生劑。 上述形成光圖案化之高度共形薄膜之方法的—實施 例包括以下步驟： -添加光驗產生劑； -使薄膜暴露於UV光；以及 -以溶劑使暴露的薄膜顯影，所述溶劑通常為有機溶劑。 13 201245353201245353 41666pif VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to the manufacture of conformal coatings and films which can be used, for example, in electronic products and optical components. These coatings and films can be made by the method of the present application in which a liquid formulation of a polymeric material such as a decane resin is dispersed on a substrate. [Prior Art] Conformal coatings are of considerable importance to the electronics industry and the optical industry. Many existing complementary metal oxide semiconductor (CMOS) image sensors place a conformal antireflective (AR) coating on top of the microlens array to increase light transmission. In the absence of an AR-coating, more than 5% of the light is lost due to reflections at the top surface of the microlens, and sensitivity is reduced and noise is increased in low light environments. Reflected light also has a negative impact on glare and contrast. In general, good anti-reflective coatings generally require conformality, although flatness is generally desirable and is used to fill gaps and trenches in products manufactured in the semiconductor industry. The too flat AR coating will in turn cause an increase in total reflectivity and cross-talk between adjacent photosensitive cells (ph〇t〇site). Moreover, low-angle performance (a reason for the use of a Μ lens) is also degraded. This will result in vignetting, and this phenomenon is more pronounced with the use of wide-angle lenses. The ideal anti-reflective coating has a uniform thickness on top of the microlens. Appropriate (proper; ^ AR coating on the reflectivity of the microlens is shown in Figures 1 to 3: 201245353 41666pif Figure 1 shows the white light on the microlens material (RI = 157) at an angle of 90° The simulated reflectance of the AR coating (RI = 丨25, Τχ = 1 〇 9 5 nm) is optimized for thickness. Figure 2 shows that at a 90° angle, the microlens material (RI = 1.57) has the most Simulated reflectance of the AR coating (RI = 丨25, Τχ = 87 5 nm) of the thickness. Figure 3 shows the simulated reflectivity of the microlens material (RI = 157) without AR coating. According to the rule of thumb, When the refractive index (also abbreviated as RI) of the anti-reflective coating is approximately equal to the square root of the RI of the microlens material used, the maximum reduction in reflectance is obtained. For example, in the atmosphere for optimal performance 'RI The 1.57 phenolic varnish microlens material (n〇v〇lac based microlens material) requires an anti-reflective coating with an RI of i 25 (1 55l/2). Other aspects can be used by &>Fresnell equations ) to calculate the optimal thickness of the above coating. In this case, according to the nature The optimal thickness of the conformal AR coating is 80 nm to 120 nm. The conformal coating of the formula is formed by chemical vapor deposition (CVD). The CVD method is a relatively expensive and slow process. The CVD method requires expensive equipment. This process can form a highly conformal coating with a minimum RI of typically greater than 14. In many cases, this RI value is It is smaller than the RI value of the microlens material, but still higher than the minimum reflectivity. The RI of the CVD film is not easy to adjust. Coating the film with a polymer solution provides a wider range of possibilities in the material selection range 201245353 muuupii. The film can be deposited by, for example, dip coating, slit coating, spray coating, or spin-on coating. Dip coating, slit coating, and spray coating Usually used for larger objects such as LCDs and solar panels' and spin coating is often used for tantalum wafers. The method of depositing spin-on materials on Shih-Ying wafers is usually to place a known amount of polymer solution in rotation. On the wafer, 're-soft baking The solvent evaporates and finally the film is cured by heat or by UV light on a heating plate or tube. The tools used in the spin coating process are inexpensive and relatively fast, especially if in a furnace tube that can hold many wafers simultaneously. Performing curing is especially fast. In general, one of the best properties of a spin-on material is its good planarity, however, planarity and conformality are opposite. The reason for this is that the use of the ✓ sizing agent allows the material to flow evenly over the wafer during deposition, and also because of the polymer reflow that typically occurs when the polymer is not fully cured during the final cure. SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved method of making conformal films for use in electronic and optical applications by coating a polymer solvent onto a surface to be treated. SUMMARY OF THE INVENTION It has surprisingly been found that a spin-on material can indeed also provide a very highly conformal coating. After many studies, it has been found that a polymer or polymer mixture that does not reflow during curing can achieve this effect. The concept of the present invention is based on the formation of a rhodium oxane material in a coating composition comprising a solvent mixture having a good low boiling point solvent mixed with a high boiling non-dissolving 201245353 41666 pif agent (non_solvent). In particular, it is an object of the present invention to formulate a composition of the above ingredients such that the polymer does not completely precipitate from the high-boiling non-solvent, but forms a transparent and clean gel with the high-boiling non-solvent during coating. . A good low boiling point solvent is necessary in order to obtain a suitable film quality' and in order to be able to remove foreign particles during the final filtration of the manufactured product. More specifically, the main feature of the method of the present invention is what is stated in the characterizing part of the first aspect of the patent application. The present invention provides considerable advantages. Thus, by using a predetermined ratio of alkali and/or acid catalyzed polymer, a highly conformal AR coating with an adjustable illusion that is optimal for microlenses or other optical materials can be fabricated. The material can also be photopatterned by the use of a photo base generator (PBG) or a photo acid generator (PAG). In the following, the embodiments will be described in detail with reference to some non-limiting operational examples to more fully explore the present invention. [Embodiment] In the preferred embodiment of the present invention, a highly conformal coating or film is manufactured by the test of the stone, which comprises a mixture of organic compounds (hereinafter also a mixture of the organic compounds referred to as "solvent blend" t), a mixture of the organic compounds of at least one low point solvent having a point of less than or equal to 145 and a maximum of or equal to 120C. The high axis combination of C is also referred to below as "non-solvent (n〇n_s〇lven〇"). The difference between the high boiling point solvent and the low 201245353 ^fiooopil boiling point solvent is at least 10 oc, preferably greater than 15 oc, especially greater than 20. (: 'usually about 25. (: to 200. 〇, for example, up to 160oC. "Low boiling solvent" can be any compound. Any compound is usually liquid at room temperature, and usually consists of Within the temperature range of the substance, it can be regarded as a good solvent for the polymer. The low-point solvent is preferably a liquid, and the initial phase of the spin-casting of the decane resin composition (the ratio (2) is also on a suitable substrate). The liquid is also a liquid. The low boiling point solvent generally has a boiling point of about 3 Torr to 145 ° C at atmospheric pressure, especially about 4 Torr to 145 〇 c, preferably about 5% to 145 0 C. Preferably, the low-foam point solvent is composed of a coating material, and the pre-selected stage during the initial step or after the initial step may be completely or substantially completely evaporated to leave the polymer material and solvent. a wet gel (wet gd) formed by the second main component of the mixture (high boiling point compound). In a preferred embodiment, the low boiling point solvent has a relatively low point of view compared to the boiling point of the high boiling point solvent. Making the film in the subsequent There is an opportunity to form a wet gel during the drying process. Also, it is preferred that the low-boiling solvent used has a relatively low toxicity, and that it does not excessively aging the polymer (哗(4)). For example, it is selected from organic compounds derived from aliphatic ketones, aromatic ketones, alcohols, esters, and ethers. Specific examples of preferred solvents include 1 (bP·56.5 °C), decylethyl _ (methyl ethyl ketone) (bp. 79.6. 〇, isopropanol (iSOpr〇pan〇i) (bp. 82.5 0C), 201245353 41666pif diethyl ketone (bp_ 100 °C), isobutanol ( Isobutanol) (bp. 108 C), propylene glycol methyl prion (pr〇pyiene giyC〇i methyl ether) (bp. 118 °C) and propylene glycol ethyl pryr (pr0pyiene giyC〇i ethyl ether) (bp. 133 °C) The boiling point given is the boiling point in the reference standard state (ie, 'ambient pressure') and represents only the boiling point of the pure compound. Although pure compounds are preferred 'but not excluded as organic as a "low boiling solvent" There are additional compounds in the compound that can change the boiling point or viscosity or other properties of the organic compound. The high boiling component of the solvent mixture may be any compound solvent which forms a gel together with the polymer after evaporation of the low boiling solvent. Moreover, the high boiling point compound is preferably in a temperature range from room temperature to coating temperature. Liquid. In the preferred embodiment 'the high boiling solvent acts like a non-solvent for the polymer. The boiling point of the high boiling solvent is usually much higher than the boiling point of the low boiling solvent to precipitate after evaporation of the low boiling solvent. The film is capable of forming a wet gel during the drying process. It is preferred that the high boiling solvent used is relatively less toxic and does not excessively accelerate polymer aging. The high-boiling non-solvent may be, for example, but the selection is not limited to di-iso-propyl ketone (bp. 124 0C), di-n-propyl ketone (bp) 145. ethyl isoamyl ketone (bp. 160. diisobutyl ketone (bp. 169.4. 〇, di-n-butyl ketone (di-n-butyl) Ketone) (bp. 186 〇C) or dipentyl ketone (bp. 186 °C). The above boiling points are for reference only. 9 201245353 4K) 〇〇pit solvent mixture usually contains 丨 parts by weight to 1〇〇 Parts by weight of the low boiling point solvent and from about 1 part by weight to about 100 parts by weight of the high boiling point compound, in particular, the weight ratio between the two components is about 1:2 to 20: 1. The molar ratio is preferably about 1 : 50 to 50 : 1, especially about 1: 20 to 20 : 1 ; etc. The molar ratio is slightly better than the stoichiometric amount of the solvent having a low boiling point. When the above polymer solvent is spin-coated On the wafer, the solvent is initially as normal as the material to be coated. That is to say 'the solvent is evenly spread throughout the wafer. However' as a good low boiling point solvent When applied, the film becomes a wet gel with greatly reduced flow characteristics. Then, when the high-boiling non-solvent dries, the gel shrinks on the structure to form a highly conformal coating. Therefore, the resulting film thickness is usually In the range of about 5 nm to 1 〇〇μηη, preferably for some applications such as microlenses, the film preferably has a thickness of about 10 nm to 500 nm 'particularly about 5 〇 11111 to 2 〇〇 nm. The value is particularly suitable for a naphthenic film. The polymer of the composition may be a siloxane polymer or a mixture of two or more siloxane polymers. According to the embodiment, a suitable amphoteric oxyalkylation polymerization The product is produced by catalytic hydrolysis or acid-catalyzed hydrolysis and condensing the Weiwei monomer Weiwei Xixizhuo t and selectively adding the Wei to improve the adhesion. A monomer of a carbon filament female or a lower alkoxy residue is particularly preferred. Therefore, the alkyl residue is usually selected from a Cl.6 filament group, such as an f group, a 201245353 41666pif and an isopropyl group. Base, n-butyl, tert-butyl, isobutyl N-amyl. Similarly, the alkoxy group preferably has from one carbon atom to six carbon atoms (Cm alkoxy group), for example, an oxirane group, an ethoxy group, a positive C group. An oxygen group and an isopropoxy group, a n-butoxy group, a neobutoxy group and an isobutoxy group, and a n-pentyloxy group. The decane monomer may include an alkyl group of 丨 to 4 and 1 to 4 Alkoxy groups and combinations thereof, for example, 4 alkoxy groups, or 3 alkoxy groups and 1 alkyl group. Specific examples of suitable monomers are methyltrialkoxysilane and tetraalkoxysilane. In particular, the following monomers are particularly advantageous: - methyltriethoxysilane selected from methyltrimethoxysilane and methyltriethoxysilane selected from methyltriethoxysilane And, - a tetraalkoxydecane selected from tetraethoxysilane or tetramethoxysilane. According to a preferred embodiment, in order to produce a highly conformal coating and film using a decyl oxide resin composition according to the present invention, the resulting stone can be obtained by controlling or changing the mixing ratio of the oxy-oxygen polymer in the mixture. The refractive index of the oxy-fired polymer is adjusted to a predetermined value. According to a preferred embodiment, the improvement of adhesion can be selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, and dimercapto曱 石 2012 201245353, ^ιοοοριι (dimethyldimethoxysilane), dimethyldiethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxy zexi ( Trifhioropropyltriethoxysilane), glycidyloxypropyltrimethoxysilane, glycidyloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyl Benzacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, propylene oxypropyl propyl propylene Trimethoxy zephyr (a Cryloxypropyltrimethoxysilane ), aeryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldifluorene Phenyl methyl dimettioxysilane and phenyl methyl diethoxysilane. Generally, the molar ratio of the trialkoxydecane or the tetraalkoxydecane or a mixture thereof to the adhesion improving decane is from 1000:1 to 1:1000, and in particular, J is about 100:1 to 1:100'. It is preferably about 100:1 to 1:1, and especially about 75:1 to 5:1. Generally, as discussed above, the sulphuric acid monomer is hydrolyzed and prepolymerized by a method known per se to produce a molecular weight of 12 201245353 41666pif of about 500 m〇1/g to 100,_m〇1 /g, especially about 5 〇〇〇 ... ... to 50, _m rain prepolymer (prepGlymer), and the coating composition is formulated after possible solvent replacement. The composition comprises from about 9% by weight to about 25% by weight of the polymeric material, preferably from about 1% by weight to about 8% by weight of the polymeric material. The highly conformable coating and film can be produced by spin coating, dip coating, slit coating or spraying with the above composition. This coating or film can be deposited on a suitable substrate. Examples of substrates (4) materials, such as rare wafers, silica materials such as glass substrates, other metal oxide materials, metals and metal alloys, secret varnishes and acrylics (aeiy microlens materials. The coating can be made photosensitive by the addition of a photoacid generator a: id generator, PAG) or a photobase generator (content of i% to wt% solids) as known in the art. A preferred example is a free radical photoinitiator, such as a free radical initiator for displays, particularly an iRGacure (g) 〇χΕ〇2 photoinitiator supplied by BASF. The above-described embodiment of the method of forming a photopatterned highly conformal film comprises the steps of: - adding a photoreceptor; - exposing the film to UV light; and - developing the exposed film with a solvent, typically Organic solvents. 13 201245353
Hiooopil 上述溶劑通常選自能夠溶解未固化之矽氧烷樹脂的 有機溶劑。針對上述目的的溶劑實例包括脂肪族酮類或芳 香族酮類，例如丙酮。 以下的非限制性實例將用來說明本發明： 實例Hiooopil The above solvents are usually selected from organic solvents capable of dissolving uncured alumoxane resins. Examples of the solvent for the above purpose include aliphatic ketones or aromatic ketones such as acetone. The following non-limiting examples will be used to illustrate the invention:
實例1A 在2 L的石英燒瓶中加入去離子水（DIW) (308 g) 及曱醇（750 g)，並在油浴中加熱至60%。添加氫氧化四 曱敍（Tetramethylammonium hydroxide，TMAH，30 g，25 %水溶液）。在500 mL的玻璃瓶中將甲基三曱氧基矽烷 (Methyltrimethoxysilane ) ( 90 g )及四乙氧矽烷 (tetraethoxysilane) ( 125 g)混合，並在1〇分鐘内將上述 混合物加入於已充分攪拌的上述燒瓶中。溶液開始進行回 流。 在所有的單體都加入燒瓶之後，使溶液回流1〇分鐘， 接著讓溶液緩冷卻（slow cooling)兩小時。然後，將順丁 醯二酸水溶液（Maleic acid water solution) (33 %，35 g) 注入以中和TMAH。加入縮水甘油醚氧基丙基三曱氧基矽 烷（Glycidyloxypropyltrimethoxysilane，GPTMOS，5 g) 並使其進行反應5为知。以旋轉蒸發器（r〇tary evap〇rat〇r) 蒸顧掉過量的甲醇。將剩下的聚合物溶液注入於裝有Diw (800 g)及曱基叔丁基醚（methyl t-butyl ether，MTBE， 600 g)之4L的燒瓶中。在攪拌溶液五分鐘之後，產生分 離的液層，並移除下層的水相。將更多的DIW (500g)加 201245353 41666pif 入’在搜拌五分鐘之後，再次產生分離的液層。收集上層 的MTBE相並儲存於冷康庫中。藉由以聚苯乙稀為標準品 的/旋膠滲透層析法（GPC)於四氫呋喃（tetrahydrofumn) 中量測聚合物的分子量為Mw/Mn = 25,563/17,052。Example 1A Deionized water (DIW) (308 g) and methanol (750 g) were added to a 2 L quartz flask and heated to 60% in an oil bath. Tetramethylammonium hydroxide (TMAH, 30 g, 25% aqueous solution) was added. Methyltrimethoxysilane (90 g) and tetraethoxysilane (125 g) were mixed in a 500 mL glass vial and the mixture was thoroughly stirred in 1 min. In the above flask. The solution begins to reflux. After all the monomers were added to the flask, the solution was refluxed for 1 minute, and then the solution was allowed to cool for two hours. Then, a Maleic acid water solution (33%, 35 g) was injected to neutralize TMAH. Glycidyloxypropyltrimethoxysilane (GPTMOS, 5 g) was added and reacted for 5 to be known. Excess methanol was distilled off by a rotary evaporator (r〇tary evap〇rat〇r). The remaining polymer solution was poured into a 4 L flask containing Diw (800 g) and methyl t-butyl ether (MTBE, 600 g). After stirring the solution for five minutes, a separate liquid layer was produced and the lower aqueous phase was removed. Add more DIW (500g) plus 201245353 41666pif to 'after mixing for five minutes, again to produce a separate liquid layer. The upper MTBE phase was collected and stored in a cold storage. The molecular weight of the polymer was measured by tetrahydrofuran using a polystyrene standard/gelatin permeation chromatography (GPC) to be Mw/Mn = 25,563/17,052.
實例1B 在2 L的石英燒瓶中加入丙酮（750 g)。加入曱基三 • f氧基魏（9G g)、四乙氧魏（125 g)及縮水甘油醚 氧基丙基二甲氧基矽烧g)。緩慢滴入稀釋的鹽酸（DUute hydrochloric acid ’ dHQ ’ 0.01M，215 g)，接著攪拌 30 分 釦。然後，將溶液加熱以進行回流，並進行反應5小時。 然後，冷卻燒瓶，並以旋轉蒸發器使揮發物蒸發，直到得 到濃稠的漿體為止。將此漿體溶於MTBE (5〇〇g)中並加 入二乙胺（tnethylamine，TEA，2 g )。使溶液回流兩小時， 在此之後讓溶液冷卻，並以dHCl (0.5 M，200 g)沖洗兩 次及以DIW沖洗三次。收集MTBE溶液並儲存在冷凍庫 中。藉由GPC量測聚合物之分子量為Mw/Mn = 15,332/5,266。 實例2 於旋轉蒸發器，將實例1A的MTBE相進行溶劑置換 成曱基乙基酮（methyl ethyl ketone，MEK)，得到具有8 重量％聚合物的溶液。 實例3 取出實例2的MEK-溶液（20·8 g)，並加入更多的 MEK (12.5 g)及乙基異戊基g同（ethyi isoamyi ketone， 15 201245353 41000plt ΕιΑΚ ’ 16.7 g)。以0.2卿的pTFE過濾器手工過濾 (hand-filtered)所得溶液。將溶液以2〇〇〇 rpm的速度旋 轉澆鑄（spin cast) ’接著在15〇 〇c下於加熱板上進行軟烤 5 min並在200 °C下進行固化5 mine得到的薄膜厚度為 168 nm且RI為1.287。上述溶劑混合物形成高度共形薄膜。 實例4 實例4與實例3相類似，十隹以二異丁基嗣㈤s〇b咖 =ne ’ DIBK)取代ElAK。同樣地，此溶劑混合物形成 南度共形薄膜。 圖4A為將此實例所得的溶液藉由旋塗 構的SEM影傻。如旦v你化σ 晃你/再未、'、〇 底部上具有幾乎等量二料，==頂部、側壁及 構的實例所得的溶液藉由旋塗塗覆在溝渠結 EM衫像。SEM影像清楚地顯示在溝竿的頂邱 側壁及底部上的材料幾 牡㈣的頂部、 的是，沒有觀察^r=krng)tr性優。重要 為函及實例1B之材料的混合比例 實例5 實例5與實例3相類似，惟除了使 1 n- utylketone，DNBK)取代用 EiAK 闩 土 劑混合物形成高度共形薄膜。戈用lAK。同樣地，此溶 實例6 ' _與實例3相類似，惟以二正丙基⑽ 16 201245353 41666pif ketone，DNPK)取代EiAK。此溶劑混合物形成共形薄膜。 然而，此共形性並不如實例3、實例4或實例5。這表示實 例2的聚合物有可能幾乎完全溶解於DNPK中，即音才t DNPK幾乎是個良溶劑。 ""曰 實例7 將實例1A及實例1B的聚合物以各種比例混合，類似 於實例3將溶劑換成MEK/EiAK溶液，並旋轉澆鑄於矽晶 圓上。得到無缺陷、均質及高度共形且折射率在一範圍的 薄膜（FIG)。此實例顯示針對各個情況，系統的幻可輕 易將各種底層光學材料（underlying opticalmaterial)最佳 化，以使反射降到最低。 實例8 取實例1A的MTBE-溶液，並加入EiAK。以旋轉蒸 發器經溶舰換將MTBE錄。得到透明娜，其無法經 f 1 μΠ1的打四過濾器來過濾、。此表示對於碎氧烧樹脂而 5，ΕιΑΚ為非溶劑。然而，當將兩份ΜΕκ加入於一份含 麵8 %之石夕氧院樹脂的EiAK溶液中時，溶液可輕易地 =由〇·2 μηι的pTFE過濾器來過濾。此顯示 為1 : 2的溶劑組合可以溶解矽氧烷樹脂。 實例9 取實例u的ΜΤΒΕ·溶液，並加入mBK。以旋轉蒸 =广溶劑置換將MTBE移除。得到透明凝膠，其無法經 f μιη或i μιη的PTFE過濾器來過濾。此表示對於矽 減树脂而言，DIBK為非溶劑。然而，當將兩份mek加 201245353 ^ιοοοριι 入於一份含有約8 %之矽氧烷樹脂的DIBK溶液中時，溶 液可輕易地經由0.2 μιη的PTFE過濾器來過濾。此顯示 DIBK : ΜΕΚ為1 : 2的溶劑組合可以溶解矽氧烷樹脂。 實例10 取實例4的溶液’並加入irgacure® 〇χΕ〇2 (由BASF 所製造的光鹼/自由基起始劑’ 1重量％的固體）。在石夕晶圓 上將此材料旋塗成105 nm的薄膜，並暴露於線uv光源 (100 mJ/cmA2)。在+23°C下歷時3分鐘後，以丙酮清洗 晶圓1分鐘藉以使晶圓顯影’得到清楚的圖案（參照圖6 )。 暴露區域之折射率為1.23。 比較例1 比較例1與實例3相類似，惟以曱基戊基酮（methyl amyl ketone，MAK)取代EiAK。此溶劑混合物無法形成 好的共形薄膜。 將部分的溶液取出，並以旋轉蒸發器蒸發MEK，剩 下的MAK-聚合物溶液仍可經由〇 2 的過滤器來過遽， 此表不對於聚合物而言，ΜΑΚ是良溶劑，因而不能形成 高度共形塗層。 比較例2 比較例2與實例3相類似，惟以丙二醇正丙基醚 (propylene glyc〇i n_propyi ether，ρηρ)取代 EiAK。此溶 劑混合物無法形成好的共形薄膜。 圖6A為溝渠結構的SEM影像，所述溝渠結構上面藉 由旋塗而塗覆有比較例2所製造的溶液，且圖6A顯示大 201245353 41666pif 里的材料積聚在溝渠的底部，复一 為溝渠結構的另—形性差。Example 1B A 2 L quartz flask was charged with acetone (750 g). Add fluorenyl tris-f-oxygen (9G g), tetraethoxy Wei (125 g) and glycidyloxypropyl dimethoxy oxime g). Dilute hydrochloric acid (DUute hydrochloric acid 'dHQ '0.01 M, 215 g) was slowly added dropwise, followed by stirring for 30 minutes. Then, the solution was heated to reflux, and the reaction was carried out for 5 hours. The flask was then cooled and the volatiles were evaporated on a rotary evaporator until a thick slurry was obtained. This slurry was dissolved in MTBE (5 〇〇g) and diethylamine (tnethylamine, TEA, 2 g) was added. The solution was refluxed for two hours, after which time the solution was allowed to cool and washed twice with dHCl (0.5 M, 200 g) and three times with DIW. The MTBE solution was collected and stored in a freezer. The molecular weight of the polymer was measured by GPC to be Mw/Mn = 15,332/5,266. Example 2 The MTBE phase of Example 1A was solvent exchanged to methyl ethyl ketone (MEK) on a rotary evaporator to give a solution having 8 wt% polymer. Example 3 The MEK-solution of Example 2 (20·8 g) was taken out, and more MEK (12.5 g) and ethyl isopentyl g (Ethyi isoamyi ketone, 15 201245353 41000plt ΕιΑΚ ' 16.7 g) were added. The resulting solution was hand-filtered with a 0.2 liter pTFE filter. The solution was spin cast at 2 rpm 'then soft-baked on a hot plate at 15 ° C for 5 min and cured at 200 ° C. The thickness of the film was 168 nm. And RI is 1.287. The above solvent mixture forms a highly conformal film. Example 4 Example 4 is similar to Example 3 in that Shiyan replaces ElAK with diisobutylphosphonium (5) s〇b coffee = ne ' DIBK). As such, the solvent mixture forms a south conformal film. Fig. 4A shows the SEM image of the solution obtained in this example by spin coating. If you have σ 晃 晃 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / The SEM image clearly shows the top of the gully and the top of the material on the bottom of the oyster (4), and there is no observation of ^r=krng)tr. Important Letters and Mixture Ratios for Materials of Example 1B Example 5 Example 5 was similar to Example 3 except that 1 n- utylketone, DNBK) was used to form a highly conformal film with an EiAK plug mixture. Ge uses lAK. Similarly, this dissolution example 6'_ was similar to Example 3 except that di-n-propyl (10) 16 201245353 41666 pif ketone, DNPK) was substituted for EiAK. This solvent mixture forms a conformal film. However, this conformality is not as in Example 3, Example 4 or Example 5. This indicates that the polymer of Example 2 is likely to be almost completely dissolved in DNPK, i.e., DNPK is almost a good solvent. "" 实例 Example 7 The polymers of Example 1A and Example 1B were mixed in various ratios, and similar to Example 3, the solvent was changed to a MEK/EiAK solution and spin-cast on a twin circle. A film (FIG) is obtained which is defect-free, homogeneous and highly conformal and has a refractive index in a range. This example shows that for each case, the system's illusion can easily optimize various underlying optical materials to minimize reflections. Example 8 The MTBE-solution of Example 1A was taken and EiAK was added. Record the MTBE with a rotary evaporator. A clear Na is obtained, which cannot be filtered by a four filter of f 1 μΠ1. This means that for ash-burning resin, 5, ΕιΑΚ is a non-solvent. However, when two parts of ΜΕκ were added to an EiAK solution containing 8% of the stone oxide resin, the solution was easily filtered by a pTFE filter of 〇·2 μηι. This shows a solvent combination of 1: 2 to dissolve the rhodium oxide resin. Example 9 The solution of Example u was taken and mBK was added. The MTBE was removed by rotary steaming = wide solvent displacement. A clear gel was obtained which could not be filtered through a PTFE filter of f μιη or i μιη. This means that DIBK is a non-solvent for the reduced resin. However, when two parts of mek plus 201245353 ^ιοοοριι were placed in a DIBK solution containing about 8% of a decane resin, the solution was easily filtered through a 0.2 μηη PTFE filter. This shows that DIBK: a solvent combination of 1:2 can dissolve the rhodium oxide resin. Example 10 The solution of Example 4 was taken and irgacure® 〇χΕ〇2 (photobase/radical starter manufactured by BASF' 1% by weight solids) was added. This material was spin coated onto a 105 nm film on a Shihwa wafer and exposed to a line uv source (100 mJ/cmA2). After 3 minutes at +23 ° C, the wafer was washed with acetone for 1 minute to develop the wafer to obtain a clear pattern (see Fig. 6). The exposed area has a refractive index of 1.23. Comparative Example 1 Comparative Example 1 was similar to Example 3 except that EiAK was replaced with methyl amyl ketone (MAK). This solvent mixture did not form a good conformal film. Part of the solution is taken out and the MEK is evaporated by a rotary evaporator. The remaining MAK-polymer solution can still be passed through the 〇2 filter. This is not a good solvent for the polymer, so it cannot be A highly conformal coating is formed. Comparative Example 2 Comparative Example 2 was similar to Example 3 except that EiAK was replaced by propylene glyc〇i n_propyi ether (ρηρ). This solvent mixture did not form a good conformal film. 6A is an SEM image of a trench structure on which the solution prepared in Comparative Example 2 is applied by spin coating, and FIG. 6A shows that the material in the large 201245353 41666pif accumulates at the bottom of the trench, and the first is a ditch. The structure is poorly shaped.
面藉由旋塗而塗覆有比較實例所述溝渠結構上 亦顯示出有大量的聚合物材料 ^造的溶液，且圖6B 共形性不良1且，有觀察到破槽的底部，其表示 將部分的溶液取出，並以 下的祕聚合物溶液仍可經由奸器蒸發ΜΕΚ，剩 此表示對㈣合物而言，Ρ · 的過_來過遽， 度共形塗層。 疋良心劑，因而不能形成高 比較例3 比較例3與實例3相類似，惟以作為單一 κ 來將;谷液稀釋到固體含量為3 3 形薄膜。 $為13/°°此溶劑無法形成好的共The surface is coated by spin coating. The trench structure also shows a large amount of polymer material, and the conformality of FIG. 6B is poor, and the bottom of the broken trench is observed. A part of the solution is taken out, and the following secret polymer solution can still be evaporated by the smuggler, and this means that the (tetra) compound has a conformal coating.疋 Conscience, and therefore cannot form high Comparative Example 3 Comparative Example 3 is similar to Example 3 except that it is treated as a single κ; the gluten is diluted to a solid film of 3 3 . $13/°° This solvent does not form a good total
比較例4A 取貝例1A的MTBE-溶液，並加入Mak。以旋轉蒸 發器經溶劑置換將MTBE移除。得到透明凝H可㈣ ^哗的FIFE過濾、器來過濾、。此表示對於魏錢脂而 言’ MAK不是非賴’而是良溶劑。上述溶劑無法形成 好的共形聚合物薄膜。 比較例5 比較例5與實例3相類似，惟以丙二醇甲基醚乙酸酯 (propylene glycol methyl ether acetate，PGMEA)取代Comparative Example 4A The MTBE-solution of Shell Example 1A was taken and Mak was added. The MTBE was removed by solvent displacement using a rotary evaporator. A transparent condensate H (four) ^ 哗 FIFE filter is obtained to filter. This means that for Wei Qianzhi, 'MAK is not a good thing' but a good solvent. The above solvent cannot form a good conformal polymer film. Comparative Example 5 Comparative Example 5 was similar to Example 3 except that it was replaced by propylene glycol methyl ether acetate (PGMEA).
EiAK°此溶劑混合物無法形成好的共形塗層。將部分的溶 液取出，並以旋轉蒸發器蒸發MEK，剩下的PGMEA-聚合 19 201245353 物溶液仍然可經由0.2 μιη的過濾器來過濾，此表示對於聚 合物而言’ PGMEA是良溶劑’此說明了共形性不良。此 外，由GPC可知PGMEA-聚合物溶液相當快速老化，顯示 了穩定性的問題。 比較例6 比較例6與實例3相類似’惟以異丙醇（isopropan〇1， IPA )取代EiAK。旋塗的薄膜充滿條紋（striation )，使得 純IPA並不適合用於旋塗。然而，純ιρΑ可用於浸塗。當 配方中沒有使用非溶劑，則所得到的薄膜無法具有高度共 形性。 【圖式簡單說明】 圖1顯示反射率對波長的關係圖，其表示在90。的角 度下，微透鏡材料（RJ=1.57)上之AR塗層（RJ=1 25， Tx=109.5 nm)的模擬反射率，其中AR塗層的厚度針 光而最佳化。 圖2顯示對應的反射率對波長的關係圖，其表示在卯。 的角—度下’微透鏡材料（RI=1.57)上關係AR塗層 (RI=1.25，Tx=87.5nm)的模擬反射率，其中放塗 厚度針對藍光而最佳化。 θ ’EiAK° This solvent mixture does not form a good conformal coating. A portion of the solution was taken out and the MEK was evaporated on a rotary evaporator. The remaining PGMEA-polymerization 19 201245353 solution was still filtered through a 0.2 μη filter, which means 'PGMEA is a good solvent' for the polymer. Poor conformality. In addition, it was known by GPC that the PGMEA-polymer solution was quite rapidly aged, showing a problem of stability. Comparative Example 6 Comparative Example 6 is similar to Example 3 except that EiAK was replaced by isopropanol (IPA). The spin-coated film is full of stripes, making pure IPA unsuitable for spin coating. However, pure ιρΑ can be used for dip coating. When no non-solvent is used in the formulation, the resulting film cannot be highly conformal. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing reflectance versus wavelength, which is shown at 90. At an angle, the simulated reflectance of the AR coating (RJ = 25, Tx = 109.5 nm) on the microlens material (RJ = 1.57), where the thickness of the AR coating is needled, is optimized. Figure 2 shows a plot of corresponding reflectance versus wavelength, which is shown in 卯. The simulated reflectance of the AR coating (RI = 1.25, Tx = 87.5 nm) on the microlens material (RI = 1.57), where the thickness of the spread is optimized for blue light. θ ’
λ圖3描繪沒有AR塗層時，微透鏡材料（RI=1 57 模擬反射率。 W 像。圖4A為實例4的溶液旋塗於溝槽結構上之的sem影 圖犯為實例4的溶液旋塗於溝槽結構上的另一犯μ 20 201245353 41666pif 影像。 圖5表示薄膜RI的變化為實例1A及實例IB所製造 之材料的混合比例的函數。 圖6為實例10中所得到之圖案的影像。 圖7A為將比較實例2所得到的溶液旋塗於溝槽結構 上的SEM影像。 圖7B為將比較實例2所得到的溶液旋塗於溝槽結構 上的另一 SEM影像。 【主要元件符號說明】 無 21λ Figure 3 depicts the microlens material (RI = 57 simulated reflectance. W image) without the AR coating. Figure 4A shows the solution of the solution of Example 4 spin-coated on the trench structure. Another effect of spin coating on the trench structure is μ 20 201245353 41666pif image. Figure 5 shows the change in film RI as a function of the mixing ratio of the materials produced in Example 1A and Example IB. Figure 6 is the pattern obtained in Example 10. Fig. 7A is an SEM image of spin-coating the solution obtained in Comparative Example 2 on a trench structure. Fig. 7B is another SEM image of spin-coating the solution obtained in Comparative Example 2 on a trench structure. Main component symbol description] No 21