ί379807 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種光學材料的製備方法，尤指 一種含♦與鈦之光學材料的製備方法。 【先前技術】 現今光電科技產業的快速發展，光學薄膜已經成 為不可或缺的重要角色，而光學薄膜鍍製技術—直是379379807 IX. Description of the Invention: [Technical Field] The present invention relates to a method for preparing an optical material, and more particularly to a method for preparing an optical material comprising ♦ and titanium. [Prior Art] Nowadays, the rapid development of the optoelectronic technology industry, optical film has become an indispensable important role, and optical film plating technology - straight
光子項域中的基礎技術。近些年來，光電資訊鱼光通 訊科技的迅速發展，不論是光通訊的主動元件^被動 兀件的開發，或是分光或合光元件，光學薄膜製鍍技 術均粉演重要的角色。 心者光電產業的大幅成長’光學薄膜的應用範圍 =廣’其品質要求也逐漸提升。光學㈣的基本要求， 需具：低能量耗損、低散射率、冑穿透率、高堆積密 度、向雷射傷害起值（laser damage ihresh〇丨d)、高化The underlying technology in the photon domain. In recent years, the rapid development of Photonics Information Technology, whether it is the development of active components of optical communication, the development of passive components, or the separation or combination of optical components, optical film plating technology plays an important role. The growth of the optical industry of the heart of the heart of the optical film's application range = wide's quality requirements have gradually improved. The basic requirements of optics (4) are: low energy consumption, low scattering rate, helium penetration rate, high bulk density, laser damage ihresh〇丨d, high
學穩定性等特性，且功能要求日趨多#、複雜。傳統 :製單-材質膜層的方法，所能提供不同折射率或微 '•、。構等特性的材料數量有限，故在光學應用上常因找 不到合適的折射率材料而須變更設計以配 學材料’使光學薄膜設計及製程見有的先 人1久表私受到限制，而逐漸失 去其競爭性。 光學薄膜材料是影響 應用材料混合材質的特性 各種特性，進而改善膜材 薄膜特性的主要因素之一， 與比例，藉此可調變薄膜的 的性質，如使用不同壓、張 5 Ϊ379807 力材質混合而成的薄膜’其膜材所呈現的應力則會隨 所混合之材質比例不同而在壓、張應力之間獲得調 節；如此即可以有效地降低膜材在製備時，因熱處理 過程導致熱脹冷縮，產生薄膜的裂紋及不均一性。且 在混合膜材料中只要加入含有少量非晶結構 (amorphous)材料即可使膜層的結構非晶化，使其薄膜 微結構可保持細緻且平坦的表面，避免造成光穿透時 多餘的耗損，提高光學系統影像清析度，且可改善因 光之折射效應所造成的迷光、眩光等光能量損失現 象。 常用的薄膜的製備方法很多，有蒸鍍法 (evaporation method)、濺鍍法（sputtering 咖⑽）以及 化學氣相沉積法（CVD method)等。但此等方式所得之 薄膜組成控制不易、膜質之均句性較差、製程溫度較 高、製作成本較高和製備過程複雜等缺點，故較不適 合於多成份光學薄膜的製備。而溶膠_凝膠法（s〇i咖 P—)為液相反應之化學合成製程，因溶液在本質 上成份非常均勻（屬分子級層 甘-r々， s人的此合），其可將多種 材質成份共溶於溶劑中4所製得之薄臈的組成幾乎 與溶液中之金屬離子成份相同。以溶膠-凝膠法製備 混合膜雖具有許多優點，如： _ ，，且成成分較易控制、較 高的純度及均勻度…等，伸仍 1-仍有缺點侷限其發展空 間，如：製程中原料收縮率大 手大易發生龜裂及產生微 裂，，文、產品易含有羥基及有機 令機不純物...等。若能改善 6 ¢379807 其製程上困難點進而改善製膜及其產品之品質，將能 擴展溶膠-凝膝技術之應用。溶耀·-凝膠法製膜的品質 及特性深受溶膠配製和鍍製之參數的影響，若要提昇 溶膠-凝膠法製膜的品質’則須對溶膠-凝膠法製膜的 關鍵因素進行充分了解。Learning stability and other characteristics, and functional requirements are increasingly more #, complex. Tradition: The method of making a single-material film layer can provide different refractive indices or micro-•. The number of materials with structural properties is limited, so in optical applications, it is often necessary to change the design to match the material for the purpose of finding a suitable refractive index material, so that the design and process of the optical film are limited. And gradually lost its competitiveness. The optical film material is one of the main factors affecting the characteristics of the mixed material of the applied material, thereby improving the film properties of the film, and the ratio, thereby adjusting the properties of the film, such as using different pressure, sheet 5 Ϊ 379807 force material mixing The film formed by the film's stress will be adjusted between the pressure and the tensile stress depending on the proportion of the material to be mixed; thus, it can effectively reduce the thermal expansion of the film during the preparation process due to the heat treatment process. Cold shrinkage produces cracks and inhomogeneities in the film. Moreover, the structure of the film layer can be amorphized by adding a small amount of amorphous material in the mixed film material, so that the film microstructure can maintain a fine and flat surface, and avoid unnecessary loss of light penetration. Improve the image clarity of the optical system, and improve the loss of light energy such as glare and glare caused by the refraction effect of light. There are many methods for preparing a conventional film, such as an evaporation method, a sputtering method (sputtering coffee (10)), and a chemical vapor deposition method (CVD method). However, the film composition obtained by such methods is difficult to control, the film quality is poor, the process temperature is high, the manufacturing cost is high, and the preparation process is complicated, so it is not suitable for the preparation of the multi-component optical film. The sol-gel method (s〇i coffee P-) is a chemical synthesis process for liquid phase reaction, because the solution is very homogeneous in nature (the molecular layer is gan-r々, s human), which can The composition of the thin bismuth prepared by dissolving a plurality of material components in a solvent is almost the same as the composition of the metal ion in the solution. The preparation of the mixed film by the sol-gel method has many advantages, such as: _, and the composition is easier to control, higher purity and uniformity, etc., and still has a disadvantage to limit its development space, such as: In the process, the raw material shrinkage rate is large and prone to cracking and microcracking. The text and products are easy to contain hydroxyl groups and organic impurities. If it can improve the difficulty of 6 ¢ 379807 and improve the quality of film making and its products, it will expand the application of sol-knee technology. The quality and characteristics of the solute-gel method are deeply influenced by the parameters of the sol preparation and plating. If the quality of the sol-gel method is to be improved, the key factors of the sol-gel method must be fully utilized. To understanding.
Si〇2(一氧化矽）與Ti〇2(二氧化鈦）兩種成分所構 成的混合膜，在光學特性方面可具有大的折射率可調 變範圍’在微結構方面則易於形成非晶質結構，進而 可提昇膜層表面的平滑度’以利於對光之散射量及其 能量損失的消減。學者已成功於矽晶片上鍍製出各種 組成比例的Si〇2_Ti〇2單層抗反射光學混合膜。研究 證實’當光波長為550 nm時，這些混合膜的折射率 可以在1.46-2.39間作調變，且可降低光之散射效應。 其應用包括.平面光波導（planar waveguides)及透鏡 光波導（lens-like waveguide)、單層抗反射膜㈨叫卜A mixed film composed of two components of Si〇2 (nitric oxide) and Ti〇2 (titanium dioxide) can have a large refractive index adjustable range in terms of optical characteristics, and an amorphous structure is easily formed in terms of microstructure. In turn, the smoothness of the surface of the film layer can be improved to facilitate the reduction of the amount of light scattering and its energy loss. Scholars have successfully plated Si〇2_Ti〇2 single-layer anti-reflection optical hybrid films of various composition ratios on germanium wafers. Studies have confirmed that when the wavelength of light is 550 nm, the refractive index of these mixed films can be modulated between 1.46 and 2.39, and the light scattering effect can be reduced. Applications include: planar waveguides and lens-like waveguides, single-layer anti-reflection films (9)
layer antirefleCti〇n)、干涉濾光片（interference filterS)[5]、梯度折射率鏡片、抗紫外光薄膜（uv Shieiding)和非線性光學薄臈（n〇n丨inear 〇ptical)等多種 不同性質的光學應用。 目前雖然已有學者製備二氧化石夕與二氧化鈦之混 合膜:但利用溶膠.凝膠法來製備二氧㈣與二氧化 鈦之薄膜，仍有許多的P弓BS & h 7夕旳問喊與挑戰尚待克服，包括如Layer antirefleCti〇n), interference filterS [5], gradient index lens, UV light film (uv Shieiding) and nonlinear optical thin 臈 (n〇n丨inear 〇ptical) and other different properties Optical application. At present, although scholars have prepared a mixed film of dioxide and titanium dioxide: but using the sol-gel method to prepare a film of dioxins and titanium dioxide, there are still many P-bows BS & h 7 Still to be overcome, including
何選擇適當之溶劑以溶紘人& A 冷解3鈦化合物，以避免含鈦化 合物因快速水解而形成不仍6 战不均勻的沈澱物，進而防止影 7 妇79807 響所形成薄膜的光學性質。 程條件來製造具高透光性之“如仃以取佳化的集 業界與學界所極力研究發展的課題。 為目則 【發明内容】 有鐘於以溶膠-凝膠法g ^ 傷3石夕與鈦之光學好粗 的方法仍待研究發展，本 材科 盥斜之目的在於提供—含矽 與鈦之光學材料的製備方法，農 含矽How to choose a suitable solvent to dissolve the human & A cold solution 3 titanium compound, in order to avoid the formation of titanium film by the rapid hydrolysis of the titanium compound is not still 6 uneven, so as to prevent the optical film formed by the film 7807 nature. The condition of the process is to produce a high-transparency "such as 仃 仃 取 仃 的 的 的 的 集 集 集 集 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The method of radiant and titanium optics is still to be studied and developed. The purpose of this material is to provide the preparation method of optical materials containing bismuth and titanium.
條件來製備之光學。 刃I備 ，達成以上的目的，本發明係包括： 提供一四乙氧基矽溶液； 提供一異丙氧基鈦溶液， 位劑； 其係以乙醯丙酮作為配 混合兩溶液：將上述兩沒、％ 〜 疋兩，合液相互混合攪拌均勻而 仵到一混合液； 調整混合液之酸鹼值：將十.Conditions to prepare the optics. The invention provides the following: the present invention comprises: providing a tetraethoxy hydrazine solution; providing a titanium isopropoxide solution, a leveling agent; and mixing the two solutions with acetamidine acetone: No, % ~ 疋 two, the mixture is mixed with each other and evenly mixed to a mixture; adjust the pH value of the mixture: ten.
將上述的混合液之酸鹼值 調整至4至6;以及 膠化反應：將該混合液於進行老化攪拌2至4小 時，待該混合液老化反應完成，即製備得一石夕欽溶 膠0 較佳的是，該矽-鈦溶膠進一步進行乾燥處理與 熱處理，而得一二氧化矽-二氧化鈦陶瓷粉末β 較佳的是，該矽-鈦溶膠係於12〇 %之溫度下進 行乾燥處理。 較佳的是’該熱處理係於6〇〇 〇C以下之溫度進行 8 浪燒。 較佳的s，該石夕-鈦ί容膠進-步利用旋轉塗佈方 /、塗佈於，月浓基材並供烤該基材而得一層薄膜，而 y進仃熱處理得到一二氧化矽_二氧化鈦陶瓷薄膜。 較佳的是，反覆實施旋轉塗佈並烘烤該基材之步 驟即獲4具有複數層之薄膜，而使該薄膜具有所需之 厚度。 本發明可達成的具體功效包括： 1 .本發明利用溶膠-凝膠法可製備之含矽與鈦 之2學材料，利用此光學材料所製備之薄膜由於含有 非晶質的二氧化矽，因此薄膜微結構均保持為非晶質 態，可使薄膜表面保持平整，減低光學損耗，提 高薄膜的透光性。 2 .本發明利用乙醯丙酮作為異丙氧基鈦溶液的 ，位劑’目異丙氧基鈦溶液係在無纟的狀態下配 '可避免異丙氧基鈦吸收水氣而水解產生不均勻沈 澱物，.進而防止最後製備薄臈的光學性質受到不均勻 沈澱物之影響。 3 ,本發明利用最佳化的f程條件，可&備得到 成膜性較佳的薄暝，避免薄膜產生龜裂現象。 【實施方式】 本發明之具體實施例係包括以下步驟： 提供四乙氧基矽溶液：該四乙氧基矽溶液係可 由將四乙氧基矽均勻分散至乙醇溶劑而得到；Adjusting the pH value of the above mixture to 4 to 6; and gelling reaction: the mixture is stirred for aging for 2 to 4 hours, and the aging reaction of the mixture is completed, that is, the preparation of a stone Xiqin sol 0 is compared Preferably, the cerium-titanium sol is further subjected to a drying treatment and a heat treatment to obtain a cerium oxide-titanium dioxide ceramic powder β. Preferably, the cerium-titanium sol is dried at a temperature of 12% by weight. Preferably, the heat treatment is carried out at a temperature below 6 〇C for 8 waves. Preferably, the Shixi-Titanium adhesive is further coated by a spin coating method, coated on a moon-concentrated substrate and used to bake the substrate to obtain a film, and y is heat-treated to obtain one or two. Cerium oxide-titanium dioxide ceramic film. Preferably, the step of repeatedly applying spin coating and baking the substrate yields a film having a plurality of layers having a desired thickness. Specific efficacies that can be achieved by the present invention include: 1. The present invention utilizes a sol-gel method to prepare a material containing bismuth and titanium, and the film prepared by using the optical material contains amorphous cerium oxide. The microstructure of the film is kept amorphous, which can keep the surface of the film flat, reduce optical loss and improve the light transmittance of the film. 2. The invention utilizes acetamidine acetone as the titanium isopropoxide solution, and the solution of the titanium-isopropoxytitanium solution in the absence of hydrazine can avoid the absorption of moisture by the titanium isopropoxide and the hydrolysis does not occur. Uniform precipitates, which in turn prevent the optical properties of the final preparation of the thin crucible from being affected by uneven deposits. 3. The present invention utilizes optimized f-conditions to prepare a thin film having better film formation and to prevent cracking of the film. [Embodiment] A specific embodiment of the present invention comprises the steps of: providing a tetraethoxy hydrazine solution: the tetraethoxy hydrazine solution can be obtained by uniformly dispersing tetraethoxy hydrazine into an ethanol solvent;