1240711 九、發明說明： 相關申請： 本發明申請是在2002年5月29日提出申請發明名稱為1240711 IX. Description of the invention: Related applications: The application for this invention was filed on May 29, 2002. The name of the invention is
Fused Silica Containing Aluminum，’之美國第 i〇/i58,68 8 5虎專利申請案，為2001年12月21日提出申請發明名稱為”Fused Silica Containing Aluminum, ’US Patent No. i0 / i58,68 8 5 Tiger patent application, the application for the invention title was filed on December 21, 2001"
Fused Silica Containing Aluminum”之美國第 i〇/〇34,97 1號專利申請案的延續部份。 、 ’ 【發明所屬之技術領域】 本發明是關於熔融矽石物體和光學組件。更詳細地說 ，本發明是關於使用在垂直於光軸的方向顯現出改良之折 射率均勻性的炼融石夕石，及溶融石夕石所製造出光學组件。 【先前4支彳标】 β "$在商業上，熔融石夕石光學組件，例如透鏡，棱鏡，濾波器 ，光學遮罩，反射器，基準板和視窗，通常是由在大型製造高 溫爐中所形成的大塊熔融矽石來製造。在大型製造高溫爐 中所製造出的大塊熔融矽石，在業界稱為人造玉石或鑄塊 ° 造玉石或禱塊切割出來，而完工的光學組件 則是利用一些製造步驟從玻璃毛胚來製造出，這些步驟包 括··但並非限制性之切割，磨光，和/或塗覆毛胚製造出玻璃 片。這些光學組件使用在各種儀器中，這些儀器在它們的 ^用b環境中會被曝露到波長大約360毫微米或更小的高能 量紫外光中，例如激元雷射光束或一些其他的高能量紫外 線f射光束。這些組件被合併到各種儀器中，包括用來製 ，南度積體電路的平版印刷術雷射曝光儀器，雷射製造儀 為，醫療為具，核溶合儀器，或其他一些使用高能量紫外線 雷射光束的儀器。 概括來看，人造玉石是經由在火焰中反應含石夕氣體分 子以形成矽石粉塵粒子來製造。這些粉塵粒子被沉積在旋 轉或振動物體的熱表面上，在那裡它們固化成玻璃狀的固 1240711 ，或二理 里所形成的任何含铜》° f溫射按程序來製造。從這類人造玉石中可造 造之透鏡树的主要光軸，通常也平^ 的光脈衝速率增加時與這些雷射-起使用 增加雷射輻射中。在這類以雷射為主 所‘致知壞的抵抗性。 田身=衧已經進展到短波長，高能量的紫外線頻譜範 圍，w成了由雷射所產生光學頻率的增加(波長降低）。特 別令人感興躺是在料線和深料線波長細運作的短 波長激元雷射包括在大約193級絲248級米波長下運 2的雷射。激元雷射系統在微平版印刷術應用中很普遍， 縮短的波長可以增加積體電路和微晶片製造中的線密度，’ 4吏我們可造料*減小零件尺柏H纟於制固各別 光子具有較高的能量，因此較短波長(較高頻率)所造成的 直接物理效應為在光束中具有較高的光子能量。在這類激 元雷射系統中，熔融石夕石光學器物會長期地曝露到高能量 光子照射量，因而導致這些光學組件之光學特性的衰退。 大家都知道，由雷射誘發的衰退會降低光的透射值，改 變折射率，改變密度，以及增加玻璃的吸收值，因而很不利 1240711 地影響炫辦石絲、崎的魏。這料來，有很多方法 !ff提出以改良熔融矽石玻璃對光學損壞的抵抗力。二 ίΐίί 方法，例如火焰水解，化學汽相沉積-粉塵 雜'^體辨汽概贼理，^姑體粉末的 包、谷融，和其他方法，所配製高純度熔融矽石都容易受到不 同程度的雷射損壞。 个 、ς、中種用來降低玻璃之吸收值和改良透身士率的已知 方法是降低例如鈉，鋁和鐵金屬的總金屬雜質含量。過去 ^公司所製造並販售的溶融石夕石玻璃，其紹雜質高到一 t之/Μ50 PPW，納含量高到100 PPb，而在193毫微米下 射率不超過99·4%/公分。一種降低玻璃中金屬雜 貝^已知方_關於使用鹵素氣體以處理熔融矽石製造高 溫爐中所使用的耐火材料。對於此方法的進一步細節描 國第6,174, 509號專利中。另一種改良炫融石夕石光學 透射率和耐久性的已知方法，在美國第6,174,謂號 專利中提出，其中說明在100(rc下將石夕石玻璃組件退火1〇 或更多個小時使得該組件的氫含量小於或等於5 X 1〇18分 ^立方公分。雖然在美國第6, m，調號專利中的方法是 ^的、因為所產生的光學組件具有優良的特性，但是此退 火處理花費相當多的時間和費用以在形成人造玉石之後製 造這類組件。 e •溶融石夕石組件亦能夠顯現出短暫吸收。如目Charlene mith，Nicholas Borrelli 和 R0ger Araujo 之，，Transient absorption in excimer-exposed silica,M Applied Optics，Vol· 39, Να 31，5778-5784(N〇v· 1，漏)所 描述的短暫吸收可取㊉獅4此處將它合併進來作 ，芩考文件：在-娜式中，當玻璃被重新曝露到光線，而 照射源2快被除去而再次變暗時，玻璃在紫外線範圍的透 射會恢復。在第二種形式中，吸收發生在玻璃最初照射時， 1240711 而且此吸收會隨著光學組件的不斷照射而降低。這類短暫 吸收在這裡稱為"吸收尖峰，，。此吸收尖峰會產生問題，因 ，為了避免吸收改變在光學組件中造成不想要的影響，光 學儀器例如步進透鏡機器製造者必須將這些光學組件曝露 於足夠數目的脈衝以便，，越過”此吸收尖峰，而降低到此吸 f收值。該曝露處理需要光學儀器製造者花費時間和資源以 ”越過”此吸收尖峰以便將吸收降低到可接受的數值。 我們需要提供熔融矽石玻璃物體，可以顯現改良的透 射率和降低的吸收尖峰。此外，我們需要提供炫融砍石玻 璃物體，可顯現出改良的偏離中心轴折射率均勻性。如果 我們可以提供這樣的熔融矽石玻璃物體，而不需要在形成 =來製造溶融矽石光學組件的玻璃人造玉石或毛胚之後， 還必須採取昂貴且耗時的處理例如退火或長期昭， 那將是有益的。 ' ’ 【發明内容】 一本發明是關於熔融矽石玻璃物體。這裡所使用的"熔 融石夕石玻璃物體”-詞，包含了在高溫爐中所製造的人造玉 石或大塊熔融矽石，從人造玉石切割出來的毛胚,以及從 融矽石毛精製融料絲赠。縣碎石 的ΐϊ可能牽涉到完工步驟，包括，但是不局_對溶 融矽石玻璃塊的切割，研磨，磨光和/或塗層。 滅贈發明的一個實施例，熔融矽‘ 30； f 先子相衷具有同抵抗力。在本發明的一個實施例 #明的熔融石夕石玻璃物體至少包含約50ppb而; 宅^的波長下’具有99. 5V公分的最小内部透射 -個貫施例中，鋁被摻雜到熔融矽石玻璃物體 d 一實施例，在光學組件中的鋁含量大於丨 x康另 實施例中，鋁的料在大約200和侧_之^在另一個 頁 第 1240711 在其他實施例中，在193毫微米波長下，玻璃物體的最 小内部透射率大於或等於99· 65%/公分。在某些實施例中， 玻璃物體在193 *微米的;^長下具有大於或等於⑽· 公 分的最小内部透射率。 跟含鋁量小於50 ppb含量的熔融矽石物體作比較，本 發明的、丨谷融石夕石物體也顯現出降低的吸收改變。當使用照 射量至少大約0· 97减/平方公分/脈衝的ι93毫微米雷射 來照射時，根據目前發明的熔融矽石物體顯現出小於大約 0· 0006/公分(基數1〇)的吸收改變。在一個優先實施例中 ，當使用照射量至少大約〇· 97毫焦/平方公分/脈衝的193毫 微米雷射來照射時，本發明的熔融石夕石物麵現出小於大 約0·麵5/公分(基數1())的吸收改變。在一個優先實施例 s使用知射1至少大約〇· 97毫焦/平方公分/脈衝的193 毫微米雷射來照射時，玻璃物體顯現出小於大 分(基數10)的吸收改變。 · 所提供的熔融石夕石物體包含财大 致上垂直於光軸的方向在至少5〇毫米而大到1〇〇毫米的深 度上顯現出折射率改變小於大約〇 〇5卿(百萬分之幾v 毫米。其他實施例所提供的熔融矽石物體在大致上垂直於 光軸的方向在至少大棚絲的深度上顯現出折射率改變 小於大約〇· 18 _/絲，優先地在至少 ^ 1〇〇毫米的深度上小於〇· 15 ppm/亳米。笔木而大到 =明的熔融矽石物體可以製造出顯現較低吸收值的 用在光刻儀器中。跟先前技術的熔融矽石物 項要優點將會在底下的詳細描述中=必 上白，疋，别面的"^描述和底下的詳細描述都只是 "ίίϊίίί料本發财料纖_純—步說明。 第 9 頁 1240711 ㈣ΐίΐ本發明的幾個實施例之前，我們要先了解本發 伽ϊίϊί底下描述所說鴨結構或處理步驟細節。本 有，、他實施例，並且可以用*同的方式加以操作 ^本發明所提供的熔融石夕石物體具有改良的特性例 ί透H，和7娜低的敵賴，以及/或偏轴折射率均勻 物體包含人造玉石，從人造玉石切 ^出，毛胚，以及從熔融矽石毛胚切割並處理的修飾光 学組件0 這些熔融矽石物體可以由熔融矽石人造玉石處理來製 造。在典型的炫融石夕石人造玉石處理中，使用一個處理氣、 f列如氮以作為運載氣體，並且加入氮氣分流以避免墓氣 流的飽和。此蒸氣反應物經由分佈構件傳送到反應位址 在那裡有多侧燒H位於高_冠_近。此反應物在燃 燒讀燃料^^混合物結合，並且社於17霞的玻璃溫 度下燃燒並氧化。在某些實施例中，鋁被引進此反應物流 中，使得由此高溫爐所產生之人造玉石的鋁含量大於通常 存在於人造玉石中的雜質含量。在物體中含有鋁的一些實 施例中，人造玉石中所存在的鋁含量優先地大於約50ρ&而 小於lOOOppb，優先地是鋁含量大於大約1〇〇{)1)1);在某些優 先貝施例中加入人造玉石中的鋁含量在大約2〇〇和4〇〇ppb 之間。用來將I呂引進此反應物流中的較好方法和儀器，由 William Peters, Daniel Serapolinski, Merrill Sproul 和Michael Wasilewski 發明，發明名稱為”Meth〇d andFused Silica Containing Aluminum ", a continuation of US Patent Application No. 0 / 〇34,97 1." Technical Field to which the Invention belongs "The present invention relates to fused silica objects and optical components. More specifically The present invention relates to an optical component manufactured by using a fused smelting stone that exhibits improved refractive index uniformity in a direction perpendicular to the optical axis, and a fused smelting stone. [Previously 4 targets] β " $ Commercially, fused lithospar optical components, such as lenses, prisms, filters, optical masks, reflectors, reference plates, and windows, are usually manufactured from large pieces of fused silica formed in large manufacturing high-temperature furnaces. Large pieces of fused silica produced in large-scale manufacturing high-temperature furnaces are known in the industry as artificial jade or ingots, and jade or prayer blocks are cut out, while the finished optical components are made from glass blanks using some manufacturing steps To manufacture, these steps include, but are not limited to, cutting, polishing, and / or coating blanks to produce glass sheets. These optical components are used in a variety of instruments, which are used in Their applications are exposed to high-energy ultraviolet light with a wavelength of about 360 nm or less, such as an excimer laser beam or some other high-energy ultraviolet f-ray beam. These components are incorporated into various instruments Includes lithography laser exposure equipment used to make and store integrated circuits, laser manufacturing equipment, medical equipment, nuclear fusion equipment, or other equipment that uses high-energy ultraviolet laser beams. It seems that artificial jade is made by reacting stone-containing gas molecules in a flame to form silica dust particles. These dust particles are deposited on the hot surface of a rotating or vibrating object, where they solidify into a glass-like solid 1240711 , Or any copper-containing thermal radiation formed in Erli according to the procedure. The main optical axis of the lens tree that can be made from this kind of artificial jade is usually also the same when the light pulse rate increases. The use of lasers to increase laser radiation. In this type of laser, the main cause is poor resistance. Tianshen = 衧 has progressed to short-wavelength, high-energy ultraviolet spectrum. , W becomes the increase (wavelength reduction) of the optical frequency generated by the laser. Particularly interesting is the short-wavelength excimer laser that operates finely on the material line and the deep material line. Lasers with a wavelength of 2. The excimer laser system is very common in microlithography applications. Shortened wavelengths can increase the line density in integrated circuit and microchip manufacturing. '4 We can make materials * reduce The part Hinoki H 纟 has a higher energy for fixing individual photons, so the direct physical effect caused by shorter wavelengths (higher frequencies) is to have higher photon energy in the beam. In this type of exciton laser In the system, fused lithospar optics will be exposed to high-energy photon exposure for a long period of time, resulting in the degradation of the optical characteristics of these optical components. As we all know, the laser-induced degradation will reduce the light transmission value and change the refraction. Rate, change the density, and increase the absorption value of glass, which is very unfavorable to 1240711 and affect the Wei of Hyunban Shisi and Qi. As a result, there are many ways to improve the resistance of fused silica glass to optical damage. Second, the methods such as flame hydrolysis, chemical vapor deposition-dust mixtures, etc. can be used to distinguish the steam, the powder and the glutinous silica, and other methods. The prepared high-purity fused silica is susceptible to varying degrees. Laser damage. The known method for reducing the absorption value of glass and improving the penetration rate is to reduce the total metal impurity content of metals such as sodium, aluminum and iron. In the past, the molten stone syrup glass manufactured and sold by the company has impurities as high as one t / M50 PPW and nano-content as high as 100 PPb, and the emissivity at 193 nm does not exceed 99.4% / cm. . A method of reducing metal impurities in glass ^ Known methods_About the use of halogen gas to treat fused silica to manufacture refractory materials used in high temperature furnaces. Further details of this method are described in US Patent No. 6,174,509. Another known method for improving the optical transmittance and durability of Xuan Rong Xishi Stone is proposed in U.S. Patent No. 6,174, which states that the Si Xishi glass component is annealed by 10 or more at 100 (rc) Hours make the hydrogen content of the module less than or equal to 5 X 1018 centimeters ^ cubic centimeters. Although the method in the US patent No. 6, m, No. is ^, because the resulting optical module has excellent characteristics, but This annealing process takes a considerable amount of time and expense to manufacture such components after the formation of artificial jade. E • Molten stone evening stone components can also exhibit transient absorption. See Charlene mith, Nicholas Borrelli and Roger Araujo, Transient absorption The short-term absorption described in excimer-exposed silica, M Applied Optics, Vol. 39, Να 31, 5778-5784 (Nov. 1, omission) is desirable. The Lion 4 incorporates it here, and considers the document: In the -na mode, when the glass is re-exposed to light, and the illumination source 2 is quickly removed and darkened again, the transmission of the glass in the ultraviolet range is restored. In the second form, absorption occurs in the glass During the initial exposure, 1240711 and this absorption will decrease with the continuous exposure of the optical component. This type of short-term absorption is referred to as " absorption spikes. This absorption spike can cause problems because, in order to avoid absorption changes in the optical components To cause undesired effects, manufacturers of optical instruments such as step-lens machines must expose these optical components to a sufficient number of pulses in order to "pass" this absorption spike and reduce it to this absorption f. The exposure process requires optics Instrument makers spend time and resources to "pass" this absorption spike in order to reduce absorption to acceptable values. We need to provide fused silica glass objects that can show improved transmission and reduced absorption spikes. Additionally, we need to provide Dazzling fused stone glass objects can show improved refractive index uniformity off the central axis. If we can provide such fused silica glass objects without the need to form = to manufacture glass artificial jade of molten silica optical components or After the blanks, expensive and time-consuming treatments such as annealing or Zhao Zhao, that would be beneficial. '[Summary of the Invention] An invention relates to fused silica glass objects. The term "fused fused stone glass objects" as used herein includes words made in high temperature furnaces. Artificial jade or large piece of fused silica, rough cut from artificial jade, and refined silk made from fused silica wool. The county's rubble may involve completion steps, including, but not limited to fused melt silicon Cutting, grinding, polishing and / or coating of stone glass blocks. One embodiment of the invention, fused silicon '30; f. In one embodiment of the present invention #the molten fused stone glass object contains at least about 50 ppb; at the wavelength of the house 'has a minimum internal transmission of 99.5 V cm-in one embodiment, aluminum is doped to the molten In one embodiment, the silica glass object d has an aluminum content greater than that in the optical component. In another embodiment, the aluminum material is about 200 and the side ^ on another page 1240711 in other embodiments, 193 At the nanometer wavelength, the minimum internal transmittance of glass objects is greater than or equal to 99.65% / cm. In some embodiments, the glass object has a minimum internal transmittance greater than or equal to ⑽ · cm at a length of 193 mm. Compared to fused silica objects having an aluminum content of less than 50 ppb, the present invention's fused lava stone spar objects also exhibit reduced absorption changes. When irradiated with a ι93 nm laser having an irradiation amount of at least about 0.97 min / cm² / pulse, a fused silica object according to the present invention exhibits an absorption change of less than about 0.000006 / cm (base 10). . In a preferred embodiment, when irradiated with a 193 nm laser with an irradiation amount of at least about 0.997 mJ / cm² / pulse, the fused stone surface of the present invention appears to be less than about 0 · 5 / Cm (base 1 ()) absorption changes. In a preferred embodiment s irradiated with a 193 nm laser with at least about 0.997 mJ / cm2 / pulse, the glass object exhibits an absorption change of less than a fraction (base 10). Provided fused lithospheric stone objects containing a direction substantially perpendicular to the optical axis exhibiting a refractive index change of less than about 0.05 mm (parts per million) at a depth of at least 50 mm and as large as 100 mm A few v millimeters. Fused silica objects provided by other embodiments exhibit a refractive index change of less than about 0. 18 _ / filament at a depth of at least the greenhouse filament in a direction substantially perpendicular to the optical axis, preferably at least ^ 1 The depth of 0.00 mm is less than 0.15 ppm / mm. The fused silica objects as large as = bright can be used in lithography equipment with lower absorption values. Compared with the prior art fused silica The key advantages of the item will be in the detailed description below = must be white, 疋, the other "" ^ description and the detailed description below are just " ίίϊίί 料 本 发财 料 纤 _pure-step description. 9 Page 1240711 Before several embodiments of the present invention, we must first understand the details of the duck structure or processing steps described in the following description. There are, and other embodiments, and can be operated in the same way. Invention Examples of fused fused stone objects have improved properties, such as low H, and low-lying adversity, and / or objects with a uniform off-axis refractive index that include artificial jade, cut from artificial jade, hair embryos, and from molten silicon. Modified optical components cut and processed by stone roughs 0 These fused silica objects can be manufactured from fused silica artificial jade processing. In a typical dazzling fused fused stone jade artificial jade processing, a processing gas, column f, such as nitrogen, is used as Carry gas, and add nitrogen to divert to avoid saturation of the grave stream. This vapor reactant is transmitted to the reaction site via the distribution member where there is multi-sided burning H located near the high_crown_. This reactant is burned to read the fuel ^^ mixture Combined, and burned and oxidized at a glass temperature of 17 Xia. In some embodiments, aluminum is introduced into the reaction stream such that the artificial jade produced by the high temperature furnace has an aluminum content greater than that normally found in artificial jade. Content of impurities. In some embodiments where the object contains aluminum, the aluminum content present in the artificial jade is preferably greater than about 50ρ & and less than 1000ppb, preferably Content greater than about 1〇〇 {) 1) 1); artificial jade added aluminum content in certain embodiments of the shellfish priority between about 2〇〇 and 4〇〇ppb. A better method and instrument for introducing I Lu into this reaction stream, invented by William Peters, Daniel Serapolinski, Merrill Sproul and Michael Wasilewski, and the invention name is "Meth〇d and
Apparatus for Adding Metals to Fused Silica，，，的本 公司相關申請之美國專利申請案中提出。然而，要了解的 是，本發明並不局限於將銘加入熔融；s夕石物體的特定方法 或儀恭，其他方法和儀器也可以使用。此外，本發明並不局 限於經由反應物流將紹加入溶融秒石中，在一此實施例中 第10 頁 1240711 也可以使用製造過程的其他方式將鋁加入到熔融石夕石物體 中。例如，我們可以在熔融石夕石製造高溫爐中使用包含高 鋁雜質的耐火材料將鋁加入到熔融石夕石物體中，因為如此 2乍可以在製造處理期間將鋁擴散到熔融石夕石物體中。繼續 說明人造玉石的製造過程，包含鋁的高純度金屬氧化物粉 ^以及由乡個燃燒n所產生的熱氣被向下將經過财火的 高溫爐冠，細齡紅淑齡触絲s，例如引取桿 材料上，並且固化成一團玻璃。Apparatus for Adding Metals to Fused Silica ,,, is filed in a US patent application related to this company. It is to be understood, however, that the present invention is not limited to the incorporation of inscriptions; specific methods or ceremonies of stone objects, other methods and instruments may be used. In addition, the present invention is not limited to the addition of Shao to the molten second stone via the reaction stream. In this embodiment, 1240711 can also use other methods of manufacturing process to add aluminum to the fused stone. For example, we can use a refractory material containing high alumina impurities to add aluminum to a molten stone stone object in a high-temperature furnace for the production of molten stone stone, because in this way, aluminum can be diffused into the molten stone stone object during the manufacturing process. in. Continue to explain the manufacturing process of artificial jade, high-purity metal oxide powder containing aluminum ^ and the heat generated by the burning of the township n will be passed down the high-temperature furnace crown of the fire, and the fine red silk will be The rod material is pulled out and cured into a ball of glass.
二在本發明特別有效的實施例中，對雷射損壞具有高抵 抗力的光學物體，是由底下的步驟來形成·· a) 製造-種碰流，其巾包含蒸氣形朗姆化合物，可以 經由氧化或火焰水解的熱分解而轉變成矽石； b) 將鋁加入此氣體流中； ’ c) 將此氣體流傳送到燃;燒器的火焰+以形成包含銘的非晶 質熔融矽石粒子； d) 將這些非晶質粒子沉積到支架上;以及 e) 將此非晶質粒子的沉積固化成透明的玻璃物體。Secondly, in a particularly effective embodiment of the present invention, an optical object having high resistance to laser damage is formed by the following steps ... a) Manufacturing-a kind of impinging stream whose towel contains a vapor-shaped rum compound, which can Transformed into silica by thermal decomposition through oxidation or flame hydrolysis; b) adding aluminum to this gas stream; 'c) transmitting this gas stream to a burner; the flame of a burner + to form amorphous molten silicon with an inscription Stone particles; d) depositing the amorphous particles on the support; and e) solidifying the deposition of the amorphous particles into a transparent glass object.
用來形成玻璃人造玉石的有用含石夕化合物，優先地包 2何無的環石夕氧燒化合物，例如多甲基石夕氧烧， = f基環魏烧，以及它們的混合。特 田1的多=基環魏烧例子，包括八甲基環四石夕氧烧，十 土％五矽氧烷，六甲基環三石夕氧烧，以及它們的混合物。 人札在本發明特別有用的方法中，無鹵化物賴石夕氧烧化 二，例如八甲基環四矽氧烷(〇MCTS)，化學式為 彳1〇(CH3)2]4 一，被用來作為熔融矽石人造玉石處理的 者使用在汽相沉積處理中，例如用來製造光學波導 應用的1%純度熔融石夕石。 品業上，人造玉石的直徑在五英叹(1 · 5公尺)的等髮 ，旱又在5’英忖(13—25公分)或更大等級，可以使用围 第11 頁 1240711 所示的高溫爐類型來製造。簡要_括來 14^1^ 14產生料粉塵收集在收絲φ 24上以形成人造^石、 ，士I上面Γ斤描 1 述的，人造玉石19的直徑通常在五英口尺的大 /、。對於這類咼溫爐之結構和運作的進一步細4 f公司細美國第5, 951，730號專利中發現，、此處將它的全 糊容合併絲作為參考文件。對於用來製 造玉石之燃燒器構造_細細節，可以在本公司 第W0 00/17115號專利案中發現。不^相關町之 我們很驚奇地發現到含鋁量大於正常紹雜質 解石夕石物體大大改良了這些組件的幾種特性。通常融 石夕〒物體包含的總金屬雜質小於則触。這些金屬雜 通常包括鹼，鹼土，鐵，錯，鈦和銅。在由本公司所黎业 型熔融石夕石物體中金屬雜質，例如鈉和鐵，都小於& 而銘雜質值則小於20 ppb。然而，在過去由本公司所製造 的熔融石夕石物體含有較高的雜質含量。例如，由本公^所 製之溶融矽石物體的鋁雜質高到5〇 ppb，而其他金屬雜 也比目刖製造的含量還高(例如，納含量高到1〇〇卯b)，使 得熔融矽石物體在193毫微米下的内部透射率不超過’99 4% /公分。然而，根據本發明的一個實施例，在熔融石夕石物體〇 中所包含的鋁含量超過正常的雜質含量，而其他金屬雜質 則維持在目前的較低含量。在一個實施例中，組件中的鋁 含量大於約50 ppb。在優先實施例中，存在本發明中的鋁 超過大約100 ppb。在高度優先的實施例中，銘含量約在 200 ppb 和 600 ppb 之間。 提供紹含量較高之溶融矽石物體的能力，使得製造過 程幸交不需要嚴格的測量以控制用來製造這些玻璃物體之高 溫爐中的銘雜質含量。因此，此製造過程對於高溫爐耐^ 材料的品質，和用來製造炫融石夕石物體的化學先驅物質，就 第12 頁 1240711 更加有彈性和更自動化。而ί火材料或化學先驅物質的改變 可以造成較低的成本，並且/或者改良高溫爐的效能，而不 需要降低光學特性。然而，優先地冑可能地使用具有最高 純度之耐火材料的溶融；5夕石製造高溫爐以避免其他不想要 的金屬污染，例如鐵和鈉。在本發明的優先實施例中，高溫 爐的耐火材料應該包含小於2 ppm的鈉，和小於5 ppm的鐵 以便增加ArF透射性。含有低雜質含量的耐火材料可以利 用美國第6,174, _號專利編號中所提出的_素氣體處理 過程而獲得。 用來製造本發明之光學組件的熔融矽石光學人造玉石 ，可以^用含氯或不含氯的化學先驅物質來產生。然而，使 用不含氯的先驅物質是比較有利的，因為所產生的低氣玻 璃可以保持較高的金屬濃度，而不會損失紫外線透射率。 在本發明另一個實施例中，我們發現在人造玉石製造 處理期間將紹加入溶融石夕石玻璃中，並且在製造之後慢慢 此人造玉石可以製造出具有特別良好之ArF透射性，和 損壞抵抗性的熔融矽石玻璃。根據傳統的熔融石夕石人造玉 石製造過程，人造玉石在小於3〇分鐘内從大約185〇。〇的溫 度冷卻到ll〇〇°C。然而，根據本發明實施例包含在人造玉 石製造過程期間所加入之添加鋁的溶融石夕石人造玉石在大 約5小時或更長的時間内從大約185(rc的溫度被冷大 約 1100°c 。 對於未照射的熔融石夕石，内部透射率是使用適當的紫 外線分光光度計(例如，Hitachi U4001)，對光學磨光試樣 進行測定二内部透射率(Ti)是由穿過此試樣所測得的透射 率，除以由這個試樣表面反射所決定的理論透射率，然後對 10毫米路徑長度標準化而測定出。根據本發明所製造的熔 融石夕石組件，使用193宅微米輪射照射的最小内部透射率超 過99· 5V公分，而有一些玻璃超過99· 65%/公分和99. 750/〇/ 第13 頁 1240711 f 2,射辭了麵含量在祕1G ppb範園内 卿石物體的透射率，相對於包含接近㈣ %/公分為im體!^卿崎® °y滅表透射率以 2所示輛代表此物體中所包含的氫含量。如圖 y、’匕έ 300ppb|呂和2χΐ〇17/立方公分奇的校 件顯現超過99 80V八八μ μκ、采^A勺合同电夕石物 氫含量之夫伽2 透射率，比触來包含相似 ^公分。“貝、谷融石夕石物體的數值通常大約是99. 75% 以接ΪΓίΙ物體中的吸收改變是使用編Hz純雷射 件以i行::、T良好之ArF平版印刷術系統中的曝光條 土且f許試樣在短時間内曝露到大量的脈 在垂直的的技術’此曝露和測量系統是安裝 ，3顯示了照射大約一百萬個脈衝之兩個熔融石夕石樣 收改_量。彳_統包含2 6 X 101?/立方 ^和小於10 _之低含量鋁的熔融矽石試樣，使用照 $ ，毫焦/平*公分/脈衝的ArF雷射來照射。此試樣 f 光a寺顯示出-個吸收尖峰，同時此試樣所顯現的 吸收改變超過〇. _7/公分(基數1〇)。此吸收尖峰是在最 初的100, 000個脈衝期間所觀察到的。第二個試樣是包含 =獅ppb _，和h 73 xl(f/立方公分氣的炫融石夕石 衰。此试樣是使用照射量〇. 97亳焦/平方公分/脈衝的 ，田射來知、射。跟含鋁量低的試樣作比較，此試樣大體上 /又有顯現吸收尖峰。特別地，其吸變小於大制.〇謝/ 公分(基數10)，對未摻雜質試樣所觀察到的吸收尖峰來說， 這是顯著的降低。 ’ 此外，對圖3的觀察也指出含鋁的試樣在照射之後，幾 乎立即顯現所導致之透射。此所導致透 是低於最初吸收值的一個負魏值。在圖3中的圖形上， 1240711 以log基數10所表示的吸收改變值，可以使用公式 (10(=收改變）-1) X 100% =所導致吸收(%/公分)，將 它轉變成所導致透射率改變。因此，在受到照射〇· 97毫焦/ 平方公分/脈衝的ArF雷射，照射小於大約25, 〇〇〇個脈衝之 後，吸Q收改變大約是-〇· 0001/公分(基數10)，相當於大約 〇· 023%/公分的所導致透射率。在照射大約40, 〇〇〇個脈衝 之後，Q吸收改變大約是-〇· 0004/公分(基數10)，相當於大約 〇·09既/公分的所導致透射率。在照射大約1，000, 000個脈 衝之後，吸收改變大約是—〇· 0005/公分(基數1〇)，相當於大 約0· 12%/公分的所導致透射率。 厂根據本發明的某些實施例所提供的熔融石夕石物體相對 於試樣厚度(平行於光軸)的偏軸(也就是，大致上垂直於光 軸的方向)均勻性已經有所改良。在優先實施例中，所顯現 改^之偏軸均勻性的物體所包含的鋁含量大於正常的雜質 含置。在某些實施例中，存在熔融石夕石物體中的鋁含量小 =大約lOOOppb，但是大於50 ppb，而在某些優先實施例中 試樣中的，含量在大約2〇〇 ppb和600 ppb之間。 i，4是關於包含所示之鋁含量的試樣顯示以百萬分之 或為單位^相對折射率相對於離試樣頂端之距離的關係圖 二圖中的資料是在平行於光軸的各種深度上，測量垂直於 光軸之方向的折射率改變產生。其中一個試樣不包含添 力！7鋁^自石夕石製造過程，標記ppb的鋁λ在大約丨2〇毫 ，的沬度上，其折射率改變大約是〇· 19 ppm/毫米。第二個 #樣包含大約2GG ppb的添加銘，在大約毫米的深度或 厚度上，其折射率改變大約是〇 〇5 ppm/毫米。第三個試樣 包含大約500 ppb的添加鋁在大約12〇毫米的深度上，其折 射，改變大約是〇· 〇5 ppm/絲。圖4 _出，包含添加銘 的试樣在大約1〇〇毫米的深度或厚度上，其折射率改變小於 大約0· 18ppm/毫米。 第15 頁 1240711 根據本發明的某些實施例所提供的光學組件相對於跟 光軸平行的試樣厚度所顯現出的偏軸折射率截面”比較平 坦換句話說，其相對於跟光軸平行之厚度的偏軸折射率 改變小於不包含添加鋁的試樣。一個平坦的折射率截面對 製造較厚的光學元件來說特別需要。改良偏軸的折射率梯 度I以增加製造良率和選擇率，特別是對厚的部分。有其 他嘗試解決偏軸折射率均勻性的方法被研究。控制熔融石夕 石之0H的嘗試並不成功，而且很困難。控制玻璃中納含量 的嘗試，則對其他的金屬特性造成了負面的影響。 根據本發明的某些實施例，所提供的熔融矽石玻璃物 件在大致上垂直於光軸的方向，在至少5〇毫米的深度上(在 一些實施例中超過1〇〇毫米的深度)所顯現的折射率改變小 於大約0· 05 ppm/毫米。在其他實施例中，所提供的熔融矽 石物體包含添加鋁，在大致上垂直於光軸的方向，在至少 100毫米的深度上(在一些實施例中，超過1〇〇毫米的深度） 所顯現的折射折射率改變小於大約〇· 18 ppm/毫米。在某 些優先實施例中所提供的熔融矽石玻璃物體在大致上垂直 於光軸的方向，在至少5〇毫米的深度上(在一些實施例中超 過100毫米的深度)所顯現的折射率改變小於大約0· 15 ppm /¾米。在一些實施例中，所提供的熔融石夕石玻璃物體在大 致上垂直於光軸的方向，在至少5〇毫米的深度上(在一些實 施例中超過1〇〇毫米的深度)所顯現的折射率改變小於大約 0· 10 ppm/毫米。 那些熟悉此技術的人將了解對於本發明可以作各種修 改，但是都不脫離本發明的精神或範圍。因此，我們可以說 ，本發明涵蓋了對本發明的修改和變動，只要它們在附加申 凊專利範圍及其同等物的範圍内。 【圖式簡單說明】 第一圖（圖1)是根據本發明製造熔融矽石光學物體之 第 16 頁 1240711 高溫爐的示意圖； 第二圖（圖2)是使用193毫微米的雷射以照射包含增加 I呂含量的炫融石夕石物體和先前技術的熔融石夕石光學組件所 顯示透射率的比較圖； 、心^三圖（圖3)是先前技術之熔融石夕石物體和含鋁量超 k ^ppb之熔融矽石光學物體的吸收變化比 本所情不含_試_必 t’、員7在垂直於光軸方向所測得的折射率變化盘相對溶 融矽石物體之深度的關係圖。™半夂化與娜合 附圖元件符號說明： 19;收集表面24;高溫 冠部12;燃燒器14;人造玉石 爐室26;高溫爐ι00。Useful stone-containing compounds for the formation of glass artificial jade include preferentially cyclic stone compounds, such as polymethyl stone compounds, f-based ring compounds, and mixtures thereof. Examples of poly-based radicals in special field 1 include octamethylcyclotetralithium oxalate, octadecane% pentasiloxane, hexamethylcyclotrilithium oxalate, and mixtures thereof. Renzha In a particularly useful method of the present invention, halide-free lysin oxide is used to burn dioxin, such as octamethylcyclotetrasiloxane (OMCTS), with the chemical formula 彳 10 (CH3) 2] 4, which is used Those who come to process fused silica artificial jade are used in vapor deposition processes, such as 1% fused fused stone used to make optical waveguide applications. In the industry, the diameter of the artificial jade is equal to five sighs (1.5 meters), and the drought is at the level of 5'yings (13-25 cm) or more. You can use the page shown in 1240711 Type of high-temperature furnace. Briefly include the 14 ^ 1 ^ 14 produced material dust collected on the wire φ24 to form artificial stone, as described above, the diameter of artificial jade 19 is usually larger than that of a five-inch ruler. . For further details on the structure and operation of this type of warming furnace, it is found in US Patent No. 5,951,730, which is incorporated herein by reference for its full-blown incorporated wire. The details of the structure of the burner used to make jade can be found in our patent No. WO 00/17115. Not relevant. We were surprised to find that the aluminum content was greater than the normal impurities. The calcite stone object greatly improved several characteristics of these components. Generally, lava stone objects contain less than total metal impurities. These metal impurities usually include alkali, alkaline earth, iron, tungsten, titanium and copper. Metal impurities, such as sodium and iron, are less than & while impurity values are less than 20 ppb. However, in the past, fused stone stone objects manufactured by our company contained a high content of impurities. For example, the aluminum impurities in fused silica objects made by this company are as high as 50 ppb, and other metal impurities are higher than the content produced by mesh (for example, the sodium content is as high as 100 μb), which makes the molten The internal transmittance of silica objects at 193 nm does not exceed '99 4% / cm. However, according to an embodiment of the present invention, the content of aluminum contained in the fused spar stone object 0 exceeds the normal impurity content, while other metal impurities are maintained at the current lower content. In one embodiment, the aluminum content in the module is greater than about 50 ppb. In the preferred embodiment, there is more than about 100 ppb of aluminum in the present invention. In the highly preferred embodiment, the nominal content is between about 200 ppb and 600 ppb. The ability to provide fused silica objects with a high content allows the manufacturing process to be conducted without the need for rigorous measurements to control the content of impurities in the high temperature furnaces used to make these glass objects. Therefore, this manufacturing process is more flexible and more automated for the quality of refractory materials used in high-temperature furnaces and the chemical precursors used to make Xuan Rong Shi Xi stone objects. However, changes in flame materials or chemical precursors can result in lower costs and / or improve the performance of high-temperature furnaces without reducing optical characteristics. However, it is preferentially possible to use melting of refractory materials with the highest purity; Mayanite manufactures high-temperature furnaces to avoid other unwanted metal contamination such as iron and sodium. In a preferred embodiment of the present invention, the refractory material of the high-temperature furnace should contain less than 2 ppm of sodium and less than 5 ppm of iron in order to increase ArF transmission. Refractory materials with a low impurity content can be obtained by the use of the elementary gas treatment process proposed in U.S. Patent No. 6,174, _. The fused silica optical artificial jade used to manufacture the optical component of the present invention can be produced using chemical precursors containing or without chlorine. However, it is advantageous to use a chlorine-free precursor because the resulting low gas glass can maintain a higher metal concentration without losing UV transmission. In another embodiment of the present invention, we found that Shao was added to the fused stone evening glass during the manufacturing process of the artificial jade, and slowly after the manufacturing, the artificial jade can produce a particularly good ArF transmission and damage resistance. Fused silica glass. According to the traditional manufacturing process of fused stone sapphire artificial jade, the artificial jade starts from about 1850 in less than 30 minutes. The temperature was cooled to 100 ° C. However, the embodiment according to the present invention includes an aluminum-added fused stone evening stone artificial jade added during the artificial jade manufacturing process from about 185 ° C. to about 1100 ° C. for about 5 hours or more. For unirradiated fused sapphire, the internal transmittance is measured on an optically polished sample using a suitable UV spectrophotometer (for example, Hitachi U4001). The internal transmittance (Ti) is determined by passing through this sample. The measured transmittance is divided by the theoretical transmittance determined by the surface reflection of this sample, and then measured by normalizing the path length of 10 mm. The fused stone stone module manufactured according to the present invention is shot using a 193 μm wheel. The minimum internal transmittance of the irradiation is more than 99.5V cm, and some glasses exceed 96.55% / cm and 99.750 / 〇 / 1240711 f 2 on page 13. The surface content is reflected in the secret stone of 1G ppb Fan Yuan The transmittance of an object is relatively close to 包含% / cm2. The body transmittance is shown in Figure 2. The transmittance shown in Fig. 2 represents the hydrogen content contained in this object. As shown in Figure y, 300 ppb | 吕 和 2χΐ〇17 / 立The odd-centimeter schoolware shows a transmission rate of more than 99 80V, 88 μ μκ, ^ A scoop, and the hydrogen content of the contract electric stone, which is similar to the touch. ^ Cm. " The value is usually about 99.75% in order to change the absorption in a ΪΓΙ object by using a pure Hz laser with a line i ::, T in a good ArF lithography system exposure strip and f A large number of pulses were exposed during the vertical technology. 'This exposure and measurement system is installed. 3 shows the amount of two molten stone samples that were irradiated with about one million pulses. The amount of stone samples was changed. X 101? / Cubic ^ and a sample of fused silica with a low aluminum content of less than 10 _ are irradiated with an ArF laser according to $, millijoules / square * cm / pulse. This sample f light a temple shows- Absorption peaks, and the change in absorption exhibited by this sample exceeds _7 / cm (base 10). This absorption peak was observed during the first 100,000 pulses. The second sample contains = Lion ppb _, and h 73 xl (f / cubic centimeter of dazzling fused stone evening stone decay. This sample is used in the amount of exposure. 97 亳 焦/ Cm2 / pulse, compared with the sample with low aluminum content, compared with the sample with low aluminum content, this sample generally / again showed absorption peaks. In particular, its absorption change is less than the large system. 〇 谢 / In centimeters (base 10), this is a significant decrease for the absorption spikes observed for the undoped samples. In addition, the observation of Figure 3 also indicates that the aluminum-containing sample appears almost immediately after irradiation. The resulting transmission. The resulting transmission is a negative Wei value below the initial absorption value. On the graph in Figure 3, the 1240711 absorption change value represented by the log base 10 can be calculated using the formula (10 (= receive change) ) -1) X 100% = the resulting absorption (% / cm), which is converted to the resulting change in transmittance. Therefore, after irradiating an ArF laser of 0.997 mJ / cm2 / pulse and irradiating less than about 25,000 pulses, the change in Q absorption is about -0.01 / cm (base 10), which is equivalent. The resulting transmittance is about 0.023% / cm. After irradiating about 40,000 pulses, the Q absorption change is about -0.4000 / cm (base 10), which is equivalent to the resulting transmittance of about 0.09 / cm. After irradiating about 1,000,000 pulses, the absorption change is about -0.050 / cm (base 10), which is equivalent to the resulting transmittance of about 0.12% / cm. The uniformity of the off-axis (i.e., the direction substantially perpendicular to the optical axis) of the fused lava stone object provided by the factory according to some embodiments of the present invention with respect to the thickness of the sample (parallel to the optical axis) has been improved. . In the preferred embodiment, the off-axis uniformity exhibited by the object exhibits an aluminum content greater than the normal impurity content. In some embodiments, the aluminum content in the presence of molten stone is small = about 1000 ppb, but greater than 50 ppb, while in some preferred embodiments, the content in the sample is between about 200 ppb and 600 ppb. between. i, 4 is shown on the sample containing the aluminum content shown in parts per million or ^ The relationship between the relative refractive index and the distance from the top of the sample Figure 2 The data in the figure is parallel to the optical axis At various depths, changes in refractive index measured in a direction perpendicular to the optical axis occur. One of the samples does not include Timing! 7Aluminium ^ From the Shi Xishi manufacturing process, the aluminum lambda marked ppb has a refractive index change of about 0.19 ppm / mm at a degree of about 20 millimeters. The second #sample contains an inscription of about 2GG ppb, and its refractive index change is about 0.05 ppm / mm at a depth or thickness of about mm. The third sample contained approximately 500 ppb of added aluminum at a depth of approximately 120 mm, and its refraction changed by approximately 0.5 ppm / filament. Figure 4 shows that the refractive index change of the sample containing the added inscription is less than about 0.18 ppm / mm at a depth or thickness of about 100 mm. Page 1240711 According to some embodiments of the present invention, the optical component provided with an off-axis refractive index cross section relative to the thickness of the sample parallel to the optical axis is relatively flat, in other words, it is parallel to the optical axis The off-axis refractive index change of the thickness is smaller than that of the sample without the addition of aluminum. A flat refractive index cross section is particularly necessary for manufacturing thicker optical elements. The off-axis refractive index gradient I is improved to increase the manufacturing yield and Selectivity, especially for thick parts. There are other methods to try to solve the off-axis refractive index uniformity. Attempts to control the 0H of fused stone stone are unsuccessful and difficult. Attempts to control the sodium content in glass, It has a negative impact on other metal properties. According to some embodiments of the present invention, the fused silica glass object is provided in a direction substantially perpendicular to the optical axis, at a depth of at least 50 mm (in some Depth of refractive index exhibited by depths greater than 100 mm in the examples is less than about 0.05 ppm / mm. In other examples, the provided fused silica objects include The addition of aluminum, in a direction substantially perpendicular to the optical axis, at a depth of at least 100 millimeters (in some embodiments, a depth of more than 100 millimeters) exhibits a change in refractive index that is less than about 0.18 ppm / mm Refraction exhibited by fused silica glass objects provided in certain preferred embodiments, at a direction substantially perpendicular to the optical axis, at a depth of at least 50 mm (in some embodiments, a depth of more than 100 mm) The rate of change is less than about 0.15 ppm / ¾ meter. In some embodiments, the provided fused stone glass object is in a direction substantially perpendicular to the optical axis, at a depth of at least 50 mm (in some embodiments Depths in excess of 100 mm) exhibited changes in refractive index of less than about 0.1 ppm / mm. Those skilled in the art will appreciate that various modifications can be made to the invention without departing from the spirit or scope of the invention . Therefore, we can say that the present invention covers modifications and changes to the present invention, as long as they are within the scope of the additional patent application and its equivalent. [Simplified description of the drawings] First Figure (Figure 1) is a schematic diagram of the 1240711 high-temperature furnace for the manufacture of fused silica optical objects according to the present invention; Figure 2 (Figure 2) is the use of a 193 nm laser to illuminate the dazzling melt containing increased I A comparison chart of the transmittance displayed by the Shixi stone object and the prior art fused Shisi stone optical components; The three figures (Figure 3) are the melting of the Shisi stone object of the prior art and the aluminum content exceeding k ^ ppb. The absorption change of silica optical objects does not include the relationship between the refractive index change disks measured by the member 7 in a direction perpendicular to the optical axis and the depth of the dissolved silica objects. Hua and Nahe Figure symbol description: 19; collection surface 24; high temperature crown 12; burner 14; artificial jade furnace chamber 26; high temperature furnace ι00.